Member Profile

@article{nokey,

title = {Cobalt-Based Catalyst Integration Into a Hierarchically Ordered Macro-Meso-microporous Carbon Cathode for High-performance Aqueous Zn-Sulfur Batteries},

author = {L Z Liu and M Z Hussain and D Lei and O Henrotte and E Cortes and A S Bandarenka and R A Fischer},

url = {\<Go to ISI\>://WOS:001554583800001},

doi = {10.1002/advs.202509945},

year  = {2025},

date = {2025-08-21},

journal = {Advanced Science},

abstract = {The pyrolytic synthesis of an ordered macro-meso-micro porous carbon cathode material (OM-PC) with integration of a Co3ZnC/Co catalyst is reported. It is derived from a Co-doped ZIF-8 framework via a templated in situ growth within the interstitial spaces of a preformed self-assembled polystyrene monolith, followed by the template removal. The hierarchical 3D architecture facilitates Zn2(+) diffusion and enhances reaction kinetics during charge-discharge processes. The integrated Co3ZnC/Co catalyst significantly improves the surface affinity of the porous carbon host for polysulfide trapping and accelerates polysulfide redox conversion, leading to enhanced sulfur utilization, mitigated shuttle effects, and longer cycling stability. The fabricated aqueous Zn-S battery with the sulfur-loaded cathode denoted as S@Co3ZnC/Co/OM-PC delivers a synergistic high discharge capacity of approximate to 1685 mA h g-1, which includes approximate to 115 mA h g-1 contributed from the I3 -/I- redox couple. The device shows low polarization and exhibits a minimal capacity decay of approximate to 0.027% per cycle over 400 cycles. It maintained a good rate performance of approximate to 1035 mA h g-1 at 3 A g-1, with long cycling stability. In-depth investigation reveals a multistep intermediate polysulfides conversion pathway in the aqueous electrolyte, which effectively avoids the sluggish solid-solid conversion.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Shifting Gears: Photochromic Metal-Organic Frameworks with Stimulus-Adaptable Performance},

author = {J Haimerl and G C Thaggard and B Kankanamalage and R B\"{u}hler and J Lim and K C Park and J Warnan and R A Fischer and N B Shustova},

url = {\<Go to ISI\>://WOS:001499947800001},

doi = {10.1021/jacs.5c04466},

issn = {0002-7863},

year  = {2025},

date = {2025-05-29},

journal = {Journal of the American Chemical Society},

abstract = {The tunability of the reaction parameter space is probed in the presented work through photoswitch-directed energy and charge transfer pathways induced by organic chromophores, hierarchically organized within a well-defined, light-harvesting metal-organic framework. Unique matrix-imposed changes in photoswitch photophysical properties, including the first report of visible light-induced photoisomerization of a spiropyran derivative, illustrate the critical synergy between the selected matrix and the photoresponsive compound. Moreover, the confined space of the utilized porous matrix allowed for mimicking isomerization kinetics of integrated sterically demanding photochromic moieties in solution. More importantly, such photoisomerization suppresses the charge transfer processes in favor of resonance energy transfer pathways instead. The demonstrated ability to shift between multiple relaxation pathways (e.g., charge transfer, energy transfer, or photoluminescence) as a function of the excitation wavelength resulted in photoswitch-directed tailoring of model phosphinylation reaction outcomes. Thus, incorporating spiropyran moieties within the framework allows for visible light to be harvested and funneled toward either a ligand-based reactive center or an acceptor molecule such as a photochromic unit. Moreover, the framework's chemical activity was promoted exclusively by organic linkers without the participation of metal nodes, the addition of (co)catalysts, or the use of harsh conditions at room temperature. Overall, this work paves the way for the development of stimulus-responsive platforms, for which chemical activity could be controlled through a photochromic moiety.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Engineering a Cu-Pd Paddle-Wheel Metal\textendashOrganic Framework for Selective CO2 Electroreduction},

author = {R Zhang and Y Liu and P Ding and J Huang and M Dierolf and S D Kelly and X Qiu and Y Chen and M Z Hussain and W Li and H Bunzen and K Achterhold and F Pfeiffer and I D Sharp and J Warnan and R A Fischer},

url = {https://doi.org/10.1002/anie.202414600},

doi = {https://doi.org/10.1002/anie.202414600},

issn = {1433-7851},

year  = {2024},

date = {2024-12-16},

journal = {Angewandte Chemie International Edition},

volume = {63},

number = {51},

pages = {e202414600},

abstract = {Abstract Optimizing the binding energy between the intermediate and the active site is a key factor for tuning catalytic product selectivity and activity in the electrochemical carbon dioxide reduction reaction. Copper active sites are known to reduce CO2 to hydrocarbons and oxygenates, but suffer from poor product selectivity due to the moderate binding energies of several of the reaction intermediates. Here, we report an ion exchange strategy to construct Cu?Pd paddle wheel dimers within Cu-based metal?organic frameworks (MOFs), [Cu3-xPdx(BTC)2] (BTC=benzentricarboxylate), without altering the overall MOF structural properties. Compared to the pristine Cu MOF ([Cu3(BTC)2], HKUST-1), the Cu?Pd MOF shifts CO2 electroreduction products from diverse chemical species to selective CO generation. In situ X-ray absorption fine structure analysis of the catalyst oxidation state and local geometry, combined with theoretical calculations, reveal that the incorporation of Pd within the Cu?Pd paddle wheel node structure of the MOF promotes adsorption of the key intermediate COOH* at the Cu site. This permits CO-selective catalytic mechanisms and thus advances our understanding of the interplay between structure and activity toward electrochemical CO2 reduction using molecular catalysts.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Electrostatic Tailoring of Freestanding Polymeric Films for Multifunctional Thermoelectrics, Hydrogels, and Actuators},

author = {S Tu and T Tian and J Zhang and S Liang and G Pan and X Ma and L Liu and R A Fischer and P M\"{u}ller-Buschbaum},

url = {https://doi.org/10.1021/acsnano.4c12502},

doi = {10.1021/acsnano.4c12502},

issn = {1936-0851},

year  = {2024},

date = {2024-12-09},

journal = {ACS Nano},

abstract = {Organic conducting polymer poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) has garnered enormous attention in organic electronics due to its low-cost solution processability, highly tunable conductivity, superior mechanical flexibility, and good biocompatibility together with excellent atmospheric stability. Nevertheless, limited electrical properties and unfavorable water instability of pristine PEDOT:PSS film impede its further implementation in a broad spectrum of practical applications. In this work, the successful tailoring of the intrinsic electrostatic interaction within PEDOT:PSS and consequent optimized electrical properties are enabled by a simple yet effective ionic salt post-treatment strategy. The choice of zinc di[bis(trifluoromethylsulfonyl)imide] (Zn(TFSI)2) not only endows the post-treated PEDOT:PSS film with high electrical properties but also other compelling characteristics, including superior water stability, excellent mechanical flexibility, and fast humidity responsiveness. Multidimensional characterizations are conducted to gain in-depth insights into the mechanisms underlying such improved performance, ranging from intermolecular interactions, polymer conformations, and doping levels to microstructural characteristics. Benefiting from these versatile properties, the as-prepared freestanding Zn(TFSI)2-post-treated PEDOT:PSS films can serve as promising candidates for high-performance polymeric materials integrated into multifunctional flexible electronics, including thermoelectric power generators, conductive hydrogels, and humidity-responsive actuators. This study demonstrates a facile methodology for the exploration of multifunctional conducting polymers, whose implications can extend across a wide range of next-generation wearable devices, bioelectronics, and soft robotics.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Ion-Transport Kinetics and Interface Stability Augmentation of Zinc Anodes Based on Fluorinated Covalent Organic Framework Thin Films},

author = {D Lei and W Shang and L Cheng and Poonam and W Kaiser and P Banerjee and S Tu and O Henrotte and J Zhang and A Gagliardi and J Jinschek and E Cort\'{e}s and P M\"{u}ller-Buschbaum and A S Bandarenka and M Z Hussain and R A Fischer},

url = {https://doi.org/10.1002/aenm.202403030},

doi = {https://doi.org/10.1002/aenm.202403030},

issn = {1614-6832},

year  = {2024},

date = {2024-12-01},

journal = {Advanced Energy Materials},

volume = {14},

number = {46},

pages = {2403030},

abstract = {Abstract Zinc (Zn) emerges as an ideal anode for aqueous-based energy storage devices because of its safety, non-toxicity, and cost-effectiveness. However, the reversibility of zinc anodes is constrained by unchecked dendrite proliferation and parasitic side reactions. To minimize these adverse effects, a highly oriented, crystalline 2D porous fluorinated covalent organic framework (denoted as TpBD-2F) thin film is in situ synthesized on the Zn anode as a protective layer. The zincophilic and hydrophobic TpBD-2F provides numerous 1D fluorinated nanochannels, which facilitate the hopping/transfer of Zn2+ and repel H2O infiltration, thus regulating Zn2+ flux and inhibiting interfacial corrosion. The resulting TpBD-2F protective film enabled stable plating/stripping in symmetric cells for over 1200 h at 2 mA cm?2. Furthermore, assembled full cells (Zn-ion capacitors) deliver an ultra-long cycling life of over 100 000 cycles at a current density of 5 A g?1, outperforming nearly all reported porous crystalline materials.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Tuning the Reconstruction of Metal\textendashOrganic Frameworks during the Oxygen Evolution Reaction},

author = {X Ma and L Schr\"{o}ck and G Gao and Q Ai and M Zarrabeitia and C Liang and M Z Hussain and R Khare and K-T Song and D J Zheng and M Koch and I E L Stephens and S Hou and Y Shao-Horn and J Warnan and A S Bandarenka and R A Fischer},

url = {https://doi.org/10.1021/acscatal.4c03618},

doi = {10.1021/acscatal.4c03618},

year  = {2024},

date = {2024-11-01},

journal = {ACS Catalysis},

volume = {14},

number = {21},

pages = {15916-15926},

abstract = {Recently, there has been growing interest in the conversion of metal\textendashorganic frameworks (MOFs) into metal-hydroxide catalysts for alkaline oxygen evolution reactions (OERs). While studies have shown that the initial OER performance of MOF-derived intermediates surpasses that of traditional metal-hydroxide catalysts, ongoing debates persist regarding these catalysts' durability and electrochemical stability. Moreover, the inevitable reorganization (aging) of MOF-derived catalysts from disordered to ordered phases, particularly those primarily composed of nickel oxyhydroxides, remains a topic of discussion. To address these issues, we propose a straightforward approach to mitigating MOF reconstruction and modulating aging in harsh alkaline environments by introducing additional organic carboxylate linkers into electrolytes. Specifically, we focus on two examples: Ni-BPDC-MOFs and NiFe-BPDC-MOFs, of formula [M2(OH)2BPDC] (M: Ni and Fe; BPDC = 4,4′-biphenyldicarboxylate). Experimental results indicate that alkaline electrolytes containing additional BPDC linkers exhibit enhanced OER activity and a prolonged electrochemical lifespan. Complemented by in situ Raman spectroscopy, our findings suggest that manipulating the coordination equilibrium of the organic linker involved in Ni-MOF formation (linker assembly) and reconstruction (linker leaching) leads to the formation of more disordered nickel oxyhydroxide phases as the active catalyst material, which shows enhanced OER performance.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Impact of Organic Anions on Metal Hydroxide Oxygen Evolution Catalysts},

