Urea Electrosynthesis Accelerated by Theoretical Simulations

Abstract Urea is not only a primary fertilizer in modern agriculture but also a crucial raw material for the chemical industry. In the past hundred years, the prevailing industrial synthesis of urea heavily relies on the Bosch–Meiser process to couple NH 3 and CO 2 under harsh conditions, resulting in high carbon emissions and energy consumption. The conversion of carbon‐ and nitrogen‐containing species into urea through electrochemical reactions under ambient conditions represents a sustainable strategy. Despite the increasing reports on urea electrosynthesis, a comprehensive review that delves into a profound, atomic‐level comprehension of the fundamental reaction mechanisms is currently absent. In this Perspective, recent advancements in electrochemical urea synthesis from CO 2 /CO and various nitrogenous species (i.e., N 2 , NO x − , and NO) under ambient conditions are presented, with special emphasis on theoretical understanding of the C─N coupling reaction mechanisms. Several key strategies to facilitate the C─N coupling are then pinpointed, which not only enhance their applicability in practical experiments but also highlight the significant progress achieved in this field. At the end, the major obstacles and potential opportunities in advancing urea electrosynthesis accelerated by theoretical simulations and in situ techniques are discussed. This review is hoped to act as a roadmap to ignite fresh insights and inspiration for the development of electrocatalytic urea synthesis.