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

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 Bi 2+ ions being highly efficient toward electron injection into the inert N 2 molecule. With sufficient catalytic sites to adsorb and activate N 2 , the bonding between N 2 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 NH 3 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.