Metal oxide supported metal catalysts show promising catalytic performance in many industry-relevant reactions. However, the enhancement of performance is often limited by the insufficient metal/metal oxide interface. In this work, we demonstrate a general synthesis of Pt-early transition metal oxide (Pt-MO_x, M = Ti, Zr, V, and Y) catalysts with rich interfacial sites, which is based on the air-induced surface segregation and oxidation of M in the supported Pt-M alloy catalysts. Systematic characterizations verify the dynamic structural response of Pt-M alloy catalysts to air and the formation of Pt-MO_x catalysts with abundant interfacial sites. The prepared Pt-TiO_x interfacial catalysts exhibit improved performance in hydrogenation reactions of benzaldehyde, nitrobenzene, styrene, and furfural, as a result of the heterolytic dissociation of H₂ at Pt-metal oxide interfacial sites.

Replacing traditional polymer-based precursors with small molecules is a promising pathway toward facile and controllable preparation of porous carbons but remains a prohibitive challenge because of the high volatility of small molecules. Herein, a simple, general, and controllable method is reported to prepare porous carbons by converting small organic molecules into organic molecular salts followed by pyrolysis. The robust electrostatic force holding organic molecular salts together leads to negligible volatility and thus ensures the formation of carbons under high-temperature pyrolysis. Meanwhile, metal moieties in organic molecular salts can be evolved into in-situ templates or activators during pyrolysis to create nanopores. The modular nature of organic molecular salts allows easy control of the porosity and chemical doping of carbons at a molecular level. The sulfur-doped carbon prepared by the ionic solid strategy can serve as robust support to prepare small-sized intermetallic PtCo catalysts, which exhibit a high mass activity of 1.62 A·mg_Pt⁻¹ in catalyzing oxygen reduction reaction for fuel cell applications.

Modulation of geometric and electronic structures of supported Pd-based catalysts by forming atomically ordered intermetallic phases enables an effective way to optimize catalytic performance. However, the synthesis of small-sized Pd-based intermetallic nanoparticle catalysts with improved mass-based activity remains formidable challenges, since high-temperature annealing generally required for atom ordering inevitably leads to severe metal sintering and thus large crystallites. Here, we present a bulky nanodiamond-confined method to prepare sub-5 nm Pd₃Pb intermetallic nanocatalysts by mitigating metal sintering at high temperatures, which is induced by the electronic interactions between metal and defect-rich graphene shells reinforced by diamond cores in the bulky nanodiamond support. The prepared small-sized Pd₃Pb intermetallic catalyst displays a high activity with a turnover frequency of 932 h⁻¹ for the semihydrogenation of phenylacetylene under mild conditions (room temperature, 3 bar H₂), along with a high selectivity of > 96% to styrene near the complete conversion of phenylacetylene.

The development of high-performance Ir-based catalyst for electrocatalysis of oxygen evolution reaction (OER) in acidic media plays a critical role in realizing the commercialization of polymer electrolyte membrane-based water electrolyzer technology. Here we report a low-Ir core–shell OER electrocatalyst consisting of an intermetallic IrGa (IrGa-IMC) core and a partially oxidized Ir (IrO_x) shell. In acidic electrolytes, the IrGa-IMC@IrO_x core–shell catalysts exhibit a low overpotential of 272 mV at 10 mA·cm⁻² with Ir loading of ~20 µg·cm⁻² and a mass activity of 841 A·g_Ir⁻¹ at 1.52 V, which is 3.6 times greater than that of commercial Ir/C (232 A·g_Ir⁻¹) catalyst. We understand by the density functional theory (DFT) calculations that the enhanced OER activity of the IrGa-IMC@IrO_x catalysts is ascribed to the lifted degeneracy of Ir 5d electron of surface IrO_x sites induced by the intermetallic IrGa core, which increases the adsorption capacity of IrO_x layer for O and OH binding and eventually lowers the energy barrier of the OER rate-determining steps.

Small-sized bimetallic nanoparticles that possess numerous accessible metal sites and optimal geometric/electronic structures show great promise for advanced synergetic catalysis but remain synthetic challenge so far. Here, an universial synthetic method is developed for building a library of bimetallic nanoparticles on mesoporous sulfur-doped carbon supports, consisting of 24 combinations of 3 noble metals (that is, Pt, Rh, Ir) and 7 other metals, with average particle sizes ranging from 0.7 to 1.4 nm. The synthetic strategy is based on the strong metal-support interaction arising from the metal-sulfur bonding, which suppresses the metal aggregation during the H₂-reduction at 700 °C and ensure the formation of small-sized and alloyed bimetallic nanoparticles. The enhanced catalytic properties of the ultrasmall bimetallic nanoparticles are demonstrated in the dehydrogenation of propane at high temperature and oxidative dehydrogenations of N-heterocycles.