author = {S Hou and L Xu and S Mukherjee and J Zhou and K-T Song and Z Zhou and S Zhang and X Ma and J Warnan and A S Bandarenka and R A Fischer},

url = {https://doi.org/10.1021/acscatal.4c01907},

doi = {10.1021/acscatal.4c01907},

year  = {2024},

date = {2024-08-16},

journal = {ACS Catalysis},

volume = {14},

number = {16},

pages = {12074-12081},

abstract = {Structural metamorphosis of metal\textendashorganic frameworks (MOFs) eliciting highly active metal-hydroxide catalysts has come to the fore lately, with much promise. However, the role of organic ligands leaching into electrolytes during alkaline hydrolysis remains unclear. Here, we elucidate the influence of organic carboxylate anions on a family of Ni or NiFe-based hydroxide type catalysts during the oxygen evolution reaction. After excluding interfering variables, i.e., electrolyte purity, Ohmic loss, and electrolyte pH, the experimental results indicate that adding organic anions to the electrolyte profoundly impacts the redox potential of the Ni species versus with only a negligible effect on the oxygen evolution activities. In-depth studies demonstrate plausible reasons behind those observations and allude to far-reaching implications in controlling electrocatalysis in MOFs, mainly where compositional modularity entails fine-tuning organic anions.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Autonomous self-healing hybrid energy harvester based on the combination of triboelectric nanogenerator and quantum dot solar cell},

author = {T Xiao and S Tu and T Tian and W Chen and W Cao and S Liang and R Guo and L Liu and Y Li and T Guan and H Liu and K Wang and M Schwartzkopf and R A Fischer and S V Roth and P M\"{u}ller-Buschbaum},

url = {https://www.sciencedirect.com/science/article/pii/S2211285524003033},

doi = {https://doi.org/10.1016/j.nanoen.2024.109555},

issn = {2211-2855},

year  = {2024},

date = {2024-06-15},

urldate = {2024-06-15},

journal = {Nano Energy},

volume = {125},

pages = {109555},

abstract = {Realization of multi-source energy harvesting with one single device would maximize power output. Thus, it is emerging as a promising strategy towards renewable energy generation and has attracted worldwide attention in the past decades. Capable of capturing mechanical energy that is ubiquitous in the ambient environment, triboelectric nanogenerator (TENG) has been considered a novel yet effective source towards next-generation energy harvesting. In this work, a flexible hybrid energy harvester (HEH) is developed via the rational integration of autonomous self-healing TENG and high bending-stable lead sulfide quantum dot (PbS QD) solar cell, enabling independent electricity generation by two different mechanisms. The single-electrode mode TENG component with self-healing is realized by a polydimethylsiloxane/Triton X-100 (PDMS/TX100) mixture as the dielectric layer and the shared gold (Au) electrode, which generates 0.39 µA of output current (Iout), 24.6 V of output voltages (Vout), 15.4 nC of transfer charges (Qsc), and 7.80 mW m−2 of output power peak density. The thin-film solar cell component is based on a PbS QD layer as the light absorber with a planar structure fabricated under low-cost and compatible conditions, achieving 22.8 mA cm−2 of short-circuit current density (Jsc) and 4.92% of power conversion efficiency (PCE). As a proof of concept, an electronic watch is successfully powered by harnessing ambient mechanical and solar energy with a hybridized energy cell. This approach will offer more opportunities to construct a versatile platform towards remote monitoring and smart home systems.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Influence of Chromophore Packing on Multiphoton Absorption in Carbazole-Based Pillar-Layered Coordination Polymers},

author = {S N Deger and Y Cui and J Warnan and R A Fischer and F \v{S}anda and J Hauer and A P\"{o}thig},

url = {https://doi.org/10.1021/acsaom.4c00080},

doi = {10.1021/acsaom.4c00080},

year  = {2024},

date = {2024-04-09},

journal = {ACS Applied Optical Materials},

volume = {2},

number = {9},

pages = {1770-1779},

abstract = {Coordination polymers (CP) and their subgroup metal\textendashorganic frameworks (MOF) are promising classes of modular multiphoton-absorption active materials. However, a detailed knowledge of the structure\textendashproperty relationship or generalized design principles remains elusive. This study examines how various packings of the chromophore linker 9,9′-stilbene-bis-carbazole-3,6-dicarboxylic acid in three synthesized zinc-based CPs affect their MPA activity. Different spatial chromophore arrangements are achieved by the so-called “pillar-layer” synthesis approach, using the chromophore and two different additional pillar linkers (4,4′-bipyridine and 1,2-bis(4-pyridyl)ethane) for CP formation. Two novel pillar-layered CPs, Zn2n(sbcd)(bpy)(DMAc)2n(H2O)3n and Zn2n(sbcd)(bpe)(DMAc)3n(H2O), are reported and examined in their two-photon-absorption-induced photoluminescence and compared to a previously synthesized CP Zn2n(sbcd)(DMAc)2n(H2O)1.5n, containing the same chromophore but no pillars. The comparison shows significant differences for the two-photon absorption cross-sections of the materials, improving it by incorporating the pillar. Our findings point toward the significance of controlling the chromophore orientation to tailor the nonlinear optical properties of the materials. These insights pave the way toward an aim-directed development of MOFs for advanced photonic applications.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Analysis of metal\textendashorganic framework-based photosynthetic CO2 reduction},

author = {P M Stanley and V Ramm and R A Fischer and J Warnan},

url = {https://doi.org/10.1038/s44160-024-00490-z},

doi = {10.1038/s44160-024-00490-z},

issn = {2731-0582},

year  = {2024},

date = {2024-03-07},

urldate = {2024-03-07},

journal = {Nature Synthesis},

volume = {3},

number = {3},

pages = {307-318},

abstract = {Solar-driven synthetic fuel production couples solar energy conversion and storage in the form of chemical bonds and therefore has potential as a clean technology. The past decade has witnessed the continuous development of metal\textendashorganic framework (MOF) materials with considerable interest towards combining light harvesting with catalytic CO2 conversion in one system. Built on a literature survey and data macroanalysis, this Perspective examines the development of this field by showcasing synthetic design approaches and highlighting attained milestones, while critically assessing pitfalls and opportunities. Five MOF-based material classifications for visible light-driven CO2 reduction are determined and discussed through key photocatalysis figures of merits and metrics. Analysis reveals MOFs as a favourable platform to achieve high product-selectivity CO2 photocatalysis. Non-standardized testing and reporting is found throughout this field and non-comparable product evolution rates, unverified carbon and electron source(s), and incomplete reporting checklists are identified as the main roadblocks towards accurate cross-laboratory benchmarking and breakthroughs. This Perspective additionally provides a balanced discussion and best practice recommendations to guide researchers investigating MOF-based materials for photocatalytic CO2 reduction.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Engineering ORR Electrocatalysts from Co8Pt4 Carbonyl Clusters via ZIF-8 Templating},

author = {P M Schneider and K L Kollmannsberger and C Cesari and R Khare and M Boniface and B Rold\'{a}n Cuenya and T Lunkenbein and M Elsner and S Zacchini and A S Bandarenka and J Warnan and R A Fischer},

url = {https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/celc.202300476},

doi = {https://doi.org/10.1002/celc.202300476},

issn = {2196-0216},

year  = {2024},

date = {2024-02-07},

journal = {ChemElectroChem},

volume = {11},

number = {5},

pages = {e202300476},

abstract = {Abstract To reduce the costs of proton exchange membrane fuel cells, the amount of Pt necessary to drive efficient oxygen reduction reaction (ORR) should be minimized. Particle nanostructuring, (nano-)alloying, and metal-doping can yield higher activities per Pt mass through tailoring catalysts owning a high number of active sites and precise electronic properties. In this work, the atom-precise [NBnMe3]2[Co8Pt4C2(CO)24] (Co8Pt4) cluster is encapsulated and activated in a zeolitic imidazolate framework (ZIF)-8, which unlocks the access to defined, bare Pt−Co nanoclusters, Co8±xPt4±yNC@ZIF-8, for the fabrication of highly active ORR catalysts. Upon controlled C-interfacing and ZIF-8-digestion, Co-doped Pt NPs (Pt27Co1) with a homogenous and narrow size distribution of (1.1±0.4) nm are produced on Vulcan® carbon. Restructuring of the Pt27Co1/C catalyst throughout the ORR measurement was monitored via high-angle annular dark field-scanning transmission electron microscopy and X-ray photoelectron spectroscopy. The measured ORR mass activity of (0.42±0.07) A mgPt−1 and the specific activity of (0.67±0.06) mA cmECSA−2 compare favourably with the catalyst obtained by direct C-interfacing the pristine Co8Pt4 cluster and with state-of-the-art Pt/C reference catalysts. Our results demonstrate the potential of ZIF-8-mediated Pt−Co NP synthesis toward devising ORR catalysts with high Pt-mass activity.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Benzene-1,4-Di(dithiocarboxylate) Linker-Based Coordination Polymers of Mn2+, Zn2+, and Mixed-Valence Fe2+/3+},

author = {M Aust and M I Sch\"{o}nherr and D P Halter and L Schr\"{o}ck and T Pickl and S N Deger and M Z Hussain and A Jentys and R B\"{u}hler and Z Zhang and K Meyer and M Kuhl and J Eichhorn and D D Medina and A P\"{o}thig and R A Fischer},

