Publikationen

@article{nokey,

title = {Smart Electrolytes for Lithium Batteries with Reversible Thermal Protection at High Temperatures},

author = {Q Yu and W Sun and S Wang and Q Qiu and W Zhang and H Tian and L Xia and P M\"{u}ller-Buschbaum},

url = {https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/batt.202400339},

doi = {https://doi.org/10.1002/batt.202400339},

year  = {2024},

date = {2024-06-19},

journal = {Batteries \& Supercaps},

volume = {n/a},

number = {n/a},

pages = {e202400339},

abstract = {Abstract Battery safety is a multifaceted concern, with thermal runaway standing out as a primary issue. In this work, we introduce a novel temperature-responsive, self-protection electrolyte governed by the phase separation dynamics of poly (butyl methacrylate) (PBMA) in lithium salt/tetraglyme (G4) blends. This innovation effectively mitigates the risks associated with thermal runaway in lithium batteries. Our electrolyte exhibits a temperature-responsive-recovery characteristic, imparting intelligent capabilities to lithium batteries. At temperatures of \>105 °C, the electrolyte transitions from a homogeneous phase to a segregated state, comprising a PBMA-rich phase with low conductivity and a high conductivity phase containing dissolved lithium salt in G4. The deposition of the PBMA-rich phase on the electrode surface obstructs the ion transport, thereby averting a thermal runaway. Subsequently, upon returning to room temperature of 25 °C, the electrolyte reverts to its homogeneous, highly conductive state, with battery capacity resuming at approximately 94 %. Thus, our electrolyte offers a robust, reversible, smart self-protection for batteries. Additionally, it demonstrates exceptional cycling performance at room temperature. Our findings open new avenues for thermo-reversible and self-protective electrolytes, advancing the safe and widespread adoption of lithium-ion batteries.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Chiral perovskite-CdSe/ZnS QDs composites with high circularly polarized luminescence performance achieved through additive-solvent engineering},

author = {H Zhu and Q Wang and W Chen and K Sun and H Zhong and T Ye and Z Wang and W Zhang and P M\"{u}ller-Buschbaum and X W Sun and D Wu and K Wang},

url = {https://doi.org/10.1063/5.0200692},

doi = {10.1063/5.0200692},

issn = {0021-9606},

year  = {2024},

date = {2024-06-17},

journal = {The Journal of Chemical Physics},

volume = {160},

number = {23},

abstract = {Chiral perovskite materials are being extensively studied as one of the most promising candidates for circularly polarized luminescence (CPL)-related applications. Balancing chirality and photoluminescence (PL) properties is of great importance for enhancing the value of the dissymmetry factor (glum), and a higher glum value indicates better CPL. Chiral perovskite/quantum dot (QD) composites emerge as an effective strategy for overcoming the dilemma that achieving strong chirality and PL in chiral perovskite while at the same time achieving high glum in this composite is very crucial. Here, we choose diphenyl sulfoxide (DPSO) as an additive in the precursor solution of chiral perovskite to regulate the lattice distortion. How structural variation affects the chiral optoelectronic properties of the chiral perovskite has been further investigated. We find that chiral perovskite/CdSe\textendashZnS QD composites with strong CPL have been achieved, and the calculated maximum |glum| of the composites increased over one order of magnitude after solvent-additive modulation (1.55 × 10−3 for R-DMF/QDs, 1.58 × 10−2 for R-NMP-DPSO/QDs, −2.63 × 10−3 for S-DMF/QDs, and −2.65 × 10−2 for S-NMP-DPSO/QDs), even at room temperature. Our findings suggest that solvent-additive modulation can effectively regulate the lattice distortion of chiral perovskite, enhancing the value of glum for chiral perovskite/CdSe\textendashZnS QD composites.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Probing Self-Diffusion of Guest Molecules in a Covalent Organic Framework: Simulation and Experiment},

author = {L Grunenberg and C Ke\ssler and T W Teh and R Schuldt and F Heck and J K\"{a}stner and J Gro\ss and N Hansen and B V Lotsch},

url = {https://doi.org/10.1021/acsnano.3c12167},

doi = {10.1021/acsnano.3c12167},

issn = {1936-0851},

year  = {2024},

date = {2024-06-11},

journal = {ACS Nano},

volume = {18},

number = {25},

pages = {16091-16100},

abstract = {Covalent organic frameworks (COFs) are a class of porous materials whose sorption properties have so far been studied primarily by physisorption. Quantifying the self-diffusion of guest molecules inside their nanometer-sized pores allows for a better understanding of confinement effects or transport limitations and is thus essential for various applications ranging from molecular separation to catalysis. Using a combination of pulsed field gradient nuclear magnetic resonance measurements and molecular dynamics simulations, we have studied the self-diffusion of acetonitrile and chloroform in the 1D pore channels of two imine-linked COFs (PI-3-COF) with different levels of crystallinity and porosity. The higher crystallinity and porosity sample exhibited anisotropic diffusion for MeCN parallel to the pore direction, with a diffusion coefficient of Dpar = 6.1(3) × 10\textendash10 m2 s\textendash1 at 300 K, indicating 1D transport and a 7.4-fold reduction in self-diffusion compared to the bulk liquid. This finding aligns with molecular dynamics simulations predicting 5.4-fold reduction, assuming an offset-stacked COF layer arrangement. In the low-porosity sample, more frequent diffusion barriers result in isotropic, yet significantly reduced diffusivities (DB = 1.4(1) × 10\textendash11 m2 s\textendash1). Diffusion coefficients for chloroform at 300 K in the pores of the high- (Dpar = 1.1(2) × 10\textendash10 m2 s\textendash1) and low-porosity (DB = 4.5(1) × 10\textendash12 m2 s\textendash1) samples reproduce these trends. Our multimodal study thus highlights the significant influence of real structure effects such as stacking faults and grain boundaries on the long-range diffusivity of molecular guest species while suggesting efficient intracrystalline transport at short diffusion times.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {The Critical Role of Anharmonic Lattice Dynamics for Macroscopic Properties of the Visible Light Absorbing Nitride Semiconductor CuTaN2},

author = {F S Hegner and A Cohen and S S Rudel and S M Kronawitter and M Grumet and X Zhu and R Korobko and L Houben and C-M Jiang and W Schnick and G Kieslich and O Yaffe and I D Sharp and D A Egger},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/aenm.202303059},

doi = {https://doi.org/10.1002/aenm.202303059},

issn = {1614-6832},

year  = {2024},

date = {2024-05-17},

journal = {Advanced Energy Materials},

volume = {14},

number = {19},

pages = {2303059},

abstract = {Abstract Ternary nitride semiconductors are rapidly emerging as a promising class of materials for energy conversion applications, offering an appealing combination of strong light absorption in the visible range, desirable charge transport characteristics, and good chemical stability. In this work, it is shown that finite-temperature lattice dynamics in CuTaN2 \textendash a prototypical ternary nitride displaying particularly strong visible light absorption \textendash exhibit a pronounced anharmonic character that plays an essential role in defining its macroscopic optoelectronic and thermal properties. Low-frequency vibrational modes that are Raman-inactive from symmetry considerations of the average crystal structure and unstable in harmonic phonon calculations are found to appear as intensive Raman features near room temperature. The atomic contributions to the anharmonic vibrations are characterized by combining Raman measurements with molecular dynamics and density functional theory calculations. This analysis reveals that anharmonic lattice dynamics have large ramifications on the fundamental properties of this compound, resulting in uniaxial negative thermal expansion and the opening of its bandgap to a near-optimal value for solar energy harvesting. The atomic-level understanding of anharmonic lattice dynamics, as well as the finding that they strongly influence key properties of this semiconductor at room temperature, have important implications for design of new functional materials, especially within the emerging class of ternary nitride semiconductors.},

keywords = {Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Autonomous battery optimisation by deploying distributed experiments and simulations},

author = {M Vogler and S Steensen and F Ramirez and L Merker and J Busk and J M Carlsson and L Rieger and B Zhang and F Liot and G Pizzi and F Hanke and E Flores and H Hajiyani and S Fuchs and A Sanin and M Gaberscek and I Castelli and S Clark and T Vegge and A Bhowmik and H S Stein},

url = {https://chemrxiv.org/engage/chemrxiv/article-details/66448bfb21291e5d1d55f2a7},

doi = {10.26434/chemrxiv-2024-vfq1n},

year  = {2024},

date = {2024-05-16},

journal = {ChemRxiv},

abstract = {Non-trivial relationships link individual materials properties to device-level performance. Device optimisation therefore calls for new automation approaches beyond the laboratory bench with tight integration of different research methods. We demonstrate a Materials Acceleration Platform (MAP) in the field of battery research based on our problem-agnostic Fast Intentional Agnostic Learning Server (FINALES) framework, which integrates simulations and physical experiments without centrally controlling them. The connected capabilities entail the formulation and characterisation of electrolytes, cell assembly and testing, early lifetime prediction, and ontology-mapped data storage provided by institutions distributed across Europe. The infrastructure is used to optimise the ionic conductivity of electrolytes and the End Of Life (EOL) of lithium-ion coin cells by varying the electrolyte formulation. We rediscover trends in ionic conductivity and investigate the effect of the electrolyte formulation on the EOL. We further demonstrate the capability of our MAP to bridge diverse research modalities, scales, and institutions enabling system-level investigations under asynchronous conditions while handling concurrent workflows on the material- and system-level, demonstrating true intention-agnosticism.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Attention towards chemistry agnostic and explainable battery lifetime prediction},

author = {F Rahmanian and R M Lee and D Linzner and K Michel and L Merker and B B Berkes and L Nuss and H S Stein},

