High-Loading, Well-Dispersed Phosphorus Confined on Nanoporous Carbon Surfaces with Enhanced Catalytic Activity and Cyclic Stability.

Phosphorus-doped carbon materials are promising alternatives to noble metal-based catalysts for the highly selective oxidation of benzyl alcohol to benzaldehyde, but it is challenging to achieve high loadings of high-activity P dopants in metal-free catalysts. Here, the preparation of high-loading and well-dispersed P atoms confined to the surfaces of cellulose-derived carbon via a dissolving-doping strategy is reported. In this method, cellulose is dissolved in phosphoric acid to generate a cellulose-phosphoric supramolecular collosol, which is then directly carbonized. The as-prepared carbon possesses a high specific surface area of 1491 cm 3 g -1 and a high P content of 8.8 wt%. The P-doped nanoporous carbon shows a superior catalytic activity and cyclic stability toward benzyl alcohol oxidation, with a high turnover frequency of 3.5 × 10 -3 mol g -1 h -1 and a low activation energy of 35.6 kJ mol -1 . Experimental results and theoretical calculations demonstrate that the graphitic C 3 PO species is the leading catalytic active center in this material. This study provides a novel strategy to prepare P dopants in nanoporous carbon materials with excellent catalytic performance.