Transition Metal Phosphide Catalysts for Hydroprocessing Applications

Transition metal phosphides have emerged as versatile hydroprocessing catalysts owing to their unique combination of metallic conductivity, tunable electronic structure and strong resistance to sintering and sulphur poisoning. Incorporating phosphorus into Ni, Co or noble metal frameworks modulates electron density at active sites, enhancing hydrogenation and C–heteroatom bond-cleavage steps essential for hydrodesulfurization, hydrodenitrogenation and hydrogenation of complex feeds. Their intrinsically high hydrogen affinity and capacity to stabilise metal phosphide phases under harsh conditions confer durable activity and selectivity, often rival-ling or surpassing conventional sulphide catalysts. Advances in synthesis—including colloidal routes, surface engineering and controlled sulphidation—have enabled precise control over particle size, phase composition and surface termination, thereby offering pathways to tailor catalytic performance for deep desulfurization of refractory molecules, upgrading of heavy oils and syngas conversion.

Research from Nature Portfolio

Recent studies have employed solid-state NMR nanocrystallography combined with density functional theory to resolve the crystal facets and electronic structure of ultrafine Ni2P nanoparticles at atomic resolution. Identification of distinct Knight shifts linked to specific surface terminations has revealed how facet exposure governs hydrogen adsorption energies and reaction specificity. This insight establishes a direct structure–function relationship, guiding the synthesis of facet-engineered metal phosphide nanocatalysts with optimised active site density for targeted hydroprocessing reactions.

Transition Metal Phosphide Catalysts for Hydroprocessing Applications publication trend

The graph below shows the total number of articles in transition metal phosphide catalysts for hydroprocessing applications across all publications each year (not limited to Nature Index journals).

Technical terms

Hydroprocessing: A suite of catalytic reactions using hydrogen to remove sulphur, nitrogen and unsaturated hydrocarbons from petroleum fractions.

Hydrodesulfurization (HDS): Catalytic removal of sulphur from organic molecules via hydrogenation and subsequent C–S bond cleavage.

Direct desulfurization (DDS): A selective HDS pathway in which C–S bonds are cleaved without complete aromatic ring hydrogenation.

Facet: A crystallographically defined surface of a nanoparticle, the orientation and atomic arrangement of which influence catalytic activity.

Solid-state NMR nanocrystallography: A combined experimental and computational approach that uses nuclear magnetic resonance to determine atomic-scale structures of nanomaterials, including identification of surface terminations.

References

1. Catalytic Activities of Noble Metal Phosphides for Hydrogenation and Hydrodesulfurization Reactions. Catalysts (2018).
2. Crystal and electronic facet analysis of ultrafine Ni2P particles by solid-state NMR nanocrystallography. Nature Communications (2021).
3. Unraveling the Role of Surface Termination in Ni2P(001) for the Direct Desulfurization Reaction of Dibenzothiophene (DBT): A Density Functional Theory (DFT) and Microkinetic Study. Industrial & Engineering Chemistry Research (2021).
4. Molecular simulation on mechanism of thiophene hydrodesulfurization on surface of Ni2P. Energy Exploration & Exploitation (2021).