Dynamic Reconstitution Between Copper Single Atoms and Clusters for Electrocatalytic Urea Synthesis

Abstract

Electrocatalytic CN coupling between carbon dioxide and nitrate has emerged to meet the comprehensive demands of carbon footprint closing, valorization of waste, and sustainable manufacture of urea. However, the identification of catalytic active sites and the design of efficient electrocatalysts remain a challenge. Herein, the synthesis of urea catalyzed by copper single atoms decorated on a CeO2 support (denoted as Cu1–CeO2) is reported. The catalyst exhibits an average urea yield rate of 52.84 mmol h−1 gcat.−1 at −1.6 V versus reversible hydrogen electrode. Operando X‐ray absorption spectra demonstrate the reconstitution of copper single atoms (Cu1) to clusters (Cu4) during electrolysis. These electrochemically reconstituted Cu4 clusters are real active sites for electrocatalytic urea synthesis. Favorable CN coupling reactions and urea formation on Cu4 are validated using operando synchrotron‐radiation Fourier transform infrared spectroscopy and theoretical calculations. Dynamic and reversible transformations of clusters to single‐atom configurations occur when the applied potential is switched to an open‐circuit potential, endowing the catalyst with superior structural and electrochemical stabilities.

Universal synthesis of rare earth-doped FeP nanorod arrays for the hydrogen evolution reaction

“…[30][31][32] More recently, rare earth (RE) elements such as La, Ce, Nb, Eu, Gd, and Yb have been proven as efficient promoters for a number of electrocatalytic reactions. [33][34][35][36][37][38][39][40] The unique 4fsubshell electron configuration, flexible valence states, and strong spin-orbital effect of RE elements can offer great potential for tuning the electronic structures and improving the electrocatalytic performance of various TM-based catalysts. [41][42][43][44] For example, Sun et al found that the combination of Yb 2 O 3 and Ni can reduce the energy barrier of water dissociation and enlarge the active-site density, which greatly enhances the HER performance of Ni.…”

Sustainable and High‐Rate Electrosynthesis of Nitrogen Fertilizer

“…When we looked further into the configurations of the intermediate *NH 2 CO adsorbed on catalysts, the −OMe group in Cu−SP−OMe demonstrates an increased O−C bond angle of 41.37° and a shorter O−H distance of 5.185 Å due to the stronger interaction with the NH 2 CO intermediate (0.981 eV) (Figure 4d). [26c] Therefore, the promoted urea production on Cu−SP−OMe may be attributable to the stronger interaction between Cu−SP−OMe and intermediates during C−N coupling and lowered energy barriers in certain steps in the pathway toward urea formation.…”

Recent Advances in Electrocatalytic Nitrate Reduction to Ammonia: Mechanism Insight and Catalyst Design

“…In addition, the recently reported electrocatalytic C–N coupling with coelectrolysis of nitrate and carbon dioxide achieved electrosynthesis of urea in oxygen vacancy (OV)-enriched CeO 2 , and *NO intermediate species insertion into OV is beneficial to couple with *CO . The electrosynthesis of urea will make it possible to simultaneously close the carbon footprint, sustain nitrogen neutrality, and reform the urea industry, − although it is still at an early stage of development and production rates are very low. With more attention in this field, the electrosynthesis of urea will have a momentous breakthrough and become an essential branch of nitrogen neutrality.…”