url = {https://doi.org/10.1021/acs.inorgchem.3c02471},

doi = {10.1021/acs.inorgchem.3c02471},

issn = {0020-1669},

year  = {2024},

date = {2024-01-08},

journal = {Inorganic Chemistry},

volume = {63},

number = {1},

pages = {129-140},

abstract = {Three new coordination polymers (CPs) constructed from the linker 1,4-di(dithiocarboxylate) (BDDTC2\textendash)─the sulfur-analog of 1,4-benzenedicarboxylate (BDC2\textendash)─together with Mn-, Zn-, and Fe-based inorganic SBUs are reported with description of their structural and electronic properties. Single-crystal X-ray diffraction revealed structural diversity ranging from one-dimensional chains in [Mn(BDDTC)(DMF)2] (1) to two-dimensional (2D) honeycomb sheets observed for [Zn2(BDDTC)3][Zn(DMF)5(H2O)] (2). Gas adsorption experiments confirmed a 3D porous structure for the mixed-valent material [Fe2(BDDTC)2(OH)] (3). 3 contains a 1:1 ratio of Fe2+/3+ ions, as evidenced by 57Fe M\"{o}ssbauer, X-band EPR, and X-ray absorption spectroscopy. Its empirical formula was established by elemental analysis, thermal gravimetric analysis, infrared vibrational spectroscopy, and X-ray absorption spectroscopy in lieu of elusive single-crystal X-ray diffraction data. In contrast to the Mn- and Zn-based compounds 1 and 2, the Fe2+/3+ CP 3 showed remarkably high electrical conductivity of 5 × 10\textendash3 S cm\textendash1 (according to van der Pauw measurements), which is within the range of semiconducting materials. Overall, our study confirms that sulfur derivatives of typical carboxylate linkers (e.g., BDC) are suitable for the construction of electrically conducting CPs, due to acceptedly higher covalency in metal\textendashligand bonding compared to the electrically insulating carboxylate CPs or metal-organic frameworks. At the same time, the direct comparison between insulating CPs 1 and 2 with CP 3 emphasizes that the electronic structure of the metal is likewise a crucial aspect to construct electrically conductive materials.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Modulation of electronic and ionic conduction in mixed polymer conductors via additive engineering: Towards targeted applications under varying humidity},

author = {S Tu and T Tian and A Vagias and L F Huber and L Liu and S Liang and R A Fischer and S Bernstorff and P M\"{u}ller-Buschbaum},

url = {https://www.sciencedirect.com/science/article/pii/S1385894723057650},

doi = {https://doi.org/10.1016/j.cej.2023.147034},

issn = {1385-8947},

year  = {2023},

date = {2023-12-01},

journal = {Chemical Engineering Journal},

volume = {477},

pages = {147034},

abstract = {Polymer solids with mixed ion and electron transport hold great promise for next-generation organic electronics, and rational regulation of ionic/electronic contribution within these materials can enable a broadened spectrum of practical applications. However, a fundamental understanding of the conduction mechanisms and their correlations with morphological characteristics remains limited, especially under varying environmental humidity conditions. In the present work, simple additive engineering enables the effective regulation of electronic and ionic contribution in poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) based conductors, giving rising to ion- and/or electron-dominant conductions. As a demonstration, PEDOT:PSS films with different electrical characteristics are successfully applied for thermal energy harvesting, healthcare monitoring and human motion detection upon humidity exposure. Combining operando alternating current (AC) impedance spectroscopy and grazing incidence small-angle X-ray scattering at low and high humidity levels, additive-dependent charge transport mechanisms are elucidated, and correlations between morphological alterations and conductivity evolutions are revealed. This work achieves highly tailorable PEDOT:PSS conduction utilizing Zonyl, dimethyl sulfoxide (DMSO) and carbon nanotubes (CNTs) as additives with distinct humidity responses and gains an in-depth comprehension of underlying mechanisms, which are expected to pave the way for next-generation organic electronics.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Optimization of p-Type Cu2O Nanocube Photocatalysts Based on Electronic Effects},

author = {R Lin and H Chen and T Cui and Z Zhang and Q Zhou and L Nan and W-C Cheong and L Schr\"{o}ck and V Ramm and Q Ding and X Liang and S Saris and F J Wendisch and S A Maier and R A Fischer and Y Zhu and D Wang and E Cortes},

url = {https://doi.org/10.1021/acscatal.3c02710},

doi = {10.1021/acscatal.3c02710},

year  = {2023},

date = {2023-08-14},

journal = {ACS Catalysis},

pages = {11352-11361},

abstract = {The size effect in semiconductor photocatalysis has been widely investigated but still remains elusive. Herein, employing p-type Cu2O nanocubes as the heterogeneous photocatalysts, we propose a feasible size optimization strategy to enhance the photocatalytic performance of semiconductors. With the size of Cu2O increasing from 2.5 nm (exciton Bohr radius) to 5 nm (twice the exciton Bohr radius), the corresponding calculated band gap of Cu2O decreases from 3.39 to 2.41 eV, indicating that controlling the size to above twice the exciton Bohr radius is vital for retaining the visible-light response of Cu2O. Based on the theoretical calculations and experimental measurements of the charge carrier dynamics, we found that the synthesized 30 nm Cu2O nanocubes have an electron diffusion length of 191 nm, while 229 nm Cu2O nanocubes show an electron diffusion length of 45 nm. An electron diffusion length larger than the semiconductor particle size lowers the electron\textendashhole recombination, resulting in a visible-light CO generation rate 23.4 times higher for the smaller Cu2O nanocubes than that for the larger ones. These results verify that confining Cu2O size to within the minority carrier diffusion length and above twice the exciton Bohr radius is a promising way to enhance Cu2O photocatalytic activity.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Mechanistic Insights into ZIF-8 Encapsulation of Atom-Precise Pt(M) Carbonyl Clusters},

author = {K L Kollmannsberger and Poonam and C Cesari and R Khare and T Kratky and M Boniface and O Tomanec and J Michali\v{c}ka and E Mosconi and A Gagliardi and S G\"{u}nther and W Kaiser and T Lunkenbein and S Zacchini and J Warnan and R A Fischer},

url = {https://doi.org/10.1021/acs.chemmater.3c00807},

doi = {10.1021/acs.chemmater.3c00807},

issn = {0897-4756},

year  = {2023},

date = {2023-07-12},

journal = {Chemistry of Materials},

volume = {35},

number = {14},

pages = {5475-5486},

abstract = {Precisely designing metal nanoparticles (NPs) is the cornerstone for maximizing their efficiency in applications like catalysis or sensor technology. Metal\textendashorganic frameworks (MOFs) with their defined and tunable pore systems provide a confined space to host and stabilize small metal NPs. In this work, the MOF encapsulation of various atom-precise clusters following the bottle-around-ship approach is investigated, providing general insights into the scaffolding mechanism. Eleven carbonyl-stabilized Pt(M) (M = Co, Ni, Fe, and Sn) clusters are employed for the encapsulation in the zeolitic imidazolate framework (ZIF)-8. Infrared and UV/Vis spectroscopy, density functional theory, and ab initio molecular dynamics revealed structure\textendashencapsulation relationship guidelines. Thereby, cluster polarization, size, and composition were found to condition the scaffolding behavior. Encaging of [NBnMe3]2[Co8Pt4C2(CO)24] (Co8Pt4) is thus achieved as the first MOF-encapsulated bimetallic carbonyl cluster, Co8Pt4@ZIF-8, and is fully characterized including X-ray absorption near edge and extended X-ray absorption spectroscopy. ZIF-8 confinement not only promotes property changes, like the T-dependent magnetism, but it also further allows heat-induced ligand-stripping without altering the cluster size, enabling the synthesis of naked, heterometallic, close to atom-precise clusters.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Structure\textendashActivity Relationships in Ni- Carboxylate-Type Metal\textendashOrganic Frameworks’ Metamorphosis for the Oxygen Evolution Reaction},

author = {X Ma and D J Zheng and S Hou and S Mukherjee and R Khare and G Gao and Q Ai and B Garlyyev and W Li and M Koch and J Mink and Y Shao-Horn and J Warnan and A S Bandarenka and R A Fischer},

url = {https://doi.org/10.1021/acscatal.3c00625},

doi = {10.1021/acscatal.3c00625},

year  = {2023},

date = {2023-05-22},

journal = {ACS Catalysis},

volume = {13},

number = {11},

pages = {7587-7596},

abstract = {Metal\textendashorganic frameworks (MOFs) have been reported to catalyze the oxygen evolution reaction (OER). Despite the established links between the pristine MOFs and their derived metal hydroxide electrocatalysts, several limitations still preclude understanding of the critical factors determining the OER performance. Of prime importance appears the choice of MOF and how its compositions relate to the catalyst stability and in turn to the reconstruction or metamorphosis mechanisms into the active species under OER conditions. An isoreticular series of Ni-carboxylate-type MOFs [Ni2(OH)2L] was chosen to elucidate the effects of the carboxylate linker length expansion and modulation of the linker\textendashlinker π\textendashπ interactions (L = 1,4-benzodicarboxylate, 2,6-napthalenedicarboxylate, biphenyl-4,4′-dicarboxylate, and p-terphenyl-4,4″-dicarboxylate). Degradation and reconstruction of MOFs were systematically investigated. The linker controls the transformation of Ni-MOF into distinct nickel hydroxide phases, and the conversion from α-Ni(OH)2 to β-Ni(OH)2, thus correlating the Ni-MOF composition with the OER activity of the Ni-MOF-derived metastable nickel hydroxide phase mixture.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Defect engineering in MIL-125-(Ti)-NH2 for enhanced photocatalytic H2 generation},

author = {L Pukdeejorhor and S Wannapaiboon and J Berger and K Rodewald and S Thongratkaew and S Impeng and J Warnan and S Bureekaew and R A Fischer},

url = {http://dx.doi.org/10.1039/D2TA09963B},

doi = {10.1039/D2TA09963B},

issn = {2050-7488},

year  = {2023},

date = {2023-03-29},

journal = {Journal of Materials Chemistry A},

volume = {11},

number = {16},

pages = {9143-9151},

abstract = {Pre-designing starting materials is a sensible approach to tailor the synthetic, optoelectronic, and physicochemical properties of a photocatalyst towards higher activity without the need for additional active species. MIL-125-(Ti)-NH2, a metal\textendashorganic framework (MOF) photocatalytically active for H2 evolution, was first successfully synthesised at a relatively low temperature of 70 °C upon employing pre-designed titanium-oxo-carboxylate clusters. While rearrangement of the original cluster enabled successful MIL-125-(Ti)-NH2 formation, its ligand stoichiometry favoured MOFs with abundant “defects” at the Ti centres which in turn acted as accessible active sites for H2 generation. The catalytic sites and their local geometry were studied by pyridine-adsorbed Fourier transform infrared spectroscopy, X-ray absorption near-edge structure, and extended X-ray absorption fine structure. Interestingly, the frameworks prepared using pre-designed titanium-oxo clusters can alter electronic optical properties and energy levels. In the presence of triethanolamine as an electron donor and under visible light irradiation, this led to a ∼3.5 times higher H2 evolution rate in the titanium-oxo cluster MOF compared to MIL-125-(Ti)-NH2 obtained by typical hydrothermal synthesis. The obtained catalyst also exhibits a good-reusable performance for at least three consecutive runs without any loss in its reactivity. Pre-designed clusters can be simply utilised to generate accessible active sites and manipulate electrical properties for enhancing catalytic performance.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Photocatalytic CO2-to-Syngas Evolution with Molecular Catalyst Metal-Organic Framework Nanozymes},

