新型铝掺杂二氧化钛介孔纳米材料的固相合成及其性能研究
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摘要
随着全球性环境污染的日趋严重,采用光催化技术治理环境污染已引起世界各国的广泛关注。能充分利用太阳光能的高效光催化剂的制备与应用,已成为材料科学、化学、环境和能源科学等领域的研究热点。TiO2光催化剂价廉易得、无毒,化学稳定性和光催化活性较高,在环境净化领域有很好的应用前景。但TiO2禁带宽度大,光响应范围窄；光生电子和空穴复合几率高,量子效率低。多年来的研究表明,通过改性可以提高TiO2的光催化效率,不同的制备方法所得材料的性能不同。因此,采用恰当的TiO2光催化材料的改性方法,研究材料性能的实际应用,具有十分重要的科学意义和应用价值。
本文采用固相反应法合成了Al掺杂TiO2介孔纳米材料,考察了乙醇、模板剂、非金属S、N对固相合成Al掺杂TiO2介孔纳米材料的结构与性能的影响。同时研究了材料晶格缺陷浓度、晶格畸变应力、微观形貌、微晶尺寸、表观酸度、掺杂元素含量对光催化活性的影响,探讨了固相合成Al掺杂TiO2材料的反应动力学与热力学,以及固相反应介孔形成机理；同时研究了温度变化对材料微结构的影响,以及光诱导对材料光催化活性的影响。通过大量的实验工作,取得了一系列创新性成果：
1.首次采用固相反应法合成了新型Al掺杂TiO2微介孔纳米材料。以CTAB为模板,通过Al2(SO4)3·18H20与TBOT的低温固相反应法制得了锐钛矿型Al-TiO2微介孔纳米材料。其反应模型符合杨德尔固相反应动力学方程。其晶粒尺寸约7.0nm,比表面积为155.7m2/g,孔容为0.3579mL/g,孔径分布中心为4.6nm。Al是以+3价进入TiO2晶格并产生较多的晶体结构缺陷,同时伴有骨架外痕量铝氧化物的产生。A13+进入TiO2晶格所形成Ti-O-Al键的弯曲振动为1134cm-1。其紫外-可见吸收光谱相应地受Ti/Al投料比的调控和铝氧化物含量的制约。金属氧化物的紫外-可见漫反射光谱吸收峰均出现在210-370nm范围内。
2.首次考察了固相反应体系中乙醇的作用。研究表明,乙醇可改变材料的微观形貌,并相应地使Al的掺杂量由3.47%提高到3.82%。乙醇使微晶生长的活化能提高,使Al-TiO2相转变温度由500提高到550℃,材料的阻抗由2.5×106Ω增大到4.5×106Ω。乙醇可使Al-TiO2微纳粉体的紫外-可见漫反射光吸收强度降低。乙醇的添加量越多,微晶尺寸越大,孔径分布范围相对增宽,介孔孔径变小,表观酸度(pH值)增大。
3.在确定模板剂、不同投料比或不同模板剂、固定投料比下,所得Al-TiO2材料的物相均为锐钛矿相。Al3+进入锐钛矿TiO6八面体晶格以同晶取代方式侧重从晶胞a-轴(平面)进入,并阻碍TiO2晶粒的生长。不同性质的模板剂对材料的微晶尺寸晶格畸变应力所产生的影响程度各不相同,但晶粒尺寸与畸变应力呈明显的负相关性。Al-TiO2材料的紫外-可见吸收光谱均使TiO2的吸收带边产生一些红移,但紫外区的光吸收强度均有所降低。光催化降解性能与可见光响应范围并不呈正相关性,与能带间隙也并不呈负相关性。
4.正电子的平均寿命与光催化活性呈正相关,而正电子的第一组分寿命强度(I1)与第二组分寿命强度(I2)的比值I1/I2与催化活性呈明显的负相关。金属Al掺杂所产生的缺陷主要以自由体积缺陷为主,微孔洞缺陷为辅。自由体积缺陷不利于吡啶的光催化降解,而微孔洞缺陷有利于该降解反应活性的提高。微孔洞缺陷浓度越大,催化活性越强。水溶液中,温度越高,Al-TiO2材料Al3+的流失越严重；并随pH值增大,Al3+离子的流失率呈抛物线型。中性时流失率相对较小,酸性或碱性则相对增大。Al-TiO2材料对吡啶的可见光降解遵循一级反应动力学规律,反应活性比未掺杂TiO2高7～18倍。
5.S掺杂对Al-TiO2材料的结构和性能产生很大影响。在S、Al共掺杂体中,S是以+6价阳离子形式进入TiO2晶格,Al是以同晶取代方式占据Ti的位置,其晶型为锐钛矿型。S、Al共掺杂能有效抑制TiO2晶粒的生长,晶胞最小值出现在S：Al=4：6。以吡啶为模板剂所得S-Al-TiO2-pyridine微纳材料比以CTAB为模板剂所得S-Al-TiO2-TAB纳米材料的结晶度大,晶粒尺寸、晶胞参数a与c值、及晶胞体积均相应地增大；当S/Al<5/5时,S-Al-TiO2-pyridine紫外-可见漫反射吸收光谱在紫外区的吸收光谱值随S/Al的增大相应增强；当S/Al≥5/5时,则逐渐降低,且发生蓝移,且在可见光区的吸收能力则相应地有所减弱。对S-Al-TiO2-CTAB纳米材料来说,其紫外-可见吸收光谱涵盖了可见光区并延伸到近红外区。材料的光催化活性决定于掺杂元素S、Al的掺杂量及其所导致的光催化剂表面酸性的变化。S-Al-TiO2材料的表观酸度(pH值)与催化降解多效唑的活性呈正相关,并通过S/A1比的变化调控晶格畸变应力使催化剂的催化活性获得最大值。当S/Al=4：6时,S-Al-TiO2(4S-6Al)-pyridine材料的催化活性(0.00414mmin-1)是S-Al-TiO2(4S-6Al)-CTAB材料(0.00111mmin’)的近4倍。
