TY - JOUR
T1 - Metal-Organic Frameworks for Electrocatalytic Reduction of Carbon Dioxide
AU - Kornienko, Nikolay
AU - Zhao, Yingbo
AU - Kley, Christopher S.
AU - Zhu, Chenhui
AU - Kim, Dohyung
AU - Lin, Song
AU - Chang, Christopher J.
AU - Yaghi, Omar M.
AU - Yang, Peidong
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/11/11
Y1 - 2015/11/11
N2 - A key challenge in the field of electrochemical carbon dioxide reduction is the design of catalytic materials featuring high product selectivity, stability, and a composition of earth-abundant elements. In this work, we introduce thin films of nanosized metal-organic frameworks (MOFs) as atomically defined and nanoscopic materials that function as catalysts for the efficient and selective reduction of carbon dioxide to carbon monoxide in aqueous electrolytes. Detailed examination of a cobalt-porphyrin MOF, Al2(OH)2TCPP-Co (TCPP-H2 = 4,4′,4″,4″-(porphyrin-5,10,15,20-tetrayl)tetrabenzoate) revealed a selectivity for CO production in excess of 76% and stability over 7 h with a per-site turnover number (TON) of 1400. In situ spectroelectrochemical measurements provided insights into the cobalt oxidation state during the course of reaction and showed that the majority of catalytic centers in this MOF are redox-accessible where Co(II) is reduced to Co(I) during catalysis.
AB - A key challenge in the field of electrochemical carbon dioxide reduction is the design of catalytic materials featuring high product selectivity, stability, and a composition of earth-abundant elements. In this work, we introduce thin films of nanosized metal-organic frameworks (MOFs) as atomically defined and nanoscopic materials that function as catalysts for the efficient and selective reduction of carbon dioxide to carbon monoxide in aqueous electrolytes. Detailed examination of a cobalt-porphyrin MOF, Al2(OH)2TCPP-Co (TCPP-H2 = 4,4′,4″,4″-(porphyrin-5,10,15,20-tetrayl)tetrabenzoate) revealed a selectivity for CO production in excess of 76% and stability over 7 h with a per-site turnover number (TON) of 1400. In situ spectroelectrochemical measurements provided insights into the cobalt oxidation state during the course of reaction and showed that the majority of catalytic centers in this MOF are redox-accessible where Co(II) is reduced to Co(I) during catalysis.
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U2 - 10.1021/jacs.5b08212
DO - 10.1021/jacs.5b08212
M3 - Article
C2 - 26509213
AN - SCOPUS:84947436493
SN - 0002-7863
VL - 137
SP - 14129
EP - 14135
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 44
ER -