磷钨酸负载MOFs功能化磁性复合材料催化氧化脱硫  

Heteropoly Acid Grafted-MOFs Functionalized Magnetic Composite Material for Catalytic Oxidative Desulfurization

作　　者：章涵 王俊二 董浩 杨旎妮 潘灵芸 沈昊宇[1] 胡美琴[1] 成瑾瑾 ZHANG Han;WANG Jun-Er;DONG Hao;YANG Ni-Ni;PAN Lin-Yun;SHEN Hao-Yu;HU Mei-Qin;CHENG Jin-Jin(Zhejiang University Ningbo Institute of Technology,Ningbo,Zhejiang 315100,China)

机构地区：[1]浙江大学宁波理工学院,宁波315100

出　　处：《无机化学学报》2020年第8期1475-1484,共10页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.51608479);浙江省公益基金(No.LGC20B070001);宁波市自然科学基金(No.2018A610206);国家级大学生创新创业训练计划项目(No.202013022009);浙江省新苗计划项目(No.2020R401181)资助。

摘　　要：采用溶剂热法制备了羧基化磁性微球(Fe3O4-COOH),进一步采用"一锅法"制备得到MIL-101(Cr)功能化磁性复合材料Fe3O4-COOH@MIL-101(Cr);以其为载体,采用超声浸渍法负载磷钨酸,得到磷钨酸负载化MOFs功能化的磁性复合材料HPW@Fe3O4-COOH@MIL-101(Cr)。通过傅里叶变换红外光谱(FT-IR)、X射线衍射(XRD)、X射线光电子能谱仪(XPS)、振动样品磁强计(VSM)、透射电子显微镜(TEM)、扫描电镜(SEM)等手段对其组成、形貌等进行表征。以其为催化剂,以双氧水为氧化剂,催化氧化以二苯并噻吩为硫源的正辛烷模拟油样。通过单因素法分别考察了超声反应时间、氧化剂用量、超声反应温度、相转移剂用量和催化剂用量等因素对脱硫效果的影响,并初步探讨了催化脱硫机理。结果表明:反应温度60℃,反应时间5 min,氧化剂用量nH2O2/nS为4,相转移剂CTAB用量为0.2%(w/w),催化剂用量为8 g·L-1时,二苯并噻吩的降解率达到73.15%;催化剂重复使用5次后降解率下降7.8%,说明该材料具有良好的催化脱硫的性能且可以重复使用。催化机理初步研究表明,活性中心可能为杂多酸阴离子,Fe3O4-COOH@MIL-101(Cr)起到载体和协同吸附的作用。Carboxylated magnetic microsphere Fe3O4-COOH was firstly synthesized by solvothermal method.MIL-101(Cr)functionalized magnetic composite Fe3O4-COOH@MIL-101(Cr)was obtained next by one-pot method.Phos-photungstic acid was finally grafted on the Fe3O4-COOH@MIL-101(Cr)by ultrasonic impregnation method to obtain HPW@Fe3O4-COOH@MIL-101(Cr).Its composition and morphology were characterized by Fourier transform infra-red spectrum(FT-IR),X-ray diffraction(XRD),X-ray photoelectron spectrometer(XPS),Vibrating sample magne-tometer(VSM),transmission electron microscopy(TEM)and scanning electron microscopy(SEM).It was used as catalyst with hydrogen peroxide as oxidant to catalyze the oxidation of n-octane simulated oil sample with dibenzo-thiophene as sulfur source.The effects of ultrasonic reaction time,oxidant dosage,reaction temperature,dosage of the phase transfer agent and the catalyst amount on the desulfurization rate were investigated by using single factor method.The presumed mechanism was discussed.The results showed that the optimized catalytic degradation rate reached when the reaction time was at 60℃,5 mins,nH2O2/nSof 4,usage amount of the phase transfer agent CTAB at 0.2%(w/w),with the catalyst amount of 8 g·L-1.The catalytic degradation rate reached 73.15%.After used for 5 times,the catalytic degradation rate decreased by 7.8%,indicating that the material has good catalytic desulfuriza-tion performance and can be reused.Primary mechanism study showed that the active center for the catalytic desul-furization might be the heteropoly acid anion of the HPW@Fe3O4-COOH@MIL-101(Cr),in which the Fe3O4-COOH@MIL-101(Cr)may act as a supporter and cooperative absorbent.

关 键 词：杂多酸 MOFs功能化 磁性复合材料 氧化脱硫 相转移剂 

分 类 号：O643.36[理学—物理化学]