分子筛负载二氧化钛的制备及光催化性能的研究
摘要
在本项研究中,采用溶胶凝胶法成功地制备了TiO_2;以不同浓度盐酸改性NaZSM-5分子筛制得的HZSM-5作为载体,制得负载型TiO_2,并在此基础上研究了掺杂金属离子对负载在HZSM-5分子筛表面的TiO_2光催化性能的影响。测试结果表明:通过分子筛的负载和铁离子掺杂,提高了TiO_2的光催化活性。在乙醇体系中,以钛酸丁酯作钛源、乙醇作溶剂、浓盐酸作催化剂,采用溶胶凝胶法制备出TiO_2。获得性能最佳的TiO_2催化剂的工艺条件为:钛酸丁酯、水、乙醇、浓盐酸的体积比例是1:0.3:3:0.1,500℃煅烧2h。
以不同浓度盐酸处理的NaZSM-5得到不同的HZSM-5分子筛,然后再负载TiO_2,考察了盐酸改性对NaZSM-5分子筛作为TiO_2载体的影响,通过光催化实验结果表明:通过盐酸改性,提高了TiO_2/NaZSM-5对甲基橙的吸附和光催化性能,确定了NaZSM-5分子筛的最佳的盐酸处理浓度0.3mol/L,TiO_2最佳负载量为30%;在400℃煅烧2h的催化剂光催化活性最好,回收且重复利用四次,光催化降解的效果基本不受影响,为初次使用效果的82.4%。利用扫描电镜、X射线衍射、红外光谱和X射线光电子能谱对催化剂进行了表征,结果表明:负载TiO_2后HZSM-5分子筛颗粒发生了团聚,TiO_2包覆在分子筛颗粒的外表面;30%TiO_2/HZSM-5中主要是锐钛矿型TiO_2,HZSM-5可提高TiO_2分散性能,降低TiO_2晶粒的尺寸;TiO_2与HZSM-5没有发生明显的化学键合作用;TiO_2和30%TiO_2/HZSM-5中,钛以四价钛的形式存在,氧化物的组成为TiO_2。
通过掺杂Fe离子提高了TiO_2和30%TiO_2/HZSM-5的光催化活性,Fe-TiO_2的最佳掺杂比为Fe/Ti的摩尔比为0.05%;30%TiO_2/HZSM-5最佳掺杂比为Fe/Ti的摩尔比为0.07%。通过表征显示:Fe~(3+)的引入不足以改变TiO_2的表面形貌;铁离子的掺入并未影响TiO_2的晶型结构,但是可以提高TiO_2的晶型转变温度;掺杂铁离子后TiO_2与HZSM-5也没有发生明显的化学键合作用。
In this paper, titanium dioxide was synthesized by acid-catalyzed sol-gel method, and then metal ions doped TiO_2 photocatalyst supported on zeolite was obtained. The experimental results showed that, the photocatalytic activity of TiO_2 was improved through being loaded onto zeolite and doped with Fe~(3+).
In the alcohol system, the sol for TiO_2 was prepared with tetrabutyl titanate as precursor, alcohol as solvent, and HCl as catalyst. The optimum photocatalytic activity of the samples was obtained after being calcinated at 500℃for 2h and at the condition that the volume ratio of tetrabutyl titanate: alcohol:H2O:HCl was 1:0.3:3:0.1.
TiO_2/HZSM-5 nano-composite photocatalysts were prepared by dispersing TiO_2 onto the external surface of HCl-modified ZSM-5 zeolite using the sol-gel process. Effects of HCl modification on NaZSM-5 zeolite as a carrier of TiO_2 were investigated. Results showed that the adsorption ability and photocatalytic degradation activity of TiO_2/HZSM-5 nano-composites was better than that of bare TiO_2, giving the optimum value of 0.3mol/L. However, HZSM-5 zeolite was not of photocatalytic activity, the optimum photocatalytic activity for the samples with 30% TiO_2 was obtained after being calcinated at 400℃for 2h. The repeatability of photocatalytic activity was also tested and the decolorization rate was 82.4% of initial decolorization rate after four cycles. These materials were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS) measurements. Results showed that modification of support by HCl did not change the surface morphology and structure of ZSM-5 zeolite. All the samples calcined at 400℃presented anatase structure. Supporting on HZSM-5 improved the dispersion of TiO_2, and restrained the increase of crystalline size. Ti-O-Si bonds were not formed between the HZSM-5 bulk and the supported TiO_2. The titanium was in the oxidation state of Ti~(4+), and the oxygen was in the form of O~(2-) in both TiO_2 and SiO_2.
