Precisely fabricated frustrated Lewis pairs in the Ni₃(BO₃)₂ nanocrystal achieve integration of the active sites and effective electrocatalytic C–N bond coupling to synthesize urea.

The local charge redistribution in BiFeO₃/BiVO₄ hybrids promotes the targeted adsorption and activation of inert gas molecules and guarantees the exothermic coupling of *NN* with generated CO via C–N coupling reactions to form *NCON* precursor.

Fuel cells and metal–air batteries will only become widely available in everyday life when the expensive platinum-based electrocatalysts used for the oxygen reduction reactions are replaced by other efficient, low-cost and stable catalysts. We report here the use of nitrogen-doped graphdiyne as a metal-free electrode with a comparable electrocatalytic activity to commercial Pt/C catalysts for the oxygen reduction reaction in alkaline fuel cells. Nitrogen-doped graphdiyne has a better stability and increased tolerance to the cross-over effect than conventional Pt/C catalysts.

The highly selective electrocatalytic activation of N₂ and CO₂ to synthesize value-added urea via a C–N coupling reaction is an extremely challenging reaction that is largely inhibited by the poor chemisorption and coupling abilities of the reactant molecules. Herein, the novel conductive MOF Co–PMDA–2-mbIM (PMDA = pyromellitic dianhydride; 2-mbIM = 2-methyl benzimidazole) is designed, attaining a record-high urea yield rate of 14.47 mmol h⁻¹ g⁻¹ with a FE of 48.97% at −0.5 V vs. RHE. The host–guest interactions involved not only generate desirable local electrophilic and nucleophilic regions but they also allow evolution from high-spin state Co³⁺ (HS: t⁴ _2ge² _g) to intermediate-spin state Co⁴⁺ (IS: t⁴ _2ge¹ _g) in CoO₆ octahedrons. Thus, N₂ and CO₂ can be adsorbed in a targeted fashion and activated to produce the desired *NN* and *CO intermediates. Subsequently, the low e_g orbital occupied Co⁴⁺ (t⁴ _2ge¹ _g) easily accepts electrons from σ orbital of *NN* and effectively triggers the C–N coupling reaction to emerge *NCON* urea precursor.