Publications

@article{nokey,

title = {Low-Temperature and Water-Based Biotemplating of Nanostructured Foam-Like Titania Films Using \ss-Lactoglobulin},

author = {J E Heger and W Chen and S Yin and N Li and V K\"{o}rstgens and C J Brett and W Ohm and S V Roth and P M\"{u}ller-Buschbaum},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adfm.202113080},

doi = {https://doi.org/10.1002/adfm.202113080},

issn = {1616-301X},

year  = {2022},

date = {2022-02-17},

journal = {Advanced Functional Materials},

volume = {n/a},

number = {n/a},

pages = {2113080},

abstract = {Abstract Given the broad use of nanostructured crystalline titania films, an environmentally friendly and more sustainable synthesis route is highly desirable. Here, a water-based, low-temperature route is presented to synthesize nanostructured foam-like crystalline titania films. A pearl necklace-like nanostructure is introduced as tailored titania morphology via biotemplating with the use of the major bovine whey protein \ss-lactoglobulin (\ss-lg). It is shown that titania crystallization in a brookite-anatase mixed phase is promoted via spray deposition at a comparatively low temperature of 120 °C. The obtained crystallites have an average grain size of (4.2 ± 0.3) nm. In situ grazing incidence small-angle and wide-angle X-ray scattering (GISAXS/GIWAXS) are simultaneously performed to understand the kinetics of film formation and the templating role of \ss-lg during spray coating. In the \ss-lg:titania biohybrid composites, the crystal growth in semicrystalline titania clusters is sterically directed by the condensing \ss-lg biomatrix. Due to using spray coating, the green chemistry approach to titania-based functional films can be scaled up on a large scale, which can potentially be used in photocatalytic processes or systems related to energy application.},

keywords = {Foundry Inorganic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Ultrafast sub-100 fs all-optical modulation and efficient third-harmonic generation in Weyl semimetal niobium phosphide thin films},

author = {B Tilmann and A K Pandeya and G Grinblat and L D S Menezes and Y Li and C Shekhar and C Felser and S S P Parkin and A Bedoya-Pinto and S A Maier},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adma.202106733},

doi = {https://doi.org/10.1002/adma.202106733},

issn = {0935-9648},

year  = {2022},

date = {2022-02-16},

journal = {Advanced Materials},

volume = {n/a},

number = {n/a},

pages = {2106733},

abstract = {Abstract Since their experimental discovery in 2015, Weyl semimetals generated a large amount of attention due their intriguing physical properties that arise from their linear electron dispersion relation and topological surface states. In particular in the field of nonlinear (NL) optics and light harvesting, Weyl semimetals have shown outstanding performances and achieved record NL conversion coefficients. In this context, we perform first steps towards Weyl semimetal nanophotonics by thoroughly characterizing the linear and NL optical behavior of epitaxially grown niobium phosphide (NbP) thin films, covering the visible to near-infrared regime of the electromagnetic spectrum. Despite the measured high linear absorption, third-harmonic generation studies demonstrate high conversion efficiencies up to 10-4%, that can be attributed to the topological electron states at the surface of the material. Furthermore, nondegenerate pump-probe measurements with sub-10 fs pulses reveal a maximum modulation depth of about 1%, completely decaying within 100 fs and therefore suggesting the possibility of developing devices based on NbP with all-optical switching bandwidths of up to 10 THz. Altogether, our work reveals promising NL optical properties of Weyl semimetal thin films that are outperforming bulk crystals of the same material, laying the grounds for nanoscale applications, enabled by top-down nanostructuring, such as light-harvesting, on-chip frequency conversion and all-optical processing. This article is protected by copyright. All rights reserved},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Halide\textendashMetal Complexes at Plasmonic Interfaces Create New Decay Pathways for Plasmons and Excited Molecules},

author = {A Stefancu and O M Biro and O Todor-Boer and I Botiz and E Cort\'{e}s and N Leopold},

url = {https://doi.org/10.1021/acsphotonics.1c01714},

doi = {10.1021/acsphotonics.1c01714},

year  = {2022},

date = {2022-02-10},

journal = {ACS Photonics},

abstract = {We show that by modifying the chemical interface of silver nanoparticles (AgNPs) with halide ions, it is possible to tune the total decay rate of adsorbed excited molecules and the plasmon damping rate. Through single-molecule surface-enhanced Raman scattering and surface-enhanced fluorescence enhancement factors of crystal violet (CV) and rhodamine 6G (R6G), we show that I\textendash-modified AgNPs (AgNPs@I) and Br\textendash-modified AgNPs (AgNPs@Br) lead to an increase in the total decay rate of excited CV and R6G by a factor between ∼1.6\textendash2.6, compared to Cl\textendash-modified AgNPs (AgNPs@Cl). In addition, we found that the chemical interface damping, which characterizes the plasmon resonance decay into surface states, is stronger on AgNPs@I and AgNPs@Br when compared to AgNPs@Cl. These results point toward the formation of metal\textendashhalide surface complexes. These new interfacial states can accept electrons from both excited molecular orbitals and surface plasmon excitations, completely altering the electronic dynamics and reactivity of plasmonic interfaces.},

keywords = {Foundry Inorganic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Accelerating CO2 Electroreduction to Multicarbon Products via Synergistic Electric\textendashThermal Field on Copper Nanoneedles},

author = {B Yang and K Liu and H Li and C Liu and J Fu and H Li and J E Huang and P Ou and T Alkayyali and C Cai and Y Duan and H Liu and P An and N Zhang and W Li and X Qiu and C Jia and J Hu and L Chai and Z Lin and Y Gao and M Miyauchi and E Cort\'{e}s and S A Maier and M Liu},

url = {https://doi.org/10.1021/jacs.1c11253},

doi = {10.1021/jacs.1c11253},

issn = {0002-7863},

year  = {2022},

date = {2022-02-03},

urldate = {2022-02-03},

journal = {Journal of the American Chemical Society},

abstract = {Electrochemical CO2 reduction is a promising way to mitigate CO2 emissions and close the anthropogenic carbon cycle. Among products from CO2RR, multicarbon chemicals, such as ethylene and ethanol with high energy density, are more valuable. However, the selectivity and reaction rate of C2 production are unsatisfactory due to the sluggish thermodynamics and kinetics of C\textendashC coupling. The electric field and thermal field have been studied and utilized to promote catalytic reactions, as they can regulate the thermodynamic and kinetic barriers of reactions. Either raising the potential or heating the electrolyte can enhance C\textendashC coupling, but these come at the cost of increasing side reactions, such as the hydrogen evolution reaction. Here, we present a generic strategy to enhance the local electric field and temperature simultaneously and dramatically improve the electric\textendashthermal synergy desired in electrocatalysis. A conformal coating of ∼5 nm of polytetrafluoroethylene significantly improves the catalytic ability of copper nanoneedles (∼7-fold electric field and ∼40 K temperature enhancement at the tips compared with bare copper nanoneedles experimentally), resulting in an improved C2 Faradaic efficiency of over 86% at a partial current density of more than 250 mA cm\textendash2 and a record-high C2 turnover frequency of 11.5 ± 0.3 s\textendash1 Cu site\textendash1. Combined with its low cost and scalability, the electric\textendashthermal strategy for a state-of-the-art catalyst not only offers new insight into improving activity and selectivity of value-added C2 products as we demonstrated but also inspires advances in efficiency and/or selectivity of other valuable electro-/photocatalysis such as hydrogen evolution, nitrogen reduction, and hydrogen peroxide electrosynthesis.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Correlated spectral fluctuations quantified by line shape analysis of fifth-order two-dimensional electronic spectra},

author = {C Heshmatpour and J Hauer and F \v{S}anda},

url = {https://aip.scitation.org/doi/abs/10.1063/5.0081053},

doi = {10.1063/5.0081053},

year  = {2022},

date = {2022-02-01},

journal = {The Journal of Chemical Physics},

volume = {156},

number = {8},

pages = {084114},

abstract = {Correlated spectral fluctuations were suggested to coordinate excitation transport inside natural light harvesting complexes. We demonstrate the capacities of 2D line shapes from fifth-order coherent electronic signals (R5-2D) to report on such fluctuations in molecular aggregates and present a stochastic approach to fluctuations in correlated site and bi-exciton binding energies in the optical dynamics of Frenkel excitons. The model is applied to R5-2D line shapes of a homodimer, and we show that the peak tilt dynamics are a measure for site energy disorder, inter-site correlation, and the strength of bi-exciton binding energy fluctuations.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Single-photon emitters in layered van der Waals materials},

author = {S Michaelis De Vasconcellos and D Wigger and U Wurstbauer and A W Holleitner and R Bratschitsch and T Kuhn},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/pssb.202100566},

