[npb—SiO2—(Pb)S—Fe PP]催化性能研究

Study on the catalytic performance of heme supported on(Pb)S-functionalized nanoporous silica rods

为了利用廉价的血红素模拟细胞色素P 450酶的轴向硫配位作用和催化活性,并调节其催化性能,通过共缩合方法合成硫铅官能团化的纳米多孔二氧化硅棒[npb—SiO2—(Pb)S],用于通过硫原子配位固定血红素[Fe PP],形成血红素催化材料[npb—SiO2—(Pb)S—Fe PP]。通过使用X射线光电子能谱(XPS)、比表面(BET)、透射电镜(TEM)、紫外可见光谱(UV-Vis)和傅里叶红外光谱(FT-IR)等技术对催化材料进行表征,并用于催化氧气氧化环己烷生产KA油。在160℃和0.9 MPa的反应条件下,含有0.5 mg血红素的固载催化材料可回收使用5次,醇酮产率、转化率和转化频次分别为12.13%、29.43%和1.93×105 h-1。相比未固载的血红素具有更高的催化活性、稳定性和可应用性。

In order to use the cheap heme for simulating the axially-sulfur-coordinating action and catalytic activity in cytochrome P 450 enzyme,and regulating its catalytic performance,(Pb)S-functionalized nanoporous silica rods was synthesized via co-condensation method,which was used to immobilize heme via sulfur atom coordination,forming heme catalyst material[npb—SiO2—(Pb)S—Fe PP].The immobilized catalyst material was characterized by the following techniques:X-ray photoelectron spectroscopy(XPS),Specific Brunauer-Emmet-Teller(BET)surface areas,transmission electron microscopy(TEM),Ultraviolet visible spectrum(UV-Vis)and Fourier transformed infrared spectrum(FT-IR).The catalyst was used for catalyzing oxidation of cyclohexane by molecular oxygen to produce KA oil.Under the reaction conditions of 160℃,0.9 MPa,the catalylst material containing 0.5 mg heme could be recycled for five times.On average,the yields of KA oil,the conversion of cyclohexane and the transformation frequency were 12.13%,29.43%and 1.93×105h-1 respectively.Compared with iron protoporphyrin,it shows higher catalytic activity,stability and reusability.