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 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.

Single atom catalysts—SACs—have received intense interest in sustainable energy research due to their enormous application potential and broad catalytic scope. In particular, SACs anchored on molecular metal oxides—polyoxometalates (POMs)—offer unrivalled possibilities as models to understand the function of these complex systems on the atomic level. Research questions which are difficult to address for classical heterogeneous SACs can be addressed by experiment and theory using POM‐SACs as prototype catalysts. This review reviews the emerging field of POM‐SAC research with a focus on fundamental properties and their application in energy conversion and storage technologies including water splitting, CO/CO₂‐ as well as N₂‐activation. Current limitations of the field are identified and possible routes to overcome these are described. Future areas of development, including polyoxometalate‐single‐site catalysts, are highlighted, and critically assessed to enable the community to develop this fast‐moving field further.

Earth‐abundant transition‐metal‐based catalysts for electrochemical water splitting are critical for sustainable energy schemes. In this work, we use a rational design method for the synthesis of ultrasmall and highly dispersed bimetallic CoMo carbide/oxide particles deposited on graphene oxide. Thermal conversion of the molecular precursors [H₃PMo₁₂O₄₀], Co(OAc)₂⋅4 H₂O and melamine in the presence of graphene oxide gives the mixed carbide/oxide (Co₆Mo₆C₂/Co₂Mo₃O₈) nanoparticle composite deposited on highly dispersed, N,P‐doped carbon. The resulting composite shows outstanding electrocatalytic water‐splitting activity for both the oxygen evolution and hydrogen evolution reaction, and superior performance to reference samples including commercial 20 % Pt/C & IrO₂. Electrochemical and other materials analyses indicate that Co₆Mo₆C₂ is the main active phase in the composite, and the N,P‐doping of the carbon matrix increases the catalytic activity. The facile design could in principle be extended to multiple bimetallic catalyst classes by tuning of the molecular metal oxide precursor.

The top-down fabrication of catalytically active molecular metal oxide anions, or polyoxometalates, is virtually unexplored, although these materials offer unique possibilities, for catalysis, energy conversion and storage. Here, we report a novel top-down route, which enables the scalable synthesis and deposition of sub-nanometer molybdenum-oxo clusters on electrically conductive mesoporous carbon. The new approach uses a unique redox-cycling process to convert crystalline Mo^IVO₂ particles into sub-nanometer molecular molybdenum-oxo clusters with a nuclearity of ∼1–20. The resulting molybdenum-oxo cluster/carbon composite shows outstanding, stable electrocatalytic performance for the oxygen reduction reaction with catalyst characteristics comparable to those of commercial Pt/C. This new material design could give access to a new class of highly reactive polyoxometalate-like metal oxo clusters as high-performance, earth abundant (electro-)catalysts.