Using pyrrole and terephthalaldehyde as raw materials, porphyrin-conjugated microporous polymer (CMP) without metal centers in the porphyrin ring was synthesized directly via the one-step method. The polymer was carbonized at different temperatures to obtain a series of carbonaceous nanospheres C-CMP-x (x is the pyrolysis temperature), of which C-CMP-900 is a multifunctional electrochemical catalyst with excellent performance. Compared to the uncarbonized polymer, C-CMP-900 is more sensitive and efficient for the reduction of nitrobenzene and exhibits a lower limit of detection. There was a significant improvement in the performance of nitrobenzene reduction over nonmetallic catalysts described in the literature. Moreover, the catalyst also shows excellent oxygen evolution reaction (OER) electrocatalytic activity, with lower overpotential than commercial RuO 2 . Even after long cycling tests, the catalyst maintained good activity. The catalyst, with an ultralow detection limit for nitrobenzene reduction and excellent OER activity, may be attributed to its high specific surface area and special porous carbon structure based on the porphyrin skeleton.
The catalytic oxidation of cycloalkanes using molecular oxygen employing porphyrin cobalt(II) as catalyst was enhanced through use of cycloalkyl hydroperoxides, which are the primary intermediates in oxidation of cycloalkanes, as additional oxidants to further oxidize cycloalkanes in the presence of porphyrin copper(II), especially for cyclohexane, for which the selectivity was enhanced from 88.6 to 97.2% to the KA oil; at the same time, the conversion of cyclohexane was enhanced from 3.88 to 4.41%. The enhanced efficiency and selectivity were mainly attributed to the avoided autoxidation of cycloalkanes and efficient utilization of oxidation intermediate cycloalkyl hydroperoxides as additional oxidants instead of conventional thermal decomposition. In addition to cyclohexane, the protocol presented in this research is also very applicable in the oxidation of other cycloalkanes such as cyclooctane, cycloheptane and cyclopentane, and can serve as a applicable and efficient strategy to boost the conversion and selectivity simultaneously in oxidation of alkanes. This work also is a very important reference for the extensive application of metalloporphyrins in catalysis chemistry.
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