6.处于热力学亚稳状态的锐钛矿相S、Al共掺杂TiO2催化剂,当其微晶尺寸D≤8nm时,D与反应速率常数k呈正相关性；当D≥8nm时,D与k呈负相关性。不同的研磨温度、不同的固相反应温度以及不同的焙烧温度对S-Al-TiO2-pyridine材料的成相及表面酸度的影响十分显著。在确定的S/Al下,焙烧温度越高,材料表面的pH值越大。
7.以CTAB或吡啶为模板所得N-Al-TiO2(3Al-7N)光催化剂均为介孔材料,其微观形貌分别为短棒形纳米粒子和不规则形貌的纳米粒子,比表面积分别为124.9和138.4m2/g。以吡啶为模板所得催化剂的微晶尺寸相应较小。但比表面积与微晶尺寸、以及晶格畸变应力对葛根素的降解并不产生明显的影响。N以阴离子N3-形式占据O的位置而进入了TiO2晶格。Al同晶取代Ti使TiO2的紫外-可见光吸光强度降低,吸光范围红移；Al与N共掺杂使TiO2的紫外吸光强度显著增大,但可见光吸收较弱；材料表面存在Ti-O、Ti-O-Al、N-Ti-O、Ti-O-N、Ti-N-O键。Al与N的掺杂量对材料的光催化活性则起决定性作用。材料的吸附性能与葛根素的可见光降解性能呈正相关性。在20℃、2h内,N-Al-TiO2(3Al-7N)-pyridine光催化剂的催化活性最高,对葛根素的降解率达97.7%,比N-Al-TiO2(3Al-7N)-CTAB材料高5%,是未加模板剂Al-N-TiO2-no材料的8.5倍。紫外光辐照,可诱使N-Al-TiO2(3N-7A1)-CTAB光催化剂的UV-Vis光响应增强,光催化活性随辐照时间的增长呈先降后增趋势。
With the development of the serious globality environmental pollution, the application of photocatalytic technology for pollution treatment has been attracted a great attention in all countries. The preparation and application of the photocatalysts with high activity and effective under the sunlight have become hot topics in the fields of materials science, chemistry, environmental science and energy science. TiO2photocatalyst is widely regarded as a promising material for photocatalytic application due to its low cost, non-toxicity, chemical stability, and high photocatalytic activity. However, TiO2displays its wide band-gap which responds to narrow range of the light absorbed and high recombination of photogenerated electrons and holes, which decreases its photocatalytic efficiency. Many studies indicate that the modification of TiO2can improve the photocatalytic efficiency, and the different preparation methods result in various properties for the same materials. Therefore, it is of scientific meaning and economic value to adopt the right methods to synthesize the modification of TiO2materials with high photocatalytic efficiency, and to investigate the performances of these materials.
