Publications

@article{nokey,

title = {Optical dipole orientation of interlayer excitons in MoSe2-WSe2 heterostacks},

author = {L Sigl and M Troue and M Katzer and M Selig and F Sigger and J Kiemle and M Brotons-Gisbert and K Watanabe and T Taniguchi and B D Gerardot and A Knorr and U Wurstbauer and A W Holleitner},

url = {https://link.aps.org/doi/10.1103/PhysRevB.105.035417},

doi = {10.1103/PhysRevB.105.035417},

year  = {2022},

date = {2022-01-14},

urldate = {2022-01-14},

journal = {Physical Review B},

volume = {105},

number = {3},

pages = {035417},

abstract = {We report on the far-field photoluminescence intensity distribution of interlayer excitons in 

MoSe2WSe2 heterostacks as measured by back focal plane imaging in the temperature range between 1.7 and 20 K. By comparing the data with an analytical model describing the dipolar emission pattern in a dielectric environment, we are able to obtain the relative contributions of the in- and out-of-plane transition dipole moments associated to the interlayer exciton photon emission. We determine the transition dipole moments for all observed interlayer exciton transitions to be (99±1)% in plane for R- and H-type stacking, independent of the excitation power and therefore the density of the exciton ensemble in the experimentally examined range. Finally, we discuss the limitations of the presented measurement technique to observe correlation effects in exciton ensembles.},

keywords = {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 = {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 = {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 = {Ultrafast carrier dynamics at organic donor\textendashacceptor interfaces\textemdasha quantum-based assessment of the hopping model},

author = {M F X Dorfner and S Hutsch and R Borrelli and M F Gelin and F Ortmann},

url = {http://dx.doi.org/10.1088/2515-7639/ac442b},

doi = {10.1088/2515-7639/ac442b},

issn = {2515-7639},

year  = {2022},

date = {2022-01-10},

journal = {Journal of Physics: Materials},

volume = {5},

number = {2},

pages = {024001},

abstract = {We investigate the charge transfer dynamics of photogenerated excitons at the donor\textendashacceptor interface of an organic solar cell blend under the influence of molecular vibrations. This is examined using an effective Hamiltonian, parametrized by density functional theory calculations, to describe the full quantum behaviour of the relevant molecular orbitals, which are electronically coupled with each other and coupled to over 100 vibrations (via Holstein coupling). This electron\textendashphonon system is treated in a numerically quasi-exact fashion using the matrix-product-state (MPS) ansatz. We provide insight into different mechanisms of charge separation and their relation to the electronic driving energy for the separation process. We find ultrafast electron transfer, which for small driving energy is dominated by kinetic processes and at larger driving energies by dissipative phonon emission connected to the prevalent vibration modes. Using this fully quantum mechanical model we perform a benchmark comparison to a recently developed semi-classical hopping approach, which treats the hopping and vibration time scales consistently. We find qualitatively and quantitatively good agreement between the results of the sophisticated MPS based quantum dynamics and the simple and fast time-consistent-hopping approach.},

keywords = {Foundry Organic},

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 = {Nickel polyphthalocyanine with electronic localization at the nickel site for enhanced CO2 reduction reaction},

author = {K Chen and M Cao and G Ni and S Chen and H Liao and L Zhu and H Li and J Fu and J Hu and E Cort\'{e}s and M Liu},

