Yang Hengpan, Wu Yu, Li Guodong, Lin Qing, Hu Qi, Zhang Qianling, Liu Jianhong, He Chuanxin
Shenzhen Key Laboratory for Functional Polymer, College of Chemistry and Environmental Engineering , Shenzhen University , Shenzhen , Guangdong 518060 , China.
Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemical Physics , University of Science and Technology of China , Hefei , Anhui 230026 , China.
J Am Chem Soc. 2019 Aug 14;141(32):12717-12723. doi: 10.1021/jacs.9b04907. Epub 2019 Aug 2.
Electrocatalytic reduction reaction of CO (CORR) is an effective way to mitigate energy and environmental issues. However, very limited catalysts are capable of converting CO resources into high-value products such as hydrocarbons or alcohols. Herein, we first propose a facile strategy for the large-scale synthesis of isolated Cu decorated through-hole carbon nanofibers (CuSAs/TCNFs). This CuSAs/TCNFs membrane has excellent mechanical properties and can be directly used as cathode for CORR, which could generate nearly pure methanol with 44% Faradaic efficiency in liquid phase. The self-supporting and through-hole structure of CuSAs/TCNFs greatly reduces the embedded metal atoms and produces abundant efficient Cu single atoms, which could actually participate in CORR, eventually causing -93 mA cm partial current density for C1 products and more than 50 h stability in aqueous solution. According to DFT calculations, Cu single atoms possess a relatively higher binding energy for *CO intermediate. Therefore, *CO could be further reduced to products like methanol, instead of being easily released from the catalyst surface as CO product. This report may benefit the design of efficient and high-yield single-atom catalysts for other electrocatalytic reactions.
CO的电催化还原反应（CORR）是缓解能源和环境问题的有效途径。然而，能够将CO资源转化为碳氢化合物或醇类等高价值产物的催化剂非常有限。在此，我们首次提出了一种简便的策略，用于大规模合成孤立铜修饰的通孔碳纳米纤维（CuSAs/TCNFs）。这种CuSAs/TCNFs膜具有优异的机械性能，可直接用作CORR的阴极，在液相中能以44%的法拉第效率生成近乎纯的甲醇。CuSAs/TCNFs的自支撑和通孔结构极大地减少了嵌入的金属原子，并产生了大量高效的铜单原子，这些单原子实际上可以参与CORR，最终在水溶液中产生-93 mA cm的C1产物分电流密度和超过50 h的稳定性。根据密度泛函理论（DFT）计算，铜单原子对*CO中间体具有相对较高的结合能。因此，*CO可以进一步还原为甲醇等产物，而不是像CO产物那样容易从催化剂表面释放。本报告可能有助于设计用于其他电催化反应的高效高产单原子催化剂。
