Ju Wen, Bagger Alexander, Hao Guang-Ping, Varela Ana Sofia, Sinev Ilya, Bon Volodymyr, Roldan Cuenya Beatriz, Kaskel Stefan, Rossmeisl Jan, Strasser Peter
Department of Chemistry, Chemical Engineering Division, Technical University Berlin, Berlin, 10623, Germany.
Department of Chemistry, University of Copenhagen, Universitetsparken 5, Copenhagen, 2100, Denmark.
Nat Commun. 2017 Oct 16;8(1):944. doi: 10.1038/s41467-017-01035-z.
Direct electrochemical reduction of CO to fuels and chemicals using renewable electricity has attracted significant attention partly due to the fundamental challenges related to reactivity and selectivity, and partly due to its importance for industrial CO-consuming gas diffusion cathodes. Here, we present advances in the understanding of trends in the CO to CO electrocatalysis of metal- and nitrogen-doped porous carbons containing catalytically active M-N moieties (M = Mn, Fe, Co, Ni, Cu). We investigate their intrinsic catalytic reactivity, CO turnover frequencies, CO faradaic efficiencies and demonstrate that Fe-N-C and especially Ni-N-C catalysts rival Au- and Ag-based catalysts. We model the catalytically active M-N moieties using density functional theory and correlate the theoretical binding energies with the experiments to give reactivity-selectivity descriptors. This gives an atomic-scale mechanistic understanding of potential-dependent CO and hydrocarbon selectivity from the M-N moieties and it provides predictive guidelines for the rational design of selective carbon-based CO reduction catalysts.Inexpensive and selective electrocatalysts for CO reduction hold promise for sustainable fuel production. Here, the authors report N-coordinated, non-noble metal-doped porous carbons as efficient and selective electrocatalysts for CO to CO conversion.
利用可再生电力将一氧化碳直接电化学还原为燃料和化学品，已引起了广泛关注，部分原因是与反应活性和选择性相关的基本挑战，部分原因是其对工业用消耗一氧化碳的气体扩散阴极的重要性。在此，我们展示了在理解含催化活性M-N部分（M = Mn、Fe、Co、Ni、Cu）的金属和氮掺杂多孔碳对一氧化碳到一氧化碳的电催化趋势方面取得的进展。我们研究了它们的固有催化反应活性、一氧化碳周转频率、一氧化碳法拉第效率，并证明Fe-N-C尤其是Ni-N-C催化剂可与金基和银基催化剂相媲美。我们使用密度泛函理论对催化活性M-N部分进行建模，并将理论结合能与实验相关联，以给出反应活性-选择性描述符。这提供了对M-N部分潜在依赖的一氧化碳和烃选择性的原子尺度机理理解，并为选择性碳基一氧化碳还原催化剂的合理设计提供了预测指导。廉价且选择性的一氧化碳还原电催化剂有望实现可持续燃料生产。在此，作者报道了氮配位、非贵金属掺杂的多孔碳作为将一氧化碳转化为一氧化碳的高效且选择性的电催化剂。