author = {P M Stanley and A Y Su and V Ramm and P Fink and C Kimna and O Lieleg and M Elsner and J A Lercher and B Rieger and J Warnan and R A Fischer},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adma.202207380},

doi = {https://doi.org/10.1002/adma.202207380},

issn = {0935-9648},

year  = {2023},

date = {2023-02-01},

urldate = {2023-02-01},

journal = {Advanced Materials},

volume = {35},

issue = {6},

pages = {2207380},

abstract = {Abstract Syngas, a mixture of CO and H2, is a high-priority intermediate for producing several commodity chemicals, e.g., ammonia, methanol, and synthetic hydrocarbon fuels. Accordingly, parallel sunlight-driven catalytic conversion of CO2 and protons to syngas is a key step toward a sustainable energy cycle. State-of-the-art catalytic systems and materials often fall short as application-oriented concurrent CO and H2 evolution requires challenging reaction conditions which can hamper stability, selectivity, and efficiency. Here a light-harvesting metal-organic framework hosting two molecular catalysts is engineered to yield colloidal, water-stable, versatile nanoreactors for photocatalytic syngas generation with highly controllable product ratios. In-depth fluorescence, X-ray, and microscopic studies paired with kinetic analysis show that the host delivers energy efficiently to active sites, conceptually yielding nanozymes. This unlocked sustained CO2 reduction and H2 evolution with benchmark turnover numbers and record incident photon conversions up to 36%, showcasing a highly active and durable all-in-one material toward application in solar energy-driven syngas generation.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Graphene-Based Metal\textendashOrganic Framework Hybrids for Applications in Catalysis, Environmental, and Energy Technologies},

author = {K Jayaramulu and S Mukherjee and D M Morales and D P Dubal and A K Nanjundan and A Schneemann and J Masa and S Kment and W Schuhmann and M Otyepka and R Zbo\v{r}il and R A Fischer},

url = {https://doi.org/10.1021/acs.chemrev.2c00270},

doi = {10.1021/acs.chemrev.2c00270},

issn = {0009-2665},

year  = {2022},

date = {2022-12-28},

journal = {Chemical Reviews},

volume = {122},

number = {24},

pages = {17241-17338},

abstract = {Current energy and environmental challenges demand the development and design of multifunctional porous materials with tunable properties for catalysis, water purification, and energy conversion and storage. Because of their amenability to de novo reticular chemistry, metal\textendashorganic frameworks (MOFs) have become key materials in this area. However, their usefulness is often limited by low chemical stability, conductivity and inappropriate pore sizes. Conductive two-dimensional (2D) materials with robust structural skeletons and/or functionalized surfaces can form stabilizing interactions with MOF components, enabling the fabrication of MOF nanocomposites with tunable pore characteristics. Graphene and its functional derivatives are the largest class of 2D materials and possess remarkable compositional versatility, structural diversity, and controllable surface chemistry. Here, we critically review current knowledge concerning the growth, structure, and properties of graphene derivatives, MOFs, and their graphene@MOF composites as well as the associated structure\textendashproperty\textendashperformance relationships. Synthetic strategies for preparing graphene@MOF composites and tuning their properties are also comprehensively reviewed together with their applications in gas storage/separation, water purification, catalysis (organo-, electro-, and photocatalysis), and electrochemical energy storage and conversion. Current challenges in the development of graphene@MOF hybrids and their practical applications are addressed, revealing areas for future investigation. We hope that this review will inspire further exploration of new graphene@MOF hybrids for energy, electronic, biomedical, and photocatalysis applications as well as studies on previously unreported properties of known hybrids to reveal potential “diamonds in the rough”.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Using Metal\textendashOrganic Frameworks to Confine Liquid Samples for Nanoscale NV-NMR},

author = {K S Liu and X Ma and R Rizzato and A L Semrau and A Henning and I D Sharp and R A Fischer and D B Bucher},

url = {https://doi.org/10.1021/acs.nanolett.2c03069},

doi = {10.1021/acs.nanolett.2c03069},

issn = {1530-6984},

year  = {2022},

date = {2022-12-08},

journal = {Nano Letters},

abstract = {Atomic-scale magnetic field sensors based on nitrogen vacancy (NV) defects in diamonds are an exciting platform for nanoscale nuclear magnetic resonance (NMR) spectroscopy. The detection of NMR signals from a few zeptoliters to single molecules or even single nuclear spins has been demonstrated using NV centers close to the diamond surface. However, fast molecular diffusion of sample molecules in and out of the nanoscale detection volumes impedes their detection and limits current experiments to solid-state or highly viscous samples. Here, we show that restricting diffusion by confinement enables nanoscale NMR spectroscopy of liquid samples. Our approach uses metal\textendashorganic frameworks (MOF) with angstrom-sized pores on a diamond chip to trap sample molecules near the NV centers. This enables the detection of NMR signals from a liquid sample, which would not be detectable without confinement. These results set the route for nanoscale liquid-phase NMR with high spectral resolution.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Porphyrinic MOF derived Single-atom electrocatalyst enables methanol oxidation},

author = {Z Zhou and J Zhang and S Mukherjee and S Hou and R Khare and M D\"{o}blinger and O Tomanec and M Otyepka and M Koch and P Gao and L Zhou and W Li and R A Fischer},

url = {https://www.sciencedirect.com/science/article/pii/S1385894722033745},

doi = {https://doi.org/10.1016/j.cej.2022.137888},

issn = {1385-8947},

year  = {2022},

date = {2022-12-01},

journal = {Chemical Engineering Journal},

volume = {449},

pages = {137888},

abstract = {Electrochemical methanol oxidation reaction (MOR) serves as a key route for renewable energy technologies. However, unmet challenges remain in the preparation of low-cost, efficient and robust electrocatalysts for MOR. Herein, a porphyrinic metal\textendashorganic framework (MOF) with spatially isolated Ni centres is prepared. Upon pyrolysis, this affords a single-atom Ni implanted nitrogen-doped porous carbon (20% Ni-N-C). Integrating abundant and accessible single-atom Ni sites, hierarchical porosity, excellent conductivity with stable Ni-N4 moieties all in one, the derived ultra-stable 20% Ni-N-C exhibits high MOR activity, impressive durability and CO tolerance, thereby outperforming state-of-the-art nonprecious metal based electrocatalysts. Computational insights reveal a low energy barrier of 1.19 eV for the rate-determining step, in agreement with the experimental observations of superior MOR activity. As the first foray into improving MOR efficiency with nonprecious metal based single-atom electrocatalysts, the yet-unrealized potential for MOFs and related modular hybrids is demonstrated.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Merging molecular catalysts and metal\textendashorganic frameworks for photocatalytic fuel production},

author = {P M Stanley and J Haimerl and N B Shustova and R A Fischer and J Warnan},

url = {https://doi.org/10.1038/s41557-022-01093-x},

doi = {10.1038/s41557-022-01093-x},

issn = {1755-4349},

year  = {2022},

date = {2022-11-28},

journal = {Nature Chemistry},

volume = {14},

number = {12},

pages = {1342-1356},

abstract = {In the effort to generate sustainable clean energy from abundant resources such as water and carbon dioxide, solar fuel production\textemdashthe combination of solar-light harvesting and the generation of efficient chemical energy carriers\textemdashby artificial molecular photosystems is very attractive. Molecular constituents that display attractive features for chemical energy conversion (such as high product selectivity and atom economy) have been developed, and their interfacing with host materials has enabled recyclability, controlled site positioning, as well as access to fundamental insights into the catalytic mechanism and environment-governed selectivity. Among the wide variety of supports, metal\textendashorganic frameworks (MOFs) possess valuable characteristics (such as their porosity and versatility) that can influence the reaction environment and material architecture in a unique fashion. Here we highlight the various existing synthetic strategies to graft molecular complexes such as catalysts and photosensitizers onto MOFs for solar fuel production. The opportunities and limitations of one-pot and stepwise approaches are critically assessed, and the resulting materials are discussed based on their photocatalytic performances and the practical applicability of selected examples.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Alkaline Earth Metal\textendashOrganic Frameworks Based on Tetratopic Anthraquinone-Based Linkers: Synthesis, Characterization, and Photochemical Applications},

author = {J G M De Carvalho and K Gei\sser and S J Weish\"{a}upl and R A Fischer and A P\"{o}thig},

url = {https://doi.org/10.1021/acs.inorgchem.2c01643},

doi = {10.1021/acs.inorgchem.2c01643},

issn = {0020-1669},

year  = {2022},

date = {2022-10-10},

journal = {Inorganic Chemistry},

volume = {61},

number = {40},

pages = {15831-15840},

abstract = {A tetratopic bis(diphenylamino)anthraquinone linker is presented, and its physicochemical properties are evaluated. The linker is shown to successfully coordinate alkaline earth metals leading to four new reported metal\textendashorganic frameworks (MOFs), which have been fully characterized, including single-crystal X-ray diffraction. The physicochemical and emissive properties of the MOF materials are investigated and compared to those of the uncoordinated ligand. Finally, the catalytic behavior of the ligand and the MOF materials toward the photooxidation of sulfides is described.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Coordination Polymers Based on Carbazole-Derived Chromophore Linkers for Optimized Multiphoton Absorption: A Structural and Photophysical Study},

author = {S J Weish\"{a}upl and Y Cui and S N Deger and H Syed and A Ovsianikov and J Hauer and A P\"{o}thig and R A Fischer},

