Few-Atom Copper Catalyst for the Electrochemical Reduction of CO to Acetate: Synergetic Catalysis between Neighboring Cu Atoms
Few-Atom Copper Catalyst for the Electrochemical Reduction of CO to Acetate: Synergetic Catalysis between Neighboring Cu Atoms
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少原子铜催化剂用于 CO 电化学还原为乙酸：相邻铜原子之间的协同催化
DOI：
10.31635/ccschem.022.202201910
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发表时间：
2022-06
期刊：
影响因子：
11.2
通讯作者：
Lele Duan
中科院分区：
文献类型：
--
作者：
Weifeng Rong;Haiyuan Zou;Sha Tan;Enyuan Hu;Fan Li;Chao Tang;Hao Dai;Shuting Wei;Yongfei Ji;Lele Duan
单原子催化剂（SACs）因其对各种反应具有优异的催化性能而受到越来越多的关注。然而，单原子催化剂的性能往往因缺乏相邻的金属中心进行协同催化而受到限制。在此，我们发现石墨炔（GDY）上的少原子催化剂（FAC）中相邻铜原子之间的协同作用，相对于铜单原子催化剂，在一氧化碳电还原反应中极大地提高了乙酸盐的生成量。在1.0 M氢氧化钾电解液中，这种铜少原子催化剂在相对于可逆氢电极-0.8 V的电压下，展现出53.8±1.5%的乙酸盐法拉第效率、液态产物高达97 wt%的超高相对纯度以及超过23小时连续电解的出色稳定性。理论研究表明，限制在石墨炔每个孔隙中的两个相邻金属原子之间的位点间催化作用，通过CH₂CO*的逐步加氢或H₂O与CH₂CO*的直接反应，促进了乙酸的形成。我们的研究证明了铜少原子催化剂在促进一氧化碳选择性电还原生成乙酸盐方面具有前所未有的协同催化作用。
Single-atom catalysts (SACs) are gaining increasing recognition because of their superior catalytic properties for various reactions. However, the performance of SACs is often limited by the lack of neighboring metal centers to cooperate in catalysis. Herein, a synergetic interaction between neighboring Cu atoms of a few-atom catalyst (FAC) on graphdiyne (GDY) is found to greatly enhance the production of acetate in the CO electroreduction reaction relative to Cu SACs. In a 1.0 M KOH electrolyte, this Cu FAC exhibits an acetate Faradaic efficiency of 53.8 ± 1.5%, an ultrahigh relative purity of up to 97 wt % for liquid products, and excellent stability over 23 h continuous electrolysis at –0.8 V versus reversible hydrogen electrode. Theoretical studies suggest that the intersite catalytic communication between two neighboring metal atoms confined in each pore of GDY facilitates the formation of acetic acid through either stepwise hydrogenation of CH2CO* or the direct reaction of H2O with CH2CO*. Our study demonstrates the unprecedented synergetic catalysis of Cu FAC in promoting the selective CO electroreduction toward acetate production.