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Enhanced Electrocatalytic Activity of a Zinc Porphyrin for CO 2 Reduction: Cooperative Effects of Triazole Units in the Second Coordination Sphere
Author(s) -
Lashgari Amir,
Williams Caroline K.,
Glover Jenna L.,
Wu Yueshen,
Chai Jingchao,
Jiang Jianbing “Jimmy”
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202002813
Subject(s) - electrocatalyst , coordination sphere , porphyrin , chemistry , carbon monoxide , triazole , electrochemistry , coordination complex , catalysis , intramolecular force , dimethylformamide , inorganic chemistry , combinatorial chemistry , photochemistry , stereochemistry , organic chemistry , molecule , electrode , solvent , metal
The control of the second coordination sphere in a coordination complex plays an important role in improving catalytic efficiency. Herein, we report a zinc porphyrin complex ZnPor8T with multiple flexible triazole units comprising the second coordination sphere, as an electrocatalyst for the highly selective electrochemical reduction of carbon dioxide (CO 2 ) to carbon monoxide (CO). This electrocatalyst converted CO 2 to CO with a Faradaic efficiency of 99 % and a current density of −6.2 mA cm −2 at −2.4 V vs. Fc/Fc + in N , N ‐dimethylformamide using water as the proton source. Structure‐function relationship studies were carried out on ZnPor8T analogs containing different numbers of triazole units and distinct triazole geometries; these unveiled that the triazole units function cooperatively to stabilize the CO 2 ‐catalyst adduct in order to facilitate intramolecular proton transfer. Our findings demonstrate that incorporating triazole units that function in a cooperative manner is a versatile strategy to enhance the activity of electrocatalytic CO 2 conversion.