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

• Published in: Angewandte Chemie International Edition 2024-11, p.e202418637
• Main Authors: Yao, Shuang, Jiang, Shi-Yi, Wang, Bai-Fan, Yin, Hua-Qing, Xiang, Xue-Yan, Tang, Zhao, An, Chang-Hua, Lu, Tong-Bu, Zhang, Zhi-Ming
• Format: Article
• Language: English
• ISSN: 1521-3773; 1521-3773
• DOI: 10.1002/anie.202418637

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.