Article
Chemistry, Multidisciplinary
Zisheng Zhang, Tsugunosuke Masubuchi, Philippe Sautet, Scott L. Anderson, Anastassia N. Alexandrova
Summary: We studied the size-dependent activity and stability of supported Pt-1, Pt-4, Pt-7, and Pt-8 for electrocatalytic hydrogen evolution reaction and found that clusters have higher activity than polycrystalline Pt, along with size-dependent stability. DFT calculations were used to understand the size effects by studying the structural fluxionality under different potentials. Our research showed that the clusters can reshape under H coverage, leading to a diverse ensemble of states with varying stoichiometry, structure, and reactivity. Both experimental and theoretical results suggest that the electrocatalytic species are hydridic states of the clusters (2 H/Pt). An ensemble-based kinetic model reproduced the experimental activity trend and highlighted the role of metastable states. The stability trend was rationalized through chemical bonding analysis. Our joint study showcases the potential- and adsorbate-coverage-dependent fluxionality of subnano clusters of different sizes and provides a systematic modeling strategy to tackle the complexities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Electrochemistry
Ende Yu, Yong Pan
Summary: The hydrogen evolution reaction activity of Pmmn borophene structure has been studied using ab-initio calculation. The results show that Pmmn borophene exhibits excellent hydrogen evolution reaction activity due to the enhanced electron transport capacity and unique charge distribution in the adsorbed state.
ELECTROCHIMICA ACTA
(2022)
Article
Biochemistry & Molecular Biology
Ruben D. Parra, Slawomir J. Grabowski
Summary: In this paper, density functional theory and wave function theory calculations were used to investigate the strength and nature of the C-X···N bond interaction as a function of the number of cyano groups. The results showed that the strength of the C-X···N interaction increased significantly and in a non-additive fashion with the number of CN groups, and the nature of the interaction was revealed through the atoms in molecules approach.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Chemistry, Multidisciplinary
Boyli Ghosh, Ambar Banerjee, Lisa Roy, Rabindra Nath Manna, Rounak Nath, Ankan Paul
Summary: This study investigates the mechanistic pathways of copper-promoted formation of aryl isocyanate from aryl aldehyde. The analysis suggests that the reaction proceeds through radical-based pathways, consistent with experimental findings. Copper salts play a role as an electron pool in this nitrogen transfer reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Markus R. P. Pielmeier, Tom Nilges
Summary: Phosphorene and SnIP are two-dimensional and one-dimensional semiconductors formed from black phosphorus and SnI2, synthesized through mineralization and short way transport with similar yet different preparation methods. Investigating the formation mechanisms of these two compounds is of crucial importance for energy conversion, storage, and catalysis applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Enrique M. Arpa, Ines Corral
Summary: Unconjugated pterins are widely present and have various enzymatic functions, potentially participating in singlet oxygen, amino acid, and nucleotide photosensitization. Under UV-A light excitation, some of these pterins degrade, leading to hydrogen peroxide production. This process, occurring in vivo, contributes to oxidative stress and melanocyte destruction in vitiligo. Our study provides mechanistic insights into the formation of transient triplet species that trigger Type I and Type II photosensitizing processes and degradation. Through calculations, we demonstrate that 6-biopterin degradation in vitiligo patients' skin produces 6-formylpterin and subsequently 6-carboxypterin. The changes in photosensitizing potential with pH are attributed to modulation of excited-state redox potentials.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Meng Wang, Muralidharan Shanmugam, Eric J. L. McInnes, Michael P. Shaver
Summary: Polymeric frustrated radical pairs (poly(FRP)s) were synthesized by in situ photoinduction of FLP moieties, enabling single electron transfer (SET). The radical generation was confirmed by monitoring stable polymeric phosphine radical cations. These new poly(FRP)s exhibited catalytic hydrogenation and radical-mediated photocatalytic perfluoroalkylations, providing new avenues for designing novel functional polymers in catalysis and photoelectrical chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Thermodynamics
Yuxiang Zhu, Chong-Wen Zhou, Alexander A. Konnov
Summary: In this study, the reaction kinetics of hydrogen-abstraction reactions from methoxymethanol by various radicals were investigated using high-level ab initio calculations. It was found that the H-abstraction reactions from the secondary carbon atom of methoxymethanol are favored pathways. Different radicals have different rate constants for hydrogen-abstraction reactions at different temperatures.
