特殊形貌二氧化钛基微纳米材料的制备及光学性能
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摘要
作为最有应用前景的半导体材料之一，二氧化钛在太阳能电池、光催化降解污染物、裂解水制氢等领域引起了研究人员的浓厚兴趣。在微纳米尺度范围内，二氧化钛可以呈现出多种微观形貌，如纳米颗粒，纳米线，纳米棒，纳米管，纳米带，微纳米球等；其晶体结构也具有多样性，如无定形态、金红石型、锐钛矿型、混晶型等。众多研究表明，二氧化钛基微纳米材料的微观形貌和晶体结构对其光学性能如紫外-可见光的吸收能力、光催化能力等有重大影响，开发具有特殊微观形貌的二氧化钛基微纳米材料，研究其制备工艺、形成机制及光学性能对推动新能源开发和环境治理、节能降耗等有积极的现实意义。
为了探究二氧化钛基材料在微纳米尺度范围内的形貌演变，制备适用于新能源和环境保护领域、具有可见光响应的高性能功能材料，研究二氧化钛基微纳米材料的复杂形貌与其光学性能的关系，本文采用成熟的水热/溶剂热方法制备了一系列二氧化钛基微纳米材料，对其微观形貌、晶体结构、光学吸收和光催化性能等进行了研究，并借助计算机模拟软件Materials Studio的CASTEP模块对相关材料进行了热力学计算，对二氧化钛基功能材料的晶体生长机制做出了进一步阐述。主要研究内容及成果如下：
(1)通过改进传统的二氧化钛纳米线、纳米管水热法制备的反应介质，开发出了一种二氧化钛介孔纳米带的溶剂热制备工艺。将无水乙醇与10mol/L的氢氧化钠溶液进行不同体积比的混合，以此为反应介质可以制备具有不同形貌的二氧化钛纳米带结构；当二者体积比为1:1时，纳米带具有规整、均一的几何形貌。将所获得的纳米带材料用pH<3的盐酸溶液浸泡24小时并经高温煅烧后可以在纳米带上引入均匀分布的介孔结构，介孔的尺寸为5~7nm，数目随着pH的减小而增加。实验结果表明，反应压力对于二氧化钛纳米材料的形貌有重要影响，压力越大越有利于纳米带形貌的形成。该纳米带制备工艺通过限制片层状钛酸盐的卷曲进一步增大了二氧化钛的比表面积，具有氢氧化钠的用量少，水热反应时间短，制备成本和能耗低的特点。
将所获得的二氧化钛介孔纳米带材料与Li~+离子复合，我们研究了该复合材料对孔雀石绿的光催化降解效果。实验结果表明，Li~+离子与二氧化钛介孔纳米带的复合未明显改变纳米带的形貌和晶相组成，但会通过置换Ti~(4+)离子破坏纳米带的晶体结构，同时提高复合材料的电负性，对其光催化降解性能有正反双重作用。
(2)相比于一维的纳米线、纳米管、纳米带等结构，三维二氧化钛微纳米结构更加复杂，其制备工艺、晶体生长机理和光学性能目前缺乏深入的研究。在强酸性条件下，以硫酸钾为形貌控制剂，通过缓慢氧化氯化亚钛制备了具有复杂形貌、可响应整个可见光区的二氧化钛混晶材料。通过控制硫酸钾的浓度可实现对二氧化钛晶体生长方向和生长速率的控制，一步合成具有典型的放射形方柱状结构的金红石型二氧化钛、八面体结构的锐钛矿型二氧化钛，以及二者共存的混晶结构。所得样品的微观形貌和晶粒尺寸对样品的光学吸收性能有明显影响，这些对可见光有强烈吸收的二氧化钛材料在太阳能电池、光催化等领域有重要的应用价值。
(3)半导体耦合是扩展二氧化钛光谱响应区间的有效手段，三维二氧化钛基微纳米材料的半导体耦合方法目前鲜有研究。以刺棒状硫化镉为基础，通过水热法一步制备了三维硫化镉/钛酸盐复合材料，该复合材料由玫瑰花状结构和纳米线结构组成。实验表明，主要原料P25的用量对于玫瑰花状微纳米结构的形成至关重要：足量P25可保证二氧化钛在参与化学反应时能有效与S2-离子竞争，抑制硫化镉的自由生长，并以其为成核和生长的基点，最终形成玫瑰花状纳米结构；当P25用量不足时，样品最终形貌则呈现多样性，如颗粒状、不规则柱状及纤维状等。S~(2-)离子的形成和释放速度从动力学上决定了硫化镉成核和生长的速度，对最终反应产物的形貌有决定性作用。从动力学角度寻求材料制备过程中可能的速率控制步骤是制备具有特定形貌、特定性能纳米材料的有效途径。
（4）为了探究二氧化钛混晶的晶体生长机制，通过计算机模拟软件MaterialsStudio的CASTEP模块对金红石型二氧化钛(110)面吸附硫酸进行了第一性原理计算分析，从热力学角度确定了主要的吸附模式。计算结果表明，在强酸性条件下硫酸钾对二氧化钛生长基元[TiO_6]八面体的螯合作用主要是通过H+HSO_4分子片段来实现的，其次是以H_2SO_4分子形式，而之前研究者提出的硫酸根螯合二氧化钛的机制是不正确的。该螯合作用改变了[TiO_6]八面体彼此之间结合的方式和结合速率，形成了锐钛矿型二氧化钛和金红石型二氧化钛共存的特殊结构。
As one of the most promising semiconductor materials, titanium dioxide hasaroused keen interest of researchers in the fields of solar cells, photocatalyticdegradation of pollutants and hydrogen production by water-splitting. In the microand nano scales, titanium dioxide shows a variety of morphology (such asnanoparticles, nanowires, nanorods, nanotubes, micro-nano-balls, etc.) and crystalstructure (such as amorphous, rutile, anatase, mixed crystal type). Many studies haveindicated that the microscopic morphologies and crystal structures of titanium dioxidebased micro-nano material have significant impacts on the UV-Vis light absorptionand photocatalytic properties; however, there are very limited researches investigatingthe morphology diversity, formation mechanism or the optical properties of titaniumdioxide based micro-nano material with complex morphologies. Such researches havepositive practical significance in promoting the development of new energy andenvironmental governance.