In the present dissertation, Al-doped mesoporous TiO2nanomaterials were prepared by a solid-phase synthesis method. The effects of ethanol, template agent, sulfur, nitrogen etc. on the structures and properties of Al-doped mesoporous TiO2 nanomaterials were discussed. The influences of defect concentration, lattice distortion, morphology, particle size, apparent acidity, doping content, and the photocatalytic property were also investigated. The reaction kinetics and thermodynamics of Al-doped TiO2with solid-phase synthesis were researched. The growth mechanism of mesoporous TiO2nanocrystals was not only proposed, the effect of temperature on the structure, and the photoinduction on the photocatalytic activity were also studied. Hence, some new and interesting results were obtained and listed as follows.
1. A novel Al-doped mesoporous TiO2nanocrystal with anatase structure was synthesized via a low temperature solid-phase reaction route using CATB as template, A12(SO4)3·18H2O and TBOT as starting reagents for the first time. The reaction mechanism was in accordance with Yangder kinetic equation. The Al-doped TiO2mesoporous material with crystals size about7.0nm, specific surface area of155.7m2/g, pore volume of0.3579mL/g and pore size of4.6nm could be easily gained. The results reveal that the Al3+doped in TiO2crystal structure which can lead to large microdefects and slightly aluminum-oxide produce, and the bending vibration of Ti-O-Al bond on the Al-TiO2materials is found at1134cm-1, their UV-Vis spectra depend on the ratio of Ti/Al and the aluminum-oxide content. The absorption peaks at210-370nm in those UV-Vis diffuse reflection spectra can be assigned to metallic oxide band.
2. The effect of ethanol in solid-phase reaction system was researched. The results reveal that the ethanol has significant effects on the morphology of defects, and secondly as microvoid defects. The photodegradation of pyridine is beneficial from the microvoid defects but decreased by the free volume defects, and the increase of the density of microvoid defects enhances the photocatalytic activity. Moreover, higher temperature leads to larger loss of Al3+in the Al-TiO2materials. The loss of Al3+first decreases with the increase of pH and reaches to a minimum value when pH approach to7, then increases as pH value is further increased. The visible light photodegradation of pyridine on the Al-TiO2material's surfaces follows the first-order reaction kinetics rule, and the phtocatalytic acitivity is7-18times higher than the undoped TiO2.
5. The doping of sulfur has the very tremendous influence to the Al-TiO2material's structure and the performance. In S and Al co-doped TiO2materials, S enters into the crystal lattice of anatase TiO2as the form of S6+, while Al3occupies the position of Ti4+. The growth of TiO2crystalites is effectively depressed due to the codope of S and Al. The unit cell minimum value appears when S:Al=4:6. The crystallinity of S-Al-TiO2-pyridine prepared using pyridine as template is higher than that of S-Al-TiO2-CTAB prepared using CTAB, as well as the crystal size, the cell parameters of a-and c-axis, and the cell volume. The absorbance of S-Al-TiO2-pyridine in ultraviolet range enhances when the ratio of S/Al≤5/5. However, the decrease of absorbance in UV and visible light range is observed when S/Al>5/5, and absorption band tend to blue shift. The uv-visible diffuse reflection absorption spectrum of S-Al-TiO2-CTAB covers the UV and visible light ranges and extends to the near infrared area. It was found that the doping quantity of S and Al and the resulting change of surface acidity of S-Al-TiO2-CTAB play the key roles in the photocatalytic activity of the samples. The apparent acidity (pH value) of S-Al-TiO2shows shows a positive correlation to the photodegradation of paclobutrazol. The photocatalytic of S-Al-TiO2can be enhanced by tailoring the ratio of S/Al. When S/Al=4:6, S-Al-TiO2shows the highest photocatalytic activity, and the photocatalytic activity of S-Al-TiO2(4S-6Al)-pyridine (0.00414mm-1) material is nearly4times higher than that of S-Al-TiO2(4S-6A1)-CTAB material (0.00111min-1).
