Article
Chemistry, Multidisciplinary
Shuanglin He, Fang Huang, Qianqian Wu, Ping Zhang, Ying Xiong, Jie Yang, Rong Zhang, Fang Wang, Lin Chen, T. Leo Liu, Fei Li
Summary: A rare mononuclear manganese complex was reported as a mimic of [FeFe]-hydrogenase, successfully mimicking the functions of its active site by utilizing two consecutive MS-CPET processes to achieve low overpotential in electrochemical hydrogen production.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Min Hu, Ke Ye, Guozhen Zhang, Xiyu Li, Jun Jiang
Summary: The catalytic activity of the oxygen/hydrogen evolution reaction (OER/HER) on dual-site catalysts on graphene has been studied using density functional theory calculations. The results show that both the maximum free energy change (Delta GMax) and the activity barrier (Ea) must be considered in evaluating the catalytic activity of the OER/HER on the dual site. Importantly, there is a negative relationship between Delta GMax and Ea, which is essential for the rational design of effective dual-site catalysts for electrochemical reactions.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Seungjin Song, Junseong Lee, Jun-Ho Choi, Junhyeok Seo
Summary: The electrochemical reactivity of a pincer-type iron complex was investigated, showing that the Fe(i) species undergo disproportionation upon electron reduction. The dissociation of a ligand on the electron-reduced Fe center creates an open coordination site for proton transfer, facilitating the efficient catalysis of the proton reduction reaction through coordination of isocyanide and a pyridine-based NNN-pincer ligand. Additionally, a Lewis basic amine site in the NNN-pincer ligand arm lowers the free energy for protonation of the Fe center during the proton reduction process. DFT calculations provided insights into a plausible catalytic pathway.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Shuhua Wang, Baibiao Huang, Ying Dai, Wei Wei
Summary: This study investigates the performance of single-atom catalysts in water electrolysis and oxygen reduction reactions, revealing how tuning the coordination microenvironment of the active metal atom can enhance catalytic activity. The findings challenge the accepted standard scaling relationship and shed light on the importance of the coordination microenvironment in electrocatalysis.
Article
Chemistry, Multidisciplinary
Lingyou Zeng, Yanju Chen, Mingzi Sun, Qizheng Huang, Kaian Sun, Jingyuan Ma, Jiong Li, Hao Tan, Menggang Li, Yuan Pan, Yunqi Liu, Mingchuan Luo, Bolong Huang, Shaojun Guo
Summary: Efficient and durable bifunctional catalysts have been designed for the co-production of biomass-upgraded chemicals and sustainable hydrogen through the oxidation of 5-hydroxymethylfurfural (HMF) and the evolution of hydrogen. Atomic-scale cooperative adsorption centers on Rh-O-5/Ni(Fe) atomic sites enable highly active and stable catalysis in alkaline conditions. The catalyst exhibits low cell voltage and excellent stability in an integrated electrolysis system.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Krishnamoorthy Sathiyan, Totan Mondal, Poulami Mukherjee, Shanti Gopal Patra, Itay Pitussi, Haya Kornweitz, Ronen Bar-Ziv, Tomer Zidki
Summary: This study improves the OER performance of MoS2 by co-doping Fe and Co atoms and optimizing the Co/Fe ratio to enhance the catalyst's activity and stability. The electronic modulation effect of the hybridized structure is supported by DFT calculations.
Article
Chemistry, Physical
Carmen Martinez-Alonso, Jose Manuel Guevara-Vela, Javier LLorca
Summary: This study investigates the effect of elastic strains on catalytic activity for hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) on thirteen late transition metals. It is found that elastic strains can be used to tune the catalytic activity of different metals, and even reach the optimal state of catalytic activity for certain metals.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Andrzej Mikula, Maciej Kubowicz, Julia Mazurkow, Krzysztof Mars, Mathias Smialkowski, Ulf-Peter Apfel, Marta Radecka
Summary: The study focuses on a multi-component approach to materials design for energy-conversion-oriented applications. It investigates a 5-component multimetallic chalcogenide compound with a pentlandite structure, which shows promise in electrocatalytic water splitting. The solubility limit of an additive, selenium, in a trimetallic Co3Fe3Ni3S8 system is determined, and the effects of consolidation conditions on the material's morphology and properties are discussed. By tailoring both the chemical composition and processing conditions, efficient electrocatalysts for water splitting can be optimized.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Physical
Wendi Peng, Dongfang Wen, Wenting Zhang, Wanping Li, Yanli Lu, Dan Zhou, Wei Hu
Summary: A novel composite composed of bimetallic phosphide nanosheets and porous Ni3S2 nanospheres was prepared and showed outstanding performance in urea-assistant water electrolysis. The composite exhibited stable performance in both urea and urine, making it a practical catalyst design for efficient water-hydrogen conversion and simultaneous sewage treatment.
