Beijing Key Laboratory for Green Catalysis and Separation, Key Laboratory of Beijing on Regional Air Pollution Control, Key Laboratory of Advanced Functional Materials, Education Ministry of China, Laboratory of Catalysis Chemistry and Nanoscience, Department of Environmental Chemical Engineering, School of Environmental and Chemical Engineering, Faculty of Environment and Life, Beijing University of Technology, Beijing 100124, P. R. China.
John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts 02138, United States.
Environ Sci Technol. 2021 Nov 2;55(21):14906-14916. doi: 10.1021/acs.est.1c05586. Epub 2021 Oct 11.
Ru-based catalysts for catalytic combustion of high-toxicity Cl-containing volatile organic compounds are inclined to produce Cl instead of ideal HCl due to the Deacon reaction. We herein reported that the three-dimensionally ordered macroporous (3DOM) WO-supported RuP nanocatalyst greatly improved HCl selectivity (at 400 °C, increased from 66.0% over Ru/3DOM WO to 96.4% over RuP/3DOM WO) and reduced chlorine-containing byproducts for 1,2-dichloroethane (1,2-DCE) oxidation. P-doping enhanced the number of structural hydroxyl groups and Brønsted acid sites. The isotopic 1,2-DCE temperature-programmed desorption experiment in the presence of HO indicated the generation of a new active oxygen species OO that participated in the reaction. Generally, P-doping and HO introduction could promote the exchange reaction between Cl and hydroxyl groups, rather than oxygen defects, and then benefit the production of HCl and reduce the generation of other chlorine species or Cl, via the reaction processes of CHCl → alcohol → aldehyde → carboxylic acids.
基于 Ru 的催化剂在用于催化燃烧高毒性含 Cl 挥发性有机化合物时，由于 Deacon 反应，易于产生 Cl 而不是理想的 HCl。本文报道了具有三维有序大孔（3DOM）WO 载体的 RuP 纳米催化剂可极大地提高 HCl 选择性（在 400°C 时，Ru/3DOM WO 上的 HCl 选择性从 66.0%增加到 RuP/3DOM WO 上的 96.4%），并减少氯代副产物生成（1,2-二氯乙烷（1,2-DCE）氧化）。P 掺杂增强了结构羟基和 Brønsted 酸位的数量。在存在 HO 的情况下进行的同位素 1,2-DCE 程序升温脱附实验表明，生成了新的活性氧物种 OO，该物种参与了反应。通常，P 掺杂和 HO 的引入可以促进 Cl 与羟基之间的交换反应，而不是氧缺陷，然后通过 CHCl → 醇 → 醛 → 羧酸的反应过程有利于 HCl 的生成和其他氯物种或 Cl 的生成减少。