doi = {https://doi.org/10.1002/pssb.202100566},

issn = {0370-1972},

year  = {2022},

date = {2022-01-28},

journal = {physica status solidi (b)},

volume = {n/a},

number = {n/a},

abstract = {Single-photon emitters have recently been discovered in various atomically thin materials. Their properties, controllability, and the possibility of their monolithic integration in electronic and photonic device structures makes them attractive candidates for a wide range of applications in quantum information and communication, and also in other fields of physics and technology. In this review article an overview of single-photon emitters in layered van der Waals materials and their physical properties is given, theoretical concepts for the modeling of their level structure and their coupling to phonons are presented, and techniques for the creation and localization of these emitters in the host material are described. Perspectives for their application in various fields, such as their coupling to photonic resonators and waveguides, their control by external electric fields or strain, and their integration in optomechanical devices are discussed. Finally, functionalities relying on properties beyond single-photon emission are briefly addressed. This article is protected by copyright. All rights reserved.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Robust excitons across the phase transition of two-dimensional hybrid perovskites},

author = {J D Ziegler and K-Q Lin and B Meisinger and X Zhu and M Kober-Czerny and P K Nayak and C Vona and T Taniguchi and K Watanabe and C Draxl},

url = {https://arxiv.org/abs/2201.11589},

doi = {arXiv:2201.11589v1},

year  = {2022},

date = {2022-01-27},

journal = {arXiv preprint arXiv:2201.11589},

abstract = {Two-dimensional halide perovskites are among intensely studied materials platforms profiting from solution based growth and chemical flexibility. They feature exceptionally strong interactions among electronic, optical as well as vibrational excitations and hold a great potential for future optoelectronic applications. A key feature for these materials is the occurrence of structural phase transitions that can impact their functional properties, including the electronic band gap and optical response dominated by excitons. However, to what extent the phase-transitions in two-dimensional perovskites alter the fundamental exciton properties remains barely explored so far. Here, we study the influence of the phase transition on both exciton binding energy and exciton diffusion, demonstrating their robust nature across the phase transition. These findings are unexpected in view of the associated substantial changes of the free carrier masses, strongly contrast broadly considered effective mass and drift-diffusion transport mechanisms, highlighting the unusual nature of excitons in two-dimensional perovskites.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Electronically Tunable Transparent Conductive Thin Films for Scalable Integration of 2D Materials with Passive 2D\textendash3D Interfaces},

author = {T Gr\"{u}nleitner and A Henning and M Bissolo and A Kleibert and C F Vaz and A V Stier and J J Finley and I D Sharp},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adfm.202111343},

doi = {https://doi.org/10.1002/adfm.202111343},

issn = {1616-301X},

year  = {2022},

date = {2022-01-22},

journal = {Advanced Functional Materials},

volume = {n/a},

number = {n/a},

pages = {2111343},

abstract = {Abstract A novel transparent conductive support structure for scalable integration of 2D materials is demonstrated, providing an electronically passive 2D\textendash3D interface while also enabling facile interfacial charge transport. This structure, which comprises an evaporated nanocrystalline carbon (nc-C) film beneath nanometer-thin atomic layer deposited AlOx, is thermally stable and allows direct chemical vapor deposition of 2D materials onto the surface. The combination of spatial uniformity, enhanced charge screening, and low interface defect concentrations yields a tenfold enhancement of MoS2 photoluminescence intensity compared to flakes on conventional Si/SiO2, while also retaining the strong optical contrast for monolayer flakes. Tunneling across the ultrathin AlOx enables facile interfacial charge injection, which is utilized for high-resolution scanning electron microscopy and photoemission electron microscopy with no detectable charging. Thus, this combination of scalable fabrication and electronic conductivity across a weakly interacting 2D\textendash3D interface opens up new opportunities for device integration and characterization of 2D materials.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Light-driven carbon nitride microswimmers with propulsion in biological and ionic media and responsive on-demand drug delivery},

author = {V Sridhar and F Podjaski and Y Alapan and J Kr\"{o}ger and L Grunenberg and V Kishore and B V Lotsch and M Sitti},

url = {https://www.science.org/doi/abs/10.1126/scirobotics.abm1421},

doi = {doi:10.1126/scirobotics.abm1421},

year  = {2022},

date = {2022-01-19},

journal = {Science Robotics},

volume = {7},

number = {62},

pages = {eabm1421},

abstract = {We propose two-dimensional poly(heptazine imide) (PHI) carbon nitride microparticles as light-driven microswimmers in various ionic and biological media. Their high-speed (15 to 23 micrometer per second; 9.5 ± 5.4 body lengths per second) swimming in multicomponent ionic solutions with concentrations up to 5 M and without dedicated fuels is demonstrated, overcoming one of the bottlenecks of previous light-driven microswimmers. Such high ion tolerance is attributed to a favorable interplay between the particle’s textural and structural nanoporosity and optoionic properties, facilitating ionic interactions in solutions with high salinity. Biocompatibility of these microswimmers is validated by cell viability tests with three different cell lines and primary cells. The nanopores of the swimmers are loaded with a model cancer drug, doxorubicin (DOX), resulting in a high (185%) loading efficiency without passive release. Controlled drug release is reported under different pH conditions and can be triggered on-demand by illumination. Light-triggered, boosted release of DOX and its active degradation products are demonstrated under oxygen-poor conditions using the intrinsic, environmentally sensitive and light-induced charge storage properties of PHI, which could enable future theranostic applications in oxygen-deprived tumor regions. These organic PHI microswimmers simultaneously address the current light-driven microswimmer challenges of high ion tolerance, fuel-free high-speed propulsion in biological media, biocompatibility, and controlled on-demand cargo release toward their biomedical, environmental, and other potential applications.},

keywords = {Foundry Inorganic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Designing multifunctional CoOx layers for efficient and stable electrochemical energy conversion},

author = {M Kuhl and A Henning and L Haller and L Wagner and C-M Jiang and V Streibel and I D Sharp and J Eichhorn},

doi = {10.26434/chemrxiv-2022-23ck4},

year  = {2022},

date = {2022-01-13},

urldate = {2022-01-13},

journal = {Cambridge: Cambridge Open Engage},

abstract = {Disordered and porous metal oxides are promising as earth-abundant and cost-effective alternatives to noble-metal electrocatalysts. Herein, we leverage non-saturated oxidation in plasma-enhanced atomic layer deposition to tune structural, mechanical, and optical properties of biphasic CoOx thin films, thereby tailoring their catalytic activities and chemical stabilities. To optimize the resulting film properties, we systematically vary the oxygen plasma power and exposure time in the deposition process. We find that short exposure times and low plasma powers incompletely oxidize the cobaltocene precursor to Co(OH)2 and result in the incorporation of carbon impurities. These Co(OH)2 films are highly porous and catalytically active, but their electrochemical stability is impacted by poor adhesion to the substrate. In contrast, long exposure times and high plasma powers completely oxidize the precursor to form Co3O4, reduce the carbon impurity incorporation, and improve the film crystallinity. While the resulting Co3O4 films are highly stable under electrochemical conditions, they are characterized by low oxygen evolution reaction activities. To overcome these competing properties, we applied the established relation between deposition parameters and functional film properties to design bilayer films exhibiting simultaneously improved electrochemical performance and chemical stability. The resulting biphasic films combine a highly active Co(OH)2 surface with a stable Co3O4 interface layer. In addition, these coatings exhibit minimal light absorption, thus rendering them well suited as protective catalytic layers on semiconductor light absorbers for application in photoelectrochemical devices.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Doubly Stabilized Perovskite Nanocrystal Luminescence Downconverters},

author = {Q Xue and C Lampe and T Naujoks and K Frank and M Gramlich and M Schoger and W Vanderlinden and P Reisbeck and B Nickel and W Br\"{u}tting},

url = {https://arxiv.org/abs/2201.05472v1},

doi = {arXiv:2201.05472v1},

year  = {2022},

date = {2022-01-13},

journal = {arXiv preprint arXiv:2201.05472},

abstract = {Halide perovskite nanocrystals (NCs) have emerged as a promising material for applications ranging from light-emitting diodes (LEDs) to solar cells and photodetectors. Still, several issues impede the realization of the nanocrystals' full potential, most notably their susceptibility to degradation from environmental stress. This work demonstrates highly stable perovskite nanocrystals (NCs) with quantum yields as high as 95 % by exploiting a ligand-assisted copolymer nanoreactor-based synthesis. The organic ligands thereby serve a dual function by enhancing the uptake of precursors and passivating the NCs. The polymer micelles and ligands thus form a double protection system, shielding the encapsulated NCs from water-, heat- and UV-light-induced degradation. We demonstrate the optoelectronic integrability by incorporating the perovskite NCs as spectrally pure downconverters on top of a deep-blue-emitting organic LED. These results establish a way of stabilizing perovskite NCs for optoelectronics while retaining their excellent optical properties.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {A novel electrically conductive perylene diimide-based MOF-74 series featuring luminescence and redox activity},

author = {P I Scheurle and A Biewald and A M\"{a}hringer and A Hartschuh and D D Medina and T Bein},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/sstr.202100195},

