Construction of rose-type Co/Mo bimetal MOF and MOF-derived W embedded composites: Structure, reactivity, and dynamic simulation

Transition metal organic framework-derived materials are potential catalysts for cycloolefins oxidation, and it is essential to develop them with sufficient intrinsic activity and more efficient structure. Herein, we designed Co/ Mo bimetallic MOF with rose-type structure as a support for synthesizing CoMo-ZIF@IL/W catalyst with lamelliform structure and abundant Co, Mo, and W active sites for cyclopentene tandem oxidation to glutaraldehyde. Characterization results reveal that: 1) Mo implantation dramatically increases pore size (2.15 -> 28.91 nm) of monometallic MOF Co-ZIF; 2) IL introduction significantly improves active (Co2+ + Co3+) / satellite content ratio from 1.85 to 2.5; 3) MOF morphology can be completely changed through post-synthetic modification via IL, rather than just during the synthesis process. Meanwhile, CoMo-ZIF@IL/W exhibits high activity and excellent reuse properties in cyclopentene oxidation. Remarkably, dynamic simulation supported via detailed kinetic parameters (pre-exponential factors A1-3 = 1.17 x 1012, 1.45 x 108, 9.58 x 106 L mol-1 s-1, activation energies E1-3 = 89.4, 57.82, 86.01 kJ mol-1) and possible synergistic catalysis mechanism of Co/Mo/ W active species were first explored.