掺钼二氧化钛光催化剂的制备与表征
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摘要
本文致力于TiO_2粉末光催化剂的掺杂改性研究。采用传统的溶胶凝胶法制备了掺钼二氧化钛粉末(Mo-TiO_2 );另外,将掺钼二氧化钛粉末投入到纯TiO_2溶胶中,经烘干、煅烧后,制得高活性TiO_2 /Mo-TiO_2复合物光催化剂。使用X射线光电子能谱、X射线衍射、透射电镜、比表面积分析、紫外-可见漫反射光谱、荧光光谱等手段对催化剂进行了表征。在紫外光照射下,以甲基橙溶液的光催化降解反应为探针,研究了Mo离子浓度对样品光催化活性的影响。通过测定施加不同偏压后掺杂不同钼离子浓度的Mo-TiO_2电极的交流阻抗图,考察掺钼后二氧化钛电极的平带电势和载流子浓度的变化,研究了样品电化学性能对光催化活性的影响。研究表明:
(1) XPS结果显示,钼离子掺杂样品表面羟基数目要比纯TiO_2多。Mo元素主要以Mo~(6+)形式存在于催化剂中,也有少量的Mo~(5+)。
(2)掺杂离子的浓度影响TiO_2的晶相和颗粒粒径。400℃煅烧时样品均为锐钛矿相;在适量掺杂浓度下,掺入金属离子能不同程度地抑制TiO_2晶粒的长大。复合型TiO_2 /Mo-TiO_2粉末的平均粒径为12.8 nm左右,稍小于纯TiO_2。
(3) BET结果表明,所制得的催化剂都具有孔结构。对于Mo-TiO_2催化剂,低浓度掺杂其比表面积比纯TiO_2小,高浓度掺杂其比表面积较大。复合型催化剂的比表面积与纯TiO_2相差不大。
(4)掺钼TiO_2的光吸收带边相对于纯TiO_2有明显的红移,并且随着掺杂离子浓度的增大,红移越明显。
(5) FS结果可以看出,随着掺杂离子浓度的增加,催化剂的荧光强度不断降低。另外,采取不同掺杂方式、掺杂浓度得到的掺钼TiO_2的荧光峰的位置基本一致。
(6) Mo-TiO_2催化剂的光催化活性比纯TiO_2差,这是因为钼离子促进了光生载流子的复合;带有n-n异质结半导体结构的TiO_2 /Mo-TiO_2复合催化剂拥有比纯TiO_2和Mo-TiO_2催化剂更高的光催化活性。其中,Mo的掺杂摩尔分数为2%、TiO_2 :Mo-TiO_2的质量比为12:1的最佳复合催化剂,其光催化活性是纯TiO_2的1.6倍。
(7) Mo-TiO_2电极的平带电势V_(fb)和载流子浓度ND值表明,当Mo含量较低时(≤2%),Mo-TiO_2的平带电势和载流子浓度与纯TiO_2的相差不大;但当Mo掺杂量大于2%时,平带电位正移、载流子浓度增加。
In order to enhance the photocatalytic activity of TiO_2 catalysts, Mo-doped TiO_2 photocatalysts (Mo-TiO_2 ) were prepared by the traditional sol–gel method using (NH_4)_6Mo_7O_(24) .4H_2O and tetrabutyl titanate [Ti(OC_4H_9)_4] as the raw materials. TiO_2 /Mo-TiO_2 composite photocatalysts were prepared by mixing TiO_2 sol with sol-gel derived Mo-TiO_2 powders, followed by drying and calcination. These photocatalysts were characterized by XPS, XRD, TEM, BET, UV-vis and FS spectroscopy. The samples were employed as catalysts for methyl orange photodegradation in aqueous suspensions under UV irradiation, used as a probe reaction. Nyquist and Bode diagrams of the impedance spectra were obtained for Mo-TiO_2 electrodes when different bias potential was present, the flat-band potential(Vfb) and the donor concentration(ND) of Mo-TiO_2 electrodes were investigated. The influence of the electrochemical properties of TiO_2 catalysts on the photocatalytic activities was studied. The results were showed as follows:
(1) XPS results indicated that the surface hydroxyl content of samples Mo-TiO_2 and TiO_2 /Mo-TiO_2 was greater than that of sample undoped TiO_2 . The elements was existed in the catalysts by the mainly of Mo~(6+) and a small amout of Mo~(5+).
