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

Abstract Urea electrosynthesis from flue gas and NO 3 − 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 BiVO 4 nanocluster by pre‐incorporating [V 10 O 28 ] 6− into NH 2 ‐MIL‐101‐Al (MIL) framework. The resulting BiVO 4 @MIL‐n can efficiently drive co‐reduction of NO 3 − and CO 2 to urea. A record urea yield of 63.4 mmol h −1 g cat −1 was achieved under CO 2 /O 2 mixed gases (33 % O 2 ) atmosphere, and comparable performance can be obtained by feeding flue gas, demonstrating remarkable O 2 /N 2 tolerance and potential feasibility for urea production under operating conditions. Systematic investigations revealed that MIL carrier with ‐NH 2 group can enrich CO 2 , and BiVO 4 nanocluster can reduce both NO 3 − and CO 2 to ensure efficient urea synthesis even in the presence of O 2 . This work demonstrates the key role of in situ growth of BiVO 4 nanocluster within a NH 2 ‐framework in facilitating urea electrosynthesis with exceptional tolerance to O 2 /N 2 .