Issue 8, 2020

Ionic-caged heterometallic bismuth–platinum complex exhibiting electrocatalytic CO2 reduction

Abstract

An air-stable heterometallic Bi–Pt complex with the formula [BiPt(SAc)5]n (1; SAc = thioacetate) was synthesized. The crystal structure, natural bond orbital (NBO) and local orbital locator (LOL) analyses, localized orbital bonding analysis (LOBA), and X-ray absorption fine structure (XAFS) measurements were used to confirm the existence of Bi–Pt bonding and an ionic cage of O atoms surrounding the Bi ion. From the cyclic voltammetry (CV) and controlled potential electrolysis (CPE) experiments, 1 in tetrahydrofuran reduced CO2 to CO, with a faradaic efficiency (FE) of 92% and a turnover frequency (TOF) of 8 s−1 after 30 min of CPE at −0.79 V vs. NHE. The proposed mechanism includes an energetically favored pathway via the ionic cage, which is supported by the results of DFT calculations and reflectance infrared spectroelectrochemistry data.

Graphical abstract: Ionic-caged heterometallic bismuth–platinum complex exhibiting electrocatalytic CO2 reduction

Associated articles

Supplementary files

Article information

Article type
Paper
Submitted
19 Dec 2019
Accepted
05 Feb 2020
First published
06 Feb 2020

Dalton Trans., 2020,49, 2652-2660

Ionic-caged heterometallic bismuth–platinum complex exhibiting electrocatalytic CO2 reduction

T. Yoshida, H. Md. Ahsan, H. Zhang, D. C. Izuogu, H. Abe, H. Ohtsu, T. Yamaguchi, B. K. Breedlove, A. J. W. Thom and M. Yamashita, Dalton Trans., 2020, 49, 2652 DOI: 10.1039/C9DT04817K

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