Huang Jinyan, Yang Ye, Liang Xuexue, Chen Bing, Shen Yue, Chen Yan, Yang Jielian, Yu Yinglin, Huang Fang, He Huibing, Chen Peican, Zhou Liya, Guan Anxiang
School of Chemistry and Chemical Engineering, Guangxi Key Laboratory of Electrochemical Energy Materials, State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures, Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, Guangxi Colleges and Universities Key Laboratory of Applied Chemistry Technology and Resource Development, Guangxi University, Nanning, 530004, China.
Adv Sci (Weinh). 2025 May;12(19):e2417247. doi: 10.1002/advs.202417247. Epub 2025 Mar 26.
Electroreduction of CO to chemical fuels offers a promising strategy for controlling the global carbon balance and addressing the need for the storage of intermittent renewable energy. In this work, it is demonstrated that tuning adjacent active sites enables the selection of different reaction pathways for generating C or C products during the electroreduction of CO. Cu and Cu-Pd alloy catalysts with different atomic ratios are synthesized and investigated to elucidate their different electroreduction selectivities for CO electroreduction. Cu catalyst favors the formation of C products since the neighboring active Cu sites are beneficial for coupling adjacently adsorbed CO and CHO intermediates. Cu alloyed with Pd introduces a blocking effect and increases the intermolecular distance between adjacent adsorbed CO and CHO intermediates. Therefore the selectivity for the CH pathway decreas while the CH pathway is enhanced. Moreover, the existence of adsorbed H species on Pd atoms also played a significant role in boosting CO electroreduction to CH by facilitating the hydrogenation of CO intermediates. This work reveals the key role of H species adsorbed on Pd atoms and the blocking effect between active sites for CH formation, which is helpful for the design of copper-based catalysts for desired products.
将CO电还原为化学燃料为控制全球碳平衡以及满足间歇性可再生能源存储需求提供了一种很有前景的策略。在这项工作中，证明了调节相邻活性位点能够在CO电还原过程中选择不同的反应途径来生成C或C产物。合成并研究了具有不同原子比的Cu和Cu-Pd合金催化剂，以阐明它们对CO电还原的不同电还原选择性。Cu催化剂有利于C产物的形成，因为相邻的活性Cu位点有利于相邻吸附的CO和CHO中间体的偶联。与Pd合金化的Cu引入了一种位阻效应，并增加了相邻吸附的CO和CHO中间体之间的分子间距离。因此，CH途径的选择性降低，而CH途径得到增强。此外，Pd原子上吸附的H物种的存在通过促进CO中间体的氢化，在推动CO电还原为CH方面也发挥了重要作用。这项工作揭示了吸附在Pd原子上的H物种的关键作用以及CH形成过程中活性位点之间的位阻效应，这有助于设计用于生成所需产物的铜基催化剂。