url = {https://doi.org/10.1021/acs.chemmater.2c01525},

doi = {10.1021/acs.chemmater.2c01525},

issn = {0897-4756},

year  = {2022},

date = {2022-08-08},

journal = {Chemistry of Materials},

volume = {34},

number = {16},

pages = {7402-7411},

abstract = {Multiphoton absorption (MPA), as a subgroup of non-linear optical effects, is of high interest in modern materials research since it has a great applicability in optoelectronics. However, most of the commonly used materials featuring MPA properties are chromophore molecules, which are limited by their thermal stability and uncontrolled aggregation in high-concentration solutions. A prominent material class which could in principle overcome these problems are metal\textendashorganic frameworks and coordination polymers (CPs) as they can be modularly tuned to possess chemical and thermal stability. In addition, by incorporating chromophores as linkers in the framework, their molecular properties can be retained or even enhanced. In this article, we report the synthesis and characterization of three new and highly MPA-active CPs, Zn2(sbcd)(DMAc)2(H2O)1.5, Sr(fbcd)(DMAc)0.25(H2O)3.5, and Ba(fbcd)(DMAc)2.5(H2O)1.5, based on two carbazole-containing chromophore linkers: a previously reported 9,9′-stilbene-bis-carbazole-3,6-dicarboxylic acid (H4sbcd) and the new 2,7-fluorene-9,9′-dimethyl-bis-carbazole-3,6-dicarboxylic acid (H4fbcd). Single-crystal structure analysis of the zinc-based CP reveals a sql network, whereas the barium- and strontium-based CPs are isostructural, showing a 4,8-c network topology. Z-scan analysis of the networks shows large two-photon absorption cross-sections σ(2) of 2100 to 33,300 GM, which is an enhancement of up to 3 orders of magnitude in comparison to the solvated linker and is also one of the highest MPA-cross-sections reported for CPs up to date.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Operando Study of Structure Degradation in Solid-State Dye-Sensitized Solar Cells with a TiO2 Photoanode Having Ordered Mesopore Arrays},

author = {N Li and R Guo and A L Oechsle and M A Reus and S Liang and L Song and K Wang and D Yang and F Allegretti and A Kumar and M Nuber and J Berger and S Bernstorff and H Iglev and J Hauer and R A Fischer and J V Barth and P M\"{u}ller-Buschbaum},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/solr.202200373},

doi = {https://doi.org/10.1002/solr.202200373},

issn = {2367-198X},

year  = {2022},

date = {2022-05-31},

journal = {Solar RRL},

volume = {n/a},

number = {n/a},

pages = {2200373},

abstract = {Via operando grazing-incidence small-angle X-ray scattering, the degradation mechanisms of solid-state dye-sensitized solar cells (ssDSSCs) using two types of ordered mesoporous TiO2 scaffolds with different pore sizes, and an exemplary dye D205, are investigated. The temporal evolution of the inner morphology shows a strong impact on device performance. The photoinduced dye aggregation on the TiO2 surface leads to an increase in the domain radius but a decreased spatial order of the photoactive layer during the burn-in stage. This dye aggregation on the TiO2 surface causes the short-circuit current density loss, which plays a major role in the power conversion efficiency decay. Finally, it is found that a larger surface area in the small-pore sample yields a faster short-circuit current density decay as compared with the big-pore sample. Therefore, a control of dye aggregation and the pore size of TiO2 photoelectrodes is crucial for the stability of TiO2-based ssDSSCs.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Recent advances of multiphoton absorption in metal\textendashorganic frameworks},

author = {S J Weish\"{a}upl and D C Mayer and Y Cui and P Kumar and H Oberhofer and R A Fischer and J Hauer and A P\"{o}thig},

url = {http://dx.doi.org/10.1039/D2TC00191H},

doi = {10.1039/D2TC00191H},

issn = {2050-7526},

year  = {2022},

date = {2022-04-14},

journal = {Journal of Materials Chemistry C},

volume = {10},

number = {18},

pages = {6912-6934},

abstract = {Inorganic\textendashorganic hybrid materials such as metal\textendashorganic frameworks (MOFs) or coordination polymers (CPs) are of high interest in chemistry and materials science due to their modular design and versatile applicability, for example in gas storage, catalysis and sensor systems. Moreover, their tunability allows for photophysically relevant applications, such as multiphoton absorption (MPA). MPA is one of the most important non-linear optical effects, employed in optical limiting and two-photon fluorescence microscopy as well as for three-dimensional data storage. In this review we outline recent advances of MOFs and CPs regarding their MPA response properties. In the first part, we discuss the theoretical background of MPA absorbing linker molecules and effect of excitonic coupling when aligned within a rigid framework assembly. Furthermore, different state-of-the-art scanning and non-scanning measurement techniques for two-photon absorption (TPA) spectroscopy are compared for their advantages as well as their limitations. Additionally, we comprehensively present the latest progress of linker-based MPA materials (MOFs or surface anchored MOFs) and the relation between their framework-structure and their MPA cross section. In the last part of this review, future applications and research directions for the above outlined materials are discussed and illustrated.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {A Perylenediimide-Based Zinc-Coordination Polymer for Photosensitized Singlet-Oxygen Generation},

author = {S N Deger and S J Weish\"{a}upl and A P\"{o}thig and R A Fischer},

url = {https://www.mdpi.com/1996-1073/15/7/2437},

issn = {1996-1073},

year  = {2022},

date = {2022-03-25},

journal = {Energies},

volume = {15},

number = {7},

pages = {2437},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Dual In-situ Laser Techniques Underpin the Role of Cations in Impacting Electrocatalysts},

author = {S Hou and L Xu and X Ding and R M Kluge and T K Sarpey and R W Haid and B Garlyyev and S Mukherjee and J Warnan and M Koch and S Zhang and W Li and A S Bandarenka and R A Fischer},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202201610},

doi = {https://doi.org/10.1002/anie.202201610},

issn = {1433-7851},

year  = {2022},

date = {2022-03-10},

journal = {Angewandte Chemie International Edition},

volume = {n/a},

number = {n/a},

abstract = {Understanding the electrode/electrolyte interface is crucial for optimizing electrocatalytic performances. Here, we demonstrate that the nature of alkali metal cations can profoundly impact the oxygen evolution activity of surface-mounted metal-organic framework (SURMOF) derived electrocatalysts, which are based on NiFe(OOH). In-situ Raman spectroscopy results show that Raman shifts of the Ni-O bending vibration are inversely proportional to the mass activities from Cs+ to Li+. Particularly, a laser-induced current transient technique was introduced to study the cation-dependent electric double layer properties and their effects on the activity. The catalytic trend appeared to be closely related to the potential of maximum entropy of the system, suggesting a strong cation impact on the interfacial water layer structure. Our results highlight how the electrolyte composition can be used to maximize the performance of SURMOF derivatives toward electrochemical water splitting.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Avoiding Pyrolysis and Calcination: Advances in the Benign Routes Leading to MOF-Derived Electrocatalysts},

author = {S Mukherjee and S Hou and S A Watzele and B Garlyyev and W Li and A S Bandarenka and R A Fischer},

url = {https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/celc.202101476},

doi = {https://doi.org/10.1002/celc.202101476},

issn = {2196-0216},

year  = {2022},

date = {2022-01-01},

urldate = {2022-01-01},

journal = {ChemElectroChem},

volume = {9},

number = {9},

pages = {e202101476},

abstract = {Abstract Taking cognizance of the United Nations Sustainable Development Goal 7 “affordable and clean energy”, metal\textendashorganic frameworks (MOFs) and derived materials have spurred research interest in electrocatalysis. New findings have made headway in water splitting (oxygen evolution reaction and hydrogen evolution reaction) and other electrocatalysis, including the oxygen reduction reaction and electrochemical CO2 reduction. Thanks to their structural versatility and compositional modularity, MOFs offer bespoke design paradigms for electrocatalyst development. Albeit most advances in this area are predicated upon direct carbonization (pyrolysis) of MOFs/MOF composites, eschewing these energy-intensive and high-cost methods, this review summarizes all recent advances in MOF-based electrocatalysts exclusively prepared through indirect post-treatments.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Hierarchical porous metal\textendashorganic framework materials for efficient oil\textendashwater separation},

author = {H Saini and E Otyepkov\'{a} and A Schneemann and R Zbo\v{r}il and M Otyepka and R A Fischer and K Jayaramulu},

url = {http://dx.doi.org/10.1039/D1TA10008D},

doi = {10.1039/D1TA10008D},

issn = {2050-7488},

year  = {2022},

date = {2022-01-01},

urldate = {2022-01-01},

journal = {Journal of Materials Chemistry A},

volume = {10},

number = {6},

pages = {2751\textendash2785},

abstract = {Oil contaminated water is a global issue, decreasing the quality of water sources and is posing a threat to the health of humans and many ecosystems. The utilization of industrial level strategies is limited mainly due to their complex and time-consuming processing. Considering this, we choose materials for separating oils from water based on their ease of handling and good performance. However, high surface area porous materials, such as linens, zeolites, cotton, etc., offer low efficiency for oil/water separation. Special wettability is the most promising property of materials and is helpful for oil\textendashwater separation. Metal\textendashorganic frameworks (MOFs), a class of highly tunable porous structures of metal clusters/ions and multidentate organic ligands, offer exciting prospects for various applications. The unique tunability of the structure and properties of these materials can endow them with special wettability for the treatment of oily water. This review focuses on hydrophobic\textendasholeophilic, hydrophilic\textendashunderwater oleophobic and switchable wettability MOFs and their implementation as oil/water separating materials. We classify different MOF-based materials as filtration materials, absorbents or adsorbents based on the methodology they are used in for separating oil/water mixtures and emulsions. We discuss different subclasses of MOF-based filtration, absorbent and adsorbent materials and summarize recent developments in their oil/water separation applications. Finally, we end our discussion by critically analyzing the importance of these MOFs for separating oils from water and highlighting potential future directions for achieving improved performance.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Prospects of Using the Laser-Induced Temperature Jump Techniques for Characterisation of Electrochemical Systems},

author = {X Ding and T K Sarpey and S Hou and B Garlyyev and W Li and R A Fischer and A S Bandarenka},

url = {https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/celc.202101175},

doi = {https://doi.org/10.1002/celc.202101175},

issn = {2196-0216},

year  = {2022},

date = {2022-01-01},

urldate = {2022-01-01},

journal = {ChemElectroChem},

volume = {9},

number = {4},

pages = {e20210117},

abstract = {Abstract Understanding the processes, phenomena, and mechanisms occurring at the electrode/electrolyte interface is a prerequisite and significant for optimizing electrochemical systems. To this end, the advent of sub-microsecond laser pulses has paved the way and eased the investigations of the electrochemical interface (e. g., electric double layer), which hitherto is difficult. The laser-induced current transient (LICT) and laser-induced potential transient (LIPT) techniques have proven to be valuable and unique tools for measuring key parameters of the electrified interface, such as the potential of maximum entropy (PME) and the potential of zero charge (PZC). Herein, we present a summary of studies performed in recent years using laser-induced temperature jump techniques. The relation between the PME/PZC and the electrocatalytic properties of various electrochemical interfaces are particularly highlighted. Special attention is given to its applications in investigating different systems and analyzing the influence of the electrolyte components, electrode composition and structure on the PME/PZC and various electrochemical processes. Moreover, possible applications of the LICT/LIPT techniques to investigate the interfacial properties of a myriad of materials, including surface-mounted metal-organic frameworks and metal oxides, are elaborated.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Introducing Benzene-1,3,5-tri(dithiocarboxylate) as a Multidentate Linker in Coordination Chemistry},

