Chen Ye, Fan Zhanxi, Wang Jiong, Ling Chongyi, Niu Wenxin, Huang Zhiqi, Liu Guigao, Chen Bo, Lai Zhuangchai, Liu Xiaozhi, Li Bing, Zong Yun, Gu Lin, Wang Jinlan, Wang Xin, Zhang Hua
Center for Programmable Materials, School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798, Singapore.
Department of Chemistry, City University of Hong Kong, Hong Kong, China.
J Am Chem Soc. 2020 Jul 22;142(29):12760-12766. doi: 10.1021/jacs.0c04981. Epub 2020 Jul 7.
The crystal phase of metal nanocatalysts significantly affects their catalytic performance. Cu-based nanomaterials are unique electrocatalysts for CO reduction reaction (CORR) to produce high-value hydrocarbons. However, studies to date are limited to the conventional face-centered cubic () Cu. Here, we report a crystal phase-dependent catalytic behavior of Cu, after the successful synthesis of high-purity 4H Cu and heterophase 4H/ Cu using the 4H and 4H/ Au as templates, respectively. Remarkably, the obtained unconventional crystal structures of Cu exhibit enhanced overall activity and higher ethylene (CH) selectivity in CORR compared to the Cu. Density functional theory calculations suggest that the 4H phase and 4H/ interface of Cu favor the CH formation pathway compared to the Cu, leading to the crystal phase-dependent CH selectivity. This study demonstrates the importance of crystal phase engineering of metal nanocatalysts for electrocatalytic reactions, offering a new strategy to prepare novel catalysts with unconventional phases for various applications.
金属纳米催化剂的晶相对其催化性能有显著影响。铜基纳米材料是用于将一氧化碳还原反应（CORR）以生产高价值碳氢化合物的独特电催化剂。然而，迄今为止的研究仅限于传统的面心立方（）铜。在此，我们分别以4H和4H/Au为模板成功合成了高纯度4H铜和异相4H/铜之后，报告了铜的晶相依赖性催化行为。值得注意的是，与铜相比，所获得的非常规铜晶体结构在CORR中表现出增强的整体活性和更高的乙烯（CH）选择性。密度泛函理论计算表明，与铜相比，铜的4H相和4H/界面有利于CH形成途径，导致晶相依赖性CH选择性。这项研究证明了金属纳米催化剂晶相工程在电催化反应中的重要性，为制备具有非常规相的新型催化剂以用于各种应用提供了一种新策略。
