Activating Bi p‐orbitals in Dispersed Clusters of Amorphous BiOx for Electrocatalytic Nitrogen Reduction. Issue 15 (28th February 2023)

• Record Type: Journal Article
• Authors: Kang, Jianxin; Chen, Xiangyu; Si, Rutong; Gao, Xiang; Zhang, Shuo; Teobaldi, Gilberto; Selloni, Annabella; Liu, Li‐Min; Guo, Lin
• Is Part Of: Angewandte Chemie international edition. Volume 62:Issue 15(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2023-02-28
• Subjects: Amorphous Nanomaterial -- Electrocatalysis -- In Situ Identification -- Nitrogen Fixation -- p-Orbitals; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202217428
• Languages: English
• ISSNs: 1433-7851

Abstract

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 pz orbitals of the Bi 2+ 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. Abstract : Combining first‐principles calculations and in situ electrochemical conversion experiments, we propose a novel and effective approach to modify the 6p ‐orbitals of bismuth by exploiting the properties of atomically dispersed amorphous clusters. In contrast to transition metals, Bi exhibits superior p‐ orbital based catalytic activity and selectivity for nitrogen fixation by transferring electrons from the half‐occupied pz into the inert N2 orbital.