url = {https://www.sciencedirect.com/science/article/pii/S0926337322000339},

doi = {https://doi.org/10.1016/j.apcatb.2022.121093},

issn = {0926-3373},

year  = {2022},

date = {2022-01-09},

journal = {Applied Catalysis B: Environmental},

volume = {306},

pages = {121093},

abstract = {Nickel phthalocyanine (NiPc) can be at first glance a compelling catalyst for CO2 reduction reaction (CO2RR) because of its Ni\textendashN4 site. Unfortunately, the pristine NiPc possesses a low catalytic activity resulting from the poor CO2 adsorption and activation capabilities of the electron-deficiency Ni site. Herein, we develop nickel polyphthalocyanine (NiPPc) with extended conjugation to tailor the electronic density at the Ni active site. The enlarged π conjugation of NiPPc evokes the d-electrons localization, increasing the electronic density at the Ni site, which enhances its CO2 adsorption and activation. Consequently, NiPPc supported on carbon nanotubes (NiPPc/CNT) in a flow cell delivers an excellent activity of −300 mA cm−2 for CO2RR with the CO selectivity of 99.8%, which is much higher than that of NiPc dispersed on carbon nanotubes. NiPPc/CNT exhibits an outstanding stability for CO2RR of more than 30 h at a current density of −100 mA cm−2 with an ultrahigh selectivity for CO, exceeding 99.7%. This work showcases a new way of tuning the electronic density of catalytic sites.},

keywords = {Foundry Organic, Molecularly-Functionalized},

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 = {CO2-Activation by size-selected tantalum cluster cations (Ta1\textendash16+): thermalization governing reaction selectivity},

author = {N Levin and J T Margraf and J Lengyel and K Reuter and M Tschurl and U Heiz},

url = {http://dx.doi.org/10.1039/D1CP04469A},

doi = {10.1039/D1CP04469A},

issn = {1463-9076},

year  = {2022},

date = {2022-01-06},

urldate = {2022-01-06},

journal = {Physical Chemistry Chemical Physics},

volume = {24},

number = {4},

pages = {2623-2629},

abstract = {The reactions of tantalum cluster cations of different sizes toward carbon dioxide are studied in an ion trap under multi-collisional conditions. For all sizes studied, consecutive reactions with several CO2 molecules are observed. This reveals two different pathways, namely oxide formation and the pickup of an entire molecule. Supported by calculations of the thermochemistry of TanO+ formation upon reaction with CO2, changes in the branching ratios at a particular cluster size are related to heat effects due to the vibrational heat capacity of the clusters and the exothermicity of the reaction.},

keywords = {Solid-Solid},

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 = {In Situ GISAXS Observation and Large Area Homogeneity Study of Slot-Die Printed PS-b-P4VP and PS-b-P4VP/FeCl3 Thin Films},

author = {S Yin and T Tian and C L Weindl and K S Wienhold and Q Ji and Y Cheng and Y Li and C M Papadakis and M Schwartzkopf and S V Roth and P M\"{u}ller-Buschbaum},

url = {https://doi.org/10.1021/acsami.1c19797},

doi = {10.1021/acsami.1c19797},

issn = {1944-8244},

year  = {2022},

date = {2022-01-04},

urldate = {2022-01-04},

journal = {ACS Applied Materials \& Interfaces},

abstract = {Mesoporous hematite (α-Fe2O3) thin films with high surface-to-volume ratios show great potential as photoelectrodes or electrochemical electrodes in energy conversion and storage. In the present work, with the assistance of an up-scalable slot-die coating technique, locally highly ordered α-Fe2O3 thin films are successfully printed based on the amphiphilic diblock copolymer poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) as a structure-directing agent. Pure PS-b-P4VP films are printed under the same conditions for comparison. The micellization of the diblock copolymer in solution, the film formation process of the printed thin films, the homogeneity of the dry films in the lateral and vertical direction as well as the morphological and compositional information on the calcined hybrid PS-b-P4VP/FeCl3 thin film are investigated. Because of convection during the solvent evaporation process, a similar dimple-type structure of vertically aligned cylindrical PS domains in a P4VP matrix developed for both printed PS-b-P4VP and hybrid PS-b-P4VP/FeCl3 thin films. The coordination effect between the Fe3+ ions and the vinylpyridine groups significantly affects the attachment ability of the P4VP chains to the silicon substrate. Accordingly, distinct feature sizes and homogeneity in the lateral direction, as well as the thicknesses in the perpendicular direction, are demonstrated in the two printed films. By removing the polymer template from the hybrid PS-b-P4VP/FeCl3 film at high temperature, a locally highly ordered mesoporous α-Fe2O3 film is obtained. Thus, a facile and up-scalable printing technique is presented for producing homogeneous mesoporous α-Fe2O3 thin films.},

keywords = {Foundry Organic, 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 = {Exploration of the Electrical Double Layer Structure: Influence of Electrolyte Components on the Double Layer Capacitance and Potential of Maximum Entropy},

