Phosphorus‐Modulated Cobalt Nanosheets with Confined Metal Defects for Enhanced Kinetics in Nitrite‐Glycerol Co‐Electrolysis
Zhangjing Yu, Kai Chen, Yun Tong, Cong Lin, Xiaonan Zheng, Pengzuo Chen
Abstract
Abstract Exploring advanced electrocatalysts for the paired electrolysis of the nitrite reduction reaction (NO 2 RR) and glycerol oxidation reaction (GOR) is of significance for the co‐production of value‐added chemicals, but remains a great challenge. Herein, a novel phosphorus‐modulated cobalt nanosheet with low‐coordination metallic sites (P 3 ‐Co) is developed as an advanced electrocatalyst for efficient nitrite‐glycerol co‐electrolysis. The membrane electrode assembled NO 2 RR‖GOR electrolyzer realizes promising operation performance with high Faradaic efficiencies and yields of NH 3 (98.2%, 29.3 mg h −1 cm −2 ) and formate (93.4%, 85.7 mg h −1 cm −2 ) at 1.5 V, as well as superior catalytic stability over a long‐term electrolysis of 300 h at 100 mA cm −2 . The in situ characterizations and theoretical calculations are employed to reveal the origin of intrinsic high activity of P 3 ‐Co, suggesting that the metal Co defects and P‐modulation are beneficial to optimizing the electronic structure and the adsorption/activation barriers of N‐containing intermediates for the accelerated conversion kinetics of both GOR and NO 2 RR. This work offers guidance for exploiting highly‐active electrocatalysts for the generation of high‐value‐added products.