doi = {https://doi.org/10.1002/sstr.202100195},

issn = {2688-4062},

year  = {2022},

date = {2022-01-11},

journal = {Small Structures},

volume = {n/a},

number = {n/a},

abstract = {Metal-organic frameworks (MOFs) featuring significant electrical conductivity constitute a growing class of materials, with intriguing possible applications as porous semiconductors or supercapacitors. If such features are combined with photoluminescence, additional functionalities such as selective chemical sensing become accessible. Here, we incorporate perylene diimide (PDI) based linear building blocks into the MOF-74 topology with the three metal ions Zn2+, Mg2+ and Ni2+, resulting in a new series of MOFs, namely PDI-MOF-74(M). PDI derivatives are dye molecules exhibiting remarkable optical properties, high electron mobilities, as well as interesting redox behavior. However, PDI-based 3D MOFs are very rare and to date were only reported once. The frameworks of the PDI-MOF-74(M) series exhibit high crystallinity, electrical conductivity and show well-defined redox activity. In addition, the frameworks of the series feature photoluminescence in the orange and red spectral regions. With this work we expand the series of electroactive MOF-74 structures as well as the group of 3D PDI-based MOFs, hence opening up the development of novel MOFs with promising optoelectronic properties comprising PDI building blocks. This article is protected by copyright. All rights reserved.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {2D/3D Hybrid Cs2AgBiBr6 Double Perovskite Solar Cells: Improved Energy Level Alignment for Higher Contact-Selectivity and Large Open Circuit Voltage},

author = {M T Sirtl and R Hooijer and M Armer and F G Ebadi and M Mohammadi and C Maheu and A Weis and B T Van Gorkom and S H\"{a}ringer and R J Janssen and T Mayer and V Dyakonov and W Tress and T Bein},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/aenm.202103215},

doi = {https://doi.org/10.1002/aenm.202103215},

issn = {1614-6832},

year  = {2022},

date = {2022-01-09},

journal = {Advanced Energy Materials},

volume = {n/a},

number = {n/a},

pages = {2103215},

abstract = {Abstract Since their introduction in 2017, the efficiency of lead-free halide perovskite solar cells based on Cs2AgBiBr6 has not exceeded 3%. The limiting bottlenecks are attributed to a low electron diffusion length, self-trapping events and poor selectivity of the contacts, leading to large non-radiative VOC losses. Here, 2D/3D hybrid double perovskites are introduced for the first time, using phenethyl ammonium as the constituting cation. The resulting solar cells show an increased efficiency of up to 2.5% for the champion cells and 2.03% on average, marking an improvement by 10% compared to the 3D reference on mesoporous TiO2. The effect is mainly due to a VOC improvement by up to 70 mV on average, yielding a maximum VOC of 1.18 V using different concentrations of phenethylammonium bromide. While these are among the highest reported VOC values for Cs2AgBiBr6 solar cells, the effect is attributed to a change in recombination behavior within the full device and a better selectivity at the interface toward the hole transporting material (HTM). This explanation is supported by voltage-dependent external quantum efficiency, as well as photoelectron spectroscopy, revealing a better energy level alignment and thus a better hole-extraction and improved electron blocking at the HTM interface.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {SnBrP-A SnIP-type representative in the Sn−Br−P system},

author = {F Reiter and M Pielmeier and A Vogel and C Jandl and M Plodinec and C Rohner and T Lunkenbein and K Nisi and A W Holleitner and T Nilges},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/zaac.202100347},

doi = {https://doi.org/10.1002/zaac.202100347},

issn = {0044-2313},

year  = {2022},

date = {2022-01-07},

urldate = {2022-01-07},

journal = {Zeitschrift f\"{u}r anorganische und allgemeine Chemie},

volume = {n/a},

number = {n/a},

pages = {e202100347},

abstract = {Abstract One-dimensional semiconductors are interesting materials due to their unique structural features and anisotropy, which grant them intriguing optical, dielectric and mechanical properties. In this work, we report on SnBrP, a lighter homologue of the first inorganic double helix compound SnIP. This class of compounds is characterized by intriguing mechanical and electronic properties, featuring a high flexibility without modulation of physical properties. Semiconducting SnBrP can be synthesized from red phosphorus, tin and tin(II)bromide at elevated temperatures and crystallizes as red-orange, cleavable needles. Raman measurements pointed towards a double helical building unit in SnBrP, showing similarities to the SnIP structure. After taking PL measurements, HR-TEM, and quantum chemical calculations into account, we were able to propose a sense full structure model for SnBrP.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Electrolyte Effects on the Stabilization of Prussian Blue Analogue Electrodes in Aqueous Sodium-Ion Batteries},

author = {X Lamprecht and F Speck and P Marzak and S Cherevko and A S Bandarenka},

url = {https://doi.org/10.1021/acsami.1c21219},

doi = {10.1021/acsami.1c21219},

issn = {1944-8244},

year  = {2022},

date = {2022-01-06},

urldate = {2022-01-06},

journal = {ACS Applied Materials \& Interfaces},

volume = {14},

pages = {3515-3525},

abstract = {Aqueous sodium-ion batteries based on Prussian Blue Analogues (PBA) are considered as promising and scalable candidates for stationary energy storage systems, where longevity and cycling stability are assigned utmost importance to maintain economic viability. Although degradation due to active material dissolution is a common issue of battery electrodes, it is hardly observable directly due to a lack of in operando techniques, making it challenging to optimize the performance of electrodes. By operating Na2Ni[Fe(CN)6] and Na2Co[Fe(CN)6] model electrodes in a flow-cell setup connected to an inductively coupled plasma mass spectrometer, in this work, the dynamics of constituent transition-metal dissolution during the charge\textendashdischarge cycles was monitored in real time. At neutral pHs, the extraction of nickel and cobalt was found to drive the degradation process during charge\textendashdischarge cycles. It was also found that the nature of anions present in the electrolytes has a significant impact on the degradation rate, determining the order ClO4\textendash \> NO3\textendash \> Cl\textendash \> SO42\textendash with decreasing stability from the perchlorate to sulfate electrolytes. It is proposed that the dissolution process is initiated by detrimental specific adsorption of anions during the electrode oxidation, therefore scaling with their respective chemisorption affinity. This study involves an entire comparison of the effectiveness of common stabilization strategies for PBAs under very fast (dis)charging conditions at 300C, emphasizing the superiority of highly concentrated NaClO4 with almost no capacity loss after 10 000 cycles for Na2Ni[Fe(CN)6].},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {The Influence of CsBr on Crystal Orientation and Optoelectronic Properties of MAPbI3-Based Solar Cells},

author = {Y Zou and S Yuan and A Buyruk and J Eichhorn and S Yin and M A Reus and T Xiao and S Pratap and S Liang and C L Weindl and W Chen and C Mu and I D Sharp and T Ameri and M Schwartzkopf and S V Roth and P M\"{u}ller-Buschbaum},

url = {https://doi.org/10.1021/acsami.1c22184},

doi = {10.1021/acsami.1c22184},

issn = {1944-8244},

year  = {2022},

date = {2022-01-06},

urldate = {2022-01-06},

journal = {ACS Applied Materials \& Interfaces},

volume = {14},

pages = {2958},

abstract = {Crystal orientations are closely related to the behavior of photogenerated charge carriers and are vital for controlling the optoelectronic properties of perovskite solar cells. Herein, we propose a facile approach to reveal the effect of lattice plane orientation distribution on the charge carrier kinetics via constructing CsBr-doped mixed cation perovskite phases. With grazing-incidence wide-angle X-ray scattering measurements, we investigate the crystallographic properties of mixed perovskite films at the microscopic scale and reveal the effect of the extrinsic CsBr doping on the stacking behavior of the lattice planes. Combined with transient photocurrent, transient photovoltage, and space-charge-limited current measurements, the transport dynamics and recombination of the photogenerated charge carriers are characterized. It is demonstrated that CsBr compositional engineering can significantly affect the perovskite crystal structure in terms of the orientation distribution of crystal planes and passivation of trap-state densities, as well as simultaneously facilitate the photogenerated charge carrier transport across the absorber and its interfaces. This strategy provides unique insight into the underlying relationship between the stacking pattern of crystal planes, photogenerated charge carrier transport, and optoelectronic properties of solar cells.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Tuning the Optical Properties of a MoSe2 Monolayer Using Nanoscale Plasmonic Antennas},

author = {M M Petri\'{c} and M Kremser and M Barbone and A Nolinder and A Lyamkina and A V Stier and M Kaniber and K M\"{u}ller and J J Finley},