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

url = {https://www.sciencedirect.com/science/article/pii/S2451910321001964},

doi = {https://doi.org/10.1016/j.coelec.2021.100882},

issn = {2451-9103},

year  = {2022},

date = {2022-01-01},

urldate = {2021-11-17},

journal = {Current Opinion in Electrochemistry},

volume = {32},

pages = {100882},

abstract = {Understanding the electrical double layer structure is of paramount importance for designing efficient electrochemical energy conversion systems. Under this aspect, this short review explores the influence of the electrolyte on parameters such as the double layer capacitance and the potential of maximum entropy. Investigation of those parameters offers a deeper understanding on how the interfacial structure changes near reaction conditions. As a consequence, one can tune the catalyst activity by creating a more favorable environment in the electrolyte. The aim of this short review is to provide the reader with recent studies examining the electrode/electrolyte interface from experimental and theoretical standpoints.},

keywords = {Solid-Liquid},

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 = {Order-Disorder Transition driven Superionic Conduction in the New Plastic Polymorph of Na4P2S6},

author = {T Scholz and C Schneider and M W Terban and Z Deng and R Eger and M Etter and R E Dinnebier and P Canepa and B V Lotsch},

url = {https://chemrxiv.org/engage/chemrxiv/article-details/61b9af53f52bc46cf0c11492},

doi = {10.26434/chemrxiv-2021-7r31q},

year  = {2021},

date = {2021-12-21},

abstract = {Sodium thiophophates are promising materials for large-scale energy storage applications benefiting from high ionic conductivities and the-political abundance of the elements. A representative of this class is Na4P2S6, which currently shows two known polymorphs\textendashα and β. This work describes a third polymorph of Na4P2S6, γ, that forms above 580◦C, exhibits fast ion conduction with low activation energy, and is mechanically soft. Based on high-temperature diffraction, pair distribution function analysis, thermal analysis, impedance spectroscopy, and ab initio molecular dynamic calculations, γ-Na4P2S6 is identified to be a plastic crystal, characterized by dynamic orientational disorder of the P2S64\textendash anions on a translationally fixed body centered cubic lattice. The prospect of stabilizing plastic crystals at operating temperatures of solid-state batteries and benefiting from their high ionic conductivities as well as mechanical properties could have a strong impact in the field of solid-state battery chemistry.},

keywords = {Solid-Solid},

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 = {Olefin Metathesis in Confinement: Towards Covalent Organic Framework Scaffolds for Increased Macrocyclization Selectivity},

author = {S T Emmerling and F Ziegler and F R Fischer and R Schoch and M Bauer and B Plietker and M R Buchmeiser and B V Lotsch},

url = {https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/chem.202104108},

doi = {https://doi.org/10.1002/chem.202104108},

issn = {0947-6539},

year  = {2021},

date = {2021-12-09},

urldate = {2021-12-09},

journal = {Chemistry \textendash A European Journal},

volume = {n/a},

number = {n/a},

pages = {e202104108},

abstract = {Abstract Covalent organic frameworks (COFs) offer vast structural and chemical diversity enabling a wide and growing range of applications. While COFs are well-established as heterogeneous catalysts, so far, their high and ordered porosity has scarcely been utilized to its full potential when it comes to spatially confined reactions in COF pores to alter the outcome of reactions. Here, we present a highly porous and crystalline, large-pore COF as catalytic support in α,ω-diene ring-closing metathesis reactions, leading to increased macrocyclization selectivity. COF pore-wall modification by immobilization of a Grubbs-Hoveyda-type catalyst via a mild silylation reaction provides a molecularly precise heterogeneous olefin metathesis catalyst. An increased macro(mono)cyclization (MMC) selectivity over oligomerization (O) for the heterogeneous COF-catalyst (MMC:O=1.35) of up to 51 % compared to the homogeneous catalyst (MMC:O=0.90) was observed along with a substrate-size dependency in selectivity, pointing to diffusion limitations induced by the pore confinement.},

keywords = {Foundry Organic, Molecularly-Functionalized},

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 = {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 = {Foundry Organic},

