Title: Metal–Organic Frameworks for Electrocatalytic Reduction of Carbon Dioxide

Journal Article · · Journal of the American Chemical Society
 [1];  [1];  [1];  [2];  [3];  [4];  [5];  [6];  [7]
  1. Univ. of California, Berkeley, CA (United States). Department of Chemistry
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  3. Univ. of California, Berkeley, CA (United States). Department of Materials Science and Engineering
  4. Univ. of California, Berkeley, CA (United States). Department of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  5. Univ. of California, Berkeley, CA (United States). Department of Chemistry, Howard Hughes Medical Institute and Department of Molecular and Cell Biology; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  6. Univ. of California, Berkeley, CA (United States). Department of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; King Abdulaziz City of Science and Technology, Riyadh (Saudi Arabia); Kavli Energy Nanosciences Institute, Berkeley, CA (United States)
  7. Univ. of California, Berkeley, CA (United States). Department of Chemistry and Department of Materials Science and Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Kavli Energy Nanosciences Institute, Berkeley, CA (United States)
+ Show Author Affiliations

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. Here, 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. Finally, 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.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1480697
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 44 Vol. 137; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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