url = {https://doi.org/10.1038/s41524-024-01286-7},

doi = {10.1038/s41524-024-01286-7},

issn = {2057-3960},

year  = {2024},

date = {2024-05-10},

journal = {npj Computational Materials},

volume = {10},

number = {1},

pages = {100},

abstract = {Predicting and monitoring battery life early and across chemistries is a significant challenge due to the plethora of degradation paths, form factors, and electrochemical testing protocols. Existing models typically translate poorly across different electrode, electrolyte, and additive materials, mostly require a fixed number of cycles, and are limited to a single discharge protocol. Here, an attention-based recurrent algorithm for neural analysis (ARCANA) architecture is developed and trained on an ultra-large, proprietary dataset from BASF and a large Li-ion dataset gathered from literature across the globe. ARCANA generalizes well across this diverse set of chemistries, electrolyte formulations, battery designs, and cycling protocols and thus allows for an extraction of data-driven knowledge of the degradation mechanisms. The model’s adaptability is further demonstrated through fine-tuning on Na-ion batteries. ARCANA advances the frontier of large-scale time series models in analytical chemistry beyond textual data and holds the potential to significantly accelerate discovery-oriented battery research endeavors.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Microstrain and Crystal Orientation Variation within Naked Triple-Cation Mixed Halide Perovskites under Heat, UV, and Visible Light Exposure},

author = {Y Zou and J Eichhorn and J Zhang and F C Apfelbeck and S Yin and L Wolz and C-C Chen and I D Sharp and P M\"{u}ller-Buschbaum},

url = {https://doi.org/10.1021/acsenergylett.3c02617},

doi = {10.1021/acsenergylett.3c02617},

year  = {2024},

date = {2024-02-09},

journal = {ACS Energy Letters},

volume = {9},

number = {2},

pages = {388-399},

abstract = {The instability of perovskite absorbers under various environmental stressors is the most significant obstacle to widespread commercialization of perovskite solar cells. Herein, we study the evolution of crystal structure and microstrain present in naked triple-cation mixed CsMAFA-based perovskite films under heat, UV, and visible light (1 Sun) conditions by grazing-incidence wide-angle X-ray scattering (GIWAXS). We find that the microstrain is gradient distributed along the surface normal of the films, decreasing from the upper surface to regions deeper within the film. Moreover, heat, UV, and visible light treatments do not interfere with the crystalline orientations within annealed polycrystalline films. However, when subjected to heat, the naked perovskite films exhibit a rapid component decomposition, induced by phase separation and ion migration. Conversely, under exposure to UV and 1 Sun light soaking, the naked perovskite films undergo a self-optimization structure evolution during degradation and develop into smoother films with reduced surface potential fluctuations.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {“T-shaped” Carbazole Alkylammonium Cation Passivation in Perovskite Solar Cells},

author = {Z Shi and R Guo and R Luo and X Wang and J Ma and J Feng and X Niu and E Alvianto and Z Jia and X Guo and H Liang and J Chen and Z Li and K Sun and X Jiang and Y Wu and P M\"{u}ller-Buschbaum and W Hu and Y Hou},

url = {https://doi.org/10.1021/acsenergylett.3c02357},

doi = {10.1021/acsenergylett.3c02357},

year  = {2024},

date = {2024-02-09},

journal = {ACS Energy Letters},

volume = {9},

number = {2},

pages = {419-427},

abstract = {Incorporating alkylammonium cations atop the 3D perovskite enables effective defect passivation and significantly enhances the power conversion efficiency of perovskite solar cells. However, the diversity and durability of this passivation strategy have been limited to the ligand type and diffusion of ligands due to high reactivity. Here, we designed bulky “T-shaped” conjugated carbazole alkylammonium cations with inner π\textendashπ interaction and enlarged steric hindrance to minimize ligand diffusion while maintaining passivation effects. As verified by grazing incidence X-ray diffraction and transient absorption spectra, these “T-shaped” passivators could keep a stable intrinsic crystal phase on the perovskite surface after thermal aging. Additionally, the devices utilizing these organic semiconductor-based “T-shaped” ligands were relatively constant in series resistance and introduced higher hole mobility than the PEAI. Finally, the champion device using the “T-shaped” passivator achieved a maximum device efficiency of 25.1% with improved operational stability under 1 sun illumination.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Metastable nickel\textendashoxygen species modulate rate oscillations during dry reforming of methane},

author = {L Sandoval-Diaz and D Cruz and M Vuijk and G Ducci and M H\"{a}vecker and W Jiang and M Plodinec and A Hammud and D Ivanov and T G\"{o}tsch and K Reuter and R Schl\"{o}gl and C Scheurer and A Knop-Gericke and T Lunkenbein},

url = {https://doi.org/10.1038/s41929-023-01090-4},

doi = {10.1038/s41929-023-01090-4},

issn = {2520-1158},

year  = {2024},

date = {2024-02-01},

journal = {Nature Catalysis},

volume = {7},

number = {2},

pages = {161-171},

abstract = {When a heterogeneous catalyst is active, it forms metastable structures that constantly transform into each other. These structures contribute differently to the catalytic function. Here we show the role of different metastable oxygen species on a Ni catalyst during dry reforming of methane by combining environmental scanning electron microscopy, near ambient pressure X-ray photoelectron spectroscopy, on-line product detection and computer vision. We highlight the critical role of dissociative CO2 adsorption in regulating the oxygen content of the catalyst and in CH4 activation. We also discover rate oscillations during dry reforming of methane resulting from the sequential transformation of metastable oxygen species that exhibit different catalytic properties: atomic surface oxygen, subsurface oxygen and bulk NiOx. The imaging approach allowed the localization of fluctuating surface regions that correlated directly with catalytic activity. The study highlights the importance of metastability and operando analytics in catalysis science and provides impetus towards the design of catalytic systems.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Wavelength-tunable ultrafast two arm fiber laser system for transient interferometric scattering microscopy on nanoscopic objects},

author = {K Birkmeier and A Hartschuh},

url = {https://opg.optica.org/josab/abstract.cfm?URI=josab-41-2-493},

doi = {10.1364/JOSAB.510611},

year  = {2024},

date = {2024-02-01},

journal = {Journal of the Optical Society of America B},

volume = {41},

number = {2},

pages = {493-499},

abstract = {Ultrafast time-resolved microscopy of single nano-objects is particularly challenging because of minute sample volumes and correspondingly small signal levels together with the possibility of photobleaching. We present a compact pulsed two arm fiber laser-based system suited for highly sensitive transient interferometric scattering (TiSCAT) microscopy of nanomaterials. A continuously tunable probe arm is used for spectrally resolved detection of the transient sample response in the range between 810 and 960\ nm upon pulsed excitation at 780\ nm by the pump arm. Coupled to a scanning confocal microscope with high numerical aperture objective, the system provides spectral maps with sub-300\ nm spatial and 300\ fs temporal resolution. We tested the platform using monolayer M o S e 2 and individual (6,4) single-walled carbon nanotubes as model samples. Confocal microscopy images recorded for an exfoliated monolayer M o S e 2 reveal spatially varying excited state decay, highlighting the need for local probing. Spectrally resolved TiSCAT measurements on individual (6,4) single-walled carbon nanotubes show that the transient response is dominated by ground-state bleaching with picosecond recovery times. The obtained data illustrate the excellent noise properties and stability of the newly developed laser system, which allow for nearly shot-noise limited TiSCAT detection at the low probe fluences required for avoiding photodegradation of sensitive nanomaterials.},

keywords = {Molecularly-Functionalized, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Enantioselective Intramolecular ortho Photocycloaddition Reactions of 2-Acetonaphthones},

author = {P Yan and S Stegbauer and Q Wu and E Kolodzeiski and C J Stein and P Lu and T Bach},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202318126},

doi = {https://doi.org/10.1002/anie.202318126},

issn = {1433-7851},

year  = {2024},

date = {2024-01-26},

journal = {Angewandte Chemie International Edition},

volume = {63},

number = {13},

pages = {e202318126},

abstract = {Abstract 2-Acetonaphthones, which bear an alkenyl group tethered to its C1 carbon atom via an oxygen atom, were found to undergo an enantioselective intramolecular ortho photocycloaddition reaction. A chiral oxazaborolidine Lewis acid leads to a bathochromic absorption shift of the substrate and enables an efficient enantioface differentiation. Visible light irradiation (λ=450 nm) triggers the reaction which is tolerant of various groups at almost any position except carbon atom C8 (16 examples, 53\textendash99 % yield, 80\textendash97 % ee). Consecutive reactions were explored including a sensitized rearrangement to tetrahydrobiphenylenes, which occurred with full retention of configuration. Evidence was collected that the catalytic photocycloaddition occurs via triplet intermediates, and the binding mode of the acetonaphthone to the chiral Lewis acid was elucidated by DFT calculations.},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {A theoretical spectroscopy study of the photoluminescence properties of narrow band Eu2+-doped phosphors containing multiple candidate doping centers. Prediction of an unprecedented narrow band red phosphor},

author = {R Shafei and P J Strobel and P J Schmidt and D Maganas and W Schnick and F Neese},

url = {http://dx.doi.org/10.1039/D3CP06039J},

doi = {10.1039/D3CP06039J},

issn = {1463-9076},

year  = {2024},

date = {2024-01-18},

journal = {Physical Chemistry Chemical Physics},

volume = {26},

number = {7},

pages = {6277-6291},

abstract = {We have previously presented a computational protocol that is based on an embedded cluster model and operates in the framework of TD-DFT in conjunction with the excited state dynamics (ESD) approach. The protocol is able to predict the experimental absorption and emission spectral shapes of Eu2+-doped phosphors. In this work, the applicability domain of the above protocol is expanded to Eu2+-doped phosphors bearing multiple candidate Eu doping centers. It will be demonstrated that this protocol provides full control of the parameter space that describes the emission process. The stability of Eu doping at various centers is explored through local energy decomposition (LED) analysis of DLPNO-CCSD(T) energies. This enables further development of the understanding of the electronic structure of the targeted phosphors, the diverse interactions between Eu and the local environment, and their impact on Eu doping probability, and control of the emission properties. Hence, it can be employed to systematically improve deficiencies of existing phosphor materials, defined by the presence of various intensity emission bands at undesired frequencies, towards classes of candidate Eu2+-doped phosphors with desired narrow band red emission. For this purpose, the chosen study set consists of three UCr4C4-based narrow-band phosphors, namely the known alkali lithosilicates RbNa[Li3SiO4]2:Eu2+ (RNLSO2), RbNa3[Li3SiO4]4:Eu2+ (RNLSO) and their isotypic nitridolithoaluminate phosphors consisting of CaBa[LiAl3N4]2:Eu2+ (CBLA2) and the proposed Ca3Ba[LiAl3N4]4:Eu2+ (CBLA), respectively. The theoretical analysis presented in this work led us to propose a modification of the CBLA2 phosphor that should have improved and unprecedented narrow band red emission properties. Finally, we believe that the analysis presented here is important for the future rational design of novel Eu2+-doped phosphor materials, with a wide range of applications in science and technology.},