author = {M Aust and A J Herold and L Niederegger and C Schneider and D C Mayer and M Drees and J Warnan and A P\"{o}thig and R A Fischer},

url = {https://doi.org/10.1021/acs.inorgchem.1c03045},

doi = {10.1021/acs.inorgchem.1c03045},

issn = {0020-1669},

year  = {2021},

date = {2021-12-06},

journal = {Inorganic Chemistry},

volume = {60},

number = {24},

pages = {19242-19252},

abstract = {Benzene-1,3,5-tri(dithiocarboxylate) (BTDTC3\textendash), the sulfur-donor analogue of trimesate (BTC3\textendash, benzene-1,3,5-tricarboxylate), is introduced, and its potential as a multidentate, electronically bridging ligand in coordination chemistry is evaluated. For this, the sodium salt Na3BTDTC has been synthesized, characterized, and compared with the sodium salt of the related ditopic benzene-1,4-di(dithiocarboxylate) (Na2BDDTC). Single-crystal X-ray diffraction of the respective tetrahydrofuran (THF) solvates reveals that such multitopic aromatic dithiocarboxylate linkers can form both discrete metal complexes (Na3BTDTC·9THF) and (two-dimensional) coordination polymers (Na2BDDTC·4THF). Additionally, the versatile coordination behavior of the novel BTDTC3\textendash ligand is demonstrated by successful synthesis and characterization of trinuclear Cu(I) and hexanuclear Mo(II)2 paddlewheel complexes. The electronic structure and molecular orbitals of both dithiocarboxylate ligands as well as their carboxylate counterparts are investigated by density functional theory computational methods. Electrochemical investigations suggest that BTDTC3\textendash enables electronic communication between the coordinated metal ions, rendering it a promising tritopic linker for functional coordination polymers.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Emerging MXene@Metal\textendashOrganic Framework Hybrids: Design Strategies toward Versatile Applications},

author = {H Saini and N Srinivasan and V \v{S}edajov\'{a} and M Majumder and D P Dubal and M Otyepka and R Zbo\v{r}il and N Kurra and R A Fischer and K Jayaramulu},

url = {https://doi.org/10.1021/acsnano.1c06402},

doi = {10.1021/acsnano.1c06402},

issn = {1936-0851},

year  = {2021},

date = {2021-11-18},

journal = {ACS Nano},

volume = {15},

number = {12},

pages = {18742-18776},

abstract = {Rapid progress on developing smart materials and design of hybrids is motivated by pressing challenges associated with energy crisis and environmental remediation. While emergence of versatile classes of nanomaterials has been fascinating, the real excitement lies in the design of hybrid materials with tunable properties. Metal\textendashorganic frameworks (MOFs) are the key materials for gas sorption and electrochemical applications, but their sustainability is challenged by limited chemical stability, poor electrical conductivity, and intricate, inaccessible pores. Despite tremendous efforts towards improving the stability of MOF materials, little progress has made researchers inclined toward developing hybrid materials. MXenes, a family of two-dimensional transition-metal carbides, nitrides and carbonitrides, are known for their compositional versatility and formation of a range of structures with rich surface chemistry. Hybridization of MOFs with functional layered MXene materials may be beneficial if the host structure provides appropriate interactions for stabilizing and improving the desired properties. Recent efforts have focused on integrating Ti3C2Tx and V2CTx MXenes with MOFs to result in hybrid materials with augmented electrochemical and physicochemical properties, widening the scope for emerging applications. This review discusses the potential design strategies of MXene@MOF hybrids, attributes of tunable properties in the resulting hybrids, and their applications in water treatment, sensing, electrochemical energy storage, smart textiles, and electrocatalysis. Comprehensive discussions on the recent efforts on rapidly evolving MXene@MOF materials for various applications and potential future directions are highlighted.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Two-dimensional MOF-based liquid marbles: surface energy calculations and efficient oil\textendashwater separation using a ZIF-9-III@PVDF membrane},

author = {H Saini and P Kallem and E Otyepkov\'{a} and F Geyer and A Schneemann and V Ranc and F Banat and R Zbo\v{r}il and M Otyepka and R A Fischer and K Jayaramulu},

url = {http://dx.doi.org/10.1039/D1TA05835E},

doi = {10.1039/D1TA05835E},

issn = {2050-7488},

year  = {2021},

date = {2021-09-30},

journal = {Journal of Materials Chemistry A},

volume = {9},

number = {41},

pages = {23651-23659},

abstract = {Superhydrophobic MOF-nanosheets assembled on the outside of an aqueous droplet form ‘liquid marbles’. A facile mechanochemical-based synthesis followed by ultrasonication was used to prepare two-dimensional superhydrophobic\textendasholeophilic MOF nanosheets of a Co2+-based zeolitic imidazolate framework, namely ZIF-9-III ([Co4(bIm)16] with bIm− = benzimidazolate). The resulting ZIF-9-III showed excellent hydrophobicity (advancing water contact angle of 144°) and oleophilicity (oil contact angle of ≈0°). The superhydrophobic behavior originated from its predominant outer (002) surface, which featured nanoscale corrugation caused by the exposed benzimidazole groups. This behavior was corroborated by inverse gas chromatography measurements to determine the surface energies of bulk exfoliated 2D ZIF-9-III nanosheets and 3D ZIF-9-I. Taking advantage of the unique surface properties, including low surface energy and good moisture stability, we prepared ZIF-9-III@PVDF (PVDF = polyvinylidene fluoride) membranes following the non-solvent induced phase inversion (NIPS) process. The resulting membranes were exploited in real-time oil/water separation and featured remarkably high adsorption capacity and anti-staining properties. Therefore, this work opens the door to developing new superhydrophobic MOF-based composite materials with permeant porosity, which may enable applications in self-cleaning membranes for oil\textendashwater separation.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Metamorphosis of Heterostructured Surface-Mounted Metal\textendashOrganic Frameworks Yielding Record Oxygen Evolution Mass Activities},

author = {S Hou and W Li and S Watzele and R M Kluge and S Xue and S Yin and X Jiang and M D\"{o}blinger and A Welle and B Garlyyev and M Koch and P M\"{u}ller-Buschbaum and C W\"{o}ll and A S Bandarenka and R A Fischer},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adma.202103218},

doi = {https://doi.org/10.1002/adma.202103218},

issn = {0935-9648},

year  = {2021},

date = {2021-08-01},

urldate = {2021-08-01},

journal = {Advanced Materials},

volume = {33},

pages = {2103218},

abstract = {Abstract Materials derived from surface-mounted metal\textendashorganic frameworks (SURMOFs) are promising electrocatalysts for the oxygen evolution reaction (OER). A series of mixed-metal, heterostructured SURMOFs is fabricated by the facile layer-by-layer deposition method. The obtained materials reveal record-high electrocatalyst mass activities of ≈2.90 kA g−1 at an overpotential of 300 mV in 0.1 m KOH, superior to the benchmarking precious and nonprecious metal electrocatalysts. This property is assigned to the particular in situ self-reconstruction and self-activation of the SURMOFs during the immersion and the electrochemical treatment in alkaline aqueous electrolytes, which allows for the generation of NiFe (oxy)hydroxide electrocatalyst materials of specific morphology and microstructure.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {A multifunctional covalently linked graphene\textendashMOF hybrid as an effective chemiresistive gas sensor},

author = {K Jayaramulu and M Esclance Dmello and K Kesavan and A Schneemann and M Otyepka and S Kment and C Narayana and S B Kalidindi and R S Varma and R Zboril and R A Fischer},

url = {http://dx.doi.org/10.1039/D1TA03246A},

doi = {10.1039/D1TA03246A},

issn = {2050-7488},

year  = {2021},

date = {2021-07-22},

journal = {Journal of Materials Chemistry A},

volume = {9},

number = {32},

pages = {17434-17441},

abstract = {A hybrid of GA@UiO-66-NH2 was synthesized based on the covalent assembly of graphene acid (GA) and the amine functionalized UiO-66 metal\textendashorganic framework through amide bonds. This strategy endows the material with unique properties, such as hierarchical pores, a porous conductive network decorated with functional groups, a high specific surface area, and a good chemical and thermal stability. The resultant hybrid has an electrical resistance of ∼104 Ω, whereas the pristine GA and UiO-66-NH2 possess an electrical resistance of ∼102 Ω and ∼109 Ω, respectively. The hybrid GA@UiO-66-NH2 was demonstrated for CO2 chemiresistive sensing and displayed a very fast response and quick recovery time of ∼18 s for 100% CO2, at 200 °C. While the pristine GA exhibits negligible response under the same conditions, GA@UiO-66-NH2 exhibited a response of 10 ± 0.6%. Further, in situ temperature dependent Raman studies during CO2 exposure confirm the presence of strong hydrogen bonding interaction between CO2 and the amide functionality present on GA@UiO-66-NH2. The resulting gas sensing characteristics of GA@UiO-66-NH2 are majorly attributed to the better interaction of CO2 at the amide/amine functional groups and the readily accessible hierarchical pores. This design strategy opens new horizons in the development of covalently linked hybrids with hierarchical porous conductive networks which can help to improve the gas sensing properties of MOF-based materials.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Host\textendashGuest Interactions in a Metal\textendashOrganic Framework Isoreticular Series for Molecular Photocatalytic CO2 Reduction},

author = {P M Stanley and J Haimerl and C Thomas and A Urstoeger and M Schuster and N B Shustova and A Casini and B Rieger and J Warnan and R A Fischer},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202102729},

doi = {https://doi.org/10.1002/anie.202102729},

issn = {1433-7851},

year  = {2021},

date = {2021-05-20},

journal = {Angewandte Chemie International Edition},

volume = {60},

number = {33},

pages = {17854-17860},

abstract = {Abstract A strategy to improve homogeneous molecular catalyst stability, efficiency, and selectivity is the immobilization on supporting surfaces or within host matrices. Herein, we examine the co-immobilization of a CO2 reduction catalyst [ReBr(CO)3(4,4′-dcbpy)] and a photosensitizer [Ru(bpy)2(5,5′-dcbpy)]Cl2 using the isoreticular series of metal\textendashorganic frameworks (MOFs) UiO-66, -67, and -68. Specific host pore size choice enables distinct catalyst and photosensitizer spatial location\textemdasheither at the outer MOF particle surface or inside the MOF cavities\textemdashaffecting catalyst stability, electronic communication between reaction center and photosensitizer, and consequently the apparent catalytic rates. These results allow for a rational understanding of an optimized supramolecular layout of catalyst, photosensitizer, and host matrix.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Understanding entrapped molecular photosystem and metal\textendashorganic framework synergy for improved solar fuel production},