6. As for the thermodynamics metastable anatase S and Al codoped TiO2catalysts, the crystal size D shows a positive correlation to the reaction rate constant k when D<8nm, while a negative correlation is observed when D≥8nm. Grinding temperature, solid-phase reaction temperature, and calcining temperature have significant effects on the phase and surface acidity of S-Al-TiO2-pyridine materials. Higher calcining temperature may result in larger pH value on the material surface when S/Al is fixed.
7. Mesoporous N-Al-TiO2(3A1-7N) photocatalysts were obtained when CTAB and pyridine were applied as templates. It was found that the samples from CTAB and pyridine as templates present short rod-like morphology and irregular shape and possess surface area of124.9and138.4m2/g, respectively. The crystal size of catalyst prepared with pyridine as a template is samller than that prepared with CTAB as a template. But the specific surface area, the crystal size and crystal lattice distortion stress don't significant affect on the degradation of puerarin. N exists in the form of N3-. N and Al enter into the crystal lattice of TiO2and occupy the positions of O and Ti, respectively. It results in the decrease of absorbence of TiO2in the UV and visible light area and the red-shift due to the doping of Al. However, the codope of Al and N gives rise to the enhancement of UV absorbance and the reduce of visible absorbance of TiO2, and there exists Ti-O、Ti-O-Al、 N-Ti-O、Ti-O-N、Ti-N-O bonds in the surface of N and Al codoped TiO2catalyst. Moreover, the results show that the doping quantities of N and Al play a key role in the photocatalytic activity, and the adsorption performance of the materials shows a positive correlation to visible light degradation of puerarin. The N-Al-TiO2(3A1-7N)-Pyridine catalyst presents the highest photocatalytic activity at20℃, which is8.5times higher than Al-N-TiO2-no prepared without template,97.7%of puerarin was degraded within2h when N-Al-TiO2(3Al-7N)-pyridine was applied, which is5%higher than the N-Al-TiO2(3A1-7N)-CTAB catalyst. The response of N-Al-TiO2(3N-7A1)-CTAB to UV and visible light is enhanced under the irradiation of UV, and its photocatalytic activity first decreases then increases.
本文采用固相反应法合成了Al掺杂TiO2介孔纳米材料,考察了乙醇、模板剂、非金属S、N对固相合成Al掺杂TiO2介孔纳米材料的结构与性能的影响。同时研究了材料晶格缺陷浓度、晶格畸变应力、微观形貌、微晶尺寸、表观酸度、掺杂元素含量对光催化活性的影响,探讨了固相合成Al掺杂TiO2材料的反应动力学与热力学,以及固相反应介孔形成机理；同时研究了温度变化对材料微结构的影响,以及光诱导对材料光催化活性的影响。通过大量的实验工作,取得了一系列创新性成果：
1.首次采用固相反应法合成了新型Al掺杂TiO2微介孔纳米材料。以CTAB为模板,通过Al2(SO4)3·18H20与TBOT的低温固相反应法制得了锐钛矿型Al-TiO2微介孔纳米材料。其反应模型符合杨德尔固相反应动力学方程。其晶粒尺寸约7.0nm,比表面积为155.7m2/g,孔容为0.3579mL/g,孔径分布中心为4.6nm。Al是以+3价进入TiO2晶格并产生较多的晶体结构缺陷,同时伴有骨架外痕量铝氧化物的产生。A13+进入TiO2晶格所形成Ti-O-Al键的弯曲振动为1134cm-1。其紫外-可见吸收光谱相应地受Ti/Al投料比的调控和铝氧化物含量的制约。金属氧化物的紫外-可见漫反射光谱吸收峰均出现在210-370nm范围内。
