Bismuth Single Atoms Resulting from Transformation of Metal-Organic Frameworks and Their Use as Electrocatalysts for CO2 Reduction

Erhuan Zhang; Tao Wang; Ke Yu; Jia Liu; Wenxing Chen; Ang Li; Hongpan Rong; Rui Lin; Shufang Ji; Xusheng Zheng; Yu Wang; Lirong Zheng; Chen Chen; Dingsheng Wang; Jiatao Zhang; Yadong Li

doi:10.1021/jacs.9b08259

Bismuth Single Atoms Resulting from Transformation of Metal-Organic Frameworks and Their Use as Electrocatalysts for CO₂ Reduction

J Am Chem Soc. 2019 Oct 23;141(42):16569-16573. doi: 10.1021/jacs.9b08259. Epub 2019 Oct 9.

Authors

Erhuan Zhang¹, Tao Wang², Ke Yu³, Jia Liu¹, Wenxing Chen¹, Ang Li⁴, Hongpan Rong¹, Rui Lin³, Shufang Ji³, Xusheng Zheng⁵, Yu Wang⁶, Lirong Zheng⁷, Chen Chen³, Dingsheng Wang³, Jiatao Zhang¹, Yadong Li³

Affiliations

¹ Beijing Key Laboratory of Construction-Tailorable Advanced Functional Materials and Green Applications, Experimental Center of Advanced Materials, School of Materials Science & Engineering , Beijing Institute of Technology , Beijing 100081 , China.
² SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering , Stanford University , Stanford , California 94305 , United States.
³ Department of Chemistry , Tsinghua University , Beijing 100084 , China.
⁴ Beijing Key Laboratory of Microstructure and Property of Advanced Materials , Beijing University of Technology , Beijing 100124 , China.
⁵ National Synchrotron Radiation Laboratory , University of Science and Technology of China , Hefei 230029 , China.
⁶ Shanghai Synchrotron Radiation Facilities, Shanghai Institute of Applied Physics , Chinese Academy of Science , Shanghai 201204 , China.
⁷ Beijing Synchrotron Radiation Facility, Institute of High Energy Physics , Chinese Academy of Sciences , Beijing 100049 , China.

PMID: 31588748
DOI: 10.1021/jacs.9b08259

Abstract

The electrocatalytic reduction reaction of CO₂ (CO₂RR) is a promising strategy to promote the global carbon balance and combat global climate change. Herein, exclusive Bi-N₄ sites on porous carbon networks can be achieved through thermal decomposition of a bismuth-based metal-organic framework (Bi-MOF) and dicyandiamide (DCD) for CO₂RR. Interestingly, in situ environmental transmission electron microscopy (ETEM) analysis not only directly shows the reduction from Bi-MOF into Bi nanoparticles (NPs) but also exhibits subsequent atomization of Bi NPs assisted by the NH₃ released from the decomposition of DCD. Our catalyst exhibits high intrinsic CO₂ reduction activity for CO conversion, with a high Faradaic efficiency (FE_CO up to 97%) and high turnover frequency of 5535 h^-1 at a low overpotential of 0.39 V versus reversible hydrogen electrode. Further experiments and density functional theory results demonstrate that the single-atom Bi-N₄ site is the dominating active center simultaneously for CO₂ activation and the rapid formation of key intermediate COOH* with a low free energy barrier.