Monolayer Molecular Functionalization Enabled by Acid–Base Interaction for High-Performance Photochemical CO2 Reduction

Shang, Bo; Zhao, Fengyi; Choi, Chungseok; Jia, Xiaofan; Pauly, Magnus; Wu, Yueshen; Tao, Zixu; Zhong, Yiren; Harmon, Nia; Maggard, Paul A.; Lian, Tianquan; Hazari, Nilay; Wang, Hailiang

doi:10.1021/acsenergylett.2c01147

Monolayer Molecular Functionalization Enabled by Acid–Base Interaction for High-Performance Photochemical CO₂ Reduction

Journal Article · Wed Jun 08 04:00:00 EDT 2022 · ACS Energy Letters

DOI:https://doi.org/10.1021/acsenergylett.2c01147· OSTI ID:1896501

Shang, Bo ^[1]; Zhao, Fengyi ^[2]; Choi, Chungseok ^[3]; ^[4]; Pauly, Magnus ^[5]; Wu, Yueshen ^[3]; ^[3]; Zhong, Yiren ^[3]; Harmon, Nia ^[3]; Maggard, Paul A. ^[5]; ^[2]; ^[4]; ^[3]

Yale Univ., New Haven, CT (United States); Yale Univ., West Haven, CT (United States); Yale University
Emory Univ., Atlanta, GA (United States)
Yale Univ., New Haven, CT (United States); Yale Univ., West Haven, CT (United States)
Yale Univ., New Haven, CT (United States)
North Carolina State Univ., Raleigh, NC (United States)

We report the development of a hybrid catalyst consisting of carbon nitride (CN_x) and cobalt phthalocyanine tetracarboxylic acid (CoPc-COOH), which converts CO₂ to CO with high reaction rate (1067 μmol/g·h) and high selectivity (over 98%), under simulated solar irradiation. The carboxylic acid substituents on the phthalocyanine ligands play a critical role as they bind to the amine groups of CN_x to enable nearly ideal monolayer coverage of the molecular co-catalyst on the semiconductor surface and promote catalytic activity from the molecular complex. Specifically, the CN_x/CoPc-COOH hybrid material achieves a reaction rate 16 times higher than a CN_x material containing unsubstituted CoPc molecules. We further show that activation and deactivation of the CN_x/CoPc-COOH composite, which are associated with the reduction and decomposition of CoPc-COOH, respectively, both proceed at a nearly constant rate regardless of the CO₂ reduction reaction rate. Here, the decoupling of charge carrier injection and CO₂ reduction catalysis has important mechanistic implications for future performance optimization and materials design of photocatalysts for CO₂ reduction.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of North Carolina, Chapel Hill, NC (United States)

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

Grant/Contract Number:: SC0021173

OSTI ID:: 1896501

Journal Information:: ACS Energy Letters, Journal Name: ACS Energy Letters Journal Issue: 7 Vol. 7; ISSN 2380-8195

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Monolayer Molecular Functionalization Enabled by Acid–Base Interaction for High-Performance Photochemical CO2 Reduction

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