非均相多钼氧簇/硅藻土催化氧化碘离子研究  

Study on heterogeneous catalytic oxidation of iodide with PMoO/Dia

作　　者：郭军 蔡丽丽[4] 解田[1,2] 周维珍 杨三可 谢泉[3] 刘其斌 秦军[5] GUO Jun;CAI Lili;XIE Tian;ZHOU Weizhen;YANG Sanke;XIE Quan;LIU Qibin;QIN Jun(State Key Laboratory for Efficient Utilization of Medium and Low-grade Phosphate Rock and Its Associated Resources, Guiyang 550014, China;Postdoctoral Workstation, Wengfu (Group) Co., Ltd., Guiyang 550014, China;Post-doctoral Mobile Station of Electronic Science and Technology, Guizhou University, Guiyang 550025, China;College of Chemistry and Materials Science, Guizhou Normal University, Guiyang 550001, China;Key Laboratory of Karst Environment and Geological Hazards, Ministry of Land and Resources, Guizhou University, Guiyang 550025, China)

机构地区：[1]中低品位磷矿及其共伴生资源高效利用国家重点实验室,贵阳550014 [2]瓮福(集团)有限责任公司博士后工作站,贵阳550014 [3]贵州大学电子科学与技术博士后流动站,贵阳550025 [4]贵州师范大学化学与材料科学学院,贵阳550001 [5]贵州大学国土资源部喀斯特环境与地质灾害重点实验室,贵阳550025

出　　处：《功能材料》2019年第9期9120-9128,共9页Journal of Functional Materials

基　　金：国家自然科学基金资助项目(21862005);贵州师范大学研究生创新基金资助项目(YC[2018]041);贵州省科技厅计划资助项目(黔科合LH字[2017]7336,黔科合基础[2019]1457,黔科合支撑[2019]2835);贵州省教育厅青年科技人才成长资助项目(黔教合KY字[2018]126);中低品位磷矿及其共伴生资源高效利用国家重点实验室开放课题资助项目(WFKF2017-03)

摘　　要：采用浸渍法制备keggin型多钼氧簇/改性硅藻土(PMoO/Dia)催化剂。分别采用FT-IR、XRD、BET、SEM和碘离子选择电极来测试并研究催化剂结构,表面形貌和碘离子催化性能。利用分子力学和量子化学方法对PMoO在Di和Dia表面的吸附进行计算模拟。研究结果显示:负载后的PMoO高度有序分散在Dia表面上且未改变其原有的Keggin结构;在加有0.5 g的7%PMoO/Dia催化剂的反应体系中反应8 min后碘离子的转化率为99.7%,反应速率达到了2.25×10^-5 mol/(L·s),与空白相比,PMoO/Dia的催化效果提高2.25×10^3倍;PMoO以物理吸附和化学吸附两种方式吸附在Di和Dia表面,Dia表面的铵基增加了PMoO与Dia之间的静电吸附和化学吸附作用力,同时降低了PMoO/Dia的前线轨道能级。催化剂重复使用10次以后仍保持着良好的催化性能,重复性好,无过氧化,具有较好的应用前景。A keggin-type poly-molybdenum cluster/modified diatomaceous earth(PMoO/Dia) catalyst was prepared by impregnation. FT-IR, XRD, BET, SEM and iodide ion selective electrodes were used to test and study the catalyst structure, surface morphology and iodide catalytic performance. Molecular mechanics and quantum chemistry methods were used to simulate the adsorption of PMoO on Di and Dia surfaces. The results show that the loaded PMoO was highly dispersed on the Dia surface without changing its original Keggin structure. The conversion of iodide ion after 8 minutes of reaction in a reaction system with 0.5 g of 7% PMoO/Dia catalyst reached 99.7% and the reaction rate reached 2.25×10^-5 mol/(L·s). Compared with the blank, the catalytic effect of PMoO/Dia increased by 2.25×10^3 times. PMoO was physically adsorbed and chemisorbed on the surface of Di and Dia. The ammonium group on the surface of Dia increased the electrostatic adsorption and chemisorption between PMoO and Dia, and reduced the frontal orbital energy level of PMoO/Dia. After repeated use of the catalyst for 10 times, it still maintained good catalytic performance, good repeatability, no peroxidation, and had a good application prospect.

关 键 词：碘离子 多钼氧簇 硅藻土 催化 氧化 

分 类 号：TQ032.4[化学工程]