Ionic-caged heterometallic bismuth–platinum complex exhibiting electrocatalytic CO2 reduction. Issue 8 (11th February 2020)

• Record Type: Journal Article
• Authors: Yoshida, Takefumi; Ahsan, Habib Md.; Zhang, Hai-Tao; Izuogu, David Chukwuma; Abe, Hitoshi; Ohtsu, Hiroyoshi; Yamaguchi, Tadashi; Breedlove, Brian K.; Thom, Alex J. W.; Yamashita, Masahiro
• Is Part Of: Dalton transactions. Volume 49:Issue 8(2020)
• Page Start: 2652
• Page End: 2660
• Publication Date: 2020-02-11
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c9dt04817k
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Heterometallic bismuth–platinum complex has strong Bi–Pt bond and ionic cage surrounding Bi ion and exhibits 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.