Electrocatalytic nitrate reduction (eNO₃⁻RR) is widely recognized as sustainable green ammonia production strategy. However, the complex adsorption–activation–hydrogenation behavior of multiple nitrogen-oxygen intermediates and the intrinsic mismatch in proton-coupled electron transfer kinetics severely hinder the NH₃ yield. Herein, a structurally engineered FeCo-MOF electrocatalyst featuring an asymmetric Co−O−Fe center was constructed via competitive coordination. The unique electronic orbital distribution in the Co−O−Fe bimetallic center promotes O-mediated charge transfer from Co to Fe. This charge redistribution induces enhanced electronic localization and asymmetry within the Co−O−Fe unit, thereby facilitating the activation and reduction of nitrogen-oxygen intermediates. Notably, in this asymmetric electronic configuration, the Co site enables efficient electron provisioning and promotes water dissociation to generate active hydrogen (H_ads) species, ensuring well-matched proton-coupled electron transfer kinetics and accelerating the rapid conversion of the key *NO intermediate on electron-enriched Fe sites. Theoretical calculations further demonstrate that the asymmetric Co−O−Fe motif significantly lowers the thermodynamic barrier of *NO → *NOH step. The catalyst delivers a NH₃ production rate of 0.653 mmol cm⁻² h⁻¹ (1306 mmol g_cat⁻¹ h⁻¹) with a near-unity Faradaic efficiency of 99.8%. This study provides comprehensive insights into optimizing proton-coupled electron transfer dynamics and elucidating structure-performance relationships for advanced green-ammonia electrocatalysis.

Electrocatalysis for C–N coupling reactions (EcnRR) plays a crucial role in the synthesis of various organic molecules. However, the C–N coupling process is inherently complex and kinetically sluggish. Single atom catalysts (SACs), with their high atomic efficiency, tunable structures, and remarkable catalytic activity, exhibit exceptional performance and hold great promise for C–N coupling reactions. The design of SACs requires a deep understanding of the reaction mechanisms, particularly the dynamic evolution of multi-component reactions. This necessitates systematic studies of multi-species coupling mechanisms to move beyond traditional trial-and-error approaches. This review elucidates the activation mechanisms of carbon- and nitrogen-containing molecules, providing fundamental insights into the SACs-mediated electrocatalytic C–N coupling process. Notably, the core focus lies in proposing novel design principles for SACs systems tailored for C–N coupling, based on theoretical frameworks and experimental findings. These insights not only guide the improvement of existing methodologies but also offer transformative pathways for electrocatalytic organic nitrogenation via C–N coupling chemistry, potentially reshaping the landscape of organic synthesis. Looking ahead, a comprehensive understanding of the structure–activity relationships in SAC design will be key to advancing this rapidly evolving field.

Organic conjugated polymers have received extensive attention due to their unique electronic properties. However, there have been relatively few reports on the dark photocatalytic reactions utilizing organic conjugated polymers. Herein, we report the successful synthesis of an organic conjugated polymer based on poly (heptazine imide) nanocrystals (CNNCs) for H₂O₂ evolution and biomedical applications using a simple salt molten method and sonication–centrifugation process. The results show that these colloid CNNCs have the characteristics of photogenerated electrons accumulation and realize dark photocatalysis with high reducibility under visible light irradiation. Notably, these accumulating photogenerated electrons can reduce O₂ in darkness to produce H₂O₂. In addition, cytotoxicity tests were conducted and it was found that H₂O₂ produced under dark conditions could oxidize L-arginine (L-Arg) to NO, which effectively killed tumors in the dark. This work provides an important strategy to construct organic conjugated semiconductor nanocrystals and applying them to future energy and biomedical fields.

The diffusion, adsorption/desorption behaviors of water molecules and hydrogen molecules are of great importance in heterogeneous photocatalytic hydrogen production. In the study of structure–property–performance relationships, nanoconfined space provides an ideal platform to promote mass diffusion and transfer due to their extraordinary properties that are different from the bulk systems. Herein, we designed and prepared a nanoconfined CdS@SiO₂-NH₂ nanoreactor, whose shell is composed of amino-functionalized silica nanochannels, and encapsulates spherical CdS as a photocatalyst inside. Experimental and simulated results reveal that the amino-functionalized nanochannels promote water molecules’ and hydrogen molecules’ directional diffusion and transport. Water molecules are enriched in the nanocavity between the core and the shell, and promote the interfacial photocatalytic reaction. As a result, the maximized water enrichment and minimized hydrogen-occupied active sites enable photocatalyst with optimized mass transfer kinetics and localization electron distribution on the CdS surface, leading to superior hydrogen production performance with activity as high as 37.1 mmol·g⁻¹·h⁻¹.