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 = {Ligand Engineering in Nickel Phthalocyanine to Boost the Electrocatalytic Reduction of CO2},

author = {K Chen and M Cao and Y Lin and J Fu and H Liao and Y Zhou and H Li and X Qiu and J Hu and X Zheng and M Shakouri and Q Xiao and Y Hu and J Li and J Liu and E Cort\'{e}s and M Liu},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adfm.202111322},

doi = {https://doi.org/10.1002/adfm.202111322},

issn = {1616-301X},

year  = {2021},

date = {2021-12-01},

urldate = {2021-12-01},

journal = {Advanced Functional Materials},

volume = {n/a},

number = {n/a},

pages = {2111322},

abstract = {Abstract Designing and synthesizing efficient molecular catalysts may unlock the great challenge of controlling the CO2 reduction reaction (CO2RR) with molecular precision. Nickel phthalocyanine (NiPc) appears as a promising candidate for this task due to its adjustable Ni active-site. However, the pristine NiPc suffers from poor activity and stability for CO2RR owing to the poor CO2 adsorption and activation at the bare Ni site. Here, a ligand-tuned strategy is developed to enhance the catalytic performance and unveil the ligand effect of NiPc on CO2RR. Theoretical calculations and experimental results indicate that NiPc with electron-donating substituents (hydroxyl or amino) can induce electronic localization at the Ni site which greatly enhances the CO2 adsorption and activation. Employing the optimal catalyst\textemdashan amino-substituted NiPc\textemdashto convert CO2 into CO in a flow cell can achieve an ultrahigh activity and selectivity of 99.8% at current densities up to −400 mA cm−2. This work offers a novel strategy to regulate the electronic structure of active sites by ligand design and discloses the ligand-directed catalysis of the tailored NiPc for highly efficient CO2RR.},

keywords = {Foundry Organic, 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 = {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 = {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 = {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 = {Achromatic frequency doubling of supercontinuum pulses for transient absorption spectroscopy},

author = {E Keil and P Malevich and J Hauer},

url = {http://www.osapublishing.org/oe/abstract.cfm?URI=oe-29-24-39042},

doi = {10.1364/OE.442400},

year  = {2021},

date = {2021-11-22},

urldate = {2021-11-22},

journal = {Optics Express},

volume = {29},

number = {24},

pages = {39042-39054},

abstract = {We present achromatic frequency doubling of supercontinuum pulses from a hollow core fiber as a technique for obtaining tunable ultrashort pulses in the near UV and blue spectral range. Pulse energies are stable on a 1.1\% level, averaged over 100 000 shots. By the use of conventional optics only, we compress a 0.2 \µJ pulse at a center wavelength of 475 nm to a pulse duration of 12 fs, as measured by X-FROG. We test the capabilities of the approach by employing the ASHG-pulses as a pump in a transient absorption experiment on \β-carotene in solution.},

keywords = {Solid-Liquid},

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 = {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 = {Static and dynamic water structures at interfaces: A case study with focus on Pt(111)},

author = {A C D L\'{o}pez and T Eggert and K Reuter and N G H\"{o}rmann},

url = {https://aip.scitation.org/doi/abs/10.1063/5.0067106},

doi = {10.1063/5.0067106},

year  = {2021},

date = {2021-11-18},

urldate = {2021-11-18},

journal = {The Journal of Chemical Physics},

volume = {155},

number = {19},

pages = {194702},

keywords = {Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Charge transport in semiconducting polymers at the nanoscale},