APPLIED SURFACE SCIENCE
(2024)
Article
Chemistry, Physical
Jiale Zhao, Qing Shi, Dengmeng Song, Bo Li, Hong Ren, Di Zhang, Xuzhuo Sun, Jun Li, Ning Wang
Summary: The dithiolato [NiN2S2] complexes were used to synthesize bimetallic models of the active site of [NiFe]-Hydrogenases. Three [NiN2S2] complexes were reacted with [NiCl2(PNP)] to investigate the influences of [NiN2S2] ligands on the structure and property of model complexes. The study found that complex 1, as a model of [NiFe]-H(2)ases, could catalyze H-2 evolution with a high rate constant in the presence of acetic acid.
Article
Chemistry, Physical
Duan Chen, Ji Qiu, Xing Chen, Shu Chen, Jie Zhang, Zhangquan Peng
Summary: We evaluated the intrinsic activity of Ni(OH)2, NiFe layered double hydroxides (LDHs), and NiFe-LDH with oxygen vacancies for oxygen evolution reaction (OER) using cavity microelectrodes (CMEs) with controllable mass loading. The number of active Ni sites (NNi-sites) was quantitatively correlated with OER current, showing that the introduction of Fe sites and vacancies increased the turnover frequency (TOF). Electrochemical surface area (ECSA) was also quantitatively correlated with NNi-sites, indicating a decrease in NNi-sites per unit ECSA (NNi-per-ECSA) due to the introduction of Fe sites and vacancies. Therefore, the difference in OER current per unit ECSA (JECSA) was reduced compared to TOF. The results demonstrate that CMEs provide a reliable platform for evaluating intrinsic activity with TOF, NNi-per-ECSA, and JECSA.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Engineering, Environmental
Longlu Wang, Lingbin Xie, Weiwei Zhao, Shujuan Liu, Qiang Zhao
Summary: It is found that the synthesis strategy of oxygen substitution in MoS2 can enhance its catalytic performance in the hydrogen evolution reaction, resulting in an increased hydrogen production rate. Proper oxygen substitution and strain can modulate the surface electronic state of MoS2, optimizing the Gibbs free energy and accelerating the catalytic efficiency.
CHEMICAL ENGINEERING JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Jun Yang, Yifan Cao, Shuyu Zhang, Qingwen Shi, Siyu Chen, Shengcai Zhu, Yunsong Li, Jianfeng Huang
Summary: Tungsten oxide (WO3) is a cost-effective and structurally adjustable electrocatalyst for the hydrogen evolution reaction (HER). However, its intrinsic activity for HER is unsatisfactory due to strong hydrogen adsorption energy. To address this issue, defect engineering by inserting hydrogen atoms into the interstitial lattice site of WO3 (H0.23WO3) is proposed. The H0.23WO3 electrocatalyst demonstrates significantly improved activity for HER, with low overpotential and long-term stability. This work enriches defect engineering strategies for enhancing catalytic performance and provides insights for the rational design of efficient HER catalysts.
Article
Chemistry, Multidisciplinary
Hoa Thi Bui, Nguyen Duc Lam, Do Chi Linh, Nguyen Thi Mai, HyungIl Chang, Sung-Hwan Han, Vu Thi Kim Oanh, Anh Tuan Pham, Supriya A. A. Patil, Nguyen Thanh Tung, Nabeen K. K. Shrestha
Summary: Developing highly efficient and durable hydrogen evolution reaction (HER) electrocatalysts is crucial. MoSe2 is a promising candidate for HER catalysis but suffers from stacking layers and low conductivity. This work presents a novel approach by incorporating diethylene glycol solvent into the interlayers of MoSe2 during synthesis, which transforms into graphene (Gr) upon thermal treatment. The resulting MoSe2-Gr composite exhibits significantly enhanced HER activity and long-term stability, surpassing the state-of-the-art Pt/C catalyst.