In this thesis, a series of titanium dioxide based micro-nano materials areprepared by hydrothermal or solvothermal method, and the morphology, crystalstructure, optical absorption and photocatalytic properties are studied exhaustively.The results are helpful to analyse the influencing factors of morphology evolution oftitanium dioxide within the range of the micro-nano scale, to synthetize titaniumdioxide with good visible light response for new energy and environmental protectionapplications, and to further study the relationship between the complex morphology oftitanium dioxide and its performance. The thermodynamic calculations by CASTEPmodule from Materials Studio are used to futher elaborate the mechanism of crystalgrowth of titanium dioxide. The main study contents and results of this paper aredescribed in detail as follows:
(1)By improving the traditional hydrothermal method for the synthesis oftitanium dioxide nanowires or nanotubes, a solvothermal process for the synthesis oftitanium dioxide mesoporous nanobelts is developed. Different volume ratio mixturesof ethanol and10mol/L sodium hydroxide solution are used as the reaction mediumto prepare titanium dioxide nanobelts with different morphologies, when the volumeratio is1:1, the nanobelts with structured and uniform geometric morphology isobtained. When soaked in hydrochloric acid solution (pH <3) for24hours andcalcined at400℃for2hours, the titanium dioxide nanobelts will change intomesoporous structure, the size of the pore is about5-7nm and the number of thesepores has a slight increase when pH decreases. The experimental results show that thereaction pressure has great impact on the morphology of the titanium dioxide: thegreater the pressure, it is the more beneficial to the formation of nanobelts. Comparedwith other systhesis methods for nanobelt, the solvothermal process can significantlyreduce the amount of sodium hydroxide and hydrothermal reaction time, and thuslower costs and energy consumption. The specific surface area of nano titaniumdioxide is further improved by maintaining the lamellar Titanate in this solvothermalprocess.
The visible light photocatalytic activity of mesoporous Li-doped titaniumdioxide nanobelts is studied. The doping of Li~+ion does not change the crystallinephase but decompose the lattice of titanium dioxide nanobelts and enhance theelectronegativity by replacing Ti~(4+)ion. The lattice breaking and the electronegativityhave important but contradictory influences on the photocatalytic activity of themesoporous Li-doped TiO_2nanobelts.
