Article
Chemistry, Physical
Zhiyao Duan, Graeme Henkelman
Summary: This study uses global optimization and constant-potential density functional theory to simulate the complete process of Pt dissolution, revealing the formation and dissolution mechanism of a two-dimensional Pt surface oxide. The findings provide a fundamental understanding of Pt dissolution under potential cycling, which is essential for the rational design of durable Pt-based cathodes for fuel cells.
Article
Chemistry, Physical
Yu-Feng Ding, Shuang-Feng Yin, Meng-Qiu Cai
Summary: This study investigates the mechanisms of photocatalytic toluene selective oxidation reactions, as well as the influence of water on these reactions. The results show that the oxidation potential of the photocatalyst is crucial for efficient catalysis, and the dehydration reaction is the rate-determining step for converting toluene into benzaldehyde. Furthermore, water has a dual role in photocatalytic reactions.
Article
Chemistry, Physical
Mingming Luo, Chao Liu, Meiling Liu, Shaik Gouse Peera, Tongxiang Liang
Summary: This study systematically investigated the mechanism of CO oxidation on doped graphene catalysts through DFT calculations, finding that FeFe@C6, FeCo@C6, and FeNi@C6 are efficient for CO oxidation. Additionally, heteronuclear dimeric catalysts FeCo@C6 and FeNi@C6 exhibit better catalytic activity and lower energy barriers compared to homonuclear dimeric catalyst FeFe@C6.
APPLIED SURFACE SCIENCE
(2021)
Article
Chemistry, Multidisciplinary
Peng Wu, Shengheng Yan, Wenhan Fang, Binju Wang
Summary: Cluster-continuum model calculations were used to investigate the mechanism of water oxidation catalyzed by a mononuclear copper complex. The most favorable pathway involved the nucleophilic attack of OH- onto the L center dot+-Cu-II-OH- intermediate. A catalytic cycle for the mononuclear copper complex-catalyzed water oxidation was proposed based on the calculations.
Article
Chemistry, Multidisciplinary
Man Li, Rong-Zhen Liao
Summary: Density functional theory calculations were used to elucidate the water oxidation mechanism catalyzed by polyanionic tetramanganese complex. Theoretical results showed that sequential proton-coupled electron transfer oxidations led to the formation of an oxygen radical, facilitating the formation of O-O bond. Subsequent oxidation reactions enabled the release of oxygen.
Article
Chemistry, Multidisciplinary
Yelu Shi, Gianna Stella, Jia-Min Chu, Yong Zhang
Summary: This study reveals the importance of HNO binding and a proton-coupled electron transfer mechanism for HNO reaction through quantum chemical research on Cu cyclams. The results indicate that steric effect is the primary factor, and electronic factor is the secondary factor, but the combined effects can lead to unexpected reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Yong Wu, Shanshan Cao, Iskander Douair, Laurent Maron, Xihe Bi
Summary: The [2+1] cycloaddition reaction of a metal carbene with an alkene often suffers from side reactions, leading to lower yields of cyclopropanation products. By adding a low concentration of diazo compound to alkenes, it was found that AgOTf catalysis can efficiently produce cyclopropane products from hindered alkenes.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
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
Marin Puget, Viacheslav Shcherbakov, Sergey Denisov, Philippe Moreau, Jean-Pierre Dognon, Mehran Mostafavi, Sophie Le Caer
Summary: The nature of the primary species formed in FEC depends on the amount of FEC in the solution, which will affect its performance in the electrolyte.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Raphael Robidas, Claude Y. Legault
Summary: A mechanism is proposed to explain the formation of benzobicyclo[3.2.0]heptane derivatives from 1,7-enyne derivatives bearing a terminal cyclopropane, which has been previously reported.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Engineering, Environmental
Nannan Wu, Mingzhu Liu, Bingru Tian, Zunyao Wang, Virender K. Sharma, Ruijuan Qu
Summary: In this study, the oxidation of five phenolic contaminants using ferrate(VI) was investigated to understand the reaction mechanisms. Experimental and theoretical calculations revealed that the reaction rate constants were correlated with the energy of the highest occupied molecular orbital. Electron-donating groups (-R) were found to be more easily oxidized by ferrate(VI) compared to weak electron withdrawing groups (-X) and strong electron-withdrawing groups (-(C=O)-). The dominance of Fe(VI) in the reaction process was determined, and four main reaction mechanisms, including single-oxygen transfer, double-oxygen transfer, ·OH attack, and electron-transfer-mediated coupling reaction, were proposed. Density functional theory calculations suggested that the presence of -(C=O)- facilitated the occurrence of double-oxygen transfer and ·OH attack reactions, while the tendency of single-oxygen transfer and electron-transfer reaction varied with different substituents. Furthermore, the double-oxygen transfer pathway was found to be a common reaction mechanism during the ferrate(VI) oxidation of phenolic compounds.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Physical
Kaili Wang, Danyang Huang, Yichi Guan, Feng Liu, Jia He, Yi Ding
Summary: The developed PtCu nanowire catalysts demonstrate superior performance and high stability in methanol oxidation reaction, with 7.5 times higher activity compared to commercial Pt/C catalysts, two times higher power density, and enhanced stability.
Article
Chemistry, Physical
Wanyi Liao, Qin Zhao, Shanshan Wang, Yiling Ran, Hong Su, Rong Gan, Shun Lu, Yan Zhang
Summary: The high energy consumption in water electrolysis systems is attributed to the slow kinetics of the oxygen evolution reaction (OER). Substituting thermodynamically advantageous small molecule oxidation reactions for OER can significantly improve energy conversion efficiency. Studying the in-depth reaction mechanism of complex substrates is necessary due to their elemental composition. This review focuses on the electrooxidation mechanism of different substrate molecules, such as ethanol, urea, and hydrazine, and introduces design ideas and strategies for high-performance electrocatalysts in relation to reaction path selectivity. The challenges in achieving industrial transformation in this field are also discussed.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Physical
B. B. Xiao, L. Yang, H. Y. Liu, X. B. Jiang, B. Aleksandr, E. H. Song, Q. Jiang
Summary: The study systematically investigates the oxygen reduction reaction and oxygen evolution reaction of graphene materials embedded with TMN4 clusters (TM = Fe, Co, Ni) using density functional theory calculations. It demonstrates that the functionalization of graphene can dramatically alter the activity and stability of TMN4 clusters, offering new insights into the design of bifunctional oxygen electrodes.
APPLIED SURFACE SCIENCE
(2021)
Article
Chemistry, Multidisciplinary
Mikalai A. Artsiusheuski, Rene Verel, Jeroen A. van Bokhoven, Vitaly L. Sushkevich
Summary: Copper(II)-containing mordenite can activate C-H bonds in C1-C3 alkanes, and the functionalization of ethane and propane shows remarkable differences compared to methane. Ethane and propane react with CuMOR to form ethylene and propylene, while methane predominantly yields methanol and dimethyl ether. The reaction mechanisms differ significantly for each alkane, with the oxidative dehydrogenation being the primary pathway for ethane and propane, and oxidative hydroxylation for methane.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)