Electrocatalytic C-N coupling from carbon dioxide and nitrate provides a sustainable alternative to the conventional energy-intensive urea synthetic protocol, enabling wastes upgrading and value-added products synthesis. The design of efficient and stable electrocatalysts is vital to promote the development of electrocatalytic urea synthesis. In this work, copper phthalocyanine (CuPc) is adopted as a modeling catalyst toward urea synthesis owing to its accurate and adjustable active configurations. Combining experimental and theoretical studies, it can be observed that the intramolecular Cu-N coordination can be strengthened with optimization in electronic structure by amino substitution (CuPc-Amino) and the electrochemically induced demetallation is efficiently suppressed, serving as the origination of its excellent activity and stability. Compared to that of CuPc (the maximum urea yield rate of 39.9 ± 1.9 mmol h⁻¹ g⁻¹ with 67.4% of decay in 10 test cycles), a high rate of 103.1 ± 5.3 mmol h⁻¹ g⁻¹ and remarkable catalytic durability have been achieved on CuPc-Amino. Isotope-labelling operando electrochemical spectroscopy measurements are performed to disclose reaction mechanisms and validate the C-N coupling processes. This work proposes a unique scheme for the rational design of molecular electrocatalysts for urea synthesis.

Enhanced A-site electronegativity in pyrochlore oxides mitigates RuO ₆ octahedron distortion to boost the activity and stability of the acidic OER.

The electrooxidation of the alcohol and aldehyde molecules instead of water coupled with H₂ production has been proven to be effective for producing high-value fine chemicals under alkaline conditions. It is also noteworthy that under acidic conditions, the stability of non-noble metal water oxidation catalysts remains a great challenge due to the lattice oxygen mechanism. Hence, we coupled the biomass-derived glucose oxidation for high-value D-glucaric acid (GRA) with ultra-durable hydrogen in acid solution over a Yb-MnO₂ catalyst. The Mn³⁺ regulated by Yb atoms doped in MnO₂ can effectively optimize the adsorption and desorption processes of the alcohol and aldehyde group and improve the intrinsic activity but cannot for H₂O. The catalyst exhibited extremely high activity and stability after 50 h for glucose oxidation, inhibiting the lattice oxygen process and MnO⁴⁻ formation, while the activity was quickly lost within 0.5 h for water oxidation. Density functional theory (DFT) calculations further demonstrated that glucose oxidation reaction proceeds preferentially due to the oxidation of aldehyde group with lower adsorption-free energy (−0.4 eV) than water (ΔG > 0 eV), avoiding the lattice oxygen mechanism. This work suggests that biomass-derived glucose oxidation not only provides a cost-effective approach for high-value chemicals, but also shows an extremely potential as an alternative to acidic oxygen evolution reaction (OER) for ultradurable H₂ production.

Perovskite oxides have been established as a promising kind of catalyst for alkaline oxygen evolution reactions (OER), because of their regulated non-precious metal components. However, the surface lattice is amorphous during the reaction, which gradually decreases the intrinsic activity and stability of catalysts. Herein, the precisely control tungsten atoms substituted perovskite oxides (Pr_0.5Ba_0.5Co_1-xW_xO₃-_δ) nanowires were developed by electrostatic spinning. The activity and Tafel slope were both dependent on the W content in a volcano-like fashion, and the optimized Pr_0.5Ba_0.5Co_0.8W_0.2O₃-_δ exhibits both excellent activity and superior stability compared with other reported perovskite oxides. Due to the outermost vacant orbitals of W⁶⁺, the electronic structure of cobalt sites could be efficiently optimized. Meanwhile, the stronger W-O bond could also significantly improve the stability of latticed oxide atoms to impede the generation of surface amorphous layers, which shows good application value in alkaline water splitting.

The electrocatalytic C−N coupling of the greenhouse gas carbon dioxide and N₂/nitrate presents a promising approach to the conventional Bosch-Meiser method for environmentally friendly urea synthesis. Two-dimensional (2D) materials exhibit significant advantages in electrocatalysis due to their unique ultrathin structure and physicochemical properties as a platform Substrates for atomic modification. Here, this review focuses on the Surface functionalization of 2D electrocatalysts (Oxides, Sulfide, MOFs, Mxene, et al.) through heteroatom doping, defect engineering, and Surface molecule functionalization to enhance the catalyst conductivity, lower the reaction barrier, and improve its cycling stability. Then, we provide a Summary of surface modified 2D electrocatalysts (the single-atom site, synergistic effects of dual-active-sites, et al.) towards C−N coupling reaction of N₂ /NO_x and CO₂ for urea synthesis, analyze the catalysis origins through combination of DFT calculations, which are widely adopted to offer a precise description of the electronic structure of catalysts and the relationship between catalytic activity and catalysts. The reaction mechanisms researches reveals the optimization of reaction pathways by the dynamic evolution of the catalyst surface, providing a new direction for the design of adaptive catalytic materials.Finally, challenges and perspectives in the field are presented.