Reticular Electronic Tuning of Porphyrin Active Sites in Covalent Organic Frameworks for Electrocatalytic Carbon Dioxide Reduction

Diercks, Christian S.; Lin, Song; Kornienko, Nikolay; Kapustin, Eugene A.; Nichols, Eva M.; Zhu, Chenhui; Zhao, Yingbo; Chang, Christopher J.; Yaghi, Omar M.

doi:10.1021/jacs.7b11940

Reticular Electronic Tuning of Porphyrin Active Sites in Covalent Organic Frameworks for Electrocatalytic Carbon Dioxide Reduction

Journal Article · Fri Dec 29 00:00:00 EST 2017 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.7b11940· OSTI ID:1480785

^[1]; ^[2]; Kornienko, Nikolay ^[3]; ^[1]; Nichols, Eva M. ^[1]; Zhu, Chenhui ^[4]; ^[1]; ^[1]; ^[1]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Cornell Univ., Ithaca, NY (United States)
Univ. of California, Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Here, the electronic character of porphyrin active sites for electrocatalytic reduction of CO₂ to CO in a two-dimensional covalent organic framework (COF) was tuned by modification of the reticular structure. Efficient charge transport along the COF backbone promotes electronic connectivity between remote functional groups and the active sites and enables the modulation of the catalytic properties of the system. A series of oriented thin films of these COFs was found to reduce CO₂ to CO at low overpotential (550 mV) with high selectivity (faradaic efficiency of 87%) and at high current densities (65 mA/mg), a performance well beyond related molecular catalysts in regard to selectivity and efficiency. The catalysts are stable for more than 12 h without any loss in reactivity. X-ray absorption measurements on the cobalt L-edge for the modified COFs enable correlations between the inductive effects of the appended functionality and the electronic character of the reticulated molecular active sites.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231; SC0001015

OSTI ID:: 1480785

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 3 Vol. 140; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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