Controlled electropositive catalytic sites on zeolites for achieving high CH 3 Cl selectivity via electrophilic CH 4 chlorination using Cl 2

The spontaneous homolytic Cl 2 cleavage to two reactive chlorine radicals is useful for activating the C–H bond in CH 4 to produce various chlorinated products (CH 3 Cl, CH 2 Cl 2 , CHCl 3 , and CCl 4 ), but it is noncatalytic and uncontrollable. Herein, zeolites with controlled electropositive Lewis acidic sites originating from transition metal cations with various oxidation states successfully promote the electrophilic CH 4 chlorination with suppressing the radical pathway, which achieved nearly 100% selectivity to a desirable monochlorinated product (CH 3 Cl). The experimental results were clearly interpreted based on the selected catalytic descriptors calculated by the DFT method, in which the calculated Cl 2 adsorption energy to the catalytic sites, and LUMO energy levels of transition metal cations showed strong correlations with conversion of reactants and the CH 3 Cl selectivity. Consequently, Zn 2+ -incorporated zeolite (ZnHY) achieved nearly 100% CH 3 Cl selectivity without deactivation. The comprehensive experimental and theoretical investigations offer valuable insights for the design of zeolite-based catalysts promoting electrophilic CH 4 chlorination using Cl 2 .