Abstract
We report the synthesis and electrochemical properties of freebase tetraphenyltetrabenzoporphyrin and its complexes of Zn(ii), Co(ii), Ni(ii), Cu(ii) and Sn(iv) towards electrochemical reduction of carbon dioxide (CO2). Based on cyclic voltammetry, it is shown that central metals significantly affect the electrocatalytic performance in the reduction of CO2 in terms of reduction potential and catalytic current enhancement. At an applied potential of -1.90 V vs. an Ag/AgCl quasi reference electrode for 20 h, the electrocatalytic reduction of CO2 realized by Zn(ii)- and Cu(ii)-tetraphenyltetrabenzoporphyrins to carbon monoxide resulted in faradaic efficiencies of around 48% and 33%, respectively.
Highlights
Rapid global economic and population growth has led to an increase in fuel consumption in industrial, transportation, commercial and residential sectors
Synthesis of the benzoporphyrins started from previously reported demetallation of Cu-TPBP32 by sulfuric acid at room temperature for 30 min, resulting in TPBP in 81% yield (Scheme 1).[33]
N2-saturated conditions, TPBP, Non-commercial compounds meso-tetraphenyltetrabenzoporphyrinatonickel(II) (Ni-TPBP), Zn-TPBP and compounds meso-tetraphenyltetrabenzoporphyrinatonickel(II) (Ni-TPBP)32 and meso-tetraphenyltetrabenzoporphyrinatocopper(II) (Cu-TPBP) exhibited a signi cant current enhancement, while Co-TPBP and Sn-TPBP gave only a slight increase in the peak current when CO2 was introduced into the solution
Summary
Rapid global economic and population growth has led to an increase in fuel consumption in industrial, transportation, commercial and residential sectors. A greenhouse relevant product from fuel combustion processes is carbon dioxide (CO2). The electrochemical reduction processes of CO2 using catalysts have attracted much attention because they require lower overpotential, compared to the direct reduction of CO2, and provide higher product selectivity.[1,2,3,4,5] As economically friendly substitutes for precious-metal catalysts, organometallic electrocatalysts have become popular.[6,7,8,9,10,11,12,13] Among such materials, porphyrin derivatives have been investigated continuously as potential electrochemical catalysts for the reduction of CO2.14,15 The great advantages of porphyrin compounds regarding this. Constant-potential electrolysis of the electrolyte solution under CO2-saturated conditions in the absence of the catalyst for 20 h did not yield any CO2 reduction product
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