(2) Doping ions content had influences on the crystal phase and crystal size of TiO_2. All TiO_2 catalysts calcined at 400℃were of anatase type. Doping metal ions inhibited the TiO_2 grain growth in varying degrees when the dopants in appropriate content. The grain size of TiO_2 /Mo-TiO_2 composites was slightly smaller than that of undoped titania, the mean crystalline sizes were about 12.8 nm.
(3) The BET results indicated the presence of mesoporous structure for all samples. For Mo-TiO_2 samples, at low Mo-doping concentration range, the samples had less surface area compared to the undoped TiO_2 ; at high Mo-doping concentration range, the SBET of catalysts larger than the undoped TiO_2 . For composite powers, the SBET was basically the same with the undoped TiO_2 .
(4) Compared with the pure sample, obvious absorption edge red-shifts were observed in the results of the doped samples with increasing molybdenum content.
(5) Photoluminescence spectra exhibited great decrease in emission intensity of doped samples compared with undoped TiO_2. Moreover, although the doping modes were different, no new luminescence was occurred.
(6) The photocatalytic activity of Mo-TiO_2 photocatalysts was worse than that of undoped TiO_2 and the photodegradation rate decreased with increase in the level of molybdenum doped (on TiO_2 ). TiO_2/Mo-TiO_2 composite photocatalysts having the n-n heterojunction, were shown to have a higher photocatalytic destruction rate than that of Mo-TiO_2 photocatalysts and undoped TiO_2 . The best TiO_2 /Mo-TiO_2 composite with the mass ratio of TiO_2 :2 at % Mo-TiO_2 equal to 12:1 demonstrates 1.6 times the photocatalytic activity of undoped TiO_2 .
(7) For Mo-TiO_2 electrodes, at low Mo-doping concentration range(≤2%), the flat-band potential(V_(fb)) and the donor concentration(ND) were basically the same with the undoped TiO_2 ; at high Mo-doping concentration range, the flat-band potential(Vfb) shifted positively, the donor concentration(ND) were increased.
(1) XPS结果显示,钼离子掺杂样品表面羟基数目要比纯TiO_2多。Mo元素主要以Mo~(6+)形式存在于催化剂中,也有少量的Mo~(5+)。
(2)掺杂离子的浓度影响TiO_2的晶相和颗粒粒径。400℃煅烧时样品均为锐钛矿相;在适量掺杂浓度下,掺入金属离子能不同程度地抑制TiO_2晶粒的长大。复合型TiO_2 /Mo-TiO_2粉末的平均粒径为12.8 nm左右,稍小于纯TiO_2。
(3) BET结果表明,所制得的催化剂都具有孔结构。对于Mo-TiO_2催化剂,低浓度掺杂其比表面积比纯TiO_2小,高浓度掺杂其比表面积较大。复合型催化剂的比表面积与纯TiO_2相差不大。
(4)掺钼TiO_2的光吸收带边相对于纯TiO_2有明显的红移,并且随着掺杂离子浓度的增大,红移越明显。
(5) FS结果可以看出,随着掺杂离子浓度的增加,催化剂的荧光强度不断降低。另外,采取不同掺杂方式、掺杂浓度得到的掺钼TiO_2的荧光峰的位置基本一致。
(6) Mo-TiO_2催化剂的光催化活性比纯TiO_2差,这是因为钼离子促进了光生载流子的复合;带有n-n异质结半导体结构的TiO_2 /Mo-TiO_2复合催化剂拥有比纯TiO_2和Mo-TiO_2催化剂更高的光催化活性。其中,Mo的掺杂摩尔分数为2%、TiO_2 :Mo-TiO_2的质量比为12:1的最佳复合催化剂,其光催化活性是纯TiO_2的1.6倍。
(7) Mo-TiO_2电极的平带电势V_(fb)和载流子浓度ND值表明,当Mo含量较低时(≤2%),Mo-TiO_2的平带电势和载流子浓度与纯TiO_2的相差不大;但当Mo掺杂量大于2%时,平带电位正移、载流子浓度增加。
