Heterogenized Pyridine-Substituted Cobalt(II) Phthalocyanine Yields Reduction of CO2 by Tuning the Electron Affinity of the Co Center

De Riccardis, Alberto; Lee, Michelle; Kazantsev, Roman V.; Garza, Alejandro J.; Zeng, Guosong; Larson, David M.; Clark, Ezra L.; Lobaccaro, Peter; Burroughs, Paul W. W.; Bloise, Ermelinda; Ager, Joel W.; Bell, Alexis T.; Head-Gordon, Martin; Mele, Giuseppe; Toma, Francesca M.

doi:10.1021/acsami.9b18924

Title: Heterogenized Pyridine-Substituted Cobalt(II) Phthalocyanine Yields Reduction of CO2 by Tuning the Electron Affinity of the Co Center

Journal Article · 23 January 2020 · ACS Applied Materials and Interfaces

DOI: https://doi.org/10.1021/acsami.9b18924 · OSTI ID:1646845

De Riccardis, Alberto ^[1];

^[2]; Kazantsev, Roman V. ^[3]; Garza, Alejandro J. ^[3]; Zeng, Guosong ^[3]; Larson, David M. ^[3]; Clark, Ezra L. ^[4]; Lobaccaro, Peter ^[3]; Burroughs, Paul W. W. ^[3]; Bloise, Ermelinda ^[5];

^[3];

^[4];

^[5];

^[3]

Univ. of Salento (Italy); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis (JCAP)
Cornell Univ., Ithaca, NY (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis (JCAP)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis (JCAP); Univ. of California, Berkeley, CA (United States)
Univ. of Salento (Italy)

Conversion of CO₂ to reduced products is a promising route to alleviate irreversible climate change. In this paper we report the synthesis of a Co-based phthalocyanine with pyridine moieties (CoPc-Pyr), which is supported on a carbon electrode and shows Faradaic efficiency ~90% for CO at 490 mV of overpotential (-0.6 V vs reversible hydrogen electrode (RHE)). In addition, its catalytic activity at -0.7 V versus RHE surpasses other Co-based molecular and metal-organic framework catalysts for CO₂ reduction at this bias. Density functional theory calculations show that pyridine moieties enhance CO₂ adsorption and electron affinity of the Co center by an inductive effect, thus lowering the overpotential necessary for CO₂ conversion. Our study shows that CoPc-Pyr reduces CO₂ at lower overpotential and with higher activity than noble metal electrodes, such as silver.

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Research Organization:: California Inst. of Technology (CalTech), Pasadena, CA (United States). Joint Center for Artificial Photosynthesis (JCAP); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences & Biosciences Division (SC-22.1)

Grant/Contract Number:: AC02-05CH11231; SC0004993

OSTI ID:: 1646845

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 5 Vol. 12; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Heterogenized Pyridine-Substituted Cobalt(II) Phthalocyanine Yields Reduction of CO2 by Tuning the Electron Affinity of the Co Center

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