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^*, Habib Md Ahsan, Hai Tao Zhang, David Chukwuma Izuogu, Hitoshi Abe, Hiroyoshi Ohtsu, Tadashi Yamaguchi, Brian K. Breedlove, Alex J.W. Thom, Masahiro Yamashita

^*Corresponding author for this work

School of Advanced Science and Engineering

Research output: Contribution to journal › Article › peer-review

7 Citations (Scopus)

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.

Original language	English
Pages (from-to)	2652-2660
Number of pages	9
Journal	Dalton Transactions
Volume	49
Issue number	8
DOIs	https://doi.org/10.1039/c9dt04817k
Publication status	Published - 2020 Feb 28

ASJC Scopus subject areas

Inorganic Chemistry

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@article{37e568636f2441d88fb87bbba02619e5,

title = "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.",

author = "Takefumi Yoshida and Ahsan, {Habib Md} and Zhang, {Hai Tao} and Izuogu, {David Chukwuma} and Hitoshi Abe and Hiroyoshi Ohtsu and Tadashi Yamaguchi and Breedlove, {Brian K.} and Thom, {Alex J.W.} and Masahiro Yamashita",

note = "Funding Information: Part of the experimental results in this research was obtained using supercomputing resources at Cyberscience Center, Tohoku University. The X-ray absorption fine structure was collected on the NW10A beamline in the Photon Factory of the High Energy Accelerator Research Organization (KEK, Proposal No. 2017P016, 2018G117). M. Yamashita thanks the support by the 111 Project (B18030) from China. We would like to thank Editage for English language editing. Publisher Copyright: This journal is {\textcopyright} 2020 The Royal Society of Chemistry.",

year = "2020",

month = feb,

day = "28",

doi = "10.1039/c9dt04817k",

language = "English",

volume = "49",

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journal = "Dalton Transactions",

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T1 - Ionic-caged heterometallic bismuth-platinum complex exhibiting electrocatalytic CO2 reduction

AU - Yoshida, Takefumi

AU - Ahsan, Habib Md

AU - Zhang, Hai Tao

AU - Izuogu, David Chukwuma

AU - Abe, Hitoshi

AU - Ohtsu, Hiroyoshi

AU - Yamaguchi, Tadashi

AU - Breedlove, Brian K.

AU - Thom, Alex J.W.

AU - Yamashita, Masahiro

N1 - Funding Information: Part of the experimental results in this research was obtained using supercomputing resources at Cyberscience Center, Tohoku University. The X-ray absorption fine structure was collected on the NW10A beamline in the Photon Factory of the High Energy Accelerator Research Organization (KEK, Proposal No. 2017P016, 2018G117). M. Yamashita thanks the support by the 111 Project (B18030) from China. We would like to thank Editage for English language editing. Publisher Copyright: This journal is © 2020 The Royal Society of Chemistry.

PY - 2020/2/28

Y1 - 2020/2/28

N2 - 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.

AB - 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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JO - Dalton Transactions

JF - Dalton Transactions

IS - 8

ER -

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

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