Synthesis Of Cu₃?BTC?₂ Composites And Their Catalytic Application In Cumene Oxidation

Metal-organic frameworks?MOFs?are a kind of promising material for a variety of applications due to their amenability to design as well as fine-tunable and uniform pore structures.Controllable integration of MOFs and functional materials is leading to the creation of new multifunctional composites/hybrids,which exhibit new properties that are superior to those of the individual components.In this research,Cu₃?BTC?₂ was selected as the supporter to prepare MOFs composites.The catalysis performance of the Cu₃?BTC?₂ composites in cumene oxidation were also investigated.Firstly,the CuO@Cu₃?BTC?₂ composite was synthesized via a facile selftemplate method using CuO as the precursor.CuO not only served as the template but also provided Cu2+ source for the formation of Cu₃?BTC?₂.As the synthesis time prolonged,the Cu₃?BTC?₂ content in CuO@Cu₃?BTC?₂ was increased.So as its surface areas and total pore size.The Cu₃?BTC?₂ content also influence the catalytic performance in cumene oxidation.When the synthesis time is 4 h,the CuO:Cu₃?BTC?₂ is 1:0.073,which owns the best catalytic performance.After reacted 12 h,the yield of CHP is 18.1%,3.5 times of no catalyst.Secondly,T?p-Cl?PPMn???@Cu₃?BTC?₂ with different T?p-Cl?PPMn???content are prepared by one-step pathway using the single DMF solvent.The products were characterized by EDS and FT-IR,in which the peaks of T?p-Cl?PPMn???confirm the successful synthesis of T?p-Cl?PPMn???@Cu₃?BTC?₂.The TEM and XRD suggest that the structure of T?p-Cl?PPMn???@Cu₃?BTC?₂ keeps complete when adding some T?p-Cl?PPMn???in the solvent.T?p-Cl?PPMn???@Cu₃?BTC?₂ shows the best catalytic performance in cumene oxidation with 0.5% content T?p-Cl?PPMn???,in which the CHP yield is 31.9%,more than 6 times of no catalyst.Moreover,the yield of CHP is about 50% when T?p-Cl?PPMn???@Cu₃?BTC?₂ used fifth time.Finally,the mechanism of cumene oxidation with T?pCl?PPMn???@Cu₃?BTC?₂ as catalyst was investigated.FT-IR result shows that T?pCl?PPMn???@Cu₃?BTC?₂ and ?-H are chemical adsorption.So ?-H is activated and cumene radical is created,so to promoting the cumene oxidation.By adding the radical scavenger,it proves that the cumene radical is the key radical in the cumene radical chain reaction.