url = {https://doi.org/10.1021/acs.nanolett.1c02676},

doi = {10.1021/acs.nanolett.1c02676},

issn = {1530-6984},

year  = {2022},

date = {2022-01-03},

journal = {Nano Letters},

volume = {22},

number = {2},

pages = {561-569},

abstract = {Nanoplasmonic systems combined with optically active two-dimensional materials provide intriguing opportunities to explore and control light\textendashmatter interactions at extreme subwavelength length scales approaching the exciton Bohr radius. Here, we present room- and cryogenic-temperature investigations of a MoSe2 monolayer on individual gold dipole nanoantennas. By controlling nanoantenna size, the dipolar resonance is tuned relative to the exciton achieving a total tuning of ∼130 meV. Differential reflectance measurements performed on \>100 structures reveal an apparent avoided crossing between exciton and dipolar mode and an exciton\textendashplasmon coupling constant of g = 55 meV, representing g/(ℏωX) ≥ 3% of the transition energy. This places our hybrid system in the intermediate-coupling regime where spectra exhibit a characteristic Fano-like shape. We demonstrate active control by varying the polarization of the excitation light to programmably suppress coupling to the dipole mode. We further study the emerging optical signatures of the monolayer localized at dipole nanoantennas at 10 K.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {A Systematic Study of the Influence of Electrolyte Ions on the Electrode Activity},

author = {X Ding and D Scieszka and S Watzele and S Xue and B Garlyyev and R W Haid and A S Bandarenka},

url = {https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/celc.202101088},

doi = {https://doi.org/10.1002/celc.202101088},

issn = {2196-0216},

year  = {2022},

date = {2022-01-01},

urldate = {2021-11-22},

journal = {ChemElectroChem},

volume = {9},

number = {1},

pages = {e202101088},

abstract = {Abstract Efficient electrocatalysis is most likely an answer to recent energy related challenges. Countless studies have been trying to find the links between the electrode/electrolyte interface structure, its composition, and the resulting activity in order to improve the performance of numerous devices, such as electrolyzers, fuel cells, and certain types of batteries. However, this scientific field currently meets serious complications associated with the prediction and explanation of an unexpected influence of seemingly inert electrolyte components on the observed activity. Herein, we investigate various electrocatalytic systems using a unique laser-induced current transient technique to answer a long-lasting fundamental question: How can “inert” electrolytes change the activity so drastically? Different metal electrodes in contact with various aqueous solutions and two energy important reactions were used as model systems. We experimentally determine the potential of maximum entropy of the electrodes and find the connections between its position and the electrocatalytic performance.},

keywords = {Foundry Inorganic},

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 = {Foundry Inorganic, Solid-Liquid},

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 = {Foundry Inorganic},

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 = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {High-Quality Optical Hotspots with Topology-Protected Robustness},

author = {C Liu and S A Maier},

url = {https://doi.org/10.1021/acsphotonics.1c01445},

doi = {10.1021/acsphotonics.1c01445},

year  = {2021},

date = {2021-12-23},

journal = {ACS Photonics},

abstract = {Optical hotspots underpin a wide variety of photonic devices ranging from sensing, nonlinear generation to photocatalysis, taking advantage of the strong light\textendashmatter interaction at the vicinity of photonic nanostructures. While plasmonic nanostructures have been widely used for strongly localized electromagnetic energy on surfaces, they suffer from high loss and consequently a low quality factor. Resonance-based dielectric structures provide an alternative solution with a larger quality factor, but there is a mismatch between the maximum values of the light confinement (quality factor) and the leakage (intensity in the near-field). Here, we propose to apply the concept of topological photonics to the formation of hotspots, producing them in both topological edge states and topological corner states. The topology secures strong light localization at the surface of the nanostructures where the underlying topological invariant shows a jump, generating a field hotspot with simultaneous increment of quality factor and light intensity. Meanwhile, it leverages a good robustness to fabrication imperfection including fluctuation in shape and misalignment. After a systematic investigation and comparison of the robustness between 1D and 2D topological structures, we conclude that the hotspots from 1D topological edge states promise a fertile playground for emerging applications that require both enhanced light intensity and high spectral resolution.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Influence of Layer Slipping on Adsorption of Light Gases in Covalent Organic Frameworks: A Combined Experimental and Computational Study},

author = {C Kessler and R Schuldt and S Emmerling and B V Lotsch and J K\"{a}stner and J Gross and N Hansen},

doi = {arXiv:2112.10137v1},

year  = {2021},

date = {2021-12-19},

urldate = {2021-12-19},

journal = {arXiv e-prints},

pages = {arXiv: 2112.10137},

abstract = {Sorption of gases in micro- and mesoporous materials is typically interpreted on the basis of idealized structural models where real structure effects such as defects and disorder are absent. For covalent organic frameworks (COFs) significant discrepancies between measured and simulated adsorption isotherms are often reported but rarely traced back to their origins. This is because little is known about the real structure of COFs and its effect on the sorption properties of these materials. In the present work molecular simulations are used to obtain adsorption isotherms of argon, nitrogen, and carbon dioxide in the COF-LZU1 at various temperatures. The (perfect) model COF has a BET surface that is higher than the experimental BET surface by a factor of approximately 1.33, suggesting defects or inclusions are present in the real structure. We find that the saturation adsorption loading of small gaseous species in COF-LZU1, as determined from grand canonical Monte Carlo simulations, is also higher by approximately the same factor compared to the experimental saturation loading. The influence of interlayer slipping on the shape of the adsorption isotherm and the adsorption capacity is studied. Comparison between simulation and experiment at lower loadings suggests the layers to be shifted instead of perfectly eclipsed. The sensitivity of the adsorption isotherms in this regime towards the underlying framework topology shows that real structure effects have significant influence on the gas uptake. Accounting for layer slipping is important to applications such as catalysis, gas storage and separation.},

keywords = {Foundry Inorganic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Detecting a Hierarchy of Deep-Level Defects in the Model Semiconductor ZnSiN2},

author = {T De Boer and J H\"{a}usler and P Strobel and T D Boyko and S S Rudel and W Schnick and A Moewes},

url = {https://doi.org/10.1021/acs.jpcc.1c08115},

doi = {10.1021/acs.jpcc.1c08115},

issn = {1932-7447},

year  = {2021},

date = {2021-12-15},

journal = {The Journal of Physical Chemistry C},

abstract = {Recent developments in the materials synthesis of the Zn\textendashIV\textendashN2 system, including the alloy-free band gap tuning and synthesis of freestanding single crystals, reveal a system with potentially very broad applications. For that, important basic properties of these materials, such as the electronic band gap and the characteristics of defects, must be well understood, which has therefore become an urgent problem. In this work, X-ray absorption spectroscopy, X-ray emission spectroscopy, and density functional theory are utilized to characterize ZnSiN2. Excellent agreement between theory and experiment is obtained, with the band gap of ZnSiN2 determined to be 4.7 ± 0.3 eV. X-ray-excited optical luminescence spectroscopy is used to determine the presence of two deep-level defects, which are identified as due to the presence of nitrogen vacancies.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Morphology\textendashIonic Conductivity Relationship in Polymer\textendashTitania Hybrid Electrolytes for Lithium-Ion Batteries},

author = {S J Schaper and E Metwalli and M V Kaeppel and A Kriele and R Gilles and K N Raftopoulos and P M\"{u}ller-Buschbaum},

url = {https://doi.org/10.1021/acsaem.1c03393},

doi = {10.1021/acsaem.1c03393},

year  = {2021},

date = {2021-12-14},

urldate = {2021-12-14},

journal = {ACS Applied Energy Materials},

volume = {4},

number = {12},

pages = {13438\textendash13443},

abstract = {The morphology and ionic conductivity of a high-molecular-weight polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymer (DBC) solid-state hybrid electrolyte, prepared entirely from solution, containing the lithium salt LiTFSI ([Li]/[EO] = 0.1) and titania (TiO2) nanoparticles (NP) were investigated at different temperatures. Structure investigation using small-angle X-ray scattering (SAXS) indicates a rupture of the DBC morphology upon increasing TiO2\textendashNP content, without a significant decrease in the ionic conductivity at high TiO2\textendashNP contents. A high number of unbound charge carriers in the hybrid DBC electrolyte, achieved by careful tuning of the materials’ ratios, is the most important contribution to a high ionic conductivity.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Nanoscale Confinement of Photo-Injected Electrons at Hybrid Interfaces},

author = {S Neppl and J Mahl and F Roth and G Mercurio and G Zeng and F M Toma and N Huse and P Feulner and O Gessner},