COMBUSTION AND FLAME
(2021)
Article
Chemistry, Multidisciplinary
Yi-Qi Tang, Ya-Jun Liu
Summary: Bioluminescence, a visible light produced by living organisms, has been widely used in biotechnology and biomedical fields due to its high sensitivity, selectivity, and signal-to-noise ratio. Despite the unknown mechanisms of most BLs, theoretical studies in the past 14 years have uncovered the mechanisms and details of several BLs.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Aleksandra A. Vidyakina, Andrey A. Shtyrov, Mikhail N. Ryazantsev, Alexander F. Khlebnikov, Ilya E. Kolesnikov, Vladimir V. Sharoyko, Dar'ya Spiridonova, Irina A. Balova, Stefan Braese, Natalia A. Danilkina
Summary: Fluorescent isocoumarin-fused cycloalkynes have been developed, which react in SPAAC and give fluorescent triazoles regardless of the azide nature. The introduction of a pi-acceptor group at the C6 position of the isocoumarin ring converts the non-fluorescent cycloalkyne/triazole pair to its fluorescent counterpart. The design of the fluorescent cycloalkyne/triazole pairs is based on theoretical studies of the deactivation mechanism and electron density redistribution.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Dipendu Mandal, Ting Chen, Zheng-Wang Qu, Stefan Grimme, Douglas W. Stephan
Summary: This study investigates the properties of the products formed by the reaction between PAr3/B(C6F5)(3) and DEAD. It is found that the steric demands and electronic structures play a crucial role in determining the nature of the products.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Biochemistry & Molecular Biology
Mahmoud A. A. Ibrahim, Mohammed N. Shehata, Al-Shimaa S. M. Rady, Hassan A. A. Abuelliel, Heba S. M. Abd Elhafez, Ahmed M. Shawky, Hesham Farouk Oraby, Tamer H. A. Hasanin, Mahmoud E. S. Soliman, Nayra A. M. Moussa
Summary: The effects of Lewis basicity and acidity on sigma-hole interactions were investigated using two sets of carbon-containing complexes. The study found that increasing Lewis basicity significantly enhanced the interaction energy, while increasing Lewis acidity had a relatively smaller effect. Dispersion forces were identified as the dominant interaction forces.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Chemistry, Physical
Yasmine S. Al-Hamdani, Andrea Zen, Dario Alfe
Summary: Molecular hydrogen has the potential to reduce carbon dioxide emissions, but hydrogen gas storage is a major bottleneck. Physisorbing molecular hydrogen at ambient pressure and temperatures is a promising alternative. However, understanding hydrogen adsorption in well-defined nanomaterials remains experimentally challenging.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Multidisciplinary Sciences
Hassan A. Tahini, Xin Tan, Sean C. Smith
Summary: The study focuses on tuning the activity of usually inert MXenes via anchored metal atoms to facilitate hydrogen evolution under alkaline conditions. Fe anchored on V2CO2, Mn on Ti2CO2 and V2CO2, and Ir on Nb2CO2 are the most promising candidates for low and facile H2O dissociation.
ADVANCED THEORY AND SIMULATIONS
(2022)
Article
Chemistry, Physical
Tao Wang, Pan Dong, Jie Li, Yu-Wei You
Summary: Systematic ab initio calculations were performed to investigate the factors affecting the diffusion properties of hydrogen in PdCu alloys. It was found that the diffusion barrier of hydrogen in BCC PdCu alloy is lower than that in FCC PdCu alloy. The interactions among interstitial hydrogen atoms are repulsive in BCC PdCu alloy, while they are attractive in FCC PdCu alloy. These results explain the weaker hydrogen penetration ability in FCC PdCu alloy compared to BCC PdCu alloy.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2022)
Article
Chemistry, Physical
Gautam Jha, Thomas Heine
Summary: Spin-orbit coupling (SOC) is essential for accurate electronic structure analysis in molecules and materials. We have incorporated SOC into the GFN-xTB method and provided validated parameters for all elements in the Periodic Table. By testing reference structures, we showed that our parameterization enables the inclusion of SOC in computationally expensive molecular systems.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Xing Huang, Shuai Fu, Cong Lin, Yang Lu, Mingchao Wang, Peng Zhang, Chuanhui Huang, Zichao Li, Zhongquan Liao, Ye Zou, Jian Li, Shengqiang Zhou, Manfred Helm, Petko St. Petkov, Thomas Heine, Mischa Bonn, Hai I. Wang, Xinliang Feng, Renhao Dong
