水热法制备负载型TiO_2薄膜及其去除给水中腐殖酸的研究
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摘要
本文以硫酸钛为前驱体,尿素为沉淀剂,采用水热法制备的玻璃弹簧负载型纳米TiO2薄膜经SEM表征,表面晶粒结合致密、大小均匀,晶粒尺寸在20~30nm左右,且均为锐钛矿型;通过紫外-可见分光光度计扫描发现,薄膜对350nm波长以内的紫外光吸收强烈;薄膜物理化学性质相对稳定,流体冲刷磨损率小。光催化采用硫酸钛、尿素的浓度分别为0.5mol/L、1.0mol/L,水热反应温度200℃及保温时间为2h的条件下所制备的催化剂对8mg/L的腐殖酸溶液光催化降解效果最佳,即pH值为6.1、紫外光强为34μW·m-2、空气通量分2L/min、反应温度控制在20℃左右时,HA的去除率最高,反应4h可达85%以上,反应8h腐殖酸的去除率更是达到了90.6%;且反应时间和腐殖酸浓度呈直线,符合一级动力学反应特征。
采用水热法制备的玻璃弹簧负载型Zn2+/ TiO2复合催化剂在玻璃弹簧上附着牢固,Zn2+掺杂量为0.6%时,催化剂表面颗粒细致紧密,平均粒径在20~50nm左右,且颗粒之间具有明显的空腔分布;其物相组成主要为锐钛矿型,同时出现了微弱的金红石相特征峰。掺杂Zn2+可以提高TiO2催化剂的光催化降解活性,掺杂量(摩尔比)为0.6%时,对8mg/L的腐殖酸溶液光催化降解反应4h时,腐殖酸的降解率达到90.1%;同时也使得TiO2的吸收光谱发生红移至400nm,为在光催化降解过程中对太阳光的利用创造了条件。
In this research, spring-loaded glass nano-TiO2 thin films was synthesized by hydrothermal method with titanium sulfate as precursor and urea as precipitation agent. It was seriously combined with the glass surface, and its grain size was uniform which size in about 20 ~ 30nm were antase. UV - visible spectrophotometer scanning analysis showed that the ultraviolet of wavelengths less than 350nm was strongly absorbed by nano-TiO2 photocatalyst; The physical and chemical properties of thin films was relatively stable, and its fluid erosion rate was small. When the concentration of titanium sulfate being 0.5mol / L, the concentration of urea being, 1.0mol / L, the hydrothermal reaction temperature being 200℃and reaction for 2 hours, the catalyst prepared could most effectively degrade the humic acid solution of 8mg/L.And and humic acid concentration and reaction time showed significant linear correlation, eing zero-order reaction.
Secondly, the products performed a high photocatalytic activity during that humic acid in water was photocatalytically degraded in the home-made devices, The results showed that when the initial humic acid concentration of 8mg / L, pH value of 6.1, ultraviolet light intensity for 34μW ? m-2 (25W), air flux at 2L/min, reaction temperature control about 20℃, when, the removal rate of HA was the highest. It was up to 85% in four hours’reaction, and 90.6% was achieved in eight hours. Compared to only TiO2 catalyst, the removal rate of humic acid was significantly increased in the UV/TiO2/O2 and UV/O2 complex systems, which confirmed that the UV and TiO2 photocatalysis had obvious synergies in HA degradation.
Lastly, spring-loaded Zn2 + / TiO2 complex catalyst prepared by hydrothermal method was tightly combined with the glass surface. When the amount of Zn2 +-doped was 0.6%, the particles of catalyst surface were significantly refined with an average particle size in about 20 ~ 50nm and the apparent cavities distributed among the particles; Their phase composition was mainly anatase, while a weak characteristic peaks of rutile phase.Zn2 +-doped could improve photocatalytic degradation ability of the catalyst TiO2. The best amount doped (molar ratio) was 0.6%, the degradation rate of humic acid was achieved 90.1% in 4h reaction. While the absorption spectra of TiO2 red shift occurred to improve its utilization of sunlight; Ozone access could significantly increase the efficiency of the degradation of HA, and increasing with the increased access, which reached 90.3% in 4h. This result confirmed that the use of sun-ray to HA degradation had a high practical value.
采用水热法制备的玻璃弹簧负载型Zn2+/ TiO2复合催化剂在玻璃弹簧上附着牢固,Zn2+掺杂量为0.6%时,催化剂表面颗粒细致紧密,平均粒径在20~50nm左右,且颗粒之间具有明显的空腔分布;其物相组成主要为锐钛矿型,同时出现了微弱的金红石相特征峰。掺杂Zn2+可以提高TiO2催化剂的光催化降解活性,掺杂量(摩尔比)为0.6%时,对8mg/L的腐殖酸溶液光催化降解反应4h时,腐殖酸的降解率达到90.1%;同时也使得TiO2的吸收光谱发生红移至400nm,为在光催化降解过程中对太阳光的利用创造了条件。
In this research, spring-loaded glass nano-TiO2 thin films was synthesized by hydrothermal method with titanium sulfate as precursor and urea as precipitation agent. It was seriously combined with the glass surface, and its grain size was uniform which size in about 20 ~ 30nm were antase. UV - visible spectrophotometer scanning analysis showed that the ultraviolet of wavelengths less than 350nm was strongly absorbed by nano-TiO2 photocatalyst; The physical and chemical properties of thin films was relatively stable, and its fluid erosion rate was small. When the concentration of titanium sulfate being 0.5mol / L, the concentration of urea being, 1.0mol / L, the hydrothermal reaction temperature being 200℃and reaction for 2 hours, the catalyst prepared could most effectively degrade the humic acid solution of 8mg/L.And and humic acid concentration and reaction time showed significant linear correlation, eing zero-order reaction.
Secondly, the products performed a high photocatalytic activity during that humic acid in water was photocatalytically degraded in the home-made devices, The results showed that when the initial humic acid concentration of 8mg / L, pH value of 6.1, ultraviolet light intensity for 34μW ? m-2 (25W), air flux at 2L/min, reaction temperature control about 20℃, when, the removal rate of HA was the highest. It was up to 85% in four hours’reaction, and 90.6% was achieved in eight hours. Compared to only TiO2 catalyst, the removal rate of humic acid was significantly increased in the UV/TiO2/O2 and UV/O2 complex systems, which confirmed that the UV and TiO2 photocatalysis had obvious synergies in HA degradation.
Lastly, spring-loaded Zn2 + / TiO2 complex catalyst prepared by hydrothermal method was tightly combined with the glass surface. When the amount of Zn2 +-doped was 0.6%, the particles of catalyst surface were significantly refined with an average particle size in about 20 ~ 50nm and the apparent cavities distributed among the particles; Their phase composition was mainly anatase, while a weak characteristic peaks of rutile phase.Zn2 +-doped could improve photocatalytic degradation ability of the catalyst TiO2. The best amount doped (molar ratio) was 0.6%, the degradation rate of humic acid was achieved 90.1% in 4h reaction. While the absorption spectra of TiO2 red shift occurred to improve its utilization of sunlight; Ozone access could significantly increase the efficiency of the degradation of HA, and increasing with the increased access, which reached 90.3% in 4h. This result confirmed that the use of sun-ray to HA degradation had a high practical value.
引文
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