Mechanistic understanding of methane combustion over H-SSZ-13 zeolite encapsulated palladium nanocluster catalysts

•Complete CH4 oxidation over H-SSZ-13 zeolite encapsulated Pd catalysts was firstly investigated.•[PdⅡ2O]2+ and [PdⅡ3O3H]+ are the most stable binuclear and trinuclear Pd species in H-SSZ-13.•Pd2+, PdO, [Pd2O]2+, [Pd3O3H]+ can be anchoring on the SSZ-13 framework firmly.•The most kinetically relevant step in the CH4 oxidation varies with the active Pd species.•The PdⅡ3O3H/H-SSZ-13 is the most active among four PdⅡxOmHn/H-SSZ-13 catalysts. Catalytic methane (CH4) combustion to CO2 and H2O is of great practical significance and an important prototype catalytic reaction. Extensive experimental studies have suggested that zeolite supported palladium (Pd) catalysts are very active for catalytic CH4 oxidation, while the structure-performance relationship is still not clear. Herein, using H-SSZ-13 zeolite encapsulated Pd nanoclusters as a demonstration case, reaction mechanisms and kinetics of complete CH4 combustion were systematically investigated using first-principles density functional theory (DFT) calculations combined with atomistic thermodynamic analysis and the energetic span model (ESM). Four H-SSZ-13 zeolite encapsulated PdⅡxOmHn model catalysts, i.e., PdⅡ/H-SSZ-13, PdⅡO/H-SSZ-13, PdⅡ2O/H-SSZ-13, and PdⅡ3O3H/H-SSZ-13 were studied. The encapsulated [PdⅡ2O]2+ and [PdⅡ3O3H]+ nanoclusters were identified as the most stable binuclear and trinuclear Pd structures under experimental oxidative conditions. DFT calculations indicated that the most kinetically relevant step in the complete CH4 oxidation reaction over four Pd model catalysts is different. The first, third, third, and fourth C–H bond cleavage were identified as the most kinetically relevant steps over PdⅡ/H-SSZ-13, PdⅡO/H-SSZ-13, PdⅡ2O/H-SSZ-13, and PdⅡ3O3H/H-SSZ-13, respectively. Using the energetic span model, the relative turnover frequencies of CH4 oxidation over four PdⅡxOmHn/H-SSZ-13 model catalysts were calculated. Consistent with recent experimental observation, the encapsulated PdⅡ3O3H/H-SSZ-13 nanocluster was found to be the most active catalyst for complete CH4 oxidation. On the basis of DFT results and the ESM model analysis, it is noted that the reaction rate of complete CH4 oxidation over the PdⅡxOmHn/H-SSZ-13 catalysts is not completely dependent on one “highest” activation barrier, i.e., the barrier for the most kinetically relevant step. Neither one specific transition state nor one reaction step carried all the kinetics information that determines the catalytic performance of the