Wang Fuli, Lan Tianwei, Hu Xiaonan, Chen Aling, Chen Xin, Xu Xinrui, Wang Mengxue, Xie Ming, Shen Yongjie, Wang Penglu, Zhang Dengsong
International Joint Laboratory of Catalytic Chemistry, State Key Laboratory of Advanced Special Steel, Innovation Institute of Carbon Neutrality, Department of Chemistry, College of Sciences, Shanghai University, Shanghai 200444, People's Republic of China.
Department of Chemical Engineering, University of Bath, Bath BA2 7AY, U.K.
Environ Sci Technol. 2025 Aug 19;59(32):17361-17371. doi: 10.1021/acs.est.5c06679. Epub 2025 Aug 4.
Synergistic catalytic removal (SyCR) of NO and chlorinated volatile organic compound (CVOCs) emission from nonelectric industries is effective to suppress PM and ozone complex air pollution. Catalysts with balanced competence to reduce NO and oxidize CVOCs, as well as the resistance to chlorine poisoning, are critical to SyCR. Here, neighboring effects over SmMnO mullite (SMO) modified by HZSM-5 composite catalysts (SMO-Z) were demonstrated in the Cl-resistant SyCR of NO and chlorobenzene (CB, a representative CVOCs). Characterizations demonstrated that HZSM-5 modification did not alter the crystal structure of SMO and retained Mn-O-Mn-Mn active sites for the SyCR of NO and CB. HZSM-5 regulated the redox ability of SMO-Z to reduce the formation of inert nitrate species and to promote the N selectivity. Acidic HZSM-5 acted as dechlorination sites to promote the breakage of the C-Cl bond via the nucleophilic substitution reaction and accelerated the formation of HCl to avoid Cl poisoning on catalysts. The fine-tuned compensation of surface acidity by HZSM-5 suppressed the competitive adsorption of NH and CB on SMO-Z, which promoted NO reduction at high temperatures, whereupon neighboring effects between HZSM-5 acidic dechlorination sites and SMO active redox sites on SMO-Z capitally promoted the SyCR efficiency and antichlorination poisoning performance.
非电力行业协同催化去除（SyCR）氮氧化物（NO）和氯化挥发性有机化合物（CVOCs）排放对于抑制颗粒物和臭氧复合空气污染十分有效。具有平衡的还原NO和氧化CVOCs能力以及抗氯中毒能力的催化剂对于SyCR至关重要。在此，通过HZSM-5复合催化剂（SMO-Z）改性的SmMnO莫来石（SMO）上的邻近效应在NO与氯苯（CB，一种代表性CVOCs）的耐氯SyCR中得到了证明。表征结果表明，HZSM-5改性并未改变SMO的晶体结构，并保留了用于NO和CB的SyCR的Mn-O-Mn-Mn活性位点。HZSM-5调节了SMO-Z的氧化还原能力，以减少惰性硝酸盐物种的形成并提高N选择性。酸性HZSM-5充当脱氯位点，通过亲核取代反应促进C-Cl键的断裂，并加速HCl的形成以避免催化剂上的Cl中毒。HZSM-5对表面酸度的微调抑制了NH和CB在SMO-Z上的竞争吸附，这促进了高温下的NO还原，于是HZSM-5酸性脱氯位点与SMO-Z上的SMO活性氧化还原位点之间的邻近效应极大地提高了SyCR效率和抗氯中毒性能。
