An interface design strategy based on CeO_x nanodomains to maximize Pd utilization for multi-step hydrogenolysis of 3D N-benzyl molecules

As a cost-effective and environment-friendly oxide, silica (SiO₂) is commonly used as a support for catalyst featuring static active sites. However, achieving accurate interface control on inert SiO₂-based catalysts, featuring uniformly dispersed and mobile metal sites, remains a significant challenge. Additionally, the multi-step hydrogenolysis of multidimensional N-benzyl compounds under mild conditions continues to attract considerable attention. Herein, a synergistic strategy is proposed to tailor the catalyst interface. The accurately loaded CeO_x nanodomains served as a bridge between the inert V-SiO₂ supports and the Pd active species. Ultrasmall Pd(OH)₂ nanoclusters were uniformly anchored onto the supports due to this bridging effect. Under mild reaction conditions, the catalytic activity outperforms previously reported catalysts in the multi-step hydrogenation debenzylation of hexabenzylhexaazaisowurtzitane (HBIW). With only 0.80 wt‰ palladium relative to HBIW, the turnover number (TON) and yield reach 172.8 and 92.1%, respectively. Experiments and theoretical calculations reveal that the interfacial synergy between highly dispersed electron-deficient Pd species and CeO_x nanodomains rich in oxygen vacancies collectively enhance the mobile catalytic reaction. This strategy brings forth a new paradigm in the designing and synthesizing heterogeneous catalysts.