Aqueous Photoelectrochemical CO 2 Reduction to CO and Methanol over a Silicon Photocathode Functionalized with a Cobalt Phthalocyanine Molecular Catalyst

Shang, Bo; Rooney, Conor L.; Gallagher, David J.; Wang, Bernie T.; Krayev, Andrey; Shema, Hadar; Leitner, Oliver; Harmon, Nia J.; Xiao, Langqiu; Sheehan, Colton; Bottum, Samuel R.; Gross, Elad; Cahoon, James F.; Mallouk, Thomas E.; Wang, Hailiang

doi:10.1002/ange.202215213

Title: Aqueous Photoelectrochemical CO ₂ Reduction to CO and Methanol over a Silicon Photocathode Functionalized with a Cobalt Phthalocyanine Molecular Catalyst

Journal Article · 19 December 2022 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202215213 · OSTI ID:1905917

Shang, Bo ^[1]; Rooney, Conor L. ^[1]; Gallagher, David J. ^[1]; Wang, Bernie T. ^[1]; Krayev, Andrey ^[2]; Shema, Hadar ^[3]; Leitner, Oliver ^[1]; Harmon, Nia J. ^[1]; Xiao, Langqiu ^[4]; Sheehan, Colton ^[4]; Bottum, Samuel R. ^[5]; Gross, Elad ^[3]; Cahoon, James F. ^[5]; Mallouk, Thomas E. ^[4];

^[1]

Department of Chemistry Yale University New Haven CT 06520 USA, Energy Sciences Institute Yale University West Haven CT 06516 USA
HORIBA Instruments Inc. 359 Bel Marin Keys Blvd, Suite 18 Novato CA 94949 USA
Institute of Chemistry and Center for Nanoscience and Nanotechnology Hebrew University of Jerusalem Jerusalem 91904 Israel
Department of Chemistry University of Pennsylvania Philadelphia PA 19104 USA
Department of Chemistry University of North Carolina at Chapel Hill Chapel Hill NC 27599-3290 USA

Abstract We report a precious‐metal‐free molecular catalyst‐based photocathode that is active for aqueous CO ₂ reduction to CO and methanol. The photoelectrode is composed of cobalt phthalocyanine molecules anchored on graphene oxide which is integrated via a (3‐aminopropyl)triethoxysilane linker to p‐type silicon protected by a thin film of titanium dioxide. The photocathode reduces CO ₂ to CO with high selectivity at potentials as mild as 0 V versus the reversible hydrogen electrode (vs RHE). Methanol production is observed at an onset potential of −0.36 V vs RHE, and reaches a peak turnover frequency of 0.18 s ⁻¹ . To date, this is the only molecular catalyst‐based photoelectrode that is active for the six‐electron reduction of CO ₂ to methanol. This work puts forth a strategy for interfacing molecular catalysts to p‐type semiconductors and demonstrates state‐of‐the‐art performance for photoelectrochemical CO ₂ reduction to CO and methanol.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0021173

OSTI ID:: 1905917

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 4 Vol. 135; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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