author = {P M Stanley and M Parkulab and B Rieger and J Warnan and R A Fischer},

url = {http://dx.doi.org/10.1039/D1FD00009H},

doi = {10.1039/D1FD00009H},

issn = {1359-6640},

year  = {2021},

date = {2021-04-27},

urldate = {2021-04-27},

journal = {Faraday Discussions},

volume = {231},

number = {0},

pages = {281-297},

abstract = {Artificial photosystems assembled from molecular complexes, such as the photocatalyst fac-ReBr(CO)3(4,4′-dcbpy) (dcbpy = dicarboxy-2,2′-bipyridine) and the photosensitiser Ru(bpy)2(5,5′-dcbpy)Cl2 (bpy = 2,2′-bipyridine), are a wide-spread approach for solar fuel production. Recently metal\textendashorganic framework (MOF) entrapping of such complexes was demonstrated as a promising concept for catalyst stabilisation and reaction environment optimisation in colloidal-based CO2 reduction. Building on this strategy, here we examined the influence of MIL-101-NH2(Al) MOF particle size, the electron donor source, and the presence of an organic base on the photocatalytic CO2-to-CO reduction performance, and the differences to homogeneous systems. A linear relation between smaller scaffold particle size and higher photocatalytic activity, longer system lifetimes for benign electron donors, and increased turnover numbers (TONs) with certain additive organic bases, were determined. This enabled understanding of key molecular catalysis phenomena and synergies in the nanoreactor-like host\textendashguest assembly, and yielded TONs of ∼4300 over 96 h of photocatalysis under optimised conditions, surpassing homogeneous TON values and lifetimes.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Open Framework Material Based Thin Films: Electrochemical Catalysis and State-of-the-art Technologies},

author = {W Li and S Mukerjee and B Ren and R Cao and R A Fischer},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/aenm.202003499},

doi = {https://doi.org/10.1002/aenm.202003499},

issn = {1614-6832},

year  = {2021},

date = {2021-04-01},

journal = {Advanced Energy Materials},

volume = {n/a},

number = {n/a},

pages = {2003499},

abstract = {Abstract Open framework materials (OFMs), such as metal-organic frameworks and covalent organic frameworks have emerged as promising electrocatalysts to address the global energy crisis and environmental problems. Powdered non-film forms, that is, bulk OFMs exhibit excellent catalytic activities toward electrocatalytic carbon dioxide reduction, water splitting, and the oxygen reduction reaction. However, electrode preparation using bulk solids suffers from a range of oft-encountered difficulties, primarily limited by challenges in controlling their thickness, roughness, and particle sizes, despite early performance promises. Targeting energy sustainability, it is a matter of growing interest to directly integrate OFMs in the form of thin films onto conductive substrates. In essence, this leads to electrocatalysts with controlled features: thickness, roughness, and particle sizes. Thus far, there are only a handful of OFM thin films developed for electrocatalysis. Exploration of these understudied OFM thin films to serve electrocatalysis still lies at its infancy. This review will cover the key discoveries of OFM thin films as electrocatalysts and will critically examine the strengths, challenges, and future goals in exploring bespoke OFM thin films for electrocatalysis, under conditions that mimic real-world applications.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Molecular Oxygen Activation by Redox-Switchable Anthraquinone-Based Metal\textendashOrganic Frameworks},

author = {J G M De Carvalho and R A Fischer and A P\"{o}thig},

url = {https://doi.org/10.1021/acs.inorgchem.0c03629},

doi = {10.1021/acs.inorgchem.0c03629},

issn = {0020-1669},

year  = {2021},

date = {2021-03-25},

journal = {Inorganic Chemistry},

volume = {60},

number = {7},

pages = {4676-4682},

abstract = {A dipyridyl-substituted anthraquinone (2,6-di(pyridin-4-yl)-9,10-anthraquinone, DPAq) was incorporated as a redox-active linker molecule into crystalline coordination networks. The oxidation state of the organic linker can be selectively controlled prior to framework formation and furthermore be maintained in the solid state. Hydrogen bonding is identified to be a substantial stabilization factor. Additionally, it is shown that the anthraquinone\textendashanthrahydroquinone redox pair can be switched reversibly even after incorporation in the solid state by a thermal treatment/soaking procedure\textemdashgoing along with the formation of hydrogen peroxide from molecular oxygen (air) during the oxidation process.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Ultrafine TiO2 Nanoparticle Supported Nitrogen-Rich Graphitic Porous Carbon as an Efficient Anode Material for Potassium-Ion Batteries},

author = {D P Dubal and A Schneemann and V Ranc and \v{S} Kment and O Tomanec and M Petr and H Kmentova and M Otyepka and R Zbo\v{r}il and R A Fischer and K Jayaramulu},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/aesr.202100042},

doi = {https://doi.org/10.1002/aesr.202100042},

issn = {2699-9412},

year  = {2021},

date = {2021-03-17},

journal = {Advanced Energy and Sustainability Research},

volume = {2},

number = {9},

pages = {2100042},

abstract = {Potassium-ion batteries (KIBs) have attracted enormous attention as a next-generation energy storage system due to their low cost, fast ionic conductivity within electrolytes, and high operating voltage. However, developing suitable electrode materials to guarantee high-energy output and structural stability to ensure long cycling performance remains a critical challenge. Herein, anatase TiO2 nanoparticles are encapsulated in nitrogen-rich graphitic carbon (TiO2@NGC) with hierarchical pores and high surface area (250 m2 g−1) using the Ti-based metal\textendashorganic framework NH2-MIL-125 (Ti8O8(OH)4(NH2-bdc)6 with NH2-bdc2− = 2-amino-1,4-benzenedicarboxylate) as a sacrificial template. Serving as the anode material in a K-ion half-cell, TiO2@NGC delivers a high capacity of 228 mA h g−1 with remarkable cycling performance (negligible loss over 2000 cycles with more than 98% Coulombic efficiency). The charge-storing mechanism is underpinned using ex situ characterization techniques such as ex situ X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis. It is revealed that the original TiO2 phase gets transformed to the anorthic Ti7O13 and monoclinic K2Ti4O9 phase after the first charge/discharge cycle, which further initiates the charge storage process via the conversion reactions.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {A nitrophenyl-carbazole based push-pull linker as a building block for non-linear optical active coordination polymers: A structural and photophysical study},

author = {S J Weish\"{a}upl and D C Mayer and E Thyrhaug and J Hauer and A P\"{o}thig and R A Fischer},

url = {https://www.sciencedirect.com/science/article/pii/S0143720820317095},

doi = {https://doi.org/10.1016/j.dyepig.2020.109012},

issn = {0143-7208},

year  = {2021},

date = {2021-02-01},

journal = {Dyes and Pigments},

volume = {186},

pages = {109012},

abstract = {Non-linear optical effects (NLO) such as multi-photon absorption, second harmonic generation (SHG) etc. have a wide range of applications. Nevertheless, the performance of many NLO-active organic dyes is limited by their thermal stability and photobleaching. These problems can be overcome by integrating the dyes into coordination polymers or metal-organic frameworks. Here, we present a structural and photophysical study of dipropyl-9-(4-nitrophenyl)-carbazole-3,6-dicarboxylate, a new “push-pull” organic dye molecule designed as a chromophore linker for NLO-active coordination polymers. Structure determination of a single-crystal showed that it crystallizes in a monoclinic crystal system P 21/c. The solvated chromophore exhibits two aromatic absorption bands at 250 nm and 275 nm as well as broad long wavelength band at 350 nm, which we assign to an intramolecular charge transfer state. Photoluminescence measurements in solvents of different polarities revealed two main effects: In nonpolar solvents, the spectrum shows an emission band at 360 nm, whereas in solvents with a higher polarity, the emission maximum broadens and redshifts. Solid-state emission measurement of sample powder exhibits an emission band at 520 nm which is redshifted compared to the measurements in solution, due to excimer formation in the solid-state. The optical as well as solvation-related properties of the investigated pigment render it to be a versatile ligand in coordination polymers.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Entrapped Molecular Photocatalyst and Photosensitizer in Metal\textendashOrganic Framework Nanoreactors for Enhanced Solar CO2 Reduction},

author = {P M Stanley and C Thomas and E Thyrhaug and A Urstoeger and M Schuster and J Hauer and B Rieger and J Warnan and R A Fischer},

url = {https://doi.org/10.1021/acscatal.0c04673},

doi = {10.1021/acscatal.0c04673},

year  = {2021},

date = {2021-01-05},

urldate = {2021-01-05},

journal = {ACS Catalysis},

volume = {11},

number = {2},

pages = {871-882},

abstract = {Herein, we report on a molecular catalyst embedding metal\textendashorganic framework (MOF) that enables enhanced photocatalytic CO2 reduction activity. A benchmark photocatalyst fac-ReBr(CO)3(4,4′-dcbpy) (dcbpy = dicarboxy-2,2′-bipyridine) and photosensitizer Ru(bpy)2(5,5′-dcbpy)Cl2 (bpy = 2,2′-bipyridine) were synergistically entrapped inside the cages of the nontoxic and inexpensive MIL-101-NH2(Al) through noncovalent host\textendashguest interactions. The heterogeneous material improved Re catalyst stabilization under photocatalytic CO2 reduction conditions as selective CO evolution was prolonged from 1.5 to 40 h compared to the MOF-free photosystem upon reactivation with additional photosensitizer. By varying ratios of immobilized catalyst to photosensitizer, we demonstrated and evaluated the effect of reaction environment modulation in defined MOF cages acting as a nanoreactor. This illustrated the optimal efficiency for two photosensitizers and one catalyst per cage and further led to the determination of ad hoc relationships between molecular complex size, MOF pore windows, and number of hostable molecules per cage. Differing from typical homogeneous systems, photosensitizer\textemdashand not catalyst\textemdashdegradation was identified as a major performance-limiting factor, providing a future route to higher turnover numbers via a rational choice of parameters.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Covalent Graphene-MOF Hybrids for High-Performance Asymmetric Supercapacitors},

author = {K Jayaramulu and M Horn and A Schneemann and H Saini and A Bakandritsos and V Ranc and M Petr and V Stavila and C Narayana and B Scheibe and \v{S} Kment and M Otyepka and N Motta and D Dubal and R Zbo\v{r}il and R A Fischer},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adma.202004560},