Review
Chemistry, Physical
Frederik C. Ostergaard, Alexander Bagger, Jan Rossmeisl
Summary: This study utilizes a data-first approach to predict catalyst activity and possible mechanisms for the Hydrogen Evolution Reaction (HER) by fitting hydrogen and hydroxide adsorption energies and work functions obtained using DFT to experimental data. Statistical proof is provided for the importance of the work function as a descriptor in both acidic and alkaline conditions, and an oxophobic HER pathway is identified in alkaline conditions.
CURRENT OPINION IN ELECTROCHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Aurore Jacq-Bailly, Martino Benvenuti, Natalie Payne, Arlette Kpebe, Christina Felbek, Vincent Fourmond, Christophe Leger, Myriam Brugna, Carole Baffert
Summary: Hnd, a tetrameric enzyme from Desulfovibrio fructosovorans, is capable of flavin-based electron bifurcation. Despite its complexity, the enzyme can catalytically exchange electrons with an electrode and demonstrates unique high potential inactivation/reactivation kinetics. The catalytic properties of Hnd are comparable to standard hydrogenases, suggesting that the additional subunits necessary for electron bifurcation do not alter the enzyme's catalytic behavior at the active site.
FRONTIERS IN CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Marta Meneghello, Ana Rita Oliveira, Aurore Jacq-Bailly, Ines A. C. Pereira, Christophe Leger, Vincent Fourmond
Summary: Mo/W formate dehydrogenases catalyze the reversible reduction of CO2 to formate, and it has been definitively demonstrated through an electrochemical method that the substrate is indeed CO2, not a hydrated species like HCO3-.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Multidisciplinary Sciences
Martin Winkler, Jifu Duan, Andreas Rutz, Christina Felbek, Lisa Scholtysek, Oliver Lampret, Jan Jaenecke, Ulf-Peter Apfel, Gianfranco Gilardi, Francesca Valetti, Vincent Fourmond, Eckhard Hofmann, Christophe Leger, Thomas Happe
Summary: The protein morphing mechanism of [FeFe]-hydrogenase CbA5H controls the reversible transition between catalytic and inactive states, with a conserved cysteine residue protecting the active site from oxygen by acting as a safety cap. This protection mechanism is regulated by three non-conserved amino acids located approximately 13 angstrom away from the active site, demonstrating remote control of the first coordination sphere chemistry of the H-cluster.
NATURE COMMUNICATIONS
(2021)
Review
Chemistry, Multidisciplinary
Vincent Fourmond, Nicolas Plumere, Christophe Leger
Summary: Understanding the relationship between reaction rate and thermodynamic driving force is crucial for developing efficient catalysts. This Perspective discusses reversible catalysis, which allows reactions to proceed rapidly and efficiently even with slight deviations from equilibrium. The perspective also covers electrochemical investigations of redox reactions, biological energy transduction, and mean-field kinetic modeling of surface catalysts, molecular catalysts, and molecular machines.
NATURE REVIEWS CHEMISTRY
(2021)
Article
Chemistry, Physical
Steffen Hardt, Stefanie Stapf, Dawit T. Filmon, James A. Birrell, Olaf Ruediger, Vincent Fourmond, Christophe Leger, Nicolas Plumere
Summary: The research describes a redox-active film for bidirectional and reversible hydrogen conversion, which can be used for electrocatalytic energy conversion. By serving as both the anode material and a highly energy efficient cathode material in a biofuel cell, the film demonstrates high performance. The understanding of reversibility through a kinetic model has simplified the design principles of highly efficient and stable bioelectrocatalytic films.
Review
Chemistry, Multidisciplinary
Marta Meneghello, Christophe Leger, Vincent Fourmond
Summary: Only two enzymes, CO dehydrogenase and formate dehydrogenase, are capable of directly reducing CO2, producing CO and formate respectively. These metalloenzymes are rapid, energy-efficient, and specific in product. Researchers have studied their mechanisms using protein film electrochemistry, and also exploited their catalytic performance to build biotechnological devices.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Electrochemistry
Vincent Fourmond, Christophe Leger
Summary: This study focuses on embedding an enzyme irreversibly inactivated by O-2 in a film of arbitrary thickness, to achieve unidirectional catalysis protection mechanism. By analytically solving the reaction/diffusion system, the time evolution of O-2 penetration is fully described, and the amount of H-2 consumed by the protection mechanism is discussed. The relations between film thickness, electron conduction, catalyst use, and lifetime are established to optimize the design of these systems.