Summary: In this study, a strategy for synthesizing high-mobility semiconducting conjugated coordination polymers (c-CPs) using novel conjugated ligands with D2h symmetry was demonstrated. The reduced symmetry of the 4 + 2 ligands compared to conventional phenyl ligands led to anisotropic coordination in the formation of c-CPs. A single-crystalline three-dimensional (3D) c-CP Cu4DHTTB with orthogonal ribbon-like pi-d conjugated chains was successfully achieved. This c-CP exhibited a small band gap, dispersive energy bands, and high charge carrier mobilities, laying the foundation for high-performance c-CP-based (opto-)electronics.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Saikat Bag, Himadri Sekhar Sasmal, Sonu Pratap Chaudhary, Kaushik Dey, Dominic Blaette, Roman Guntermann, Yingying Zhang, Miroslav Poloz, Agnieszka Kuc, Ankita Shelke, Ratheesh K. Vijayaraghavan, Thalasseril G. Ajithkumar, Sayan Bhattacharyya, Thomas Heine, Thomas Bein, Rahul Banerjee
Summary: We successfully synthesized uniform covalent organic framework (COF) thin films using a solution-processable sphere transmutation process, which exhibited good crystallinity, porosity, and uniform thickness on a fluorine-doped tin oxide (FTO) surface. Four different COF thin films with different functional backbones were synthesized, and the TpEtBr COF film showed the lowest optical band gap and highest excited-state lifetime. All of the COF films exhibited significant photocurrent after illumination with visible light, indicating good photoactive characteristics. The out-of-plane photodetector device based on the TpEtBr COF thin film showed high photocurrent density and hole mobility, demonstrating the best photoactive properties.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Jiaye Jin, Toshiki Wulf, Marcel Jorewitz, Thomas Heine, Knut R. Asmis
Summary: The vibrational spectra of copper(I) cation-dihydrogen complexes Cu+(H-2)(4), Cu+(D-2)(4), and Cu+(D-2)(3)H-2 were studied using cryogenic ion trap vibrational spectroscopy and quantum chemical calculations. The IRPD spectra were assigned based on comparison to calculated IR spectra. The observed vibrational features indicate the excitations of dihydrogen stretching fundamentals and the interconversion of dihydrogen positions.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Review
Chemistry, Multidisciplinary
Irena Senkovska, Volodymyr Bon, Leila Abylgazina, Matthias Mendt, Jan Berger, Gregor Kieslich, Petko Petkov, Jhonatan Luiz Fiorio, Jan-Ole Joswig, Thomas Heine, Larissa Schaper, Christopher Bachetzky, Rochus Schmid, Roland A. A. Fischer, Andreas Poeppl, Eike Brunner, Stefan Kaskel
Summary: Flexible porous frameworks are a cutting-edge area of materials research due to their ability to adaptively open and close pores induced by chemical and physical stimuli, offering a wide range of functions. However, the factors influencing the switchability are still poorly understood, including the role of building blocks, crystal size, defects, cooperativity, and host-guest interactions. This review discusses an integrated approach using idealized model materials to systematically investigate and understand the critical factors affecting framework dynamics, leading to progress in their understanding and application.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Carlos de la Cruz, Roberto Sanz, Anisley Suarez, Edgar Ventosa, Rebeca Marcilla, Andreas Mavrandonakis
Summary: This article utilizes density functional theory calculations to screen around 100 phenazine derivatives in aqueous media and identifies crucial positions for functionalization with multiple hydroxy groups to design new anolytes. The combination of experimental and computational methods guides the development of a new molecule with a record low reversible redox potential as a potential anolyte for aqueous redox flow batteries.
Article
Chemistry, Multidisciplinary
Kalipada Koner, Arnab Sadhukhan, Suvendu Karak, Himadri Sekhar Sasmal, Yutaro Ogaeri, Yusuke Nishiyama, Shuangjie Zhao, Miroslav Polozij, Agnieszka Kuc, Thomas Heine, Rahul Banerjee
Summary: Few-layer organic nanosheets are gaining attention as 2D materials due to their precise atomic connectivity and tailor-made pores. Most synthesis strategies rely on surface-assisted methods or top-down exfoliation, but a bottom-up approach with well-designed building blocks is more convenient for bulk-scale synthesis of 2D nanosheets. Crystalline covalent organic framework nanosheets were successfully synthesized by reacting tetratopic thianthrene tetraaldehyde (THT) and aliphatic diamines, with the bent geometry of thianthrene and flexible diamines contributing to nanosheet formation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Isabel del Castillo-Velilla, Ahmad Sousaraei, Ignacio Romero-Muniz, Celia Castillo-Blas, S. J. Alba Mendez, Freddy E. Oropeza, Victor A. de la Pena O'Shea, Juan Cabanillas-Gonzalez, Andreas Mavrandonakis, Ana E. Platero-Prats
Summary: Luminescent metal-organic frameworks are a new type of optical sensor capable of capturing and detecting toxic gases. In this study, synergistic binding sites were incorporated into MOF-808 through post-synthetic modification with copper for optical sensing of NO2 at remarkably low concentrations. Computational modelling and advanced synchrotron characterization tools were used to understand the atomic structure of the copper sites.
