Review
Chemistry, Applied
Xue-Peng Zhang, Hong-Yan Wang, Haoquan Zheng, Wei Zhang, Rui Cao
Summary: Water oxidation is a crucial reaction in both natural and artificial energy conversion processes, with the formation of O-O bonds being a key step that determines the rate of the reaction. Developing efficient water oxidation catalysts is essential for achieving large-scale water splitting.
CHINESE JOURNAL OF CATALYSIS
(2021)
Review
Energy & Fuels
Matthew Sheridan, Benjamin D. Sherman, Yi Xie, Ying Wang
Summary: Research on ruthenium-based molecular complexes as catalysts for light-driven water splitting shows promising results, with most studies focusing on homogeneous solutions. However, in order to develop devices for light-driven water splitting, catalysts need to be translated to metal-oxide surfaces, emphasizing the importance of research in this area.
Article
Chemistry, Applied
Biaobiao Zhang, Shaoqi Zhan, Tianqi Liu, Linqin Wang, A. Ken Inge, Lele Duan, Brian J. J. Timmer, Oleksandr Kravchenko, Fei Li, Marten S. G. Ahlquist, Licheng Sun
Summary: This study provides insights into the structure-activity relationship of water-oxidation catalysts based on Ru-bnda and related catalysts, emphasizing the importance of seven coordination for the reaction pathway and conditions necessary for O-O bond formation.
JOURNAL OF ENERGY CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Hong-Tao Zhang, Yu-Hua Guo, Yao Xiao, Hao-Yi Du, Ming-Tian Zhang
Summary: We reported here the development of a heterobimetallic NiFe molecular platform to investigate the synergistic effect of NiFe in water oxidation catalysis. Compared to homonuclear bimetallic compounds (NiNi and FeFe), the NiFe complex exhibited significant catalytic activity in water oxidation. Mechanistic studies showed that this enhanced activity is attributed to the effective promotion of O-O bond formation by NiFe synergy. The formation of Ni-III(mu-O)Fe-IV=O intermediate is the key step for O-O bond formation through intramolecular oxyl-oxo coupling between bridged O radical and terminal Fe-IV=O moiety.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Tim Schlossarek, Vladimir Stepanenko, Florian Beuerle, Frank Wuerthner
Summary: This study investigates water-soluble multinuclear complexes based on ruthenium 2,2'-bipyridine-6,6'-dicarboxylate (bda) and ditopic bipyridine linker units for three-component visible light-driven water oxidation catalysis. The catalytic efficiency is significantly enhanced in the absence of organic co-solvents and with increasing oligomer length, which is attributed to the self-assembly of linear Ru(bda) oligomers into aggregated superstructures. The obtained turnover frequencies (up to 14.9 s(-1)) and turnover numbers (more than 1000) per ruthenium center are the highest reported so far for Ru(bda)-based photocatalytic water oxidation systems.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Qiming Zhuo, Shaoqi Zhan, Lele Duan, Chang Liu, Xiujuan Wu, Marten S. G. Ahlquist, Fusheng Li, Licheng Sun
Summary: The study immobilized a molecular [Ru(bda)]-type water oxidation catalyst on glassy carbon electrodes using electrochemical polymerization and found that different immobilization methods affect the O-O bond formation pathways and water oxidation reaction kinetics. Comparisons of the results indicate that the second coordination sphere of the water oxidation catalyst plays a crucial role in the reaction.
CHINESE JOURNAL OF CATALYSIS
(2021)
Review
Chemistry, Inorganic & Nuclear
Abolfazl Ghaderian, Samrana Kazim, Mohammad Khaja Nazeeruddin, Shahzada Ahmad
Summary: Energy conversion through sustainable means is crucial to combat global warming, with molecular ruthenium complexes being key in producing H-2 gas. Different categories of RWOCs have been proposed for improvements, leading to a new family of RWOCs.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Multidisciplinary Sciences
Yuki Tanahashi, Kosuke Takahashi, Yuta Tsubonouchi, Shunsuke Nozawa, Shin-ichi Adachi, Masanari Hirahara, Eman A. Mohamed, Zaki N. Zahran, Kenji Saito, Tatsuto Yui, Masayuki Yagi
Summary: The formation of O-O bond is induced by deprotonation of one of the OH ligands of Ru-2(III)(OH)(2) and requires two RuIII centers to transfer two electrons to their ligands. The intersystem crossing between singlet and triple states of RuII2(mu-OOH) can be easily switched by exchange of H+ between the mu-OOH bridge and the auxiliary backbone ligand.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2021)
Article
Chemistry, Multidisciplinary
Qi-Fa Chen, Yao Xiao, Rong-Zhen Liao, Ming-Tian Zhang
Summary: In this study, a molecular trinuclear nickel (TNC-Ni) catalyst for water oxidation was reported. The catalyst exhibited high catalytic performance and stability under neutral conditions (pH 7). The cooperation among the three nickel sites was found to play a vital role in charge accumulation and O-O bond formation.