2.首次考察了固相反应体系中乙醇的作用。研究表明,乙醇可改变材料的微观形貌,并相应地使Al的掺杂量由3.47%提高到3.82%。乙醇使微晶生长的活化能提高,使Al-TiO2相转变温度由500提高到550℃,材料的阻抗由2.5×106Ω增大到4.5×106Ω。乙醇可使Al-TiO2微纳粉体的紫外-可见漫反射光吸收强度降低。乙醇的添加量越多,微晶尺寸越大,孔径分布范围相对增宽,介孔孔径变小,表观酸度(pH值)增大。
3.在确定模板剂、不同投料比或不同模板剂、固定投料比下,所得Al-TiO2材料的物相均为锐钛矿相。Al3+进入锐钛矿TiO6八面体晶格以同晶取代方式侧重从晶胞a-轴(平面)进入,并阻碍TiO2晶粒的生长。不同性质的模板剂对材料的微晶尺寸晶格畸变应力所产生的影响程度各不相同,但晶粒尺寸与畸变应力呈明显的负相关性。Al-TiO2材料的紫外-可见吸收光谱均使TiO2的吸收带边产生一些红移,但紫外区的光吸收强度均有所降低。光催化降解性能与可见光响应范围并不呈正相关性,与能带间隙也并不呈负相关性。
4.正电子的平均寿命与光催化活性呈正相关,而正电子的第一组分寿命强度(I1)与第二组分寿命强度(I2)的比值I1/I2与催化活性呈明显的负相关。金属Al掺杂所产生的缺陷主要以自由体积缺陷为主,微孔洞缺陷为辅。自由体积缺陷不利于吡啶的光催化降解,而微孔洞缺陷有利于该降解反应活性的提高。微孔洞缺陷浓度越大,催化活性越强。水溶液中,温度越高,Al-TiO2材料Al3+的流失越严重；并随pH值增大,Al3+离子的流失率呈抛物线型。中性时流失率相对较小,酸性或碱性则相对增大。Al-TiO2材料对吡啶的可见光降解遵循一级反应动力学规律,反应活性比未掺杂TiO2高7～18倍。
5.S掺杂对Al-TiO2材料的结构和性能产生很大影响。在S、Al共掺杂体中,S是以+6价阳离子形式进入TiO2晶格,Al是以同晶取代方式占据Ti的位置,其晶型为锐钛矿型。S、Al共掺杂能有效抑制TiO2晶粒的生长,晶胞最小值出现在S：Al=4：6。以吡啶为模板剂所得S-Al-TiO2-pyridine微纳材料比以CTAB为模板剂所得S-Al-TiO2-TAB纳米材料的结晶度大,晶粒尺寸、晶胞参数a与c值、及晶胞体积均相应地增大；当S/Al<5/5时,S-Al-TiO2-pyridine紫外-可见漫反射吸收光谱在紫外区的吸收光谱值随S/Al的增大相应增强；当S/Al≥5/5时,则逐渐降低,且发生蓝移,且在可见光区的吸收能力则相应地有所减弱。对S-Al-TiO2-CTAB纳米材料来说,其紫外-可见吸收光谱涵盖了可见光区并延伸到近红外区。材料的光催化活性决定于掺杂元素S、Al的掺杂量及其所导致的光催化剂表面酸性的变化。S-Al-TiO2材料的表观酸度(pH值)与催化降解多效唑的活性呈正相关,并通过S/A1比的变化调控晶格畸变应力使催化剂的催化活性获得最大值。当S/Al=4：6时,S-Al-TiO2(4S-6Al)-pyridine材料的催化活性(0.00414mmin-1)是S-Al-TiO2(4S-6Al)-CTAB材料(0.00111mmin’)的近4倍。
6.处于热力学亚稳状态的锐钛矿相S、Al共掺杂TiO2催化剂,当其微晶尺寸D≤8nm时,D与反应速率常数k呈正相关性；当D≥8nm时,D与k呈负相关性。不同的研磨温度、不同的固相反应温度以及不同的焙烧温度对S-Al-TiO2-pyridine材料的成相及表面酸度的影响十分显著。在确定的S/Al下,焙烧温度越高,材料表面的pH值越大。
7.以CTAB或吡啶为模板所得N-Al-TiO2(3Al-7N)光催化剂均为介孔材料,其微观形貌分别为短棒形纳米粒子和不规则形貌的纳米粒子,比表面积分别为124.9和138.4m2/g。以吡啶为模板所得催化剂的微晶尺寸相应较小。但比表面积与微晶尺寸、以及晶格畸变应力对葛根素的降解并不产生明显的影响。N以阴离子N3-形式占据O的位置而进入了TiO2晶格。Al同晶取代Ti使TiO2的紫外-可见光吸光强度降低,吸光范围红移；Al与N共掺杂使TiO2的紫外吸光强度显著增大,但可见光吸收较弱；材料表面存在Ti-O、Ti-O-Al、N-Ti-O、Ti-O-N、Ti-N-O键。Al与N的掺杂量对材料的光催化活性则起决定性作用。材料的吸附性能与葛根素的可见光降解性能呈正相关性。在20℃、2h内,N-Al-TiO2(3Al-7N)-pyridine光催化剂的催化活性最高,对葛根素的降解率达97.7%,比N-Al-TiO2(3Al-7N)-CTAB材料高5%,是未加模板剂Al-N-TiO2-no材料的8.5倍。紫外光辐照,可诱使N-Al-TiO2(3N-7A1)-CTAB光催化剂的UV-Vis光响应增强,光催化活性随辐照时间的增长呈先降后增趋势。
With the development of the serious globality environmental pollution, the application of photocatalytic technology for pollution treatment has been attracted a great attention in all countries. The preparation and application of the photocatalysts with high activity and effective under the sunlight have become hot topics in the fields of materials science, chemistry, environmental science and energy science. TiO2photocatalyst is widely regarded as a promising material for photocatalytic application due to its low cost, non-toxicity, chemical stability, and high photocatalytic activity. However, TiO2displays its wide band-gap which responds to narrow range of the light absorbed and high recombination of photogenerated electrons and holes, which decreases its photocatalytic efficiency. Many studies indicate that the modification of TiO2can improve the photocatalytic efficiency, and the different preparation methods result in various properties for the same materials. Therefore, it is of scientific meaning and economic value to adopt the right methods to synthesize the modification of TiO2materials with high photocatalytic efficiency, and to investigate the performances of these materials.
