纳米SiO_(2)与MCM-41固载[FeFe]模型物的合成及光催化性能研究

Synthesis and Photocatalytic Properties of[FeFe]Model Compound Immobilized on Nano-SiO_(2) and MCM-41

通过含膦硅烷偶联剂在纳米SiO_(2)、介孔分子筛MCM-41结构中引入膦配体,再通过羰基取代反应引入[FeFe]模型物,得到催化剂SiO_(2)@P[FeFe](1)/MCM-41@P[FeFe](1a)。采用透射电镜(TEM)、X射线能谱(EDX)、红外光谱(FI-IR)、X射线衍射(XRD)、热重(TG-DTA)、电感耦合等离子体质谱(ICP-MS)对原料、中间体SiO_(2)@P(2)/MCM-41@P(2a)、催化剂1和1a进行了表征。测试结果表明,催化剂1和1a中[FeFe]模型物的浓度分别为0.1648和0.2790 mmol/g。作为非均相[FeFe]模型物催化剂,催化剂1和1a在水相及有机相均能完成光催化产氢反应。在最优化条件[V(DMF)∶V(H2O)∶V(TEA)=8∶1∶1]下,催化剂1和1a在1 h内的催化循环数分别为34.7和14.7,催化寿命约为3.5 h。

Phosphine ligands were introduced into nano-SiO_(2)and mobile crystalline material(MCM-41)by silane coupling agent.The catalyst of[SiO_(2)@P[FeFe](1)/MCM-41@P[FeFe](1 a)]was obtained by introducing[FeFe]model compound through carbonyl substitution reaction.The intermediate of[SiO_(2)@P(2)/MCM-41@P(2 a)]and final product(1/1 a)were characterized by transmission electron microscope(TEM),energy dispersive X-ray spectroscopy(EDX),fourier transform(FT-IR),X-ray diffraction(XRD),thermogravimetric Analysis(TG-DTA)and inductively coupled plasma mass spectrometry(ICP-MS).The results showed that the content of[FeFe]model compounds in the catalyst is 0.1648 mmol/g(1)and 0.2790 mmol/g(1 a),respectively.As heterogeneous[FeFe]model catalysts,catalysts 1 and 1 a can complete photocatalytic hydrogen production in both aqueous and organic phases.Under the optimal conditions[V(DMF)∶V(H2O)∶V(TEA)=8∶1∶1],the number of catalytic cycles in 1 hour is 34.7(1)and 14.7(1 a),and the catalyst life is about 3.5 h.