Sun Yimeng, Tao Lin, Wu Mingjie, Dastan Davoud, Rehman Javed, Li Lixiang, An Baigang
School of Chemical Engineering, University of Science and Technology Liaoning, Anshan 114051, China.
State Key Laboratory of New Textile Materials and Advanced Processing Technologies, Wuhan Textile University, Wuhan 430200, China.
Nanoscale. 2024 May 23;16(20):9791-9801. doi: 10.1039/d4nr01082e.
In recent years, the development of highly active and selective electrocatalysts for the electrochemical reduction of CO to produce CO and formic acid has aroused great interest, and can reduce environmental pollution and greenhouse gas emissions. Due to the high utilization of atoms, atom-dispersed catalysts are widely used in CO reduction reactions (CORRs). Compared with single-atom catalysts (SACs), multi-atom catalysts have more flexible active sites, unique electronic structures and synergistic interatomic interactions, which have great potential in improving the catalytic performance. In this study, we established a single-layer nitrogen-graphene-supported transition metal catalyst (TM-CN) based on density functional theory, facilitating the reduction of CO to CO or HCOOH with single-atom and multi-atomic catalysts. For the first time, the TM-CN monolayer was systematically screened for its catalytic activity with molecular dynamics, density of states, and charge density, confirming the stability of the TM-CN catalyst structure. Furthermore, the Gibbs free energy and electronic structure analysis of 3TM-CN revealed excellent catalytic performance for CO and HCOOH in the CORR with a lower limiting potential. Importantly, this work highlights the moderate adsorption energy of the intermediate on 3TM-CN. It is particularly noteworthy that 3Mo-CN exhibited the best catalytic performance for CO, with a limiting potential () of -0.62 V, while 3Ti-CN showed the best performance for HCOOH, with a corresponding of -0.18 V. Additionally, 3TM-CN significantly inhibited competitive hydrogen evolution reactions. We emphasize the crucial role of the d-band center in determining products, as well as the activity and selectivity of triple-atom catalysts in the CORR. This theoretical research not only advances our understanding of multi-atomic catalysts, but also offers new avenues for promoting sustainable CO conversion.
近年来，用于将CO电化学还原以生成CO和甲酸的高活性和选择性电催化剂的开发引起了极大的兴趣，并且可以减少环境污染和温室气体排放。由于原子利用率高，原子分散催化剂被广泛用于CO还原反应（CORR）。与单原子催化剂（SAC）相比，多原子催化剂具有更灵活的活性位点、独特的电子结构和协同的原子间相互作用，在提高催化性能方面具有巨大潜力。在本研究中，我们基于密度泛函理论建立了一种单层氮石墨烯负载的过渡金属催化剂（TM-CN），促进了单原子和多原子催化剂将CO还原为CO或HCOOH。首次通过分子动力学、态密度和电荷密度对TM-CN单层的催化活性进行了系统筛选，证实了TM-CN催化剂结构的稳定性。此外，对3TM-CN的吉布斯自由能和电子结构分析表明，在CORR中，3TM-CN对CO和HCOOH具有优异的催化性能，且极限电位较低。重要的是，这项工作突出了中间体在3TM-CN上的适度吸附能。特别值得注意的是，3Mo-CN对CO表现出最佳的催化性能，极限电位（）为-0.62 V，而3Ti-CN对HCOOH表现出最佳性能，相应的极限电位为-0.18 V。此外，3TM-CN显著抑制了竞争性析氢反应。我们强调d带中心在决定产物以及三原子催化剂在CORR中的活性和选择性方面的关键作用。这项理论研究不仅推进了我们对多原子催化剂的理解，也为促进可持续的CO转化提供了新途径。
