Deciphering Ni0/Ni(OH)+ interfacial sites for deep hydrogenation of dicyclopentadiene resin

Deep hydrogenation of dicyclopentadiene resin (DCPD resin) plays an important role in enhancing its performance and broadening its applications. However, designing suitable catalysts for promoting DCPD resin deep hydrogenation remains a challenge due to the high steric hindrance and abundant unsaturated bonds in DCPD resin, requiring strong binding to C=C double bonds. We herein propose a strategy for simultaneously constructing highly-dispersed Ni particles for hydrogen dissociation and interfacial Ni 0 /Ni(OH) + sites for C=C adsorption by controlled reduction of Ni phyllosilicate (Ni PS). The catalyst, after reduction at 400 °C, demonstrated balanced ratio between Ni 0 and interfacial Ni 0 /Ni(OH) + sites, and achieved a hydrogenation degree of 99.8% (TOF: 68.8 h −1 ) while maintaining 99.3% efficiency after seven consecutive cycles. Through in-situ DRIFTS analysis and density functional theory (DFT) calculations, it is confirmed that the introduction of Ni 0 /Ni(OH) + interfacial sites results in superior activity compared to pure Ni 0 or unreduced PS due to optimized charge transfer and electronic configuration. This work not only establishes a simple and environmentally-friendly approach to design efficient catalysts for polymer hydrogenation, but also provides insights into the mechanism of unsaturated bond hydrogenation through the synergistic effects of Ni 0 and Ni 0 /Ni(OH) + interfacial sites.