keywords = {Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Dendritic Copper Current Collectors as a Capacity Boosting Material for Polymer-Templated Si/Ge/C Anodes in Li-Ion Batteries},

author = {C L Weindl and C E Fajman and Z Xu and T Zheng and G E M\"{o}hl and N Chaulagain and K Shankar and R Gilles and T F F\"{a}ssler and P M\"{u}ller-Buschbaum},

url = {https://doi.org/10.1021/acsami.3c15735},

doi = {10.1021/acsami.3c15735},

issn = {1944-8244},

year  = {2024},

date = {2024-01-17},

journal = {ACS Applied Materials \& Interfaces},

volume = {16},

number = {2},

pages = {2309-2318},

abstract = {Dendritic copper offers a highly effective method for synthesizing porous copper anodes due to its intricate branching structure. This morphology results in an elevated surface area-to-volume ratio, facilitating shortened electron pathways during aqueous and electrolyte permeation. Here, we demonstrate a procedure for a time- and cost-efficient synthesis routine of fern-like copper microstructures as a host for polymer-templated Si/Ge/C thin films. Dissolvable Zintl clusters and sol\textendashgel chemistry are used to synthesize nanoporous coating as the anode. Cyclic voltammetry (CV) with KOH as the electrolyte is used to estimate the surface area increase in the dendritic copper current collectors (CCs). Half cells are assembled and tested with battery-related techniques such as CV, galvanostatic cycling, and electrochemical impedance spectroscopy, showing a capacity increase in the dendritic copper cells. Energy-dispersive X-ray spectroscopy is used to estimate the removal of K in the bulk after oxidizing the Zintl phase K12Si8Ge9 in the polymer/precursor blend with SiCl4. Furthermore, scanning electron microscopy images are provided to depict the thin films after synthesis and track the degradation of the half cells after cycling, revealing that the morphological degradation through alloying/dealloying is reduced for the dendritic Cu CC anodes as compared with the bare reference. Finally, we highlight this time- and cost-efficient routine for synthesizing this capacity-boosting material for low-mobility and high-capacity anode coatings.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Imaging built-in electric fields and light matter by Fourier-precession TEM},

author = {T Lorenzen and B M\"{a}rz and T Xue and A Beyer and K Volz and T Bein and K M\"{u}ller-Caspary},

url = {https://doi.org/10.1038/s41598-024-51423-x},

doi = {10.1038/s41598-024-51423-x},

issn = {2045-2322},

year  = {2024},

date = {2024-01-15},

journal = {Scientific Reports},

volume = {14},

number = {1},

pages = {1320},

abstract = {We report the precise measurement of electric fields in nanostructures, and high-contrast imaging of soft matter at ultralow electron doses by transmission electron microscopy (TEM). In particular, a versatile method based on the theorem of reciprocity is introduced to enable differential phase contrast imaging and ptychography in conventional, plane-wave illumination TEM. This is realised by a series of TEM images acquired under different tilts, thereby introducing the sampling rate in reciprocal space as a tuneable parameter, in contrast to momentum-resolved scanning techniques. First, the electric field of a p\textendashn junction in GaAs is imaged. Second, low-dose, in-focus ptychographic and DPC characterisation of Kagome pores in weakly scattering covalent organic frameworks is demonstrated by using a precessing electron beam in combination with a direct electron detector. The approach offers utmost flexibility to record relevant spatial frequencies selectively, while acquisition times and dose requirements are significantly reduced compared to the 4D-STEM counterpart.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Impedance Response Analysis of Anion Exchange Membrane Electrolyzers for Determination of the Electrochemically Active Catalyst Surface Area},

author = {S A Watzele and R M Kluge and A Maljusch and P Borowski and A S Bandarenka},

url = {https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/cmtd.202300035},

doi = {https://doi.org/10.1002/cmtd.202300035},

issn = {2628-9725},

year  = {2024},

date = {2024-01-12},

journal = {Chemistry\textendashMethods},

volume = {4},

number = {3},

pages = {e202300035},

abstract = {Abstract Polymer membrane electrolyzers benefit from high-pressure operation conditions and low gas cross-over and can either conduct protons (H+) or hydroxide ions (OH−). Both types of electrolyzers have a similar design, but differ in power density and the choice of catalysts. Despite the significant endeavor of their optimization, to date, there is no well-established impedance model for detailed analysis for either type of these devices. This complicates the in-situ characterization of electrolyzers, hindering the investigation of degradation mechanisms and electrocatalytic processes as a function of applied current density or time. Nevertheless, a detailed understanding of such individual processes and distinguishing the performance-limiting factors are the keystones for sophisticated device optimization. In this work, an impedance model based on electrode processes has been developed for an anion exchange membrane electrolyzer utilizing iridium oxide anode and platinum cathode electrocatalysts. This model allows to deconvolute the measured impedances into constituents related to the individual electrode processes and to estimate actual physico-chemical quantities such as the reaction kinetic parameters and double-layer capacitances. We discuss the meaning of the fitting parameters and show that this model enables, for the first time, the estimation of the electrochemically active surface area of the anode electrocatalysts under reaction conditions.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Nanogels Containing Gold Nanoparticles on Cotton Fabrics for Comfort Control via Localized Surface Plasmon Resonance},

author = {Z Zhu and D Qi and Z Yang and Y Wang and P M\"{u}ller-Buschbaum and Q Zhong},

url = {https://doi.org/10.1021/acsanm.3c05211},

doi = {10.1021/acsanm.3c05211},

year  = {2024},

date = {2024-01-12},

journal = {ACS Applied Nano Materials},

volume = {7},

number = {1},

pages = {1222-1232},

abstract = {The wearing comfort of fabrics is strongly related to moisture permeability and thermal insulation. To enhance comfort, the localized surface plasmon resonance (LSPR) effect is applied on cotton fabrics by densely packed hybrid nanogels containing gold nanoparticles on the surface. The nanogels are prepared by emulsion polymerization using di(ethylene glycol) methyl ether methacrylate (MEO2MA), (ethylene glycol) methyl ether methacrylate (OEGMA300), and ethylene glycol methacrylate (EGMA) as monomers. Because of the different transition temperatures of MEO2MA (25 °C) and OEGMA300 (60 °C), the obtained nanogels present a linear shrinkage behavior between 20 to 50 °C. Further treated with in situ reduction, gold nanoparticles (Au NPs) are embedded in the nanogels. After cross-linking the hybrid nanogels onto cotton fabrics and exposure to visible light irradiation (0.1029 W), the ratio of moisture permeability of the cotton fabrics cross-linked with hybrid nanogels (weight gain ratio, WGR of 8%) at 30 °C to that at 20 °C is 1.67. It is 45% better than that of cross-linked pure nanogels without any Au NPs. When the WGR is increased to 15%, the ratio is up to 2.18, thereby almost doubling that of the cross-linked pure nanogels. Such improvement is caused by the LSPR effect from the densely packed hybrid nanogels on the cotton fabric, which induces a more efficient photothermal conversion and prominent shrinkage of the hybrid nanogels. In addition, because the Au NPs can well absorb light irradiation, the cotton fabrics cross-linked with hybrid nanogels are able to efficiently shield the incident light and present a good capability of heat insulation. Therefore, the obtained cotton fabrics can adjust their comfort according to the external light conditions, well suited for outdoor scenarios such as running and hiking.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Top-down Surfactant-Free Synthesis of Supported Palladium-Nanostructured Catalysts},

author = {C M Schott and P M Schneider and K Sadraoui and K-T Song and B Garlyyev and S A Watzele and J Michali\v{c}ka and J M Macak and A Viola and F Maillard and A Senyshyn and J A Fischer and A S Bandarenka and E L Gubanova},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/smsc.202300241},

doi = {https://doi.org/10.1002/smsc.202300241},

issn = {2688-4046},

year  = {2024},

date = {2024-01-11},

journal = {Small Science},

volume = {4},

number = {3},

pages = {2300241},

abstract = {Nanostructured palladium (Pd) is a universal catalyst that is widely used in applications ranging from catalytic converters of combustion engine cars to hydrogenation catalysts in industrial processes. Standard protocols for synthesizing such nanoparticles (NPs) typically use bottom-up approaches. They utilize special and often expensive physical techniques or wet-chemical methods requiring organic surfactants. These surfactants should often be removed before catalytic applications. In this article, the synthesis of Pd NPs immobilized on carbon support by electrochemical erosion without using any surfactants or toxic materials is reported. The Pd NPs synthesis essentially relies on a Pd bulk pretreatment, which causes material embrittlement and allows the erosion process to evolve more efficiently, producing homogeneously distributed NPs on the support. Moreover, the synthesized catalyst is tested for hydrogen evolution reaction. The activity evaluations identify optimal synthesis parameters related to the erosion procedure. The electrocatalytic properties of the Pd NPs produced with sizes down to 6.4 ± 2.9 nm are compared with a commercially available Pd/C catalyst. The synthesized catalyst outperforms the commercial catalyst within all properties, like specific surface area, geometric activity, mass activity, specific activity, and durability.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Potential Alignment in Tandem Catalysts Enhances CO2-to-C2H4 Conversion Efficiencies},

