ABSTRACT The rapidly increasing global demand for urea, coupled with the energy‐intensive and environmentally detrimental Bosch‐Meiser process, underscores the urgent need for sustainable production alternatives. Electrocatalytic (EC), photocatalytic (PC), and photoelectrocatalytic (PEC) pathways have emerged as promising green strategies to synthesize urea under ambient conditions by coupling carbon dioxide reduction with nitrogen activation. Central to the success of these approaches is the rational design of functional materials that can simultaneously promote C─N coupling and suppress competing reactions. In this review, recent advances in catalyst and system engineering, including size regulation, morphology engineering, alloying, defect engineering, crystal facet control, surface tailoring, heterojunction construction, and local environment regulation, are systematically summarized. We highlight that while universal design principles exist, the requirements to achieve optimal performance differ significantly among EC, PC, and PEC systems. In addition, prevailing mechanistic hypotheses, state‐of‐the‐art catalytic materials, and verification methodologies are critically evaluated before outlining key challenges and opportunities for future research. This work provides a timely and comprehensive overview that deepens understanding of sustainable urea synthesis and offers guidance for the rational design of next‐generation catalytic systems.
Zhao et al. (Sat,) studied this question.