Advanced design strategies for active metals in LOHC dehydrogenation: From static catalyst architectures to dynamic site evolution

Abstract

The catalytic dehydrogenation of liquid organic hydrogen carriers (LOHC) is recognized as a structure-sensitive reaction, where the geometry, coordination and electronic environment of active sites govern activity, selectivity and durability in a collective fashion. Previous studies on monometallic catalysts revealed the critical roles of particle size, facet exposure and local coordination structures in controlling H2 release rate and byproduct formation. Built on these principles, bimetallic catalysts and metal-metal oxide hybrid catalysts have recently attracted growing interest. The former enables tunable metal compositions to modulate active site ensembles, while the latter introduces interfacial structures tailoring both electronic properties and structural resilience. However, their surfaces undergo dynamic evolution under realistic reaction environments. These include atom migration, metal redistribution and metal-oxide interface reconstruction, which can generate metastable active states that differ significantly from as-synthesized structures. To capture these complexities, in situ/operando characterization needs to be integrated with adaptive modeling approaches that can represent transient configurations and reaction-driven structural transformations. This review highlights recent advances in designing active sites across monometallic, bimetallic and metal-metal oxide systems. Furthermore, it outlines future directions toward the rational catalyst design affording dynamically resilient active sites for LOHC dehydrogenation.