Review
Chemistry, Multidisciplinary
Sven T. Stripp, Benjamin R. Duffus, Vincent Fourmond, Christophe Leger, Silke Leimkueshler, Shun Hirota, Yilin Hu, Andrew Jasniewski, Hideaki Ogata, Markus W. Ribbe
Summary: Gases like H-2, N-2, CO2, and CO are important feedstock for green energy conversion and as sources of nitrogen and carbon. However, their industrial transformation and production require significant energy input, whereas nature efficiently converts them at ambient conditions using gas-processing metalloenzymes (GPMs). In this review, the importance of the cofactor/protein interface in GPMs is emphasized, and the effects of second and outer coordination sphere on catalytic activity are discussed.
Article
Chemistry, Physical
Andreas Rutz, Chandan K. Das, Andrea Fasano, Jan Jaenecke, Shanika Yadav, Ulf-Peter Apfel, Vera Engelbrecht, Vincent Fourmond, Christophe Leger, Lars Schaefer, Thomas Happe
Summary: The active site of [FeFe]-hydrogenases degrades upon contact with oxygen, but the protein structure of a certain hydrogenase (CbA5H) allows its active site to be protected, reducing degradation caused by oxygen. By modifying the surface residue, the hydrogenase's resistance to oxygen can be increased.
Article
Chemistry, Inorganic & Nuclear
Cheriehan Hessin, Jules Schleinitz, Nolwenn Le Breton, Sylvie Choua, Laurence Grimaud, Vincent Fourmond, Marine Desage-El Murr, Christophe Leger
Summary: Potential inversion refers to the phenomenon where the second electron transfer is easier than the first, and it is significant for understanding enzyme catalysis and developing efficient catalysts. Currently, there is a lack of analytical predictions to interpret voltammetric peak potentials when potential inversion occurs, and cyclic voltammograms are often analyzed without considering overfitting or estimating error. In this study, a theory for voltammetry of two-electron redox species in the irreversible limit is formulated and applied to analyze the voltammetry of a nickel complex with redox-active ligands, highlighting the intrinsic underdetermination of the model. Characterizing the thermodynamics of two-electron electron-transfer reactions is crucial for catalyst design.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Raphael J. Labidi, Bruno Faivre, Philippe Carpentier, Giulia Veronesi, Albert Solei-Daura, Ragnar Bjornsson, Christophe Leïger, Philipp Gotico, Yun Li, Mohamed Atta, Marc Fontecave
Summary: In this study, the performance of the orange protein (Orp) as a catalyst for photocatalytic reduction of protons into H-2 under visible light irradiation was investigated. It was found that Orp exhibited excellent photocatalytic activity in the presence of ascorbate as the sacrificial electron donor and [Ru(bpy)(3)]Cl-2 as the photosensitizer. Density functional theory (DFT) calculations were used to propose a consistent reaction mechanism.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Correction
Chemistry, Multidisciplinary
Vincent Fourmond, Carole Baffert, Kateryna Sybirna, Thomas Lautier, Abbas Abou Hamdan, Sebastien Dementin, Philippe Soucaille, Isabelle Meynial-Salles, Herve Bottin, Christophe Leger
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Andrea Fasano, Chloe Guendon, Aurore Jacq-Bailly, Arlette Kpebe, Jeremy Wozniak, Carole Baffert, Melisa del Barrio, Vincent Fourmond, Myriam Brugna, Christophe Leger
Summary: The observation that some homologous enzymes have the same active site but very different catalytic properties demonstrates the importance of long-range effects in enzyme catalysis. In this study, the catalytic bias and sensitivity of hydrogenase 1 (Hyd 1) were found to be determined by the catalytic subunit rather than the electron transfer chain, and the proximal cluster was confirmed to play a role in the enzyme's resistance to long-term exposure to O-2. This research provides insights into the structure-function relationships of hydrogenases and offers possibilities for engineering useful hydrogenases with desired properties.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Correction
Chemistry, Multidisciplinary
Vincent Fourmond, Carole Baffert, Kateryna Sybirna, Thomas Lautier, Abbas Abou Hamdan, Philippe Soucaille, Isabelle Meynial-Salles, Christophe Leger
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Physical
Matteo Sensi, Carole Baffert, Vincent Fourmond, Luca de Gioia, Luca Bertini, Christophe Leger
Summary: This review presents evidence that hydrogenases are photosensitive, focusing on FeFe hydrogenases with their active site called the H-cluster, consisting of a [4Fe4S] cluster and a diiron site. It discusses the effects of UV-visible light irradiation on the enzyme and warns about FeFe hydrogenase photoinhibition when using them for artificial photosynthesis.
SUSTAINABLE ENERGY & FUELS
(2021)