author = {M Liu and Q Wang and T Luo and M Herran and X Cao and W Liao and L Zhu and H Li and A Stefancu and Y-R Lu and T-S Chan and E Pensa and C Ma and S Zhang and R Xiao and E Cort\'{e}s},

url = {https://doi.org/10.1021/jacs.3c09632},

doi = {10.1021/jacs.3c09632},

issn = {0002-7863},

year  = {2024},

date = {2024-01-10},

journal = {Journal of the American Chemical Society},

volume = {146},

number = {1},

pages = {468-475},

abstract = {The in-tandem catalyst holds great promise for addressing the limitation of low *CO coverage on Cu-based materials for selective C2H4 generation during CO2 electroreduction. However, the potential mismatch between the CO-formation catalyst and the favorable C\textendashC coupling Cu catalyst represents a bottleneck in these types of electrocatalysts, resulting in low tandem efficiencies. In this study, we propose a robust solution to this problem by introducing a wide-CO generation-potential window nickel single atom catalyst (Ni SAC) supported on a Cu catalyst. The selection of Ni SAC was based on theoretical calculations, and its excellent performance was further confirmed by using in situ IR spectroscopy. The facilitated carbon dimerization in our tandem catalyst led to a ∼370 mA/cm2 partial current density of C2H4, corresponding to a faradic efficiency of ∼62%. This performance remained stable and consistent for at least ∼14 h at a high current density of 500 mA/cm2 in a flow-cell reactor, outperforming most tandem catalysts reported so far.},

keywords = {Molecularly-Functionalized, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Please Mind the Gap: Highly Condensed P\textendashN Networks in LiP4N7 and Li3−xP6N11−x(NH)x},

author = {S Schneider and S Klenk and S D Kloss and W Schnick},

url = {https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/chem.202303251},

doi = {https://doi.org/10.1002/chem.202303251},

issn = {0947-6539},

year  = {2024},

date = {2024-01-04},

urldate = {2023-10-24},

journal = {Chemistry \textendash A European Journal},

volume = {30},

pages = {e202303251},

abstract = {Abstract Alkali nitridophosphates AP4N7 and A3P6N11 (A=Na, K, Rb, Cs) have been known for decades. However, their Li homologues have remained elusive. In this work, the highly condensed lithium (imido)nitridophosphates LiP4N7 and Li3−xP6N11−x(NH)x (x=1.66(3)) were synthesized from LiPN2 and P3N5 in the multianvil press at 10 GPa. They constitute the first lithium nitridophosphates with 3D networks exhibiting a degree of condensation larger than 0.5 and high thermal stability. LiP4N7 crystallizes in the orthorhombic space group P212121 with a=4.5846(6) r{A}},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Discovery of multi-anion antiperovskites X6NFSn2 (X = Ca, Sr) as promising thermoelectric materials by computational screening},

author = {D Han and B Zhu and Z Cai and K B Spooner and S S Rudel and W Schnick and T Bein and D O Scanlon and H Ebert},

url = {https://www.sciencedirect.com/science/article/pii/S2590238523005234},

doi = {https://doi.org/10.1016/j.matt.2023.10.022},

issn = {2590-2385},

year  = {2024},

date = {2024-01-03},

urldate = {2024-01-03},

journal = {Matter},

volume = {7},

issue = {1},

pages = {158-174},

abstract = {Summary The thermoelectric performance of existing perovskites lags far behind that of state-of-the-art thermoelectric materials such as SnSe. Despite halide perovskites showing promising thermoelectric properties, namely, high Seebeck coefficients and ultralow thermal conductivities, their thermoelectric performance is significantly restricted by low electrical conductivities. Here, we explore new multi-anion antiperovskites X6NFSn2 (X = Ca, Sr, and Ba) via B-site anion mutation in antiperovskite and global structure searches and demonstrate their phase stability by first-principles calculations. Ca6NFSn2 and Sr6NFSn2 exhibit decent Seebeck coefficients and ultralow lattice thermal conductivities (\<1 W m−1 K−1). Notably, Ca6NFSn2 and Sr6NFSn2 show remarkably larger electrical conductivities compared to the halide perovskite CsSnI3. The combined superior electrical and thermal properties of Ca6NFSn2 and Sr6NFSn2 lead to high thermoelectric figures of merit (ZTs) of ∼1.9 and ∼2.3 at high temperatures. Our exploration of multi-anion antiperovskites X6NFSn2 (X = Ca, Sr) realizes the “phonon-glass, electron-crystal” concept within the antiperovskite structure.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Exact inversion of partially coherent dynamical electron scattering for picometric structure retrieval},

author = {B Diederichs and Z Herdegen and A Strauch and F Filbir and K M\"{u}ller-Caspary},

url = {https://doi.org/10.1038/s41467-023-44268-x},

doi = {10.1038/s41467-023-44268-x},

issn = {2041-1723},

year  = {2024},

date = {2024-01-02},

journal = {Nature Communications},

volume = {15},

number = {1},

pages = {101},

abstract = {The greatly nonlinear diffraction of high-energy electron probes focused to subatomic diameters frustrates the direct inversion of ptychographic data sets to decipher the atomic structure. Several iterative algorithms have been proposed to yield atomically-resolved phase distributions within slices of a 3D specimen, corresponding to the scattering centers of the electron wave. By pixelwise phase retrieval, current approaches do not only involve orders of magnitude more free parameters than necessary, but also neglect essential details of scattering physics such as the atomistic nature of the specimen and thermal effects. Here, we introduce a parametrized, fully differentiable scheme employing neural network concepts which allows the inversion of ptychographic data by means of entirely physical quantities. Omnipresent thermal diffuse scattering in thick specimens is treated accurately using frozen phonons, and atom types, positions and partial coherence are accounted for in the inverse model as relativistic scattering theory demands. Our approach exploits 4D experimental data collected in an aberration-corrected momentum-resolved scanning transmission electron microscopy setup. Atom positions in a 20 nm thick PbZr0.2Ti0.8O3 ferroelectric are measured with picometer precision, including the discrimination of different atom types and positions in mixed columns.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Quantum sensors in diamonds for magnetic resonance spectroscopy: Current applications and future prospects},

author = {R Rizzato and N R Von Grafenstein and D B Bucher},

url = {https://doi.org/10.1063/5.0169027},

doi = {10.1063/5.0169027},

issn = {0003-6951},

year  = {2023},

date = {2023-12-26},

journal = {Applied Physics Letters},

volume = {123},

number = {26},

abstract = {Nuclear magnetic resonance (NMR) and electron spin resonance (ESR) methods are indispensable techniques that utilize the spin of particles to probe matter, with applications in various disciplines, including fundamental physics, chemistry, biology, and medicine. Despite their versatility, the technique's sensitivity, particularly for NMR, is intrinsically low, which typically limits the detection of magnetic resonance (MR) signals to macroscopic sample volumes. In recent years, atom-sized magnetic field quantum sensors based on nitrogen-vacancy (NV) centers in diamond paved the way to detect MR signals at the micro- and nanoscale, even down to a single spin. In this perspective, we offer an overview of the most promising directions in which this evolving technology is developing. Significant advancements are anticipated in the life sciences, including applications in single molecule and cell studies, lab-on-a-chip analytics, and the detection of radicals or ions. Similarly, NV-MR is expected to have a substantial impact on various areas in the materials research, such as surface science, catalysis, 2D materials, thin films, materials under extreme conditions, and quantum technologies.},

keywords = {Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Plasmonic bimetallic two-dimensional supercrystals for H2 generation},

author = {M Herran and S Juergensen and M Kessens and D Hoeing and A K\"{o}ppen and A Sousa-Castillo and W J Parak and H Lange and S Reich and F Schulz and E Cort\'{e}s},

url = {https://doi.org/10.1038/s41929-023-01053-9},

doi = {10.1038/s41929-023-01053-9},

issn = {2520-1158},

year  = {2023},

date = {2023-12-01},

journal = {Nature Catalysis},

volume = {6},

issue = {12},

pages = {1205-1214},

abstract = {Sunlight-driven H2 generation is a central technology to tackle our impending carbon-based energy collapse. Colloidal photocatalysts consisting of plasmonic and catalytic nanoparticles are promising for H2 production at solar irradiances, but their performance is hindered by absorption and multiscattering events. Here we present a two-dimensional bimetallic catalyst by incorporating platinum nanoparticles into a well-defined supercrystal of gold nanoparticles. The bimetallic supercrystal exhibited an H2 generation rate of $$139,mathrmmmol,mathrmg_mathrmcat^-1,mathrmh^-1$$via formic acid dehydrogenation under visible light illumination and solar irradiance. This configuration makes it possible to study the interaction between the two metallic materials and the influence of this in catalysis. We observe a correlation between the intensity of the electric field in the hotspots and the boosted catalytic activity of platinum nanoparticles, while identifying a minor role of heat and gold-to-platinum charge transfer in the enhancement. Our results demonstrate the benefits of two-dimensional configurations with optimized architecture for liquid-phase photocatalysis.},

keywords = {Molecularly-Functionalized, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Combining Nitridoborates, Nitrides and Hydrides\textemdashSynthesis and Characterization of the Multianionic Sr6N[BN2]2H3},

author = {S L Wandelt and A Mutschke and D Khalyavin and R Calaminus and J Steinadler and B V Lotsch and W Schnick},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202313564},

doi = {https://doi.org/10.1002/anie.202313564},

issn = {1433-7851},

year  = {2023},

date = {2023-10-31},

urldate = {2023-10-31},

journal = {Angewandte Chemie International Edition},

volume = {62},

number = {50},

pages = {e202313564},

abstract = {Abstract Multianionic metal hydrides, which exhibit a wide variety of physical properties and complex structures, have recently attracted growing interest. Here we present Sr6N[BN2]2H3, prepared in a solid-state ampoule reaction at 800 °C, as the first combination of nitridoborate, nitride and hydride anions within a single compound. The crystal structure was solved from single-crystal X-ray and neutron powder diffraction data in space group P21/c (no. 14), revealing a three-dimensional network of undulated layers of nitridoborate units, strontium atoms and hydride together with nitride anions. Magic angle spinning (MAS) NMR and vibrational spectroscopy in combination with quantum chemical calculations further confirm the structure model. Electrochemical measurements suggest the existence of hydride ion conductivity, allowing the hydrides to migrate along the layers.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Defect Engineering of Ta3N5 Photoanodes: Enhancing Charge Transport and Photoconversion Efficiencies via Ti Doping},

