Fuqing Yu, Guangyao Zhang, Minxing Shu, Hongming Wang
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引用次数: 0
摘要
利用可再生能源进行电催化二氧化碳还原(ECR)催化剂的研究在能源转换研究中尤为重要,特别是在可行的碳氢化合物生产中。本研究利用密度泛函理论计算筛选了一系列非放射性镧系二维金属有机框架 (MOF),以确定其在 ECR 中的产物选择性。在理论筛选的基础上,我们重点研究了一种基于镥(Lu)的导电 MOF(Lu-HHTP),它在甲烷(CH4)生产中的法拉第效率约为 77%,并能在 -1.1 V 对 RHE 的电压下保持 -280 mA/cm2 的稳定电流密度。原位电化学实验和材料表征证明,在催化 CO2 还原过程中,Lu 位点具有很高的配位稳定性和结构可恢复性,这归功于 Lu 的 f 轨道与配体 O 的 π* 轨道之间的重叠,以及 Lu 的 f 轨道与 CO 的 π* 轨道之间形成的反键轨道有助于提高 CH₄ 的选择性和降低电位。本研究利用稀土 MOF 型材料,提供了一种解决低传导性和稳定稀土材料的新方法,从而建立了线性吸附 *CO 转化为碳氢化合物的理论框架。
f-π* Back Bonding Orbital Induced by Lutetium-Based Conducting MOF Promotes Highly Selective CO 2 to CH 4 at Low Potential
The research on electrocatalytic carbon dioxide reduction (ECR) catalysts using renewable energy is particularly crucial in energy conversion studies, especially for viable hydrocarbon production. This study employs density functional theory calculations to screen a series of non-radioactive lanthanide two-dimensional metal-organic frameworks (MOFs) for product selectivity in ECR. Based on theoretical screening, our focus is on a lutetium (Lu)-based conducting MOF (Lu-HHTP), which exhibits a Faradaic efficiency of approximately 77% for methane (CH4) production and maintains a stable current density of -280 mA/cm2 at -1.1 V vs. RHE. In situ electrochemical experiments and material characterization demonstrate that the Lu sites possess high coordination stability and structural recoverability during catalytic CO2 reduction, attributed to the overlap between Lu's f-orbitals and the π*-orbitals of the ligand O, and the formation of back bonding orbitals between the f-orbitals of Lu and the π* orbitals of CO contribute increasing CH₄ selectivity and lowering the potential. This study leverages rare-earth MOF-type materials, offering a novel approach to addressing low conductivity and stabilizing rare-earth materials, thereby establishing a theoretical framework for the conversion of linearly adsorbed *CO into hydrocarbons.
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.