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

被引：46

作者：

De Riccardis, Alberto ^{[1
,2
]}

Lee, Michelle ^{[3
,4
]}

Kazantsev, Roman V. ^{[2
,3
]}

Garza, Alejandro J. ^{[2
,3
]}

Zeng, Guosong ^{[2
,3
]}

Larson, David M. ^{[2
]}

Clark, Ezra L. ^{[2
,3
,5
]}

Lobaccaro, Peter ^{[2
,3
,6
]}

Burroughs, Paul W. W. ^{[2
,3
]}

Bloise, Ermelinda ^{[1
]}

Ager, Joel W. ^{[2
,3
,6
]}

Bell, Alexis T. ^{[2
,3
,5
]}

Head-Gordon, Martin ^{[2
,3
,5
]}

Mele, Giuseppe ^{[1
]}

Toma, Francesca M. ^{[2
,3
]}

机构：

[1] Univ Salento, Dept Engn Innovat, I-73100 Lecce, Italy

[2] Lawrence Berkeley Natl Lab, Joint Ctr Artificial Photosynth, Berkeley, CA 94720 USA

[3] Lawrence Berkeley Natl Lab, Chem Sci Div, Berkeley, CA 94720 USA

[4] Cornell Univ, Dept Chem & Chem Biol, Ithaca, NY 14850 USA

[5] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA

[6] Lawrence Berkeley Natl Lab, Mat Sci Div, Berkeley, CA 94720 USA

来源：

ACS APPLIED MATERIALS & INTERFACES | 2020年 / 12卷 / 05期

关键词：

phthalocyanine; CO2; electroreduction; heterogenized catalysis; electronic properties; molecular catalyst; ELECTROCHEMICAL REDUCTION; CARBON-DIOXIDE; PHOTOCHEMICAL REDUCTION; COMPLEXES; PORPHYRINS; OPPORTUNITIES; INSIGHTS; CH4;

D O I：

10.1021/acsami.9b18924

中图分类号：

TB3 [工程材料学];

学科分类号：

0805 ; 080502 ;

摘要：

Conversion of CO2 to reduced products is a promising route to alleviate irreversible climate change. Here 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 similar to 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.

引用

页码：5251 / 5258

页数：8

共 38 条

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