url = {https://doi.org/10.1021/acs.jpclett.1c02648},

doi = {10.1021/acs.jpclett.1c02648},

year  = {2021},

date = {2021-12-09},

journal = {The Journal of Physical Chemistry Letters},

volume = {12},

number = {49},

pages = {11951-11959},

abstract = {A prerequisite for advancing hybrid solar light harvesting systems is a comprehensive understanding of the spatiotemporal dynamics of photoinduced interfacial charge separation. Here, we demonstrate access to this transient charge redistribution for a model hybrid system of nanoporous zinc oxide (ZnO) and ruthenium bipyridyl chromophores. The site-selective probing of the molecular electron donor and semiconductor acceptor by time-resolved X-ray photoemission provides direct insight into the depth distribution of the photoinjected electrons and their interaction with the local band structure on a nanometer length scale. Our results show that these electrons remain localized within less than 6 nm from the interface, due to enhanced downward band bending by the photoinjected charge carriers. This spatial confinement suggests that light-induced charge generation and transport in nanoscale ZnO photocatalytic devices proceeds predominantly within the defect-rich surface region, which may lead to enhanced surface recombination and explain their lower performance compared to titanium dioxide (TiO2)-based systems.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Conductivity Mechanism in Ionic 2D Carbon Nitrides: From Hydrated Ion Motion to Enhanced Photocatalysis},

author = {J Kr\"{o}ger and F Podjaski and G Savasci and I Moudrakovski and A Jim\'{e}nez-Solano and M W Terban and S Bette and V Duppel and M Joos and A Senocrate and R Dinnebier and C Ochsenfeld and B V Lotsch},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adma.202107061},

doi = {https://doi.org/10.1002/adma.202107061},

issn = {0935-9648},

year  = {2021},

date = {2021-12-06},

journal = {Advanced Materials},

volume = {34},

number = {7},

pages = {2107061},

abstract = {Abstract Carbon nitrides are among the most studied materials for photocatalysis; however, limitations arise from inefficient charge separation and transport within the material. Here, this aspect is addressed in the 2D carbon nitride poly(heptazine imide) (PHI) by investigating the influence of various counterions, such as M = Li+, Na+, K+, Cs+, Ba2+, NH4+, and tetramethyl ammonium, on the material's conductivity and photocatalytic activity. These ions in the PHI pores affect the stacking of the 2D layers, which further influences the predominantly ionic conductivity in M-PHI. Na-containing PHI outperforms the other M-PHIs in various relative humidity (RH) environments (0\textendash42%RH) in terms of conductivity, likely due to pore-channel geometry and size of the (hydrated) ion. With increasing RH, the ionic conductivity increases by 4\textendash5 orders of magnitude (for Na-PHI up to 10-5 S cm-1 at 42%RH). At the same time, the highest photocatalytic hydrogen evolution rate is observed for Na-PHI, which is mirrored by increased photogenerated charge-carrier lifetimes, pointing to efficient charge-carrier stabilization by, e.g., mobile ions. These results indicate that also ionic conductivity is an important parameter that can influence the photocatalytic activity. Besides, RH-dependent ionic conductivity is of high interest for separators, membranes, or sensors.},

keywords = {Foundry Inorganic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Local Growth Mediated by Plasmonic Hot Carriers: Chirality from Achiral Nanocrystals Using Circularly Polarized Light},

author = {L V Besteiro and A Movsesyan and O \'{A}valos-Ovando and S Lee and E Cort\'{e}s and M A Correa-Duarte and Z M Wang and A O Govorov},

url = {https://doi.org/10.1021/acs.nanolett.1c03503},

doi = {10.1021/acs.nanolett.1c03503},

issn = {1530-6984},

year  = {2021},

date = {2021-12-03},

journal = {Nano Letters},

abstract = {Plasmonic nanocrystals and their assemblies are excellent tools to create functional systems, including systems with strong chiral optical responses. Here we study the possibility of growing chiral plasmonic nanocrystals from strictly nonchiral seeds of different types by using circularly polarized light as the chirality-inducing mechanism. We present a novel theoretical methodology that simulates realistic nonlinear and inhomogeneous photogrowth processes in plasmonic nanocrystals, mediated by the excitation of hot carriers that can drive surface chemistry. We show the strongly anisotropic and chiral growth of oriented nanocrystals with lowered symmetry, with the striking feature that such chiral growth can appear even for nanocrystals with subwavelength sizes. Furthermore, we show that the chiral growth of nanocrystals in solution is fundamentally challenging. This work explores new ways of growing monolithic chiral plasmonic nanostructures and can be useful for the development of plasmonic photocatalysis and fabrication technologies.},

keywords = {Foundry Inorganic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Probing the Disorder inside the Cubic Unit Cell of Halide Perovskites from First-Principles},

author = {X Zhu and S Caicedo-D\'{a}vila and C Gehrmann and D A Egger},

doi = {arXiv:2111.14668v1},

year  = {2021},

date = {2021-11-29},

journal = {arXiv preprint arXiv:2111.14668},

abstract = {Strong deviations in the finite temperature atomic structure of halide perovskites from their average geometry can have profound impacts on optoelectronic and other device-relevant properties. Detailed mechanistic understandings of these structural fluctuations and their consequences remain, however, limited by the experimental and theoretical challenges involved in characterizing strongly anharmonic vibrational characteristics and their impact on other properties. We overcome some of these challenges by a theoretical characterization of the vibrational interactions that occur among the atoms in the prototypical cubic CsPbBr3. Our investigation based on first-principles molecular dynamics calculations finds that the motions of neighboring Cs-Br atoms interlock, which appears as the most likely Cs-Br distance being significantly shorter than what is inferred from an ideal cubic structure. This form of dynamic Cs-Br coupling coincides with very shallow dynamic potential wells for Br motions that occur across a locally and dynamically disordered energy landscape. We reveal an interesting dynamic coupling mechanism among the atoms within the nominal unit cell of cubic CsPbBr3 and quantify the important local structural fluctuations on an atomic scale.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Optimizing hydrogen binding on Ru sites with RuCo alloy nanosheets for efficient alkaline hydrogen evolution},

author = {C Cai and K Liu and Y Zhu and P Li and Q Wang and B Liu and S Chen and H Li and L Zhu and H Li and J Fu and Y Chen and E Pensa and J Hu and Y-R Lu and T-S Chan and E Cortes and M Liu},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202113664},

doi = {https://doi.org/10.1002/anie.202113664},

issn = {1433-7851},

year  = {2021},

date = {2021-11-25},

urldate = {2021-11-25},

journal = {Angewandte Chemie International Edition},

volume = {n/a},

number = {n/a},

abstract = {Ruthenium (Ru)-based catalysts, with considerable performance and desirable cost, become highly concerned candidates to replace platinum (Pt) in alkaline hydrogen evolution reaction (HER). The hydrogen binding at Ru sites (Ru-H) is an important factor limiting the HER activity. Herein, density functional theory (DFT) simulations show that the essence of Ru-H binding energy is the strong interaction between the 4dz 2 orbital of Ru and 1s orbital of H. The charge transfer between Ru sites and substrates (Co and Ni) causes the appropriate downward shift of the 4dz 2 -band center of Ru, which results in a Gibbs free energy of 0.022 eV for H* in RuCo system, much decrease compared to 0.133 eV in pure Ru system. This theoretical prediction has been experimentally confirmed using RuCo alloy nanosheets (RuCo ANSs). They were prepared via fast co-precipitation method followed with a mild electrochemical reduction. Structure characterizations reveal that the Ru atoms are embed into Co substrate as isolated active sites with the planar symmetric and Z-direction asymmetric coordination structure, obtaining an optimal 4dz 2 modulated electronic structure. Hydrogen sensor and temperature program desorption (TPD) tests demonstrate the enhanced Ru-H interactions in RuCo ANSs than pure Ru nanoparticles. As a result, the RuCo ANSs reach an ultra-low overpotential of 10 mV at 10 mA/cm 2 and a Tafel slope of 20.6 mV/dec in 1 M KOH, outperforming that of the commercial Pt/C. This holistic work provides a new insight to promote alkaline HER by optimizing metal-H binding energy of active sites.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Kernel Charge Equilibration: Efficient and Accurate Prediction of Molecular Dipole Moments with a Machine-Learning Enhanced Electron Density Model},

author = {C Staacke and S Wengert and C Kunkel and G Cs\'{a}nyi and K Reuter and J T Margraf},

doi = {10.26434/chemrxiv-2021-73w0p},

year  = {2021},

date = {2021-11-25},

journal = {ChemRxiv, Cambridge: Cambridge Open Engage},

abstract = {State-of-the-art machine learning (ML) interatomic potentials use local representations of atomic environments to ensure linear scaling and size-extensivity. This implies a neglect of long-range interactions, most prominently related to electrostatics. To overcome this limitation, we herein present a ML framework for predicting charge distributions and their interactions termed kernel Charge Equilibration (kQEq). This model is based on classical charge equilibration models like QEq, expanded with an environment dependent electronegativity. In contrast to previously reported neural network models with a similar concept, kQEq takes advantage of the linearity of both QEq and Kernel Ridge Regression to obtain a closed-form linear algebra expression for training the models. Furthermore, we avoid the ambiguity of charge partitioning schemes by using dipole moments as reference data. As a first application, we show that kQEq can be used to generate accurate and highly data-efficient models for molecular dipole moments.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Surface-confined formation of conjugated porphyrin-based nanostructures on Ag(111)},

