Experimental and Theoretical Studies of Ultrafine Pd-Based Biochar Catalyst for Dehydrogenation of Formic Acid and Application of In Situ Hydrogenation

作者：Liangyu Zou, Qi Liu, Daoyun Zhu, Yangqiang Huang, Yu Mao, Xiao Luo, Zhiwu Liang · 发表于：ACS Applied Materials & Interfaces · 年份：2022 · DOI：10.1021/acsami.2c00343 · 被引用次数：27 · 研究领域：Carbon dioxide utilization in catalysis、Catalysis for Biomass Conversion、Asymmetric Hydrogenation and Catalysis

In this work, a novel “foaming” strategy uses sodium bicarbonate (NaHCO 3 ) and ammonium oxalate ((NH 4 ) 2 C 2 O 4 ) as the foaming agent, turning biomass-derived carboxymethyl cellulose (CMC) into N-doped porous carbon. Highly active palladium nanoparticles (Pd NPs) immobilized on nitrogen-doped porous carbon (Pd@MC(2)-P) are produced through a phosphate-mediation approach. The phosphoric acid (H 3 PO 4 ) becomes the key to the synthesis of highly dispersed ultrafine Pd NPs on active Pd-cluster-edge (the edge of the Pd-cluster-100 and Pd-cluster-111 surfaces). The Pd@MC(2)-P exhibits high activity for formic acid (FA) dehydrogenation with an initial TOF g of 971 h –1 at room temperature. The subsequent hydrogenation of phenol using FA as an in situ hydrogen source on Pd@MC(2)-P and the highly efficient hydrogenation of phenol to cyclohexanone reaches more than 90% selectivity and 80% conversion. Density functional theory (DFT) calculations reveal that the reduced H poisoning and more exposed (100) surface over Pd nanoparticles are the keys to the Pd nanoparticles’ high activity.