Review
Chemistry, Multidisciplinary
Xue-Peng Zhang, Anirban Chandra, Yong-Min Lee, Rui Cao, Kallol Ray, Wonwoo Nam
Summary: This article summarizes the information obtained so far in enzymatic and biomimetic systems that fuels the debate regarding the nature of the active oxidants and the mechanistic uncertainties associated with the transition metal-mediated O-O bond formation and cleavage reactions.
CHEMICAL SOCIETY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Xiang-Zhu Wei, Tian-Yu Ding, Yang Wang, Bing Yang, Qing-Qing Yang, Shengfa Ye, Chen-Ho Tung, Li-Zhu Wu
Summary: In this work, an electron-rich and oxidation-resistant ligand was introduced to stabilize high-valent iron-oxo species for water oxidation reactions. Advanced spectroscopies and electrochemical studies revealed the formation of a high-valent Fe-V(O) species in water. Kinetic and oxygen isotope labelling experiments, along with organic reactions, demonstrated that the Fe-V(O) species is responsible for O-O bond formation via water nucleophilic attack under real catalytic water oxidation conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Editorial Material
Chemistry, Physical
Claire C. Cody, Gary W. Brudvig
Summary: The key step in the oxidation of water to dioxygen is the formation of the O-O bond, which remains not fully understood. A recent report in Nature Chemistry features the structural characterization of a catalytically relevant elusive peroxo intermediate.
Article
Chemistry, Physical
N. Liu, J. Guan
Summary: The rational fabrication of OER electrocatalysts using earth-abundant elements is important for sustainable energy applications. By creating a core-shell Co3O4@FeOx catalyst with an ultrathin FeOx coating, higher OER activity can be achieved due to the promotion of reaction, enhanced charge transfer ability, and accelerated diffusion attributed to the introduction of ultrathin FeOx.
MATERIALS TODAY ENERGY
(2021)
Article
Materials Science, Multidisciplinary
Weinan Xing, Tingting Zhang, Taihua Li, Jiangang Han, Guangyu Wu
Summary: The study presents a highly efficient NiFeP nanoribbons catalyst synthesized through a one-step solvothermal process, showing superior activity and stability in both photocatalytic and electrocatalytic water oxidation, with the potential to replace noble metals for energy storage and conversion.
JOURNAL OF MATERIALS SCIENCE
(2021)
Article
Chemistry, Physical
Avinava Kundu, Brajesh Kumar, Biswarup Chakraborty
Summary: The mechanistic pathway of the oxygen evolution reaction (OER) changes with the surface structure of the catalyst. Electrokinetic study is critical for interpreting the rate-limiting step and other intrinsic parameters. In this study, Fe3S4 nanosheets were used as an OER catalyst and the formation of alpha-FeO(OH) was identified as the active species. The OER performance was improved at higher temperatures and the size of the electrolyte's cation affected the mechanism.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Multidisciplinary
Qi-Fa Chen, Yao Xiao, Rong-Zhen Liao, Ming-Tian Zhang
Summary: In this study, a molecular trinuclear nickel (TNC-Ni) catalyst for water oxidation was reported. The catalyst exhibited high catalytic performance and stability under neutral conditions (pH 7). The cooperation among the three nickel sites was found to play a vital role in charge accumulation and O-O bond formation.
Article
Chemistry, Multidisciplinary
Wen-Hao Deng, Rong-Zhen Liao
Summary: In this study, a quantum chemical investigation was conducted to elucidate the reaction mechanism of TokK. A stepwise "push-pull" radical relay mechanism was proposed, and the origin of selectivity in different methylations was uncovered. These findings have significant implications for studying other B-12-dependent radical SAM enzymes.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Jingwen Xue, Rong-Zhen Liao, Jinjin Li, Yu-Chen Cao, Ya-Qiong Zhang
Summary: In this study, the mechanism of carbonyl sulfide (COS) absorption by N-methyldiethanolamine (MDEA) aqueous solution was explored using theoretical computations. The most favorable pathway for COS removal by MDEA involves a three-step mechanism with hydrolysis as the rate-determining step. Comparisons with other amines indicate that MDEA shows better performance in terms of thermodynamics.
JOURNAL OF THE CHINESE CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Wen-Jie Wei, Rong-Zhen Liao
Summary: This study used QM/MM calculations to elucidate the mechanism and stereoselectivity of the (R)-2-hydroxyisocaproyl-CoA dehydratase enzyme. The research found that the binding mode of the substrate switched from carbonyl oxygen coordination to a-hydroxy group coordination, which led to the formation of a hydrogen bond between the substrate carbonyl oxygen and a second-shell serine residue. The results highlighted the importance of using a redox pathway to activate inert substrates for dehydration.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Yu-Chen Cao, Le-Le Shi, Man Li, Bo You, Rong-Zhen Liao
Summary: Density functional theory (DFT) calculations were used to investigate the cobalt porphyrin-catalyzed electro-reduction of CO2 to CO in water. The study found that Co-II-porphyrin undergoes ligand-based reduction to generate a reactive species, Co-II-porphyrin.(-). This species then attacks CO2, undergoes protonation and reduction to form Co-II-porphyrin-COOH. The rate-determining step is the nucleophilic attack on CO2, and the substituent effects suggest that CoPor-R3 has the highest activity and selectivity as a molecular catalyst.
