Dae-Hyun Nam Bushuyev, Oleksandr S. Li, Jun De Luna, Phil Seifitokaldani, Ali Cao-Thang Dinh de Arquer, F. Pelayo Garcia Wang, Yuhang Liang, Zhiqin Proppe, Andrew H. Tan, Chih Shan Todorovic, Petar Shekhah, Osama Gabardo, Christine M. Jo, Jea Woong Choi, Jongmin Choi, Min-Jae Baek, Se-Woong Kim, Junghwan Sinton, David Kelley, Shana O. Eddaoudi, Mohamed Sargent, Edward H. 2024-01-19T22:01:05Z 2024-01-19T22:01:05Z 2022-01-25 2018-09 0002-7863 https://pubs.kist.re.kr/handle/201004/120945 The electrochemical carbon dioxide reduction reaction (CO2RR) produces diverse chemical species. Cu clusters with a judiciously controlled surface coordination number (CN) provide active sites that simultaneously optimize selectivity, activity, and efficiency for CO2RR. Here we report a strategy involving metal-organic framework (MOF)-regulated Cu cluster formation that shifts CO2 electroreduction toward multiple-carbon product generation. Specifically, we promoted undercoordinated sites during the formation of Cu clusters by controlling the structure of the Cu dimer, the precursor for Cu clusters. We distorted the symmetric paddle-wheel Cu dimer secondary building block of HKUST-1 to an asymmetric motif by separating adjacent benzene tricarboxylate moieties using thermal treatment. By varying materials processing conditions, we modulated the asymmetric local atomic structure, oxidation state and bonding strain of Cu dimers. Using electron paramagnetic resonance (EPR) and in situ X-ray absorption spectroscopy (XAS) experiments, we observed the formation of Cu clusters with low CN from distorted Cu dimers in HKUST-1 during CO2 electroreduction. These exhibited 45% C2H4 faradaic efficiency (FE), a record for MOF-derived Cu cluster catalysts. A structure-activity relationship was established wherein the tuning of the Cu-Cu CN in Cu clusters determines the CO2RR selectivity. English AMER CHEMICAL SOC Metal-Organic Frameworks Mediate Cu Coordination for Selective CO2 Electroreduction Article 10.1021/jacs.8b06407 1 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.140, no.36, pp.11378 - 11386 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 140 36 11378 11386 N scie scopus 000444793400036 Chemistry, Multidisciplinary Chemistry Article CARBON-DIOXIDE REDUCTION ELECTROCATALYTIC REDUCTION ELECTROCHEMICAL REDUCTION THIN-FILMS COPPER CATALYSTS NANOPARTICLES MORPHOLOGY HKUST-1 HYDROCARBONS