In order to enhance the photocatalytic activity of TiO_2 catalysts, Mo-doped TiO_2 photocatalysts (Mo-TiO_2 ) were prepared by the traditional sol–gel method using (NH_4)_6Mo_7O_(24) .4H_2O and tetrabutyl titanate [Ti(OC_4H_9)_4] as the raw materials. TiO_2 /Mo-TiO_2 composite photocatalysts were prepared by mixing TiO_2 sol with sol-gel derived Mo-TiO_2 powders, followed by drying and calcination. These photocatalysts were characterized by XPS, XRD, TEM, BET, UV-vis and FS spectroscopy. The samples were employed as catalysts for methyl orange photodegradation in aqueous suspensions under UV irradiation, used as a probe reaction. Nyquist and Bode diagrams of the impedance spectra were obtained for Mo-TiO_2 electrodes when different bias potential was present, the flat-band potential(Vfb) and the donor concentration(ND) of Mo-TiO_2 electrodes were investigated. The influence of the electrochemical properties of TiO_2 catalysts on the photocatalytic activities was studied. The results were showed as follows:
(1) XPS results indicated that the surface hydroxyl content of samples Mo-TiO_2 and TiO_2 /Mo-TiO_2 was greater than that of sample undoped TiO_2 . The elements was existed in the catalysts by the mainly of Mo~(6+) and a small amout of Mo~(5+).
(2) Doping ions content had influences on the crystal phase and crystal size of TiO_2. All TiO_2 catalysts calcined at 400℃were of anatase type. Doping metal ions inhibited the TiO_2 grain growth in varying degrees when the dopants in appropriate content. The grain size of TiO_2 /Mo-TiO_2 composites was slightly smaller than that of undoped titania, the mean crystalline sizes were about 12.8 nm.
(3) The BET results indicated the presence of mesoporous structure for all samples. For Mo-TiO_2 samples, at low Mo-doping concentration range, the samples had less surface area compared to the undoped TiO_2 ; at high Mo-doping concentration range, the SBET of catalysts larger than the undoped TiO_2 . For composite powers, the SBET was basically the same with the undoped TiO_2 .
(4) Compared with the pure sample, obvious absorption edge red-shifts were observed in the results of the doped samples with increasing molybdenum content.
(5) Photoluminescence spectra exhibited great decrease in emission intensity of doped samples compared with undoped TiO_2. Moreover, although the doping modes were different, no new luminescence was occurred.
(6) The photocatalytic activity of Mo-TiO_2 photocatalysts was worse than that of undoped TiO_2 and the photodegradation rate decreased with increase in the level of molybdenum doped (on TiO_2 ). TiO_2/Mo-TiO_2 composite photocatalysts having the n-n heterojunction, were shown to have a higher photocatalytic destruction rate than that of Mo-TiO_2 photocatalysts and undoped TiO_2 . The best TiO_2 /Mo-TiO_2 composite with the mass ratio of TiO_2 :2 at % Mo-TiO_2 equal to 12:1 demonstrates 1.6 times the photocatalytic activity of undoped TiO_2 .
(7) For Mo-TiO_2 electrodes, at low Mo-doping concentration range(≤2%), the flat-band potential(V_(fb)) and the donor concentration(ND) were basically the same with the undoped TiO_2 ; at high Mo-doping concentration range, the flat-band potential(Vfb) shifted positively, the donor concentration(ND) were increased.
引文
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