doi = {https://doi.org/10.1002/adma.202004560},

issn = {0935-9648},

year  = {2020},

date = {2020-12-04},

journal = {Advanced Materials},

volume = {33},

number = {4},

pages = {2004560},

abstract = {Abstract In this work, the covalent attachment of an amine functionalized metal-organic framework (UiO-66-NH2 = Zr6O4(OH)4(bdc-NH2)6; bdc-NH2 = 2-amino-1,4-benzenedicarboxylate) (UiO-Universitetet i Oslo) to the basal-plane of carboxylate functionalized graphene (graphene acid = GA) via amide bonds is reported. The resultant GA@UiO-66-NH2 hybrid displayed a large specific surface area, hierarchical pores and an interconnected conductive network. The electrochemical characterizations demonstrated that the hybrid GA@UiO-66-NH2 acts as an effective charge storing material with a capacitance of up to 651 F g−1, significantly higher than traditional graphene-based materials. The results suggest that the amide linkage plays a key role in the formation of a π-conjugated structure, which facilitates charge transfer and consequently offers good capacitance and cycling stability. Furthermore, to realize the practical feasibility, an asymmetric supercapacitor using a GA@UiO-66-NH2 positive electrode with Ti3C2TX MXene as the opposing electrode has been constructed. The cell is able to deliver a power density of up to 16 kW kg−1 and an energy density of up to 73 Wh kg−1, which are comparable to several commercial devices such as Pb-acid and Ni/MH batteries. Under an intermediate level of loading, the device retained 88% of its initial capacitance after 10 000 cycles.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Metal Halide Perovskite@Metal-Organic Framework Hybrids: Synthesis, Design, Properties, and Applications},

author = {S K Yadav and G K Grandhi and D P Dubal and J C De Mello and M Otyepka and R Zbo\v{r}il and R A Fischer and K Jayaramulu},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/smll.202004891},

doi = {https://doi.org/10.1002/smll.202004891},

issn = {1613-6810},

year  = {2020},

date = {2020-10-30},

journal = {Small},

volume = {16},

number = {47},

pages = {2004891},

abstract = {Abstract Metal halide perovskites (MHPs) have excellent optoelectronic and photovoltaic applications because of their cost-effectiveness, tunable emission, high photoluminescence quantum yields, and excellent charge carrier properties. However, the potential applications of the entire MHP family are facing a major challenge arising from its weak resistance to moisture, polar solvents, temperature, and light exposure. A viable strategy to enhance the stability of MHPs could lie in their incorporation into a porous template. Metal-organic frameworks (MOFs) have outstanding properties, with a unique network of ordered/functional pores, which render them promising for functioning as such a template, accommodating a wide range of MHPs to the nanosized region, alongside minimizing particle aggregation and enhancing the stability of the entrapped species. This review highlights recent advances in design strategies, synthesis, characterization, and properties of various hybrids of MOFs with MHPs. Particular attention is paid to a critical review of the emergence of MHP@MOF for comprehensive studies of next-generation materials for various technological applications including sensors, photocatalysis, encryption/decryption, light-emitting diodes, and solar cells. Finally, by summarizing the state-of-the-art, some promising future applications of reported hybrids are proposed. Considering the inherent correlation and synergic functionalities of MHPs and MOFs, further advancement; new functional materials; and applications can be achieved through designing MHP@MOF hybrids.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Advanced Bifunctional Oxygen Reduction and Evolution Electrocatalyst Derived from Surface-Mounted Metal-Organic Frameworks},

author = {W J Li and S Xue and S Watzele and S J Hou and J Fichtner and A L Semrau and L J Zhou and A Welle and A S Bandarenka and R A Fischer},

url = {\<Go to ISI\>://WOS:000509752400001},

doi = {10.1002/anie.201916507},

issn = {1433-7851},

year  = {2020},

date = {2020-01-08},

journal = {Angewandte Chemie-International Edition},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Recent Approaches to Design Electrocatalysts Based on Metal\textendashOrganic Frameworks and Their Derivatives},

author = {J Liu and S Hou and W Li and A S Bandarenka and R A Fischer},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/asia.201900748},

doi = {https://doi.org/10.1002/asia.201900748},

issn = {1861-4728},

year  = {2019},

date = {2019-08-20},

journal = {Chemistry \textendash An Asian Journal},

volume = {14},

number = {20},

pages = {3474-3501},

abstract = {Abstract Rational design and synthesis of efficient electrocatalysts are important constituents in addressing the currently growing provision issues. Typical reactions, which are important to catalyze in this respect, include CO2 reduction, the hydrogen and oxygen evolution reactions as well as the oxygen reduction reaction. The most efficient catalysts known up-to-date for these processes usually contain expensive and scarce elements, substantially impeding implementation of such electrocatalysts at a larger scale. Metal-organic frameworks (MOFs) and their derivatives containing affordable components and building blocks, as an emerging class of porous functional materials, have been recently attracting a great attention thanks to their tunable structure and composition together with high surface area, just to name a few. Up to now, several MOFs and MOF-derivatives have been reported as electrode materials for the energy-related electrocatalytic application. In this review article, we summarize and analyze current approaches to design such materials. The design strategies to improve the Faradaic efficiency and selectivity of these catalysts are discussed. Last but not least, we discuss some novel strategies to enhance the conductivity, chemical stability and efficiency of MOF-derived electrocatalysts.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Generation and Stabilization of Small Platinum Clusters Pt-12 +/- x Inside a Metal-Organic Framework},

author = {K Kratzl and T Kratky and S Gunther and O Tomanec and R Zboril and J Michalicka and J M Macak and M Cokoja and R A Fischer},

url = {\<Go to ISI\>://WOS:000484828900039},

doi = {10.1021/jacs.9b07083},

issn = {0002-7863},

year  = {2019},

date = {2019-08-09},

journal = {Journal of the American Chemical Society},

volume = {141},

number = {35},

pages = {13962-13969},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Hydrophobic Metal\textendashOrganic Frameworks},

author = {K Jayaramulu and F Geyer and A Schneemann and \v{S} Kment and M Otyepka and R Zboril and D Vollmer and R A Fischer},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adma.201900820},

doi = {https://doi.org/10.1002/adma.201900820},

issn = {0935-9648},

year  = {2019},

date = {2019-06-03},

journal = {Advanced Materials},

volume = {31},

number = {32},

pages = {1900820},

abstract = {Abstract Metal\textendashorganic frameworks (MOFs) have diverse potential applications in catalysis, gas storage, separation, and drug delivery because of their nanoscale periodicity, permanent porosity, channel functionalization, and structural diversity. Despite these promising properties, the inherent structural features of even some of the best-performing MOFs make them moisture-sensitive and unstable in aqueous media, limiting their practical usefulness. This problem could be overcome by developing stable hydrophobic MOFs whose chemical composition is tuned to ensure that their metal\textendashligand bonds persist even in the presence of moisture and water. However, the design and fabrication of such hydrophobic MOFs pose a significant challenge. Reported syntheses of hydrophobic MOFs are critically summarized, highlighting issues relating to their design, characterization, and practical use. First, wetting of hydrophobic materials is introduced and the four main strategies for synthesizing hydrophobic MOFs are discussed. Afterward, critical challenges in quantifying the wettability of these hydrophobic porous surfaces and solutions to these challenges are discussed. Finally, the reported uses of hydrophobic MOFs in practical applications such as hydrocarbon storage/separation and their use in separating oil spills from water are summarized. Finally, the state of the art is summarized and promising future developments of hydrophobic MOFs are highlighted.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Optimizing the Size of Platinum Nanoparticles for Enhanced Mass Activity in the Electrochemical Oxygen Reduction Reaction},

author = {B Garlyyev and K Kratzl and M R\"{u}ck and J Michali\v{c}ka and J Fichtner and J M Macak and T Kratky and S G\"{u}nther and M Cokoja and A S Bandarenka and A Gagliardi and R A Fischer},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201904492},

doi = {10.1002/anie.201904492},

issn = {1433-7851},

year  = {2019},

date = {2019-05-03},

journal = {Angewandte Chemie International Edition},

volume = {58},

number = {28},

pages = {9596-9600},

abstract = {Abstract High oxygen reduction (ORR) activity has been for many years considered as the key to many energy applications. Herein, by combining theory and experiment we prepare Pt nanoparticles with optimal size for the efficient ORR in proton-exchange-membrane fuel cells. Optimal nanoparticle sizes are predicted near 1, 2, and 3 nm by computational screening. To corroborate our computational results, we have addressed the challenge of approximately 1 nm sized Pt nanoparticle synthesis with a metal\textendashorganic framework (MOF) template approach. The electrocatalyst was characterized by HR-TEM, XPS, and its ORR activity was measured using a rotating disk electrode setup. The observed mass activities (0.87±0.14 A mgPt−1) are close to the computational prediction (0.99 A mgPt−1). We report the highest to date mass activity among pure Pt catalysts for the ORR within similar size range. The specific and mass activities are twice as high as the Tanaka commercial Pt/C catalysis.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Unprecedented High Oxygen Evolution Activity of Electrocatalysts Derived from Surface-Mounted Metal\textendashOrganic Frameworks},

author = {W Li and S Watzele and H A El-Sayed and Y Liang and G Kieslich and A S Bandarenka and K Rodewald and B Rieger and R A Fischer},

url = {https://doi.org/10.1021/jacs.9b00549},

doi = {10.1021/jacs.9b00549},

issn = {0002-7863},

year  = {2019},

date = {2019-03-19},

journal = {Journal of the American Chemical Society},

volume = {141},

number = {14},

pages = {5926-5933},

abstract = {The oxygen evolution reaction (OER) is a key process for renewable energy storage. However, developing non-noble metal OER electrocatalysts with high activity, long durability and scalability remains a major challenge. Herein, high OER activity and stability in alkaline solution were discovered for mixed nickel/cobalt hydroxide electrocatalysts, which were derived in one-step procedure from oriented surface-mounted metal\textendashorganic framework (SURMOF) thin films that had been directly grown layer-by-layer on macro- and microelectrode substrates. The obtained mass activity of ∼2.5 mA·μg\textendash1 at the defined overpotential of 300 mV is 1 order of magnitude higher than that of the benchmarked IrO2 electrocatalyst and at least 3.5 times higher than the mass activity of any state-of-the-art NiFe-, FeCoW-, or NiCo-based electrocatalysts reported in the literature. The excellent morphology of the SURMOF-derived ultrathin electrocatalyst coating led to a high exposure of the most active Ni- and Co-based sites.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}