author = {L I Wagner and E Sirotti and O Brune and G Gr\"{o}tzner and J Eichhorn and S Santra and F Munnik and L Olivi and S Pollastri and V Streibel and I D Sharp},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adfm.202306539},

doi = {https://doi.org/10.1002/adfm.202306539},

issn = {1616-301X},

year  = {2023},

date = {2023-10-19},

urldate = {2023-10-19},

journal = {Advanced Functional Materials},

volume = {34},

pages = {2306539},

abstract = {Abstract While Ta3N5 shows excellent potential as a semiconductor photoanode for solar water splitting, its performance is hindered by poor charge carrier transport and trapping due to native defects that introduce electronic states deep within its bandgap. Here, it is demonstrated that controlled Ti doping of Ta3N5 can dramatically reduce the concentration of deep-level defects and enhance its photoelectrochemical performance, yielding a sevenfold increase in photocurrent density and a 300 mV cathodic shift in photocurrent onset potential compared to undoped material. Comprehensive characterization reveals that Ti4+ ions substitute Ta5+ lattice sites, thereby introducing compensating acceptor states, reducing the concentrations of deleterious nitrogen vacancies and reducing Ta3+ states, and thereby suppressing trapping and recombination. Owing to the similar ionic radii of Ti4+ and Ta5+, substitutional doping does not introduce lattice strain or significantly affect the underlying electronic structure of the host semiconductor. Furthermore, Ti can be incorporated without increasing the oxygen donor content, thereby enabling the electrical conductivity to be tuned by over seven orders of magnitude. Thus, Ti doping of Ta3N5 provides a powerful basis for precisely engineering its optoelectronic characteristics and to substantially improve its functional characteristics as an advanced photoelectrode for solar fuels applications.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Nonlinear potentiodynamic battery charging protocols for fun, education, and application},

author = {H S Stein},

url = {https://chemrxiv.org/engage/chemrxiv/article-details/650ef57ab927619fe7acea3e},

doi = {10.26434/chemrxiv-2023-vj5n0},

year  = {2023},

date = {2023-09-25},

abstract = {Most secondary batteries in academia are (dis)charged by applying a constant current (CC) followed by a constant voltage (CV) i.e. a CCCV procedure. The usual concept is then to condense data for interpretation into representations such as differential capacity, or dQ/dV, graphs. This is done to extract information related to phenomena such as the growth of the solid electrolyte interphase (SEI) or, more broadly, degradation. Typically, these measurements take several months because measurements for differential capacity analysis need to be performed at relatively low C-rates. An alternate charging schedule to CCCV is pulsed charging, where CC sections are interrupted by an open-circuit measurement on the second time scale. These and similar partially constant current strategies primarily target diffusive effects during charging and broadly fall into a linear charging category, where the time derivative for the actuated property is mostly zero. Herein, I explore nonlinear charging i.e., the process of actively applying a potential with a nontrivial time derivate and a resulting non-trivial current time derivative to engineer (dis)charge cycles with enhanced information density. This method of nonlinear charging is then used to charge a cell such that some potential ranges in the differential capacity diagram are omitted. This study is purely a simulative endeavor and not backed by experimentation, owing mainly to the lack of facile implementation of arbitrary function inputs for battery cyclers and might point to limitations of the underlying theory. If found to be confirmed through an experiment, this technique would, however motivate a new roadmap to better understand secondary battery degradation inspired by electrocatalyst degradation.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {How Metal/Insulator Interfaces Enable the Enhancement of the Hydrogen Evolution Reaction Kinetics in Two Ways},

author = {T L Maier and L B De Kam and M Golibrzuch and T Angerer and M Becherer and K Krischer},

url = {https://arxiv.org/abs/2309.02229},

doi = {https://doi.org/10.48550/arXiv.2309.02229},

year  = {2023},

date = {2023-09-05},

journal = {arXiv preprint arXiv:2309.02229},

abstract = {Laterally nanostructured surfaces give rise to a new dimension of understanding and improving electrochemical reactions. In this study, we present a peculiar mechanism appearing at a metal/insulator interface, which can significantly enhance the Hydrogen Evolution Reaction (HER) from water reduction by altering the local reaction conditions in two ways: facilitated adsorption of hydrogen on the metal catalyst surface and improved transfer of ions through the double layer. The mechanism is uncovered using electrodes consisting of well-defined nanometer-sized metal arrays (Au, Cu, Pt) embedded in an insulator layer (silicon nitride), varying various parameters of both the electrode (size of the metal patches, catalyst material) and the electrolyte (cationic species, cation concentration, pH). In addition, simulations of the electrochemical double layer are carried out, which support the elaborated mechanism. Knowledge of this mechanism will enable new design principles for novel composite electrocatalytic systems.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Finding Order in Disorder: The Highly Disordered Lithium Oxonitridophosphate Double Salt Li8+xP3O10−xN1+x (x=1.4(5))},

author = {S Schneider and S T Kreiner and L G Balzat and B V Lotsch and W Schnick},

url = {https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/chem.202301986},

doi = {https://doi.org/10.1002/chem.202301986},

issn = {0947-6539},

year  = {2023},

date = {2023-07-12},

journal = {Chemistry \textendash A European Journal},

volume = {29},

number = {55},

pages = {e202301986},

abstract = {Abstract The crystalline lithium oxonitridophosphate Li8+xP3O10−xN1+x, was obtained in an ampoule synthesis from P3N5 and Li2O. The compound crystallizes in the triclinic space group P with a=5.125(2)},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Postsynthetic Transformation of Imine- into Nitrone-Linked Covalent Organic Frameworks for Atmospheric Water Harvesting at Decreased Humidity},

author = {L Grunenberg and G Savasci and S T Emmerling and F Heck and S Bette and A Cima Bergesch and C Ochsenfeld and B V Lotsch},

url = {https://doi.org/10.1021/jacs.3c02572},

doi = {10.1021/jacs.3c02572},

issn = {0002-7863},

year  = {2023},

date = {2023-05-25},

journal = {Journal of the American Chemical Society},

volume = {145},

number = {24},

pages = {13241-13248},

abstract = {Herein, we report a facile postsynthetic linkage conversion method giving synthetic access to nitrone-linked covalent organic frameworks (COFs) from imine- and amine-linked COFs. The new two-dimensional (2D) nitrone-linked covalent organic frameworks, NO-PI-3-COF and NO-TTI-COF, are obtained with high crystallinity and large surface areas. Nitrone-modified pore channels induce condensation of water vapor at 20% lower humidity compared to their amine- or imine-linked precursor COFs. Thus, the topochemical transformation to nitrone linkages constitutes an attractive approach to postsynthetically fine-tune water adsorption properties in framework materials.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Ionic liquids tailoring crystal orientation and electronic properties for stable perovskite solar cells},

author = {Y Zou and J Eichhorn and S Rieger and Y Zheng and S Yuan and L Wolz and L V Spanier and J E Heger and S Yin and C R Everett and L Dai and M Schwartzkopf and C Mu and S V Roth and I D Sharp and C-C Chen and J Feldmann and S D Stranks and P M\"{u}ller-Buschbaum},

url = {https://www.sciencedirect.com/science/article/pii/S2211285523002860},

doi = {https://doi.org/10.1016/j.nanoen.2023.108449},

issn = {2211-2855},

year  = {2023},

date = {2023-04-21},

journal = {Nano Energy},

volume = {112},

pages = {108449},

abstract = {The crystallization behavior of perovskite films has a profound influence on the resulting defect densities, charge carrier dynamics and photovoltaic performance. Herein, we introduce ionic liquids into the perovskite component to tailor the crystal growth of perovskite films from a disordered to a preferential corner-up orientation and accordingly increase the charge carrier mobility to accelerate electron transport and extraction. Using time-resolved measurements, we probe the charge carrier generation, transport and recombination behavior in these films and related devices. We find the ionic liquid-containing samples exhibit lower defects, faster charge carrier transport and suppressed non-radiative recombination, contributing to higher efficiency and fill factor. Via operando grazing-incidence small- and wide-angle X-ray scattering measurements, we observe a light-induced lattice compression and grain fragmentation in the control devices, whereas the ionic liquid-containing devices exhibit a slight light-induced crystal reconstitution and stronger tolerance against illumination. Under ambient conditions, the non-encapsulated device with the pyrrolidinium-based ionic compound (Pyr14BF4) maintains 97% of its initial efficiency after 4368 h.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Formation of active sites on transition metals through reaction-driven migration of surface atoms},

author = {L Xu and K G Papanikolaou and B A J Lechner and L Je and G A Somorjai and M Salmeron and M Mavrikakis},

