Wu Zexing, Wu Hengbo, Cai Weiquan, Wen Zhenhai, Jia Baohua, Wang Lei, Jin Wei, Ma Tianyi
State Key Laboratory Base of Eco-chemical Engineering, College of Chemistry and Molecular Engineering, Qingdao University of Science & Technology, 53 Zhengzhou Road, Qingdao, 266042, P. R. China.
State Key Laboratory of Pollution Control and Resources Reuse, School of Environmental Science and Engineering, Tongji University, 1239 Siping Road, Shanghai, 200092, China.
Angew Chem Int Ed Engl. 2021 May 25;60(22):12554-12559. doi: 10.1002/anie.202102832. Epub 2021 Apr 26.
Electrochemical reduction of CO (CO RR) into valuable hydrocarbons is appealing in alleviating the excessive CO level. We present the very first utilization of metallic bismuth-tin (Bi-Sn) aerogel for CO RR with selective HCOOH production. A non-precious bimetallic aerogel of Bi-Sn is readily prepared at ambient temperature, which exhibits 3D morphology with interconnected channels, abundant interfaces and a hydrophilic surface. Superior to Bi and Sn, the Bi-Sn aerogel exposes more active sites and it has favorable mass transfer properties, which endow it with a high FE of 93.9 %. Moreover, the Bi-Sn aerogel achieves a FE of ca. 90 % that was maintained for 10 h in a flow battery. In situ ATR-FTIR measurements confirmed that the formation of *HCOO is the rate-determining step toward formic acid generation. DFT demonstrated the coexistence of Bi and Sn optimized the energy barrier for the production of HCOOH, thereby improving the catalytic activity.
将一氧化碳电化学还原（CO RR）为有价值的碳氢化合物，对于缓解过量的一氧化碳水平具有吸引力。我们首次利用金属铋锡（Bi-Sn）气凝胶进行CO RR以选择性生产甲酸。一种非贵金属双金属Bi-Sn气凝胶在室温下很容易制备，它呈现出具有相互连接通道、丰富界面和亲水表面的三维形态。与Bi和Sn相比，Bi-Sn气凝胶暴露了更多的活性位点，并且具有良好的传质性能，这使其具有93.9%的高法拉第效率（FE）。此外，Bi-Sn气凝胶在液流电池中实现了约90%的FE，并保持了10小时。原位ATR-FTIR测量证实，*HCOO的形成是生成甲酸的速率决定步骤。密度泛函理论（DFT）表明，Bi和Sn的共存优化了生成HCOOH的能垒，从而提高了催化活性。