author = {N Cao and A Riss and E Corral-Rascon and A Meindl and W Auw\"{a}rter and M O Senge and M Ebrahimi and J V Barth},

url = {http://dx.doi.org/10.1039/D1NR06451G},

doi = {10.1039/D1NR06451G},

issn = {2040-3364},

year  = {2021},

date = {2021-11-25},

journal = {Nanoscale},

volume = {13},

number = {47},

pages = {19884-19889},

abstract = {Porphyrin-based oligomers were synthesized from the condensation of adsorbed 4-benzaldehyde-substituted porphyrins through the formation of CC linkages, following a McMurry-type coupling scheme. Scanning tunneling microscopy, non-contact atomic force microscopy, and X-ray photoelectron spectroscopy data evidence both the dissociation of aldehyde groups and the formation of CC linkages. Our approach provides a path for the on-surface synthesis of porphyrin-based oligomers coupled by CC bridges \textendash as a means to create functional conjugated nanostructures.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Nanosized and metastable molybdenum oxides as negative electrode materials for durable high-energy aqueous Li-ion batteries},

author = {J Yun and R Sagehashi and Y Sato and T Masuda and S Hoshino and H B Rajendra and K Okuno and A Hosoe and A S Bandarenka and N Yabuuchi},

url = {https://www.pnas.org/doi/abs/10.1073/pnas.2024969118},

doi = {doi:10.1073/pnas.2024969118},

year  = {2021},

date = {2021-11-23},

urldate = {2021-11-23},

journal = {Proceedings of the National Academy of Sciences},

volume = {118},

number = {48},

pages = {e2024969118},

abstract = {The development of inherently safe energy devices is a key challenge, and aqueous Li-ion batteries draw large attention for this purpose. Due to the narrow electrochemical stable potential window of aqueous electrolytes, the energy density and the selection of negative electrode materials are significantly limited. For achieving durable and high-energy aqueous Li-ion batteries, the development of negative electrode materials exhibiting a large capacity and low potential without triggering decomposition of water is crucial. Herein, a type of a negative electrode material (i.e., LixNb2/7Mo3/7O2) is proposed for high-energy aqueous Li-ion batteries. LixNb2/7Mo3/7O2 delivers a large capacity of ∼170 mA ⋅ h ⋅ g−1 with a low operating potential range of 1.9 to 2.8 versus Li/Li+ in 21 m lithium bis(trifluoromethanesulfonyl)amide (LiTFSA) aqueous electrolyte. A full cell consisting of Li1.05Mn1.95O4/Li9/7Nb2/7Mo3/7O2 presents high energy density of 107 W ⋅ h ⋅ kg−1 as the maximum value in 21 m LiTFSA aqueous electrolyte, and 73% in capacity retention is achieved after 2,000 cycles. Furthermore, hard X-ray photoelectron spectroscopy study reveals that a protective surface layer is formed at the surface of the negative electrode, by which the high-energy and durable aqueous batteries are realized with LixNb2/7Mo3/7O2. This work combines a high capacity with a safe negative electrode material through delivering the Mo-based oxide with unique nanosized and metastable characters.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {On the Role of Long-Range Electrostatics in Machine-Learned Interatomic Potentials for Complex Battery Materials},

author = {C G Staacke and H H Heenen and C Scheurer and G Cs\'{a}nyi and K Reuter and J T Margraf},

url = {https://doi.org/10.1021/acsaem.1c02363},

doi = {10.1021/acsaem.1c02363},

year  = {2021},

date = {2021-11-22},

journal = {ACS Applied Energy Materials},

volume = {4},

number = {11},

pages = {12562-12569},

abstract = {Modeling complex energy materials such as solid-state electrolytes (SSEs) realistically at the atomistic level strains the capabilities of state-of-the-art theoretical approaches. On one hand, the system sizes and simulation time scales required are prohibitive for first-principles methods such as the density functional theory. On the other hand, parameterizations for empirical potentials are often not available, and these potentials may ultimately lack the desired predictive accuracy. Fortunately, modern machine learning (ML) potentials are increasingly able to bridge this gap, promising first-principles accuracy at a much reduced computational cost. However, the local nature of these ML potentials typically means that long-range contributions arising, for example, from electrostatic interactions are neglected. Clearly, such interactions can be large in polar materials such as electrolytes, however. Herein, we investigate the effect that the locality assumption of ML potentials has on lithium mobility and defect formation energies in the SSE Li7P3S11. We find that neglecting long-range electrostatics is unproblematic for the description of lithium transport in the isotropic bulk. In contrast, (field-dependent) defect formation energies are only adequately captured by a hybrid potential combining ML and a physical model of electrostatic interactions. Broader implications for ML-based modeling of energy materials are discussed.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {How Exciton\textendashPhonon Coupling Impacts Photoluminescence in Halide Perovskite Nanoplatelets},

author = {M Gramlich and C Lampe and J Drewniok and A S Urban},

url = {https://doi.org/10.1021/acs.jpclett.1c03437},

doi = {10.1021/acs.jpclett.1c03437},

year  = {2021},

date = {2021-11-18},

journal = {The Journal of Physical Chemistry Letters},

pages = {11371-11377},

abstract = {Semiconductor nanocrystals are receiving increased interest as narrow-band emitters for display applications. Here, we investigate the underlying photoluminescence (PL) linewidth broadening mechanisms in thickness-tunable 2D halide perovskite (Csn−1PbnBr3n+1) nanoplatelets (NPLs). Temperature-dependent PL spectroscopy on NPL thin films reveals a blue-shift of the PL maximum for thicker NPLs, no shift for three monolayer (ML) thick NPLs, and a red-shift for the thinnest (2 ML) NPLs with increasing temperature. Emission linewidths also strongly depend on NPL thickness, with the thinnest NPLs showing the smallest temperature-induced broadening. We determine the combined interaction of exciton\textendashphonon coupling and thermal lattice expansion to be responsible for both effects. Additionally, the 2 ML NPLs exhibit a significantly larger Fr\"{o}hlich coupling constant and optical phonon energy, possibly due to an inversion in the exciton fine structure. These results illustrate that ultrathin halide perovskite NPLs could illuminate the next generation of displays, provided a slightly greater sample homogeneity and improved stability.},

keywords = {Foundry Inorganic},

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 = {Foundry Inorganic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Modular Assembly of Vibrationally and Electronically Coupled Rhenium Bipyridine Carbonyl Complexes on Silicon},

author = {J D Bartl and C Thomas and A Henning and M F Ober and G Savasci and B Yazdanshenas and P S Deimel and E Magnano and F Bondino and P Zeller and L Gregoratti and M Amati and C Paulus and F Allegretti and A Cattani-Scholz and J V Barth and C Ochsenfeld and B Nickel and I D Sharp and M Stutzmann and B Rieger},

url = {https://doi.org/10.1021/jacs.1c09061},

doi = {10.1021/jacs.1c09061},

issn = {0002-7863},

year  = {2021},

date = {2021-11-12},

urldate = {2021-11-12},

journal = {Journal of the American Chemical Society},

volume = {143},

pages = {19505},

abstract = {Hybrid inorganic/organic heterointerfaces are promising systems for next-generation photocatalytic, photovoltaic, and chemical-sensing applications. Their performance relies strongly on the development of robust and reliable surface passivation and functionalization protocols with (sub)molecular control. The structure, stability, and chemistry of the semiconductor surface determine the functionality of the hybrid assembly. Generally, these modification schemes have to be laboriously developed to satisfy the specific chemical demands of the semiconductor surface. The implementation of a chemically independent, yet highly selective, standardized surface functionalization scheme, compatible with nanoelectronic device fabrication, is of utmost technological relevance. Here, we introduce a modular surface assembly (MSA) approach that allows the covalent anchoring of molecular transition-metal complexes with sub-nanometer precision on any solid material by combining atomic layer deposition (ALD) and selectively self-assembled monolayers of phosphonic acids. ALD, as an essential tool in semiconductor device fabrication, is used to grow conformal aluminum oxide activation coatings, down to sub-nanometer thicknesses, on silicon surfaces to enable a selective step-by-step layer assembly of rhenium(I) bipyridine tricarbonyl molecular complexes. The modular surface assembly of molecular complexes generates precisely structured spatial ensembles with strong intermolecular vibrational and electronic coupling, as demonstrated by infrared spectroscopy, photoluminescence, and X-ray photoelectron spectroscopy analysis. The structure of the MSA can be chosen to avoid electronic interactions with the semiconductor substrate to exclusively investigate the electronic interactions between the surface-immobilized molecular complexes.},

keywords = {Foundry Inorganic, Foundry Organic, Molecularly-Functionalized, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Strong Potential Gradients and Electron Confinement in ZnO Nanoparticle Films: Implications for Charge-Carrier Transport and Photocatalysis},