url = {https://www.science.org/doi/abs/10.1126/science.add0089},

doi = {doi:10.1126/science.add0089},

year  = {2023},

date = {2023-04-06},

urldate = {2023-04-06},

journal = {Science},

volume = {380},

number = {6640},

pages = {70-76},

abstract = {Adopting low-index single-crystal surfaces as models for metal nanoparticle catalysts has been questioned by the experimental findings of adsorbate-induced formation of subnanometer clusters on several single-crystal surfaces. We used density functional theory calculations to elucidate the conditions that lead to cluster formation and show how adatom formation energies enable efficient screening of the conditions required for adsorbate-induced cluster formation. We studied a combination of eight face-centered cubic transition metals and 18 common surface intermediates and identified systems relevant to catalytic reactions, such as carbon monoxide (CO) oxidation and ammonia (NH3) oxidation. We used kinetic Monte Carlo simulations to elucidate the CO-induced cluster formation process on a copper surface. Scanning tunneling microscopy of CO on a nickel (111) surface that contains steps and dislocations points to the structure sensitivity of this phenomenon. Metal-metal bond breaking that leads to the evolution of catalyst structures under realistic reaction conditions occurs much more broadly than previously thought. In heterogeneous catalysis, it is often assumed that adsorbates have minimal effects on the bonding between surface metal atoms at low temperatures and pressures. Xu et al. used density functional theory to find conditions in which adsorbed molecules can scavenge transition metal atoms by breaking bonds at the surface. These atoms can then form clusters, as observed in kinetic Monte Carlo simulations of carbon monoxide on copper and in scanning tunneling microscopy studies of carbon monoxide on a Ni(111) surface containing steps and dislocations. The reaction mechanisms of several catalytic systems may be dominated by in situ adsorbate-induced active site formation. \textemdashPDS Metal atoms freed from transition metal surfaces during reaction can then form clusters that are catalytically active.},

keywords = {Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Room-temperature synthesis of lead-free copper(I)-antimony(III)-based double perovskite nanocrystals},

author = {S Wang and D Han and C Maheu and Z Xu and A Biewald and H Illner and R Hooijer and T Mayer and A Hartschuh and H Ebert and T Bein},

url = {https://aip.scitation.org/doi/abs/10.1063/5.0144708},

doi = {10.1063/5.0144708},

year  = {2023},

date = {2023-04-05},

journal = {APL Materials},

volume = {11},

number = {4},

pages = {041110},

abstract = {In the field of perovskite solar cells, explorations of new lead-free all-inorganic perovskite materials are of great interest to address the instability and toxicity issues of lead-based hybrid perovskites. Recently, copper-antimony-based double perovskite materials have been reported with ideal band gaps, which possess great potential as absorbers for photovoltaic applications. Here, we synthesize Cs2CuSbCl6 double perovskite nanocrystals (DPNCs) at ambient conditions by a facile and fast synthesis method, namely, a modified ligand-assisted reprecipitation method. We choose methanol as a solvent for precursor salts as it is less toxic and easily removed in contrast to widely used dimethylformamide. Our computational structure search shows that the Cs2CuSbCl6 structure containing alternating [CuCl6]5− and [SbCl6]3− octahedral units is a metastable phase that is 30 meV/atom higher in energy compared to the ground state structure with [CuCl3]2− and [SbCl6]3− polyhedra. However, this metastable Cs2CuSbCl6 double perovskite structure can be stabilized through solution-based nanocrystal synthesis. Using an anion-exchange method, Cs2CuSbBr6 DPNCs are obtained for the first time, featuring a narrow bandgap of 0.9 eV. Finally, taking advantage of the solution processability of DPNCs, smooth and dense Cs2CuSbCl6 and Cs2CuSbBr6 DPNC films are successfully fabricated.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Optical Properties of Slot-Die Coated Hybrid Colloid/Cellulose-Nanofibril Thin Films},

author = {C Harder and A E Alexakis and Y Bulut and S Xiong and B Sochor and G Pan and H Zhong and K Goordeyeva and M A Reus and V K\"{o}rstgens and A Jeromin and T F Keller and L D S\"{o}derberg and E Malmstr\"{o}m and P M\"{u}ller-Buschbaum and S V Roth},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adom.202203058},

doi = {https://doi.org/10.1002/adom.202203058},

issn = {2195-1071},

year  = {2023},

date = {2023-04-05},

journal = {Advanced Optical Materials},

volume = {n/a},

number = {n/a},

pages = {2203058},

abstract = {Abstract Correlating nanostructure and optical properties of thin hybrid films is the crucial ingredient for designing sustainable applications ranging from structural colors in anticounterfeiting to sensors. Here, the tailoring of the refractive index of hybrid cellulose nanofibril/water-dispersed colloidal ink thin films is presented. The authors apply scalable, layer-by-layer slot-die coating for preparing the cellulose nanofibril and hybrid thin films. Making use of the mobility of the polymer chains in the colloids upon annealing, the influence of the different colloid sizes and their glass transition temperature on the refractive index of the hybrid material is shown. The complex refractive indices of the thin films are characterized by spectroscopic ellipsometry and correlated to the different nanostructures of the thin films. The authors find that post-deposition annealing changes the colloidal nanostructure from particulate to agglomerates. Depending on the size of the colloids, imbibition of the colloids into the cellulose nanofibril template is observed. This scalable approach offers new avenues in structural color functional biomaterial hybrid layers.},

keywords = {Foundry Organic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Elucidating the Roles of Nafion/Solvent Formulations in Copper-Catalyzed CO2 Electrolysis},

author = {P Ding and H An and P Zellner and T Guan and J Gao and P M\"{u}ller-Buschbaum and B M Weckhuysen and W Van Der Stam and I D Sharp},

url = {https://doi.org/10.1021/acscatal.2c05235},

doi = {10.1021/acscatal.2c05235},

year  = {2023},

date = {2023-04-05},

journal = {ACS Catalysis},

pages = {5336-5347},

abstract = {Nafion ionomer, composed of hydrophobic perfluorocarbon backbones and hydrophilic sulfonic acid side chains, is the most widely used additive for preparing catalyst layers (CLs) for electrochemical CO2 reduction, but its impact on the performance of CO2 electrolysis remains poorly understood. Here, we systematically investigate the role of the catalyst ink formulation on CO2 electrolysis using commercial CuO nanoparticles as the model pre-catalyst. We find that the presence of Nafion is essential for achieving stable product distributions due to its ability to stabilize the catalyst morphology under reaction conditions. Moreover, the Nafion content and solvent composition (water/alcohol fraction) regulate the internal structure of Nafion coatings, as well as the catalyst morphology, thereby significantly impacting CO2 electrolysis performance, resulting in variations of C2+ product Faradaic efficiency (FE) by \>3×, with C2+ FE ranging from 17 to 54% on carbon paper substrates. Using a combination of ellipsometry and in situ Raman spectroscopy during CO2 reduction, we find that such selectivity differences stem from changes to the local reaction microenvironment. In particular, the combination of high water/alcohol ratios and low Nafion fractions in the catalyst ink results in stable and favorable microenvironments, increasing the local CO2/H2O concentration ratio and promoting high CO surface coverage to facilitate C2+ production in long-term CO2 electrolysis. Therefore, this work provides insights into the critical role of Nafion binders and underlines the importance of optimizing Nafion/solvent formulations as a means of enhancing the performance of electrochemical CO2 reduction systems.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Low Temperature Optical Properties of Novel Lead-Free Cs2NaFeCl6 Perovskite Single Crystals},

author = {M Armer and P D\"{o}rflinger and A Weis and C B\"{u}chner and A Gottscholl and J H\"{o}cker and K Frank and L Nusser and M T Sirtl and B Nickel and T Bein and V Dyakonov},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adpr.202300017},

doi = {https://doi.org/10.1002/adpr.202300017},

issn = {2699-9293},

year  = {2023},

date = {2023-04-02},

journal = {Advanced Photonics Research},

volume = {n/a},

number = {n/a},

pages = {2300017},

abstract = {Lead-free double perovskites have attracted much attention as possible alternatives to lead halide based perovskites in photovoltaic applications. However, to date only few double perovskites have been successfully employed in optoelectronic device prototypes. Therefore, the search for stable and lead-free materials is ongoing. Here, we present the successful growth of high-quality Cs2NaFeCl6 single crystals and their temperature-dependent structural and optical properties. By combining electron paramagnetic resonance (EPR), crystal structure analysis and density functional theory (DFT) we could determine a cubic crystal structure with a spin of 5/2 for this material, showing strongly spin polarized character. Furthermore, combining photoluminescence (PL) and optical absorption measurements we find a bandgap of approximately 2.1 eV at room temperature as well as the presence of excitonic states. Using Elliot's formula, we are able to extract the temperature-dependent behavior of the bandgap as well as an estimated exciton binding energy of only 20 meV at 80 K.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Investigating Plasmonic Catalysis Kinetics on Hot-Spot Engineered Nanoantennae},

author = {L Nan and J Gir\'{a}ldez-Mart\'{i}nez and A Stefancu and L Zhu and M Liu and A O Govorov and L V Besteiro and E Cort\'{e}s},

url = {https://doi.org/10.1021/acs.nanolett.3c00219},

doi = {10.1021/acs.nanolett.3c00219},

issn = {1530-6984},

year  = {2023},

date = {2023-03-31},

journal = {Nano Letters},

abstract = {Strong hot-spots can facilitate photocatalytic reactions potentially providing effective solar-to-chemical energy conversion pathways. Although it is well-known that the local electromagnetic field in plasmonic nanocavities increases as the cavity size reduces, the influence of hot-spots on photocatalytic reactions remains elusive. Herein, we explored hot-spot dependent catalytic behaviors on a highly controlled platform with varying interparticle distances. Plasmon-meditated dehalogenation of 4-iodothiophenol was employed to observe time-resolved catalytic behaviors via in situ surface-enhanced Raman spectroscopy on dimers with 5, 10, 20, and 30 nm interparticle distances. As a result, we show that by reducing the gap from 20 to 10 nm, the reaction rate can be sped up more than 2 times. Further reduction in the interparticle distance did not improve reaction rate significantly although the maximum local-field was ∼2.3-fold stronger. Our combined experimental and theoretical study provides valuable insights in designing novel plasmonic photocatalytic platforms.},

keywords = {Molecularly-Functionalized, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Electron Tunneling at Electrocatalytic Interfaces},

author = {M R Nouri and R M Kluge and R W Haid and J Fortmann and A Ludwig and A S Bandarenka and V Alexandrov},