author = {J Lenz and R T Weitz},

url = {https://aip.scitation.org/doi/abs/10.1063/5.0068098},

doi = {10.1063/5.0068098},

year  = {2021},

date = {2021-11-17},

urldate = {2021-11-17},

journal = {APL Materials},

volume = {9},

number = {11},

pages = {110902},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {A flavin-inspired covalent organic framework for photocatalytic alcohol oxidation},

author = {S Trenker and L Grunenberg and T Banerjee and G Savasci and L M Poller and K I M Muggli and F Haase and C Ochsenfeld and B V Lotsch},

url = {http://dx.doi.org/10.1039/D1SC04143F},

doi = {10.1039/D1SC04143F},

issn = {2041-6520},

year  = {2021},

date = {2021-11-15},

urldate = {2021-11-15},

journal = {Chemical Science},

volume = {12},

number = {45},

pages = {15143-15150},

abstract = {Covalent organic frameworks (COFs) offer a number of key properties that predestine them to be used as heterogeneous photocatalysts, including intrinsic porosity, long-range order, and light absorption. Since COFs can be constructed from a practically unlimited library of organic building blocks, these properties can be precisely tuned by choosing suitable linkers. Herein, we report the construction and use of a novel COF (FEAx-COF) photocatalyst, inspired by natural flavin cofactors. We show that the functionality of the alloxazine chromophore incorporated into the COF backbone is retained and study the effects of this heterogenization approach by comparison with similar molecular photocatalysts. We find that the integration of alloxazine chromophores into the framework significantly extends the absorption spectrum into the visible range, allowing for photocatalytic oxidation of benzylic alcohols to aldehydes even with low-energy visible light. In addition, the activity of the heterogeneous COF photocatalyst is less dependent on the chosen solvent, making it more versatile compared to molecular alloxazines. Finally, the use of oxygen as the terminal oxidant renders FEAx-COF a promising and “green” heterogeneous photocatalyst.},

keywords = {Foundry Organic, 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 = {How Blinking Affects Photon Correlations in Multichromophoric Nanoparticles},

author = {T Schr\"{o}der and S Bange and J Schedlbauer and F Steiner and J M Lupton and P Tinnefeld and J Vogelsang},

url = {https://doi.org/10.1021/acsnano.1c06649},

doi = {10.1021/acsnano.1c06649},

issn = {1936-0851},

year  = {2021},

date = {2021-11-04},

urldate = {2021-11-04},

journal = {ACS Nano},

abstract = {A single chromophore can only emit a maximum of one single photon per excitation cycle. This limitation results in a phenomenon commonly referred to as photon antibunching (pAB). When multiple chromophores contribute to the fluorescence measured, the degree of pAB has been used as a metric to “count” the number of chromophores. But the fact that chromophores can switch randomly between bright and dark states also impacts pAB and can lead to incorrect chromophore numbers being determined from pAB measurements. By both simulations and experiment, we demonstrate how pAB is affected by independent and collective chromophore blinking, enabling us to formulate universal guidelines for correct interpretation of pAB measurements. We use DNA-origami nanostructures to design multichromophoric model systems that exhibit either independent or collective chromophore blinking. Two approaches are presented that can distinguish experimentally between these two blinking mechanisms. The first one utilizes the different excitation intensity dependence on the blinking mechanisms. The second approach exploits the fact that collective blinking implies energy transfer to a quenching moiety, which is a time-dependent process. In pulsed-excitation experiments, the degree of collective blinking can therefore be altered by time gating the fluorescence photon stream, enabling us to extract the energy-transfer rate to a quencher. The ability to distinguish between different blinking mechanisms is valuable in materials science, such as for multichromophoric nanoparticles like conjugated-polymer chains as well as in biophysics, for example, for quantitative analysis of protein assemblies by counting chromophores.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Optical dipole orientation of interlayer excitons in MoSe2-WSe2 heterostacks},

