Metastability of palladium carbide nanoparticles during hydrogen release from liquid organic hydrogen carriers.

Efficient hydrogen release from liquid organic hydrogen carriers (LOHCs) requires a high level of control over the catalytic properties of supported noble metal nanoparticles. Here, the formation of carbon-containing phases under operation conditions has a direct influence on the activity and selectivity of the catalyst. We studied the formation and stability of carbide phases using well-defined Pd/α-Al2O3(0001) model catalysts during dehydrogenation of a model LOHC, methylcyclohexane, in a flow reactor by in situ high-energy grazing incidence X-ray diffraction. The phase composition of supported Pd nanoparticles was investigated as a function of particle size and reaction conditions. Under operating conditions, we detected the formation of a PdxC phase followed by its conversion to Pd6C. The dynamic stability of the Pd6C phase results from the balance between uptake and release of carbon by the supported Pd nanoparticles in combination with the thermodynamically favorable growth of carbon deposits in the form of graphene. For small Pd nanoparticles (6 nm), the Pd6C phase is dynamically stable under low flow rate of reactants. At the high reactant flow, the Pd6C phase decomposes shortly after its formation due to the growth of graphene. Structural analysis of larger Pd nanoparticles (15 nm) reveals the formation and simultaneous presence of two types of carbides, PdxC and Pd6C. Formation and decomposition of Pd6C proceeds via a PdxC phase. After an incubation period, growth of graphene triggers the decomposition of carbides. The process is accompanied by segregation of carbon from the bulk of the nanoparticles to the graphene phase. Notably, nucleation of graphene is more favorable on bigger Pd nanoparticles. Our studies demonstrate that metastability of palladium carbides associated with dynamic formation and decomposition of the Pd6C and PdxC phases is an intrinsic phenomenon in LOHC dehydrogenation on Pd-based catalysts and strongly depends on particle size and reaction conditions.