Unveiling the importance of reactant mass transfer in environmental catalysis: Taking catalytic chlorobenzene oxidation as an example

To date, investigations onto the regulation of reactants mass transfer has been paid much less attention in environmental catalysis. Herein, we demonstrated that by rationally designing the adsorption sites of multi-reactants, the pollutant destruction efficiency, product selectivity, reaction stability and secondary pollution have been all affected in the catalytic chlorobenzene oxidation (CBCO). Experimental results revealed that the co-adsorption of chlorobenzene (CB) and gaseous O₂ at the oxygen vacancies of CeO₂ led to remarkably high CO₂ generation, owning to their short mass transfer distance on the catalyst surface, while their separated adsorptions at Brönsted HZSM-5 and CeO₂ vacancies resulted in a much lower CO₂ generation, and produced significant polychlorinated byproducts in the off-gas. However, this separated adsorption model yielded superior long-term stability for the CeO₂/HZSM-5 catalyst, owning to the protection of CeO₂ oxygen vacancies from Cl poisoning by the preferential adsorption of CB on the Brönsted acidic sites. This work unveils that design of environmental catalysts needs to consider both of the catalyst intrinsic property and reactant mass transfer; investigations of the latter could pave a new way for the development of highly efficient catalysts towards environmental pollution control.