Changli Wang, Zunhang Lv, Yarong Liu, Lu Dai, Rui Liu, Caiting Sun, Weiyi Liu, Xiao Feng, Wenxiu Yang, Bo Wang
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引用次数: 0
摘要
二维功能多孔框架为研究电催化二氧化碳还原反应(CO2RR)过程中的结构-活性关系提供了一个平台。然而,要突破位点构型(典型的 M-O4 或 M-N4 单元)和产物选择性(常见的 CO2 到 CO 的转化)方面的关键限制仍然存在挑战。在此,我们构建了一种具有平面不对称 N/O 混合配位 Cu-N1O3 单元的新型二维金属有机框架 (MOF),命名为 BIT-119。当应用于 CO2RR 时,BIT-119 可在流动池中实现 CO2 到 C2 的转化,C2 部分电流密度范围为 36.9 到 165.0 mA cm-2。与典型的对称 Cu-O4 单元相比,不对称 Cu-N1O3 单元导致了局部电子结构的重新分布,从而调节了几种关键吸附剂的吸附强度和后续催化选择性。通过实验和理论分析,Cu-N1O3 位点可同时耦合*C1 物种的顶式(在 Cu 位点上)和桥式(在 Cu-N 位点上)吸附,从而实现 CO2 到 C2 的转化。这项研究拓宽了二维功能多孔框架上可行的 C-C 耦合机制。
Asymmetric Cu-N1O3 Sites Coupling Atop-type and Bridge-type Adsorbed *C1 for Electrocatalytic CO2-to-C2 Conversion.
2D functional porous frameworks offer a platform for studying the structure-activity relationships during electrocatalytic CO2 reduction reaction (CO2RR). Yet challenges still exist to breakthrough key limitations on site configuration (typical M-O4 or M-N4 units) and product selectivity (common CO2-to-CO conversion). Herein, a novel 2D metal-organic framework (MOF) with planar asymmetric N/O mixed coordinated Cu-N1O3 unit is constructed, labeled as BIT-119. When applied to CO2RR, BIT-119 could reach a CO2-to-C2 conversion with C2 partial current density ranging from 36.9 to 165.0 mA cm-2 in flow cell. Compared to the typical symmetric Cu-O4 units, asymmetric Cu-N1O3 units lead to the re-distribution of local electron structure, regulating the adsorption strength of several key adsorbates and the following catalytic selectivity. From experimental and theoretical analyses, Cu-N1O3 sites could simultaneously couple the atop-type (on Cu site) and bridge-type (on Cu-N site) adsorption of *C1 species to reach the CO2-to-C2 conversion. This work broadens the feasible C-C coupling mechanism on 2D functional porous frameworks.
期刊介绍:
Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.