Electrochemical C–N Bond Formation within Boron Imidazolate Cages Featuring Single Copper Sites

Gerke, Carter S.; Xu, Yuting; Yang, Yuwei; Foley, Gregory D.; Zhang, Briana; Shi, Ethan; Bedford, Nicholas M.; Che, Fanglin; Thoi, V. Sara

doi:10.1021/jacs.3c08359

Title: Electrochemical C–N Bond Formation within Boron Imidazolate Cages Featuring Single Copper Sites

Journal Article · 26 November 2023 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.3c08359 · OSTI ID:2345068

Gerke, Carter S. ^[1]; Xu, Yuting ^[2]; Yang, Yuwei ^[3]; Foley, Gregory D. ^[4]; Zhang, Briana ^[4]; Shi, Ethan ^[4];

^[3];

^[2];

^[4]

Johns Hopkins Univ., Baltimore, MD (United States); Johns Hopkins University
Univ. of Massachusetts, Lowell, MA (United States)
Univ. of New South Wales, Sydney, NSW (Australia)
Johns Hopkins Univ., Baltimore, MD (United States)

Electrocatalysis expands the ability to generate industrially relevant chemicals locally and on-demand with intermittent renewable energy, thereby improving grid resiliency and reducing supply logistics. Herein, we report the feasibility of using molecular copper boron-imidazolate cages, BIF-29(Cu), to enable coupling between the electroreduction reaction of CO₂ (CO₂RR) with NO₃^– reduction (NO₃RR) to produce urea with high selectivity of 68.5% and activity of 424 μA cm^–2. Remarkably, BIF-29(Cu) is among the most selective systems for this multistep C–N coupling to-date, despite possessing isolated single-metal sites. The mechanism for C–N bond formation was probed with a combination of electrochemical analysis, in situ spectroscopy, and atomic-scale simulations. We found that NO₃RR and CO₂RR occur in tandem at separate copper sites with the most favorable C–N coupling pathway following the condensation between *CO and NH₂OH to produce urea. In conclusion, this work highlights the utility of supramolecular metal–organic cages with atomically discrete active sites to enable highly efficient coupling reactions.

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Research Organization:: Johns Hopkins Univ., Baltimore, MD (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); US Department of the Navy, Office of Naval Research (ONR)

Grant/Contract Number:: SC0021955; AC02-06CH11357

OSTI ID:: 2345068

Alternate ID(s):: OSTI ID: 2371804; OSTI ID: 2427276

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 48 Vol. 145; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Electrochemical C–N Bond Formation within Boron Imidazolate Cages Featuring Single Copper Sites

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