author = {J Mahl and O Gessner and J V Barth and P Feulner and S Neppl},

url = {https://doi.org/10.1021/acsanm.1c02730},

doi = {10.1021/acsanm.1c02730},

year  = {2021},

date = {2021-11-11},

journal = {ACS Applied Nano Materials},

volume = {4},

number = {11},

pages = {12213-12221},

abstract = {Zinc oxide (ZnO) nanomaterials are promising components for chemical and biological sensors and photocatalytic conversion and operate as electron collectors in photovoltaic technologies. Many of these applications involve nanostructures in contact with liquids or exposed to ambient atmosphere. Under these conditions, single-crystal ZnO surfaces are known to form narrow electron accumulation layers with few nanometer spatial penetration into the bulk. A key question is to what extent such pronounced surface potential gradients can develop in the nanophases of ZnO, where they would dominate the catalytic activity by modulating charge-carrier mobility and lifetimes. Here, we follow the temperature-dependent surface electronic structure of nanoporous ZnO with photoemission spectroscopy to reveal a sizable, spatially averaged downward band bending for the hydroxylated state and a conservative upper bound of \<6 nm for the spatial extent of the associated potential gradient. This nanoscale confinement of conduction-band electrons to the nanoparticle film surface is crucial for a microscopic understanding and further optimization of charge transport and photocatalytic function in complex ZnO nanomaterials.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Probing the Role of Atomic Defects in Photocatalytic Systems through Photoinduced Enhanced Raman Scattering},

author = {D Glass and R Quesada-Cabrera and S Bardey and P Promdet and R Sapienza and V Keller and S A Maier and V Caps and I P Parkin and E Cort\'{e}s},

url = {https://doi.org/10.1021/acsenergylett.1c01772},

doi = {10.1021/acsenergylett.1c01772},

year  = {2021},

date = {2021-11-10},

journal = {ACS Energy Letters},

pages = {4273-4281},

abstract = {Even in ultralow quantities, oxygen vacancies (VO) drastically impact key properties of metal oxide semiconductors, such as charge transport, surface adsorption, and reactivity, playing central roles in functional materials performance. Current methods used to investigate VO often rely on specialized instrumentation under far from ideal reaction conditions. Hence, the influence of VO generated in situ during catalytic processes has yet to be probed. In this work, we assess in situ extrinsic surface VO formation and lifetime under photocatalytic conditions which we compare to photocatalytic performance. We show for the first time that lifetimes of in situ generated atomic VO play more significant roles in catalysis than their concentration, with strong correlations between longer-lived VO and higher photocatalytic activity. Our results indicate that enhanced photocatalytic efficiency correlates with goldilocks VO concentrations, where VO densities must be just right to encourage carrier transport while avoiding charge carrier trapping.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {The Effect of Dynamic Structural Flexibility in Halide Perovskites},

author = {C Gehrmann and S Caicedo-D\'{a}vila and X Zhu and D A Egger},

year  = {2021},

date = {2021-11-01},

journal = {J. Mater. Sci.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Biopolymer-Templated Deposition of Ordered and Polymorph Titanium Dioxide Thin Films for Improved Surface-Enhanced Raman Scattering Sensitivity},

author = {Q Chen and M Betker and C Harder and C J Brett and M Schwartzkopf and N M Ulrich and M E Toimil-Molares and C Trautmann and L D S\"{o}derberg and C L Weindl and V K\"{o}rstgens and P M\"{u}ller-Buschbaum and M Ma and S V Roth},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adfm.202108556},

doi = {https://doi.org/10.1002/adfm.202108556},

issn = {1616-301X},

year  = {2021},

date = {2021-10-27},

journal = {Adv. Funct. Mater.},

volume = {n/a},

number = {n/a},

pages = {2108556},

abstract = {Abstract Titanium dioxide (TiO2) is an excellent candidate material for semiconductor metal oxide-based substrates for surface-enhanced Raman scattering (SERS). Biotemplated fabrication of TiO2 thin films with a 3D network is a promising route for effectively transferring the morphology and ordering of the template into the TiO2 layer. The control over the crystallinity of TiO2 remains a challenge due to the low thermal stability of biopolymers. Here is reported a novel strategy of the cellulose nanofibril (CNF)-directed assembly of TiO2/CNF thin films with tailored morphology and crystallinity as SERS substrates. Polymorphous TiO2/CNF thin films with well-defined morphology are obtained by combining atomic layer deposition and thermal annealing. A high enhancement factor of 1.79 × 106 in terms of semiconductor metal oxide nanomaterial (SMON)-based SERS substrates is obtained from the annealed TiO2/CNF thin films with a TiO2 layer thickness of 10 nm fabricated on indium tin oxide (ITO), when probed by 4-mercaptobenzoic acid molecules. Common SERS probes down to 10 nm can be detected on these TiO2/CNF substrates, indicating superior sensitivity of TiO2/CNF thin films among SMON SERS substrates. This improvement in SERS sensitivity is realized through a cooperative modulation of the template morphology of the CNF network and the crystalline state of TiO2.},

keywords = {Foundry Inorganic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Bimolecular Generation of Excitonic Luminescence from Dark Photoexcitations in Ruddlesden\textendashPopper Hybrid Metal-Halide Perovskites},

author = {M Nuber and D Sandner and T Neumann and R Kienberger and F Deschler and H Iglev},

url = {https://doi.org/10.1021/acs.jpclett.1c03099},

doi = {10.1021/acs.jpclett.1c03099},

year  = {2021},

date = {2021-10-21},

journal = {The Journal of Physical Chemistry Letters},

volume = {12},

number = {42},

pages = {10450-10456},

abstract = {The nature of photoexcitations in Ruddlesden\textendashPopper (RP) hybrid metal halide perovskites is still under debate. While the high exciton binding energy in the hundreds of millielectronvolts indicates excitons as the primary photoexcitations, recent reports found evidence for dark, Coulombically screened populations, which form via strong coupling of excitons and the atomic lattice. Here, we use time-resolved mid-infrared spectroscopy to gain insights into the nature and recombination of such dark excited states in (BA)2(MA)n−1PbnI3n+1 (n = 1,2,3) via their intraband electronic absorption. In stark contrast to results in the bulk perovskites, all samples exhibit a broad, unstructured mid-IR photoinduced absorbance with no infrared activated modes, independent of excitonic confinement. Further, the recombination dynamics are dominated by a bimolecular process. In combination with steady-state photoluminescence experiments, we conclude that screened, dark photoexcitations act as a population reservoir in the RP hybrid perovskites, from which nongeminate formation of bright excitons precedes generation of photoluminescence.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {A self-healing catalyst for electrocatalytic and photoelectrochemical oxygen evolution in highly alkaline conditions},

author = {C Feng and F Wang and Z Liu and M Nakabayashi and Y Xiao and Q Zeng and J Fu and Q Wu and C Cui and Y Han and N Shibata and K Domen and I D Sharp and Y Li},

url = {https://doi.org/10.1038/s41467-021-26281-0},

doi = {10.1038/s41467-021-26281-0},

issn = {2041-1723},

year  = {2021},

date = {2021-10-13},

journal = {Nature Communications},

volume = {12},

number = {1},

pages = {5980},

abstract = {While self-healing is considered a promising strategy to achieve long-term stability for oxygen evolution reaction (OER) catalysts, this strategy remains a challenge for OER catalysts working in highly alkaline conditions. The self-healing of the OER-active nickel iron layered double hydroxides (NiFe-LDH) has not been successful due to irreversible leaching of Fe catalytic centers. Here, we investigate the introduction of cobalt (Co) into the NiFe-LDH as a promoter for in situ Fe redeposition. An active borate-intercalated NiCoFe-LDH catalyst is synthesized using electrodeposition and shows no degradation after OER tests at 10 mA cm−2 at pH 14 for 1000 h, demonstrating its self-healing ability under harsh OER conditions. Importantly, the presence of both ferrous ions and borate ions in the electrolyte is found to be crucial to the catalyst’s self-healing. Furthermore, the implementation of this catalyst in photoelectrochemical devices is demonstrated with an integrated silicon photoanode. The self-healing mechanism leads to a self-limiting catalyst thickness, which is ideal for integration with photoelectrodes since redeposition is not accompanied by increased parasitic light absorption.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {The Flexible On-Surface Self-Assembly of a Low-Symmetry Mabiq Ligand: An Unconventional Metal-Assisted Phase Transformation on Ag(111)},

author = {F Haag and P S Deimel and P Knecht and L Niederegger and K Seufert and M G. Cuxart and Y Bao and A C Papageorgiou and M Muntwiler and W Auw\"{a}rter and C R Hess and J V Barth and F Allegretti},