In the present dissertation, Al-doped mesoporous TiO2nanomaterials were prepared by a solid-phase synthesis method. The effects of ethanol, template agent, sulfur, nitrogen etc. on the structures and properties of Al-doped mesoporous TiO2 nanomaterials were discussed. The influences of defect concentration, lattice distortion, morphology, particle size, apparent acidity, doping content, and the photocatalytic property were also investigated. The reaction kinetics and thermodynamics of Al-doped TiO2with solid-phase synthesis were researched. The growth mechanism of mesoporous TiO2nanocrystals was not only proposed, the effect of temperature on the structure, and the photoinduction on the photocatalytic activity were also studied. Hence, some new and interesting results were obtained and listed as follows.
1. A novel Al-doped mesoporous TiO2nanocrystal with anatase structure was synthesized via a low temperature solid-phase reaction route using CATB as template, A12(SO4)3·18H2O and TBOT as starting reagents for the first time. The reaction mechanism was in accordance with Yangder kinetic equation. The Al-doped TiO2mesoporous material with crystals size about7.0nm, specific surface area of155.7m2/g, pore volume of0.3579mL/g and pore size of4.6nm could be easily gained. The results reveal that the Al3+doped in TiO2crystal structure which can lead to large microdefects and slightly aluminum-oxide produce, and the bending vibration of Ti-O-Al bond on the Al-TiO2materials is found at1134cm-1, their UV-Vis spectra depend on the ratio of Ti/Al and the aluminum-oxide content. The absorption peaks at210-370nm in those UV-Vis diffuse reflection spectra can be assigned to metallic oxide band.
2. The effect of ethanol in solid-phase reaction system was researched. The results reveal that the ethanol has significant effects on the morphology of defects, and secondly as microvoid defects. The photodegradation of pyridine is beneficial from the microvoid defects but decreased by the free volume defects, and the increase of the density of microvoid defects enhances the photocatalytic activity. Moreover, higher temperature leads to larger loss of Al3+in the Al-TiO2materials. The loss of Al3+first decreases with the increase of pH and reaches to a minimum value when pH approach to7, then increases as pH value is further increased. The visible light photodegradation of pyridine on the Al-TiO2material's surfaces follows the first-order reaction kinetics rule, and the phtocatalytic acitivity is7-18times higher than the undoped TiO2.
