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

Takefumi Yoshida; Habib Md Ahsan; Hai-Tao Zhang; David Chukwuma Izuogu; Hitoshi Abe; Hiroyoshi Ohtsu; Tadashi Yamaguchi; Brian K Breedlove; Alex J W Thom; Masahiro Yamashita

doi:10.1039/c9dt04817k

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

Dalton Trans. 2020 Feb 25;49(8):2652-2660. doi: 10.1039/c9dt04817k.

Authors

Affiliations

¹ Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aza-aoba, Aramaki, Sendai 980-8578, Japan. takefumi.yoshida.b7@tohoku.ac.jp.
² Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aza-aoba, Aramaki, Sendai 980-8578, Japan. takefumi.yoshida.b7@tohoku.ac.jp and Chemistry Discipline, Khulna University, Khulna-9208, Bangladesh.
³ Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aza-aoba, Aramaki, Sendai 980-8578, Japan. takefumi.yoshida.b7@tohoku.ac.jp and Department of Pure & Industrial Chemistry, University of Nigeria, 410001, Nsukka, Nigeria and Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK.
⁴ Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK), 1-1 Oho, Tsukuba, Ibaraki 305-0801, Japan and Department of Materials Structure Science, School of High Energy Accelerator Science, SOKENDAI (the Graduate University for Advanced Studies), 1-1 Oho, Tsukuba, Ibaraki 305-0801, Japan.
⁵ Department of Chemistry, School of Science, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8550, Japan.
⁶ Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo 169-8555, Japan.
⁷ Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK.
⁸ Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aza-aoba, Aramaki, Sendai 980-8578, Japan. takefumi.yoshida.b7@tohoku.ac.jp and WPI-Advanced Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Sendai 980-8577, Japan and School of Materials Science and Engineering, Nankai University, Tianjin 300350, China.

PMID: 32043108
DOI: 10.1039/c9dt04817k

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.