url = {https://doi.org/10.1021/acs.jpcc.3c00207},

doi = {10.1021/acs.jpcc.3c00207},

issn = {1932-7447},

year  = {2023},

date = {2023-03-27},

journal = {The Journal of Physical Chemistry C},

volume = {127},

number = {13},

pages = {6321-6327},

abstract = {It was recently proposed that tunneling current fluctuations in electrochemical scanning tunneling microscopy (EC-STM) can be used to map the electrocatalytic activity of surfaces with high spatial resolution. However, the relation between the increased noise in the electron tunneling signal and the local reactivity for such complex electrode/electrolyte interfaces is only explained qualitatively or hypothetically. Herein, we employ electron transport calculations to examine tunneling at Pt surfaces under the conditions of the oxygen reduction reaction as a case study. By computing current\textendashvoltage characteristics, we reveal that the tunneling barrier strongly depends on the chemical identity of the adsorbed reaction intermediate as well as on the orientation of the average dipole moment of water species mediating electron tunneling. Our theoretical results combined with EC-STM measurements suggest that detecting reaction intermediates at electrified interfaces in operando conditions is possible based on tunneling noise amplitudes. This study also aims to stimulate further explorations of tunneling-based electron-proton transfers to enable quantum electrocatalysis beyond conventional approaches.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Large-area synthesis of high electrical performance MoS2 by a commercially scalable atomic layer deposition process},

author = {N Aspiotis and K Morgan and B M\"{a}rz and K M\"{u}ller-Caspary and M Ebert and E Weatherby and M E Light and C-C Huang and D W Hewak and S Majumdar and I Zeimpekis},

url = {https://doi.org/10.1038/s41699-023-00379-z},

doi = {10.1038/s41699-023-00379-z},

issn = {2397-7132},

year  = {2023},

date = {2023-03-27},

journal = {npj 2D Materials and Applications},

volume = {7},

number = {1},

pages = {18},

abstract = {This work demonstrates a large area process for atomically thin 2D semiconductors to unlock the technological upscale required for their commercial uptake. The new atomic layer deposition (ALD) and conversion technique yields large area performance uniformity and tunability. Like graphene, 2D Transition Metal Dichalcogenides (TMDCs) are prone to upscaling challenges limiting their commercial uptake. They are challenging to grow uniformly on large substrates and to transfer on alternative substrates while they often lack in large area electrical performance uniformity. The scalable ALD process of this work enables uniform growth of 2D TMDCs on large area with independent control of layer thickness, stoichiometry and crystallinity while allowing chemical free transfers to application substrates. Field effect transistors (FETs) fabricated on flexible substrates using the process present a field effect mobility of up to 55 cm2/Vs, subthreshold slope down to 80 mV/dec and on/off ratios of 107. In addition, non-volatile memory transistors using ferroelectric FETs (FeFETs) operating at ±5 V with on/off ratio of 107 and a memory window of 3.25 V are demonstrated. These FeFETs demonstrate state-of-the-art performance with multiple state switching, suitable for one-transistor non-volatile memory and for synaptic transistors revealing the applicability of the process to flexible neuromorphic applications.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Transient absorption spectroscopy based on uncompressed hollow core fiber white light proves pre-association between a radical ion photocatalyst and substrate},

author = {A Kumar and P Malevich and L Mewes and S Wu and J P Barham and J Hauer},

url = {https://aip.scitation.org/doi/abs/10.1063/5.0142225},

doi = {10.1063/5.0142225},

year  = {2023},

date = {2023-03-24},

journal = {The Journal of Chemical Physics},

volume = {158},

number = {14},

pages = {144201},

abstract = {We present a hollow-core fiber (HCF) based transient absorption experiment, with capabilities beyond common titanium:sapphire based setups. By spectral filtering of the HCF spectrum, we provide pump pulses centered at 425 nm with several hundred nJ of pulse energy at the sample position. By employing the red edge of the HCF output for seeding CaF2, we obtain smooth probing spectra in the range between 320 and 900 nm. We demonstrate the capabilities of our experiment by following the ultrafast relaxation dynamics of a radical cationic photocatalyst to prove its pre-association with an arene substrate, a phenomenon that was not detectable previously by steady-state spectroscopic techniques. The detected preassembly rationalizes the successful participation of radical ionic photocatalysts in single electron transfer reactions, a notion that has been subject to controversy in recent years.},

keywords = {Molecularly-Functionalized, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {A re-useable microreactor for dynamic and sensitive photocatalytic measurements: Exemplified by the photoconversion of ethanol on Pt-loaded titania P25},

author = {C C Aletsee and D Hochfilzer and A Kwiatkowski and M Becherer and J Kibsgaard and I Chorkendorff and M Tschurl and U Heiz},

url = {https://aip.scitation.org/doi/abs/10.1063/5.0134287},

doi = {10.1063/5.0134287},

year  = {2023},

date = {2023-03-23},

journal = {Review of Scientific Instruments},

volume = {94},

number = {3},

pages = {033909},

abstract = {Despite numerous advancements in synthesizing photoactive materials, the evaluation of their catalytic performance remains challenging since their fabrication often involves tedious strategies, yielding only low quantities in the μ-gram scale. In addition, these model catalysts exhibit different forms, such as powders or film(-like) structures grown on various supporting materials. Herein, we present a versatile gas phase μ-photoreactor, compatible with different catalyst morphologies, which is, in contrast to existing systems, re-openable and \textendashuseable, allowing not only post-characterization of the photocatalytic material but also enabling catalyst screening studies in short experimental time intervals. Sensitive and time-resolved reaction monitoring at ambient pressure is realized by a lid-integrated capillary, transmitting the entire gas flow from the reactor chamber to a quadrupole mass spectrometer. Due to the microfabrication of the lid from borosilicate as base material, 88% of the geometrical area can be illuminated by a light source, further enhancing sensitivity. Gas dependent flow rates through the capillary were experimentally determined to be 1015\textendash1016 molecules s−1, and in combination with a reactor volume of 10.5 μl, this results in residence times below 40 s. Furthermore, the reactor volume can easily be altered by adjusting the height of the polymeric sealing material. The successful operation of the reactor is demonstrated by selective ethanol oxidation over Pt-loaded TiO2 (P25), which serves to exemplify product analysis from dark-illumination difference spectra.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Solution-processed NiPS3 thin films from Liquid Exfoliated Inks with Long-Lived Spin-Entangled Excitons},

author = {A Shcherbakov and K Synnatschke and S Bodnar and J Zerhoch and L Eyre and F Rauh and M W Heindl and S Liu and J Konecny and I D Sharp},

url = {https://arxiv.org/abs/2303.11788},

doi = {https://doi.org/10.48550/arXiv.2303.11788},

year  = {2023},

date = {2023-03-21},

journal = {arXiv preprint arXiv:2303.11788},

abstract = {Antiferromagnets are promising materials for future opto-spintronic applications since they show spin dynamics in the THz range and no net magnetization. Recently, layered van der Waals (vdW) antiferromagnets have been reported, which combine low-dimensional excitonic properties with complex spin-structure. While various methods for the fabrication of vdW 2D crystals exist, formation of large area and continuous thin films is challenging because of either limited scalability, synthetic complexity, or low opto-spintronic quality of the final material. Here, we fabricate centimeter-scale thin films of the van der Waals 2D antiferromagnetic material NiPS3, which we prepare using a crystal ink made from liquid phase exfoliation (LPE). We perform statistical atomic force microscopy (AFM) and scanning electron microscopy (SEM) to characterize and control the lateral size and number of layers through this ink-based fabrication. Using ultrafast optical spectroscopy at cryogenic temperatures, we resolve the dynamics of photoexcited excitons. We find antiferromagnetic spin arrangement and spin-entangled Zhang-Rice multiplet excitons with lifetimes in the nanosecond range, as well as ultranarrow emission linewidths, despite the disordered nature of our films. Thus, our findings demonstrate scalable thin-film fabrication of high-quality NiPS3, which is crucial for translating this 2D antiferromagnetic material into spintronic and nanoscale memory devices and further exploring its complex spin-light coupled states.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Interpreting Ultrafast Electron Transfer on Surfaces with a Converged First-Principles Newns-Anderson Chemisorption Function},

author = {S Ghan and E Diesen and C Kunkel and K Reuter and H Oberhofer},

url = {https://arxiv.org/abs/2303.11412},

doi = {https://doi.org/10.48550/arXiv.2303.11412},

year  = {2023},

date = {2023-03-20},

journal = {arXiv preprint arXiv:2303.11412},

abstract = {We study the electronic coupling between an adsorbate and a metal surface by calculating tunneling matrix elements Had directly from first principles. For this we employ a projection of the Kohn-Sham Hamiltonian upon a diabatic basis using a version of the popular Projection-Operator Diabatization approach. An appropriate integration of couplings over the Brillouin zone allows the first calculation of a size-convergent Newns-Anderson chemisorption function, a coupling-weighted density of states measuring the line broadening of an adsorbate frontier state upon adsorption. This broadening corresponds to the experimentally-observed lifetime of an electron in the state, which we confirm for core-excited Ar∗(2p−13/24s) atoms on a number of transition metal (TM) surfaces. Yet, beyond just lifetimes, the chemisorption function is highly interpretable and encodes rich information on orbital phase interactions on the surface. The model thus captures and elucidates key aspects of the electron transfer process. Finally, a decomposition into angular momentum components reveals the hitherto unresolved role of the hybridized d-character of the TM surface in the resonant electron transfer, and elucidates the coupling of the adsorbate to the surface bands over the entire energy scale.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Improved In Situ Characterization of Electrochemical Interfaces Using Metasurface-Driven Surface-Enhanced IR Absorption Spectroscopy},

author = {L M Berger and M Duportal and L D S Menezes and E Cort\'{e}s and S A Maier and A Tittl and K Krischer},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adfm.202300411},

