The Pt-Enriched PtNi Alloy Surface and its Excellent Catalytic Performance in Hydrolytic Hydrogenation of Cellulose

Ni-based catalysts are currently a subject of intense research in the hydrolytic hydrogenation of cellulose. We previously reported that Ni/ZSM-5 catalyst gave high yield of hexitols. However, Ni-based catalysts suffered fast deactivation in hot-compressed water. In this follow-up study we designed highly active Ni-based bimetallic catalysts with excellent hydrothermal stability for the hydrolytic hydrogenation of microcrystalline cellulose. PtNi/ZSM-5 shows a 76.9% yield of hexitols, which is the best obtained so far in the hydrolytic hydrogenation of microcrystalline cellulose over Ni-based catalysts. Furthermore, the yield of hexitols remained greater than 55% after the catalyst was reused for 4times. The results showed that PtNi nanoparticles were formed with a Pt-enriched alloy surface as confirmed by XRD, H-2-TPR (temperature-programmed H-2 reduction), XPS (X-ray photoelectron spectroscopy), and H-2-TPD (temperature-programmed H-2 desorption). The surface features of these nano-particles were characterized by CO-TPD (temperature-programmed CO desorption), CO-FTIR (CO adsorption FTIR spectroscopy), HRTEM (high resolution TEM), and O-2-TPO (temperature programmed oxidation) and this special surface structure may be responsible for the high activity, selectivity, and stability in the hydrolytic hydrogenation of cellulose in hot-compressed water.