5. The doping of sulfur has the very tremendous influence to the Al-TiO2material's structure and the performance. In S and Al co-doped TiO2materials, S enters into the crystal lattice of anatase TiO2as the form of S6+, while Al3occupies the position of Ti4+. The growth of TiO2crystalites is effectively depressed due to the codope of S and Al. The unit cell minimum value appears when S:Al=4:6. The crystallinity of S-Al-TiO2-pyridine prepared using pyridine as template is higher than that of S-Al-TiO2-CTAB prepared using CTAB, as well as the crystal size, the cell parameters of a-and c-axis, and the cell volume. The absorbance of S-Al-TiO2-pyridine in ultraviolet range enhances when the ratio of S/Al≤5/5. However, the decrease of absorbance in UV and visible light range is observed when S/Al>5/5, and absorption band tend to blue shift. The uv-visible diffuse reflection absorption spectrum of S-Al-TiO2-CTAB covers the UV and visible light ranges and extends to the near infrared area. It was found that the doping quantity of S and Al and the resulting change of surface acidity of S-Al-TiO2-CTAB play the key roles in the photocatalytic activity of the samples. The apparent acidity (pH value) of S-Al-TiO2shows shows a positive correlation to the photodegradation of paclobutrazol. The photocatalytic of S-Al-TiO2can be enhanced by tailoring the ratio of S/Al. When S/Al=4:6, S-Al-TiO2shows the highest photocatalytic activity, and the photocatalytic activity of S-Al-TiO2(4S-6Al)-pyridine (0.00414mm-1) material is nearly4times higher than that of S-Al-TiO2(4S-6A1)-CTAB material (0.00111min-1).
6. As for the thermodynamics metastable anatase S and Al codoped TiO2catalysts, the crystal size D shows a positive correlation to the reaction rate constant k when D<8nm, while a negative correlation is observed when D≥8nm. Grinding temperature, solid-phase reaction temperature, and calcining temperature have significant effects on the phase and surface acidity of S-Al-TiO2-pyridine materials. Higher calcining temperature may result in larger pH value on the material surface when S/Al is fixed.
7. Mesoporous N-Al-TiO2(3A1-7N) photocatalysts were obtained when CTAB and pyridine were applied as templates. It was found that the samples from CTAB and pyridine as templates present short rod-like morphology and irregular shape and possess surface area of124.9and138.4m2/g, respectively. The crystal size of catalyst prepared with pyridine as a template is samller than that prepared with CTAB as a template. But the specific surface area, the crystal size and crystal lattice distortion stress don't significant affect on the degradation of puerarin. N exists in the form of N3-. N and Al enter into the crystal lattice of TiO2and occupy the positions of O and Ti, respectively. It results in the decrease of absorbence of TiO2in the UV and visible light area and the red-shift due to the doping of Al. However, the codope of Al and N gives rise to the enhancement of UV absorbance and the reduce of visible absorbance of TiO2, and there exists Ti-O、Ti-O-Al、 N-Ti-O、Ti-O-N、Ti-N-O bonds in the surface of N and Al codoped TiO2catalyst. Moreover, the results show that the doping quantities of N and Al play a key role in the photocatalytic activity, and the adsorption performance of the materials shows a positive correlation to visible light degradation of puerarin. The N-Al-TiO2(3A1-7N)-Pyridine catalyst presents the highest photocatalytic activity at20℃, which is8.5times higher than Al-N-TiO2-no prepared without template,97.7%of puerarin was degraded within2h when N-Al-TiO2(3Al-7N)-pyridine was applied, which is5%higher than the N-Al-TiO2(3A1-7N)-CTAB catalyst. The response of N-Al-TiO2(3N-7A1)-CTAB to UV and visible light is enhanced under the irradiation of UV, and its photocatalytic activity first decreases then increases.
引文
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