author = {L Sigl and M Troue and M Katzer and M Selig and F Sigger and J Kiemle and M Brotons-Gisbert and K Watanabe and T Taniguchi and B D Gerardot},

year  = {2021},

date = {2021-11-02},

journal = {Cond-Mat. Mes-Hall},

keywords = {Solid-Solid},

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 = {Scalable Fabrication of Metallic Nanogaps at the Sub-10 nm Level},

author = {S Luo and B H Hoff and S A Maier and J C De Mello},

doi = {10.1002/advs.202102756},

issn = {2198-3844},

year  = {2021},

date = {2021-10-31},

journal = {Adv Sci (Weinh)},

pages = {e2102756},

abstract = {Metallic nanogaps with metal-metal separations of less than 10 nm have many applications in nanoscale photonics and electronics. However, their fabrication remains a considerable challenge, especially for applications that require patterning of nanoscale features over macroscopic length-scales. Here, some of the most promising techniques for nanogap fabrication are evaluated, covering established technologies such as photolithography, electron-beam lithography (EBL), and focused ion beam (FIB) milling, plus a number of newer methods that use novel electrochemical and mechanical means to effect the patterning. The physical principles behind each method are reviewed and their strengths and limitations for nanogap patterning in terms of resolution, fidelity, speed, ease of implementation, versatility, and scalability to large substrate sizes are discussed.},

keywords = {Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Abiotic Formation of an Amide Bond via Surface-Supported Direct Carboxyl\textendashAmine Coupling},

author = {B Yang and K Niu and F Haag and N Cao and J Zhang and H Zhang and Q Li and F Allegretti and J Bj\"{o}rk and J V Barth and L Chi},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202113590},

doi = {https://doi.org/10.1002/anie.202113590},

issn = {1433-7851},

year  = {2021},

date = {2021-10-28},

journal = {Angewandte Chemie International Edition},

volume = {61},

number = {5},

pages = {e202113590},

abstract = {Abstract Amide bond formation is one of the most important reactions in biochemistry, notably being of crucial importance for the origin of life. Herein, we combine scanning tunneling microscopy and X-ray photoelectron spectroscopy studies to provide evidence for thermally activated abiotic formation of amide bonds between adsorbed precursors through direct carboxyl\textendashamine coupling under ultrahigh-vacuum conditions by means of on-surface synthesis. Complementary insights from temperature-programmed desorption measurements and density functional theory calculations reveal the competition between cross-coupling amide formation and decarboxylation reactions on the Au(111) surface. Furthermore, we demonstrate the critical influence of the employed metal support: whereas on Au(111) the coupling readily occurs, different reaction scenarios prevail on Ag(111) and Cu(111). The systematic experiments signal that archetypical bio-related molecules can be abiotically synthesized in clean environments without water or oxygen.},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Bifurcations of Clusters and Collective Oscillations in Networks of Bistable Units},

author = {M Salman and C Bick and K Krischer},

year  = {2021},

date = {2021-10-28},

journal = {arXiv preprint arXiv:2110.15004},

abstract = {We investigate dynamics and bifurcations in a mathematical model that captures electrochemical experiments on arrays of microelectrodes. In isolation, each individual microelectrode is described by a one-dimensional unit with a bistable current-potential response. When an array of such electrodes is coupled by controlling the total electric current, the common electric potential of all electrodes oscillates in some interval of the current. These coupling-induced collective oscillations of bistable one-dimensional units are captured by the model. Moreover, any equilibrium is contained in a cluster subspace, where the electrodes take at most three distinct states. We systematically analyze the dynamics and bifurcations of the model equations: We consider the dynamics on cluster subspaces of successively increasing dimension and analyze the bifurcations occurring therein. Most importantly, the system exhibits an equivariant transcritical bifurcation of limit cycles. From this bifurcation, several limit cycles branch, one of which is stable for arbitrarily many bistable units.},

keywords = {Solid-Solid},

pubstate = {published},

tppubtype = {article}

}