NATURE COMMUNICATIONS
(2023)
Article
Electrochemistry
Diego Alvan, Rebecca Grieco, Nagaraj Patil, Andreas Mavrandonakis, Marta Liras, Rebeca Marcilla
Summary: Incorporating redox active units in a 3D porous network has been shown to enhance the electrochemical performance of organic electrode materials. In this study, a hybrid material composed of phenazine-based conjugated microporous polymer (IEP-27-SR), single-walled carbon nanotubes (SWCNTs), and graphene oxide (RGO) was synthesized and characterized. The hybrid material exhibited excellent electrochemistry in both alkaline and acidic solutions, but showed superior performance, including high specific capacity, redox kinetics, and cycle stability, in acidic electrolyte.
BATTERIES & SUPERCAPS
(2023)
Article
Materials Science, Multidisciplinary
Florian M. Arnold, Alireza Ghasemifard, Agnieszka Kuc, Jens Kunstmann, Thomas Heine
Summary: Manipulating the twist angle between layers has a significant impact on the properties of layered two-dimensional crystals. In this study, the characteristics of twisted bilayer MoS2 were monitored as a function of the twist angle. Different structural regimes were identified, each with specific structural and electronic properties. The results showed the emergence of extended stacking domains, soliton networks, and superlattices, which contribute to exciting electronic effects.
Article
Chemistry, Physical
Damien Monti, Nagaraj Patil, Ashley P. P. Black, Dionysios Raptis, Andreas Mavrandonakis, George E. E. Froudakis, Ibraheem Yousef, Nicolas Goujon, David Mecerreyes, Rebeca Marcilla, Alexandre Ponrouch
Summary: Ca- and Mg-based batteries are more sustainable alternatives to Li-ion batteries, but suffer from poor mass transport of cations. Organic positive electrodes, although most sustainable and potentially low-cost, currently have the best electrochemical performances in Ca and Mg cells but suffer from low capacity retention upon cycling, the origin of which is not yet fully understood.
ACS APPLIED ENERGY MATERIALS
(2023)
Article
Multidisciplinary Sciences
Jonas Schabernack, Augusto Faria Oliveira, Thomas Heine, Cornelius Fischer
Summary: In deep geological repositories for nuclear waste, the surrounding rock formation acts as an essential barrier to prevent the migration of radionuclides. Phyllosilicates found in various potential host rocks have demonstrated high efficiency in sorbing radionuclides. This study investigates the energetic differences of surface sorption sites on nanotopographic structures and provides a mechanistic explanation for the heterogeneous sorption observed on mineral surfaces.
ADVANCED THEORY AND SIMULATIONS
(2023)
Article
Chemistry, Physical
Junyong Min, Lei Liu, Fengjuan Chen, Xuekun Jin, Tianjiao Yuan, Xiaoqian Yao
Summary: Controlling the structure of single-atom catalysts (SACs) is a promising strategy for enhancing the carbon dioxide reduction reaction (CO2RR) activity. Using density functional theory (DFT) calculations, the influence of structure and coordination environment on the electrocatalytic CO2RR activity of single-atom copper catalysts (Cu-N/C) was investigated. Among 11 different Cu-N/C catalysts, CuN3V and CuN2V2 showed better CO2RR activity and lower limiting potentials. The change in catalyst structure not only affected adsorption properties but also determined the potential-determining step of CO2RR.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Xing Huang, Shuai Fu, Cong Lin, Yang Lu, Mingchao Wang, Peng Zhang, Chuanhui Huang, Zichao Li, Zhongquan Liao, Ye Zou, Jian Li, Shengqiang Zhou, Manfred Helm, Petko St Petkov, Thomas Heine, Mischa Bonn, Hai I. Wang, Xinliang Feng, Renhao Dong
Summary: This study demonstrates a strategy for synthesizing high-mobility semiconducting coordination polymers (c-CPs) using novel conjugated ligands with reduced symmetry. The synthesized c-CPs exhibit a small band gap, dispersive energy bands, and high charge carrier mobilities, outperforming previously reported conductive coordination polymers. This molecular design strategy lays the foundation for achieving high-performance c-CP-based (opto-)electronics.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Xipeng Shu, Liang Hu, Thomas Heine, Yu Jing
Summary: By introducing pyridinic N in the skeletons of carbonyl aromatic compounds, the electrochemical performance can be significantly improved, making them promising organic cathode materials for lithium-ion batteries.