The results showed that doping of Fe~(3+) enhanced the photocatalytic activity of TiO_2 and 30%TiO_2/HZSM-5, and the optimum Fe~(3+) doping of Fe/Ti mole ratios for TiO_2 and 30%TiO_2/HZSM-5 were 0.05% and 0.07%, respectively. Doping Fe~(3+) did not change the surface morphology of TiO_2 and 30%TiO_2/HZSM-5, but inhibited phase transformation of TiO_2 from anatase to rutile, Ti-O-Si bonds were not formed between the HZSM-5 bulk and the supported TiO_2 either.
以不同浓度盐酸处理的NaZSM-5得到不同的HZSM-5分子筛,然后再负载TiO_2,考察了盐酸改性对NaZSM-5分子筛作为TiO_2载体的影响,通过光催化实验结果表明:通过盐酸改性,提高了TiO_2/NaZSM-5对甲基橙的吸附和光催化性能,确定了NaZSM-5分子筛的最佳的盐酸处理浓度0.3mol/L,TiO_2最佳负载量为30%;在400℃煅烧2h的催化剂光催化活性最好,回收且重复利用四次,光催化降解的效果基本不受影响,为初次使用效果的82.4%。利用扫描电镜、X射线衍射、红外光谱和X射线光电子能谱对催化剂进行了表征,结果表明:负载TiO_2后HZSM-5分子筛颗粒发生了团聚,TiO_2包覆在分子筛颗粒的外表面;30%TiO_2/HZSM-5中主要是锐钛矿型TiO_2,HZSM-5可提高TiO_2分散性能,降低TiO_2晶粒的尺寸;TiO_2与HZSM-5没有发生明显的化学键合作用;TiO_2和30%TiO_2/HZSM-5中,钛以四价钛的形式存在,氧化物的组成为TiO_2。
通过掺杂Fe离子提高了TiO_2和30%TiO_2/HZSM-5的光催化活性,Fe-TiO_2的最佳掺杂比为Fe/Ti的摩尔比为0.05%;30%TiO_2/HZSM-5最佳掺杂比为Fe/Ti的摩尔比为0.07%。通过表征显示:Fe~(3+)的引入不足以改变TiO_2的表面形貌;铁离子的掺入并未影响TiO_2的晶型结构,但是可以提高TiO_2的晶型转变温度;掺杂铁离子后TiO_2与HZSM-5也没有发生明显的化学键合作用。
In this paper, titanium dioxide was synthesized by acid-catalyzed sol-gel method, and then metal ions doped TiO_2 photocatalyst supported on zeolite was obtained. The experimental results showed that, the photocatalytic activity of TiO_2 was improved through being loaded onto zeolite and doped with Fe~(3+).
In the alcohol system, the sol for TiO_2 was prepared with tetrabutyl titanate as precursor, alcohol as solvent, and HCl as catalyst. The optimum photocatalytic activity of the samples was obtained after being calcinated at 500℃for 2h and at the condition that the volume ratio of tetrabutyl titanate: alcohol:H2O:HCl was 1:0.3:3:0.1.
TiO_2/HZSM-5 nano-composite photocatalysts were prepared by dispersing TiO_2 onto the external surface of HCl-modified ZSM-5 zeolite using the sol-gel process. Effects of HCl modification on NaZSM-5 zeolite as a carrier of TiO_2 were investigated. Results showed that the adsorption ability and photocatalytic degradation activity of TiO_2/HZSM-5 nano-composites was better than that of bare TiO_2, giving the optimum value of 0.3mol/L. However, HZSM-5 zeolite was not of photocatalytic activity, the optimum photocatalytic activity for the samples with 30% TiO_2 was obtained after being calcinated at 400℃for 2h. The repeatability of photocatalytic activity was also tested and the decolorization rate was 82.4% of initial decolorization rate after four cycles. These materials were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS) measurements. Results showed that modification of support by HCl did not change the surface morphology and structure of ZSM-5 zeolite. All the samples calcined at 400℃presented anatase structure. Supporting on HZSM-5 improved the dispersion of TiO_2, and restrained the increase of crystalline size. Ti-O-Si bonds were not formed between the HZSM-5 bulk and the supported TiO_2. The titanium was in the oxidation state of Ti~(4+), and the oxygen was in the form of O~(2-) in both TiO_2 and SiO_2.
The results showed that doping of Fe~(3+) enhanced the photocatalytic activity of TiO_2 and 30%TiO_2/HZSM-5, and the optimum Fe~(3+) doping of Fe/Ti mole ratios for TiO_2 and 30%TiO_2/HZSM-5 were 0.05% and 0.07%, respectively. Doping Fe~(3+) did not change the surface morphology of TiO_2 and 30%TiO_2/HZSM-5, but inhibited phase transformation of TiO_2 from anatase to rutile, Ti-O-Si bonds were not formed between the HZSM-5 bulk and the supported TiO_2 either.
引文
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