Catalytic Oxidation of Chlorobenzene: From Mechanistic Insights to the Design of Chlorine-Resistant Catalysts—A Review

Chlorobenzene (CB), a typical chlorinated volatile organic compound (CVOC), serves as a critical precursor to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Efficient catalytic oxidation of CB is vital for air pollution control and solid-waste incineration tail-gas treatment. Based on 123 representative studies, this review addresses five key scientific issues: CB reaction pathways over catalysts and the intrinsic correlation between lattice-oxygen activity and Brønsted acid sites; the nature of active sites (isolated transition-metal centres, interfacial bridges or atomically dispersed noble metals) and the generality of corresponding structure-activity relationships; molecular origins, thermodynamic driving forces and microkinetics of partially reversible chlorine poisoning; effects of real flue-gas components (NOx, toluene, SO2, Hg, etc.) via competitive adsorption, redox disturbance and composite poisoning; and non-thermal-field assistance (plasma, Joule heating, photocatalysis) for overcoming low-temperature activation barriers of thermal catalysis. Assumptions and experimental prerequisites for existing conclusions are highlighted. Critical research gaps are identified in mechanism validation, chlorine mass balance, long-term stability and practical-condition verification. The results indicate that rational design of chlorine-resistant catalysts should not pursue the optimisation of single-performance index, but realise systematic trade-offs among activity, selectivity and durability.