Mingyang Tan,Liang Zhu,Hao Liu,Yajun Fu,Shuang-Feng Yin,Weijun Yang
A Cobalt porphyrin conjugated porous polymer (Co/PCP) was obtained by hybrid polymerization of a mixture of Co(II)(5,10,15,20-tetrakis(4-bromophenyl)-21H,23H-porphyrin) (CoTBPP) and 5,10,15,20-tetrakis(4-bromophenyl)-21H,23H-porphyrin (TBPP) (3:7 M ratio) with the coupling reagent of p-phenyldiboric acid. This Co/PCP was carbonized at 400 °C and the obtained catalyst (denoted as Co 3 O 4 @PNC-400) was composed of Co 3 O 4 nanoclusters wrapped in the nitrogen-carbon materials. This catalyst has an extremely high catalytic activity for the aerobic oxidation of C–H bonds. It can efficiently catalyze the oxidation of the C–H bonds in toluene and cyclohexane with high conversion and high selectivity of (alcohol + aldehyde), (alcohol + ketone) compounds, respectively. When heat-treated at 400 °C, the porous framework structure of the porphyrin polymer was partially retained, and the highly active Co 3 O 4 nanoclusters were generated in situ. The reaction of C N to C N and connection with the Co 3 O 4 nanoclusters also occurred. Co 3 O 4 @PNC-400 has obvious synergistic catalytic effect between Co 3 O 4 and nitrogen-carbon framework during the catalytic reaction. The defective structure caused by the migration of cobalt also greatly improved the catalytic activity. Co/PCPs with different cobalt contents were also synthesized and heat treated at different temperature. These catalysts were a new type of efficient C–H oxidation catalysts with excellent potential application value.
Ming Li,Haixin Sun,Chen Wang,Yongzhuang Liu,Qinqin Xia,Juan Meng,Haipeng Yu,Shuo Dou
The electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) represents an environmentally friendly approach to generate high-value-added chemicals from biomass. The successful electrochemical transformation of HMF during the oxidation reaction (HMFOR) necessitates an ideal adsorption interaction between HMF and OH − on the electrode surface. Yet, catalysts with a singular active site offer limited flexibility in managing the competitive adsorption of HMF and OH − . To this end, different active sites are customized in this work to construct a P and N co-doped porous carbon that wrapped Co 3 O 4 (Co 3 O 4 @PNC). Co-doping with these two heteroatoms generates C 3 P = O and pyrrolic N as adsorption sites to better balance the adsorption of HMF and OH − , respectively, rather than promoting competition between the HMF and OH − on a single active site. With this design strategy, Co 3 O 4 @PNC demonstrates significant HMFOR activity, the conversion rate of HMF surpassed 99% with a 2,5-furandicarboxylic acid (FDCA) yield exceeding 95% after 2 h of electrolysis. Furthermore, it shows universal applicability in the electrooxidation of other alcohol/aldehyde substrates, yielding efficiencies of 90–99%. This work not only provides guidance for advanced electrocatalysts design toward alcohol/aldehyde oxidation but also offers insights into the utilization of biomass-derived platform chemicals.
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