Article
Chemistry, Multidisciplinary
Hong-Tao Zhang, Yu-Hua Guo, Yao Xiao, Hao-Yi Du, Ming-Tian Zhang
Summary: We reported here the development of a heterobimetallic NiFe molecular platform to investigate the synergistic effect of NiFe in water oxidation catalysis. Compared to homonuclear bimetallic compounds (NiNi and FeFe), the NiFe complex exhibited significant catalytic activity in water oxidation. Mechanistic studies showed that this enhanced activity is attributed to the effective promotion of O-O bond formation by NiFe synergy. The formation of Ni-III(mu-O)Fe-IV=O intermediate is the key step for O-O bond formation through intramolecular oxyl-oxo coupling between bridged O radical and terminal Fe-IV=O moiety.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Hongmei Liu, Qing Huang, Rong-zhen Liao, Man Li, Youwei Xie
Summary: In this article, the authors challenge the traditional mechanism of transetherification between ethers and alcohols by using Re2O7-mediated annulation. They demonstrate that the activation of the alcohol hydroxy group followed by nucleophilic attack of the ether, instead of ether activation, is the primary step in this reaction. This alternative mechanism is suitable for substrates with multiple ether moieties, which is unprecedented in previous methods.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Hong-Tao Zhang, Fei Xie, Yu-Hua Guo, Yao Xiao, Ming-Tian Zhang
Summary: We report the first nonheme CuFe oxygen reduction catalyst, which shows exceptional selectivity and turnover frequency in the reduction of oxygen to water. The collaborative efforts of copper and iron play a crucial role in achieving these outstanding catalytic properties.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Yu-Qing Bai, Xin-Wei Wang, Bo Wu, Xiao-Qing Wang, Rong-Zheng Liao, Man Li, Yong-Gui Zhou
Summary: The development of chiral ligands for precise stereocontrol is essential in asymmetric catalysis. However, the utilization of chiral oxazole-pyridine-type ligands has been limited compared to established chiral pyridine-pyridine and pyridine-oxazoline-type ligands. In this study, a new class of planar-chiral oxazole-pyridine N,N-ligands based on [2.2]paracyclophane was designed and synthesized. These ligands exhibited excellent performance in the enantioselective palladium-catalyzed acetoxylative cyclization, providing chiral cis-hydrobenzofurans with potent NF-κB inhibition, thereby demonstrating the promising potential of chiral oxazole-pyridine ligands as an efficient N,N-ligand scaffold.
Article
Chemistry, Physical
Die Bai, Man Li, Rong-Zhen Liao
Summary: The merging of transition-metal-catalyzed C-H bond activation with electro-oxidation has become a promising approach for oxidative C-H bond functionalization. However, the specific effects of electro-oxidation on the reaction mechanism of transition-metal catalysis have rarely been studied. In this computational study, the rhodium-catalyzed electrochemical C-H phosphorylation of 2-phenylpyridine by diphenylphosphine oxide was investigated to reveal the mechanistic details. The calculations showed that C-H activation prefers to occur at the Rh(III) state, P-H activation at the Rh(IV) state, and reductive elimination at the Rh(V) state. The mechanistic insights obtained from this study are valuable for understanding transition-metal-catalyzed electro-oxidative C-H bond functionalization.
Article
Chemistry, Multidisciplinary
Yongxian Li, Jia-Yi Chen, Xinchao Zhang, Zhiqiang Peng, Qiyi Miao, Wang Chen, Fei Xie, Rong-Zhen Liao, Shengfa Ye, Chen-Ho Tung, Wenguang Wang
Summary: Selective electrochemical interconversion between CO2 and HCO2- has been successfully achieved using an iron-thiolate platform, showing high catalytic activity and Faraday efficiency. Mechanistic studies reveal that the HCO2--to-CO2 transformation proceeds via an unconventional oxidation reaction, while the CO2-to-HCO2- conversion involves an intermediate [Fe(II)-H](-).
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Ya-Qiong Zhang, Yu Zhang, Guoping Zeng, Rong-Zhen Liao, Man Li
Summary: The mechanism and selectivity of CO2 reduction under visible light were investigated using density functional calculations. The results showed that a tetradentate PNNP-type Iridium(III) complex exhibited high activity and selectivity in the reaction.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Applied
Jing Shi, Yu-Hua Guo, Fei Xie, Ming -Tian Zhang, Hong-Tao Zhang
Summary: The process of water oxidation is a challenging task in the development of artificial photosynthetic systems. The use of redox-active ligands in conjunction with metals has been recognized as an effective approach for managing this process. However, the detailed mechanisms of how the electronic effect of these ligands affects the reactivity of the catalytic centers are still unclear. In this study, the electronic effect of a series of mononuclear Ru complexes with redox-active ligands was investigated, and it was found that the ligand-centered oxidation plays a crucial role in the water oxidation process. This study provides important insights into the role of redox-active ligands in controlling the water oxidation process.
CHINESE JOURNAL OF CATALYSIS
(2023)