Polyoxometalate Confined Synthesis of BiVO4 Nanocluster for Urea Production with Remarkable O2/N2 Tolerance

Urea electrosynthesis from flue gas and NO3‐ under operating conditions represents a promising alternative technology to traditional energy‐intensive industrial process. Herein, we explore a polyoxometalate confined synthesis strategy to prepare ultrafine BiVO4 nanocluster by pre‐incorporating [V10O28]6‐ into NH2‐MIL‐101‐Al (MIL) framework. The resulting BiVO4@MIL‐n can efficiently drive co‐reduction of NO3‐ and CO2 to urea. A record urea yield of 63.4 mmol h‐1 gcat‐1 was achieved under CO2/O2 mixed gases (33% O2) atmosphere, and comparable performance can be obtained by feeding flue gas, demonstrating remarkable O2/N2 tolerance and potential feasibility for urea production under operating conditions. Systematic investigations revealed that MIL carrier with ‐NH2 group can enrich CO2, and BiVO4 nanocluster can reduce both NO3‐ and CO2 to ensure efficient urea synthesis even in the presence of O2. This work demonstrates the key role of in situ growth of BiVO4 nanocluster within a NH2‐framework in facilitating urea electrosynthesis with exceptional tolerance to O2/N2.