doi = {https://doi.org/10.1002/adfm.202300411},

issn = {1616-301X},

year  = {2023},

date = {2023-03-20},

urldate = {2023-03-20},

journal = {Advanced Functional Materials},

volume = {33},

issue = {25},

pages = {2300411},

abstract = {Abstract Electrocatalysis plays a crucial role in realizing the transition toward a zero-carbon future, driving research directions from green hydrogen generation to carbon dioxide reduction. Surface-enhanced infrared absorption spectroscopy (SEIRAS) is a suitable method for investigating electrocatalytic processes because it can monitor with chemical specificity the mechanisms of the reactions. However, it remains difficult to detect many relevant aspects of electrochemical reactions such as short-lived intermediates. Herein, an integrated nanophotonic-electrochemical SEIRAS platform is developed and experimentally realized for the in situ investigation of molecular signal traces emerging during electrochemical experiments. A platinum nano-slot metasurface featuring strongly enhanced electromagnetic near fields is implemented and spectrally targets the weak vibrational mode of the adsorbed carbon monoxide at ≈2033 cm−1. The metasurface-driven resonances can be tuned over a broad range in the mid-infrared spectrum and provide high molecular sensitivity. Compared to conventional unstructured platinum films, this nanophotonic-electrochemical platform delivers a 27-fold improvement of the experimentally detected characteristic absorption signals, enabling the detection of new species with weak signals, fast conversions, or low surface concentrations. By providing a deeper understanding of catalytic reactions, the nanophotonic-electrochemical platform is anticipated to open exciting perspectives for electrochemical SEIRAS, surface-enhanced Raman spectroscopy, and other fields of chemistry such as photoelectrocatalysis.},

keywords = {Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Nanomechanics with plasmonic nanoantennas: ultrafast and local exchange between electromagnetic and mechanical energy},

author = {A V Bragas and S A Maier and H D Boggiano and G Grinblat and R Bert\'{e} and L D S Menezes and E Cort\'{e}s},

url = {https://opg.optica.org/josab/abstract.cfm?doi=10.1364/JOSAB.482384},

doi = {https://doi.org/10.1364/JOSAB.482384},

year  = {2023},

date = {2023-03-10},

journal = {J. Opt. Soc. Am. B},

abstract = {Converted into mechanical nanoresonators after optical pulsed excitation and electron decay into coherent acoustic phonons, plasmonic nanoantennas produce a periodic modulation of their optical properties, allowing, in turn, an optical reading of these extremely small movements. In this work we review the physics of these nanoresonators and their acoustic vibrations, whose frequencies are in the range of a few to tens of GHz. The accurate determination of their oscillation frequencies allows them to act as mechanical nanoprobes, measure local mechanical moduli of the environment, and perform high-resolution imaging using phononic reconstruction. Furthermore, the internal and external damping mechanisms which affect the quality factor of the nanoresonator and, in particular, the role of the substrate when the nanoantennas are integrated into platforms and probed individually are also reviewed. Finally, we discuss the all-optical generation of hypersonic surface acoustic waves with nanoantennas and the importance of their manipulation for potential acousto-plasmonic devices operating in the GHz range and the nanoscale.},

keywords = {Molecularly-Functionalized, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Atomically Local Electric Field Induced Interface Water Reorientation for Alkaline Hydrogen Evolution Reaction},

author = {C Cai and K Liu and L Zhang and F Li and Y Tan and P Li and Y Wang and M Wang and Z Feng and D Motta Meira and W Qu and A Stefancu and W Li and H Li and J Fu and H Wang and D Zhang and E Cort\'{e}s and M Liu},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202300873},

doi = {https://doi.org/10.1002/anie.202300873},

issn = {1433-7851},

year  = {2023},

date = {2023-03-08},

journal = {Angewandte Chemie International Edition},

volume = {n/a},

number = {n/a},

pages = {e202300873},

abstract = {Abstract The slow water dissociation process in alkaline electrolyte severely limits the kinetics of HER. The orientation of H2O is well known to affect the dissociation process, but H2O orientation is hard to control because of its random distribution. Herein, an atomically asymmetric local electric field was designed by IrRu dizygotic single-atom sites (IrRu DSACs) to tune the H2O adsorption configuration and orientation, thus optimizing its dissociation process. The electric field intensity of IrRu DSACs is over 4.00×1010 N/C. The ab initio molecular dynamics simulations combined with in situ Raman spectroscopy analysis on the adsorption behavior of H2O show that the M−H bond length (M=active site) is shortened at the interface due to the strong local electric field gradient and the optimized water orientation promotes the dissociation process of interfacial water. This work provides a new way to explore the role of single atomic sites in alkaline hydrogen evolution reaction.},

keywords = {Molecularly-Functionalized, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Imaging local diffusion in microstructures using NV-based pulsed field gradient NMR},

author = {R Allert and N Neuling and K Briegel},

url = {https://arxiv.org/abs/2303.03516},

doi = {https://doi.org/10.48550/arXiv.2303.03516},

year  = {2023},

date = {2023-03-06},

journal = {arXiv preprint arXiv:2303.03516},

abstract = {Understanding diffusion in microstructures plays a crucial role in many scientific fields, including neuroscience, cancer- or energy research. While magnetic resonance methods are the gold standard for quantitative diffusion measurements, they lack sensitivity in resolving and measuring diffusion within individual microstructures. Here, we introduce nitrogen-vacancy (NV) center based nuclear magnetic resonance (NMR) spectroscopy as a novel tool to probe diffusion in individual structures on microscopic length scales. We have developed a novel experimental scheme combining pulsed gradient spin echo (PGSE) with optically detected NV-NMR, which allows for the quantification of molecular diffusion and flow within nano-to-picoliter sample volumes. We demonstrate correlated optical imaging with spatially resolved PGSE NV-NMR experiments to probe anisotropic water diffusion within a model microstructure. Our method will extend the current capabilities of investigating diffusion processes to the microscopic length scale with the potential of probing single-cells, tissue microstructures, or ion mobility in thin film materials for battery applications.},

keywords = {Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Revealing Surface and Interface Evolution of Molybdenum Nitride as Carrier-Selective Contacts for Crystalline Silicon Solar Cells},

author = {Y Li and Y Li and J E Heger and J Zhou and T Guan and C R Everett and W Wei and Z Hong and Y Wu and X Jiang and S Yin and X Yang and D Li and C Jiang and B Sun and P M\"{u}ller-Buschbaum},

url = {https://doi.org/10.1021/acsami.2c22781},

doi = {10.1021/acsami.2c22781},

issn = {1944-8244},

year  = {2023},

date = {2023-03-06},

journal = {ACS Applied Materials \& Interfaces},

volume = {15},

number = {10},

pages = {13753-13760},

abstract = {Molybdenum nitride (MoNx) was perceived as carrier-selective contacts (CSCs) for crystalline silicon (c-Si) solar cells due to having proper work functions and excellent conductivities. However, the poor passivation and non-Ohmic contact at the c-Si/MoNx interface endow an inferior hole selectivity. Here, the surface, interface, and bulk structures of MoNx films are systematically investigated by X-ray scattering, surface spectroscopy, and electron microscope analysis to reveal the carrier-selective features. Surface layers with the composition of MoO2.51N0.21 form upon air exposure, which induces the overestimated work function and explains the origin of inferior hole selectivities. The c-Si/MoNx interface is confirmed to adopt long-term stability, providing guidance for designing stable CSCs. A detailed evolution of the scattering length density, domain sizes, and crystallinity in the bulk phase is presented to elucidate its superior conductivity. These multiscale structural investigations offer a clear structure\textendashfunction correlation of MoNx films, providing key inspiration for developing excellent CSCs for c-Si solar cells.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {On-surface synthesis of enetriynes},

author = {N Cao and B Yang and A Riss and J Rosen and J Bj\"{o}rk and J V Barth},

url = {https://doi.org/10.1038/s41467-023-36828-y},

doi = {10.1038/s41467-023-36828-y},

issn = {2041-1723},

year  = {2023},

date = {2023-03-06},

journal = {Nature Communications},

volume = {14},

number = {1},

pages = {1255},

abstract = {Belonging to the enyne family, enetriynes comprise a distinct electron-rich all-carbon bonding scheme. However, the lack of convenient synthesis protocols limits the associated application potential within, e.g., biochemistry and materials science. Herein we introduce a pathway for highly selective enetriyne formation via tetramerization of terminal alkynes on a Ag(100) surface. Taking advantage of a directing hydroxyl group, we steer molecular assembly and reaction processes on square lattices. Induced by O2 exposure the terminal alkyne moieties deprotonate and organometallic bis-acetylide dimer arrays evolve. Upon subsequent thermal annealing tetrameric enetriyne-bridged compounds are generated in high yield, readily self-assembling into regular networks. We combine high-resolution scanning probe microscopy, X-ray photoelectron spectroscopy and density functional theory calculations to examine the structural features, bonding characteristics and the underlying reaction mechanism. Our study introduces an integrated strategy for the precise fabrication of functional enetriyne species, thus providing access to a distinct class of highly conjugated π-system compounds.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Anharmonic Fluctuations Govern the Band Gap of Halide Perovskites},

author = {S A Seidl and X Zhu and G Reuveni and S Aharon and C Gehrmann and S Caicedo-D\'{a}vila and O Yaffe and D A Egger},

url = {https://arxiv.org/abs/2303.01603},

doi = {https://doi.org/10.48550/arXiv.2303.01603},

year  = {2023},

date = {2023-03-02},

journal = {arXiv preprint arXiv:2303.01603},

abstract = {We determine the impact of anharmonic thermal vibrations on the fundamental band gap of CsPbBr3, a prototypical model system for the broader class of halide perovskite semiconductors. Through first-principles molecular dynamics and stochastic calculations, we find that anharmonic fluctuations are a key effect in the electronic structure of these materials. We present experimental and theoretical evidence that important characteristics, such as a mildly changing band-gap value across a temperature range that includes phase-transitions, cannot be explained by harmonic phonons thermally perturbing an average crystal structure and symmetry. Instead, the thermal characteristics of the electronic structure are microscopically connected to anharmonic vibrational contributions to the band gap that reach a fairly large magnitude of 450 meV at 425 K.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}