玻璃球负载非晶态有机钛聚合物提高光催化还原CO_(2)的转换频率  

Glass Sphere Supported Amorphous Organotitanium Polymer to Improve the Turnover Frequency in Photocatalytic Reduction of CO_(2)

作　　者：叶祥志 邓云水 刘源[1] 周咏柳 贺建雄 熊春荣[1] YE Xiang-Zhi;DENG Yun-Shui;LIU Yuan;ZHOU Yong-Liu;HE Jian-Xiong;XIONG Chun-Rong(Skate Key Laboratory of Marine Resource Utilization in South China Sea,Special Glass Key Laboratory of Hainan Province,Hainan University,Haikou 570228,China;Hainan Special Glass Technology Co.,Ltd.,Chengmai 571900,China)

机构地区：[1]海南大学南海海洋资源与利用国家重点实验室,海南省特种玻璃重点实验室,海口570228 [2]海南海控特玻科技有限公司,澄迈571900

出　　处：《应用化学》2022年第10期1554-1563,共10页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金项目(Nos.ZDF2020015,51761010);海南大学科研平台建设(No.ZY2019HN09)资助。

摘　　要：化学蚀刻玻璃球,表面产生纳米孔缝,再通过溶剂热法在孔缝内制备了非晶态有机钛聚合物。通过扫描电子显微镜(SEM)、X射线衍射(XRD)、电感耦合等离子体原子发射光谱(ICP-AES)、紫外-可见漫反射光谱(UV-Vis)、荧光光谱(PL)、有机元素分析(OEA)、紫外光电子能谱(UPS)和傅里叶变换红外光谱(FT-IR)等表征了材料的结构及光电性能。结果表明,负载的非晶态有机钛聚合物对可见光有明显的吸收,且荧光强度较NH_(2)-MIL-125(Ti)大幅度降低,光生电子-空穴对更加稳定。玻璃球负载的非晶态有机钛聚合物为催化剂,300 W氙灯为光源催化还原CO_(2),反应4 h后,甲醇的产量达941.6μmol,相应的转换频率(TOF)值为46.4 h^(−1)。使用具有相同有机配体及金属离子的NH_(2)-MIL-125(Ti)及P25为对比催化剂,在相同的光催化条件下,其相应的TOF分别为0.28和0.019 h^(−1)。催化剂热处理实验表明玻璃球载体对有机钛聚合物的化学稳定性有明显的保护作用,经过300℃处理,负载的有机钛聚合物光催化性能仍然稳定,而NH_(2)-MIL-125(Ti)的光催化活性衰减了54%,这是由于其化学结构及晶体结构被破坏。The glass spheres are chemically etched to produce nano-pores on the surface,on which amorphous organotitanium polymer is prepared by the solvothermal method.The structures and optoelectronic properties of the materials are characterized by scanning electron microscopy(SEM),X-ray diffraction(XRD),inductively coupled plasma atomic emission spectroscopy(ICP-AES),ultraviolet-visible diffuse reflectance spectroscopy(UV-Vis),fluorescence spectroscopy(PL),organic element analysis(OEA),ultraviolet photoelectron spectroscopy(UPS),fourier transform infrared spectroscopy(FT-IR)and so on.The supported amorphous organotitanium polymer exhibits an obvious absorption of visible light,and the fluorescence intensity is much lower than that of NH_(2)-MIL-125(Ti),indicating more stable photogenerated electrons.In the photocatalysis of CO_(2) with a 300 W xenon lamp as light source,the methanol yield reaches 941.6μmol over the supported organotitanium polymer within 4 h of illumination,and the corresponding turnover frequency(TOF)is 46.4 h^(-1).For comparison,NH_(2)-MIL-125(Ti),consisting of the same organic ligands and metal ions,is prepared for the photocatalysis of CO_(2).A TOF of only 0.28 h^(-1) is obtained under the same performance conditions.Under the same conditions,the TOF of P25 is 0.019 h^(-1).Upon heat treatment,it shows that the glass spheres as the carrier have an obvious protective effect on the chemical stability of the organotitanium polymer.After treatment at 300℃,the supported organotitanium polymer exhibits a relatively stable photocatalytic performance.Comparatively,the methanol yield over the heat treated NH_(2)-MIL-125(Ti)is decreased by 54%,as the result of the destruction of chemical structure and crystal structure.

关 键 词：玻璃球 负载 非晶态有机钛聚合物 光催化 二氧化碳还原 

分 类 号：O634.4[理学—高分子化学]