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†

Takefumi Yoshida,

‡*^a Habib Md. Ahsan,

‡*^ab Hai-Tao Zhang,^a David Chukwuma Izuogu,

^acd Hitoshi Abe,

^ef Hiroyoshi Ohtsu,

^g Tadashi Yamaguchi,

^h Brian K. Breedlove,

^a Alex J. W. Thom^d and Masahiro Yamashita*^aij

Author affiliations

* Corresponding authors

^a Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aza-aoba, Aramaki, Sendai 980-8578, Japan
E-mail: takefumi.yoshida.b7@tohoku.ac.jp

^b Chemistry Discipline, Khulna University, Khulna-9208, Bangladesh

^c Department of Pure & Industrial Chemistry, University of Nigeria, Nsukka, Nigeria

^d Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, UK

^e Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK), 1-1 Oho, Tsukuba, Ibaraki 305-0801, Japan

^f 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

^g Department of Chemistry, School of Science, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8550, Japan

^h Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo 169-8555, Japan

ⁱ WPI-Advanced Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Sendai 980-8577, Japan

^j School of Materials Science and Engineering, Nankai University, Tianjin 300350, China

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.

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

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