Activating Bi p-orbitals in Dispersed Clusters of Amorphous BiOx for Electrocatalytic Nitrogen Reduction

Jianxin Kang; Xiangyu Chen; Rutong Si; Xiang Gao; Shuo Zhang; Gilberto Teobaldi; Annabella Selloni; Li-Min Liu; Lin Guo

doi:10.1002/anie.202217428

Activating Bi p-orbitals in Dispersed Clusters of Amorphous BiO_x for Electrocatalytic Nitrogen Reduction

Angew Chem Int Ed Engl. 2023 Apr 3;62(15):e202217428. doi: 10.1002/anie.202217428. Epub 2023 Feb 28.

Authors

Jianxin Kang¹, Xiangyu Chen¹, Rutong Si^{2

3}, Xiang Gao⁴, Shuo Zhang⁵, Gilberto Teobaldi^{6

7}, Annabella Selloni⁸, Li-Min Liu³, Lin Guo¹

Affiliations

¹ School of Chemistry, Beijing Advanced Innovation Center for Biomedical Engineering, Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology, Beihang University, Beijing, 100191, China.
² Beijing Computational Science Research Center, Beijing, 100193, China.
³ School of Physics, Beihang University, Beijing, 100191, China.
⁴ Center for High Pressure Science and Technology Advanced Research, Beijing, 100190, China.
⁵ Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201204, China.
⁶ Scientific Computing Department, STFC UKRI, Rutherford Appleton Laboratory, Didcot, OX11 0QX, UK.
⁷ School of Chemistry, University of Southampton Highfield, Southampton, SO17 1BJ, UK.
⁸ Department of Chemistry, Princeton University, Princeton, NJ 08544, USA.

PMID: 36775803
DOI: 10.1002/anie.202217428

Abstract

Catalytic strategies based on main group metals are significantly less advanced than those of transition metal catalysis, leaving untapped areas of potentially fruitful research. We here demonstrate an effective approach for the modulation of Bi 6p energy levels during the construction of atomically dispersed clusters of amorphous BiO_x . Bi oxidation state is proposed to strongly affects the nitrogen fixation activity, with the half-occupied p_z orbitals of the Bi²⁺ ions being highly efficient toward electron injection into the inert N₂ molecule. With sufficient catalytic sites to adsorb and activate N₂ , the bonding between N₂ and catalyst is able to be in situ identified. The catalyst shows an outstanding Faraday efficiency (≈30 %) and high yield (≈113 μg h^-1 mg^-1 _cat ) in NH₃ production, outperforming most of the existing catalysts in aqueous solution. These results lay the basis for developing the potential of p-block elements for catalysis of multi-electron reactions.

Keywords: Amorphous Nanomaterial; Electrocatalysis; In Situ Identification; Nitrogen Fixation; p-Orbitals.

Abstract

Grants and funding