Tuning N‐Species Adsorption/Desorption Equilibrium by Ni 1 Au n ‐SrTiO 3 for Artificial Urea Photosynthesis

ABSTRACT Inefficient generation of N‐related intermediates, stemming from inert adsorption/photoactivation of N 2 , has hindered efficient artificial photosynthesis of urea from N 2 , CO 2 , and H 2 O. To overcome this bottleneck, we herein propose a strategy for modulating the adsorption/desorption equilibrium of N‐related species using precisely designed bimetallic Ni 1 Au n active sites supported on a strontium titanate (NiAu‐STO) semiconductor photocatalyst. This strategy significantly enhances N 2 adsorption/activation and effective generation of N‐related intermediates to facilitate C–N coupling for the photocatalytic urea synthesis, affording a considerable urea production rate of 1333.63 µg g cat. −1 , with successful crystallization of a collectible solid‐phase urea product. Furthermore, we developed a novel reaction‐temperature programmed desorption‐mass spectrometry tandem monitoring system to elucidate the adsorption behavior of N 2 , which can clarify the adsorption behavior of N 2 and confirm the formation of critical N‐related intermediates (e.g., *NH 2 ) on the NiAu‐STO photocatalyst. In addition, in situ Raman spectroscopy results further validated the formation of a distinctive C–N coupling intermediate (*NH 2 COO – ) on the photocatalyst surface, providing mechanistic insights into urea photosynthesis from N 2 , CO 2 , and H 2 O.