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受限的C2吸附物取向使CO能够电还原为乙酸盐
作者:小柯机器人 发布时间:2023/5/6 14:57:48


华中科技大学庞元杰研究团队报道了受限的C2吸附物取向使CO能够电还原为乙酸盐。相关研究成果于2023年5月3日发表在国际顶尖学术期刊《自然》。

当使用低碳电力供电时,二氧化碳和一氧化碳的电还原反应为化学制造的脱碳提供了途径。如今,铜(Cu)被依赖于碳-碳偶联,在这种偶联中,它产生了十多种C2+化学物质的混合物,其中实现对单一主要C2+产物的选择性是一个长期的挑战。乙酸盐就是这样一种C2化合物,正走向庞大但化石衍生的乙酸市场。

该文中,研究人员试图将低浓度的Cu原子分散在主体金属中,以有利于烯酮化学中间体的稳定,这些中间体以单齿的方式结合到电催化剂上。研究人员在Ag稀释(约占Cu的1原子%)合金材料中合成Cu。研究发现,在10atm压力下,在高*CO覆盖率下,从CO进行乙酸盐电合成具有高度选择性。操作X射线吸收光谱表明,原位生成的由<4个原子组成的Cu簇作为活性位点。研究人员报告了相对于从一氧化碳电还原反应中观察到的所有其他产物,乙酸盐的选择性为12:1,与之前的最佳报告相比增加了一个数量级。

结合催化剂设计和反应器工程,实现了91%的CO到乙酸盐的法拉第效率,并报告了在820小时的操作时间内85%的法拉第效率。高选择性有利于所有碳基电化学转化的能源效率和下游分离,突出了最大化法拉第效率对单一C2+产物的重要性。

附:英文原文

Title: Constrained C2 adsorbate orientation enables CO-to-acetate electroreduction

Author: Jin, Jian, Wicks, Joshua, Min, Qiuhong, Li, Jun, Hu, Yongfeng, Ma, Jingyuan, Wang, Yu, Jiang, Zheng, Xu, Yi, Lu, Ruihu, Si, Gangzheng, Papangelakis, Panagiotis, Shakouri, Mohsen, Xiao, Qunfeng, Ou, Pengfei, Wang, Xue, Chen, Zhu, Zhang, Wei, Yu, Kesong, Song, Jiayang, Jiang, Xiaohang, Qiu, Peng, Lou, Yuanhao, Wu, Dan, Mao, Yu, Ozden, Adnan, Wang, Chundong, Xia, Bao Yu, Hu, Xiaobing, Dravid, Vinayak P., Yiu, Yun-Mui, Sham, Tsun-Kong, Wang, Ziyun, Sinton, David, Mai, Liqiang, Sargent, Edward H., Pang, Yuanjie

Issue&Volume: 2023-05-03

Abstract: The carbon dioxide and carbon monoxide electroreduction reactions, when powered using low-carbon electricity, offer pathways to the decarbonization of chemical manufacture1,2. Copper (Cu) is relied on today for carbon–carbon coupling, in which it produces mixtures of more than ten C2+ chemicals3,4,5,6: a long-standing challenge lies in achieving selectivity to a single principal C2+ product7,8,9. Acetate is one such C2 compound on the path to the large but fossil-derived acetic acid market. Here we pursued dispersing a low concentration of Cu atoms in a host metal to favour the stabilization of ketenes10—chemical intermediates that are bound in monodentate fashion to the electrocatalyst. We synthesize Cu-in-Ag dilute (about 1 atomic per cent of Cu) alloy materials that we find to be highly selective for acetate electrosynthesis from CO at high *CO coverage, implemented at 10atm pressure. Operando X-ray absorption spectroscopy indicates in situ-generated Cu clusters consisting of <4 atoms as active sites. We report a 12:1 ratio, an order of magnitude increase compared to the best previous reports, in the selectivity for acetate relative to all other products observed from the carbon monoxide electroreduction reaction. Combining catalyst design and reactor engineering, we achieve a CO-to-acetate Faradaic efficiency of 91% and report a Faradaic efficiency of 85% with an 820-h operating time. High selectivity benefits energy efficiency and downstream separation across all carbon-based electrochemical transformations, highlighting the importance of maximizing the Faradaic efficiency towards a single C2+ product11.

DOI: 10.1038/s41586-023-05918-8

Source: https://www.nature.com/articles/s41586-023-05918-8

期刊信息
Nature:《自然》,创刊于1869年。隶属于施普林格·自然出版集团,最新IF:69.504
官方网址:http://www.nature.com/