url = {https://doi.org/10.1021/acs.jpcc.1c07400},

doi = {10.1021/acs.jpcc.1c07400},

issn = {1932-7447},

year  = {2021},

date = {2021-10-12},

journal = {The Journal of Physical Chemistry C},

volume = {125},

number = {42},

pages = {23178-23191},

abstract = {The self-assembly of metal\textendashorganic complexes and networks of increasing complexity on solid surfaces is important for their application in a variety of fields, such as catalysis, sensing, and molecular magnetism. Here, we have selected a low-symmetry, free-base macrocyclic biquinazoline ligand, H-Mabiq, which upon metalation has the potential to incorporate cations in two different coordination sites, affording multi-valency and multi-electron transfer capacity. We show that H-Mabiq molecules readily self-assemble onto the Ag(111) surface at room temperature, forming a well-ordered monolayer of closely packed molecules. Upon increasing the temperature, a new phase with a different long-range order and molecular packing is obtained. By means of scanning tunneling microscopy and photoelectron spectroscopy, we show that this new phase is characterized by a distinctive silver-bridged dimeric motif, entailing a Ag adatom accommodated at the peripheral coordination site of two opposing H-Mabiq molecules. Thus, the present work reveals the ability of the bio-inspired Mabiq ligands to form surface-confined two-dimensional assemblies incorporating metal adatoms. The results bode promise for the use of metal-containing Mabiq compounds to engineer regular bimetallic arrays with atomic precision.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Ion Dynamics and Polymorphism in Cu20Te11Cl3},

author = {A Vogel and T Nilges},

url = {https://doi.org/10.1021/acs.inorgchem.1c01764},

doi = {10.1021/acs.inorgchem.1c01764},

issn = {0020-1669},

year  = {2021},

date = {2021-10-04},

journal = {Inorganic Chemistry},

volume = {60},

number = {20},

pages = {15233-15241},

abstract = {Coinage metal polychalcogenide halides are an intriguing class of materials, and many representatives are solid ion conductors and thermoelectric materials. The materials show high ion mobility, polymorphism, and various attractive interactions in the cation and anion substructures. Especially the latter feature leads to complex electronic structures and the occurrence of charge-density waves (CDWs) and, as a result, the first p\textendashn\textendashp switching materials. During our systematic investigations for new p\textendashn\textendashn switching materials in the Cu\textendashTe\textendashCl phase diagram, we were able to isolate polymorphic Cu20Te11Cl3, which we characterized structurally and with regard to its electronic and thermoelectric properties. Cu20Te11Cl3 is trimorphic, with phase transitions occurring at 288 and 450 K. The crystal structures of two polymorphs, the α phase, stable above 450 K, and the β polymorph (288\textendash450 K), are reported, and the complex structure chemistry featuring twinning upon a phase change is illustrated. We identified a dynamic cation substructure and a static anion substructure for all polymorphs, characterizing Cu20Te11Cl3 as a solid Cu-ion conductor. Temperature-dependent measurements of the Seebeck coefficient and total conductivity were performed and substantiated a linear response of the Seebeck coefficient, a lack of CDWs, and no p\textendashn\textendashp switching. Reasons for a lack of CDWs in Cu20Te11Cl3 are discussed and illustrated in the context of existing p\textendashn\textendashp switching materials.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Targetable Conformationally Restricted Cyanines Enable Photon-Count-Limited Applications**},

author = {P Eiring and R Mclaughlin and S S Matikonda and Z Han and L Grabenhorst and D A Helmerich and M Meub and G Beliu and M Luciano and V Bandi and N Zijlstra and Z-D Shi and S G Tarasov and R Swenson and P Tinnefeld and V Glembockyte and T Cordes and M Sauer and M J Schnermann},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202109749},

doi = {https://doi.org/10.1002/anie.202109749},

issn = {1433-7851},

year  = {2021},

date = {2021-10-04},

urldate = {2021-10-04},

journal = {Angewandte Chemie International Edition},

volume = {60},

number = {51},

pages = {26685-26693},

abstract = {Abstract Cyanine dyes are exceptionally useful probes for a range of fluorescence-based applications, but their photon output can be limited by trans-to-cis photoisomerization. We recently demonstrated that appending a ring system to the pentamethine cyanine ring system improves the quantum yield and extends the fluorescence lifetime. Here, we report an optimized synthesis of persulfonated variants that enable efficient labeling of nucleic acids and proteins. We demonstrate that a bifunctional sulfonated tertiary amide significantly improves the optical properties of the resulting bioconjugates. These new conformationally restricted cyanines are compared to the parent cyanine derivatives in a range of contexts. These include their use in the plasmonic hotspot of a DNA-nanoantenna, in single-molecule F\"{o}rster-resonance energy transfer (FRET) applications, far-red fluorescence-lifetime imaging microscopy (FLIM), and single-molecule localization microscopy (SMLM). These efforts define contexts in which eliminating cyanine isomerization provides meaningful benefits to imaging performance.},

keywords = {Foundry Inorganic, Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Tunable 2D Group-III Metal Alloys},

author = {S Rajabpour and A Vera and W He and B N Katz and R J Koch and M Lassauni\`{e}re and X Chen and C Li and K Nisi and H El-Sherif and M T Wetherington and C Dong and A Bostwick and C Jozwiak and A C T Van Duin and N Bassim and J Zhu and G-C Wang and U Wurstbauer and E Rotenberg and V Crespi and S Y Quek and J A Robinson},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adma.202104265},

doi = {https://doi.org/10.1002/adma.202104265},

issn = {0935-9648},

year  = {2021},

date = {2021-10-04},

journal = {Advanced Materials},

volume = {33},

number = {44},

pages = {2104265},

abstract = {Abstract Chemically stable quantum-confined 2D metals are of interest in next-generation nanoscale quantum devices. Bottom-up design and synthesis of such metals could enable the creation of materials with tailored, on-demand, electronic and optical properties for applications that utilize tunable plasmonic coupling, optical nonlinearity, epsilon-near-zero behavior, or wavelength-specific light trapping. In this work, it is demonstrated that the electronic, superconducting, and optical properties of air-stable 2D metals can be controllably tuned by the formation of alloys. Environmentally robust large-area 2D-InxGa1−x alloys are synthesized byConfinement Heteroepitaxy (CHet). Near-complete solid solubility is achieved with no evidence of phase segregation, and the composition is tunable over the full range of x by changing the relative elemental composition of the precursor. The optical and electronic properties directly correlate with alloy composition, wherein the dielectric function, band structure, superconductivity, and charge transfer from the metal to graphene are all controlled by the indium/gallium ratio in the 2D metal layer.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Dark and Bright Excitons in Halide Perovskite Nanoplatelets},

author = {M Gramlich and M W Swift and C Lampe and M D\"{o}blinger and J L Lyons and A L Efros and P C Sercel and A S Urban},

year  = {2021},

date = {2021-10-01},

journal = {arXiv preprint arXiv},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Degradation mechanisms of perovskite solar cells under vacuum and one atmosphere of nitrogen},

author = {R Guo and D Han and W Chen and L Dai and K Ji and Q Xiong and S Li and L K Reb and M A Scheel and S Pratap and N Li and S Yin and T Xiao and S Liang and A L Oechsle and C L Weindl and M Schwartzkopf and H Ebert and P Gao and K Wang and M Yuan and N C Greenham and S D Stranks and S V Roth and R H Friend and P M\"{u}ller-Buschbaum},

url = {https://doi.org/10.1038/s41560-021-00912-8},

doi = {10.1038/s41560-021-00912-8},

issn = {2058-7546},

year  = {2021},

date = {2021-10-01},

urldate = {2021-10-01},

journal = {Nature Energy},

volume = {6},

number = {10},

pages = {977-986},

abstract = {Extensive studies have focused on improving the operational stability of perovskite solar cells, but few have surveyed the fundamental degradation mechanisms. One aspect overlooked in earlier works is the effect of the atmosphere on device performance during operation. Here we investigate the degradation mechanisms of perovskite solar cells operated under vacuum and under a nitrogen atmosphere using synchrotron radiation-based operando grazing-incidence X-ray scattering methods. Unlike the observations described in previous reports, we find that light-induced phase segregation, lattice shrinkage and morphology deformation occur under vacuum. Under nitrogen, only lattice shrinkage appears during the operation of solar cells, resulting in better device stability. The different behaviour under nitrogen is attributed to a larger energy barrier for lattice distortion and phase segregation. Finally, we find that the migration of excessive PbI2 to the interface between the perovskite and the hole transport layer degrades the performance of devices under vacuum or under nitrogen.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Role of Polycyclic Aromatic Alkylammonium Cations in Tuning the Electronic Properties and Band Alignment of Two-Dimensional Hybrid Perovskite Semiconductors},

author = {D Han and S Chen and M-H Du},

url = {https://doi.org/10.1021/acs.jpclett.1c02603},

doi = {10.1021/acs.jpclett.1c02603},

year  = {2021},

date = {2021-09-30},

journal = {The Journal of Physical Chemistry Letters},

volume = {12},

number = {40},

pages = {9754-9760},

abstract = {Two-dimensional hybrid organic\textendashinorganic perovskites (HOIPs) have recently drawn intense attention as potential photovoltaic materials. However},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}