(2) Compared to the one-dimensional nanowire, nanotube and nanobeltstructures, three-dimensional titanium dioxide micro-nano structures are morecomplex, while their synthesis technology, crystal growth mechanism or opticalproperties are lack of in-depth research.Titanium dioxide mixed crystals, havingcomplex morphologies and responsing to the whole visible region, are prepared under strong acidic conditions by hydrothermal method. The potassium sulfate is believed tochelate with the octahedral growth unit [TiO_6], which will change the crystal growthdirection and the growth rate of titanium dioxide. As a result, morphology control canbe achieved through the concentration control of potassium sulfate. Rutile with atypical radial prismatic structure, anatase with an octahedral structure, as well asrutile-anatase coexistence structures is synthesized. Both the morphology and grainsize of the samples have significant effects on the optical absorption properties oftitanium dioxide. These materials with visible light response have importantapplications prospects in solar cells, photocatalysis and other fields.
(3) The semiconductor coupling is an effective means to extend the visible lightresponse range; however, there are few researches involving the coupling methods forthere-dimensional titanium dioxide based mirco-nano materials. Based on the thornyrod-like CdS, CdS/titanate composite nanostructure, consisting of nanoroses andnanowires, is prepared by hydrothermal method. The amount of P25is vital for theformation of rose-like nanostructure: a sufficient amount of titanium dioxide caneffectively compete with S2-ion in all related reactions, inhibit the free growth of CdSand make the transition from nanoparticle to nanoroses; inadequate amount oftitanium dioxide, however, gaves rise to diverse morphologies, such as particles,irregular columns and fibres. The formation and release rate of S~(2-)ion determines thenucleation and growth rate of CdS dynamically, which has a decisive role on themorphology of the final products. From the kinetic point of view, the rate controllingstep of chemical reactions is the key to prepare nanomaterials with specificmorphologies and properties.
(4) The interaction of sulfuric acid with rutile titanium dioxide (110) surfacefrom density functional theory calculations is carried on the CASTEP module ofMaterials Studio to determine the major adsorption mode from a thermodynamicpoint of view. The results show that, under strong acidic conditions, the chelationeffect between the potassium sulfate and [TiO_6] is mainly achieved by H+HSO_4 molecular fragment, partly by H_2SO_4molecular, but unlikely by2H+SO_4; the resultsfurther elaborate the crystal growth mechanism of titanium dioxide mixed crystalsfrom the energy point of view.
为了探究二氧化钛基材料在微纳米尺度范围内的形貌演变，制备适用于新能源和环境保护领域、具有可见光响应的高性能功能材料，研究二氧化钛基微纳米材料的复杂形貌与其光学性能的关系，本文采用成熟的水热/溶剂热方法制备了一系列二氧化钛基微纳米材料，对其微观形貌、晶体结构、光学吸收和光催化性能等进行了研究，并借助计算机模拟软件Materials Studio的CASTEP模块对相关材料进行了热力学计算，对二氧化钛基功能材料的晶体生长机制做出了进一步阐述。主要研究内容及成果如下：
(1)通过改进传统的二氧化钛纳米线、纳米管水热法制备的反应介质，开发出了一种二氧化钛介孔纳米带的溶剂热制备工艺。将无水乙醇与10mol/L的氢氧化钠溶液进行不同体积比的混合，以此为反应介质可以制备具有不同形貌的二氧化钛纳米带结构；当二者体积比为1:1时，纳米带具有规整、均一的几何形貌。将所获得的纳米带材料用pH<3的盐酸溶液浸泡24小时并经高温煅烧后可以在纳米带上引入均匀分布的介孔结构，介孔的尺寸为5~7nm，数目随着pH的减小而增加。实验结果表明，反应压力对于二氧化钛纳米材料的形貌有重要影响，压力越大越有利于纳米带形貌的形成。该纳米带制备工艺通过限制片层状钛酸盐的卷曲进一步增大了二氧化钛的比表面积，具有氢氧化钠的用量少，水热反应时间短，制备成本和能耗低的特点。
将所获得的二氧化钛介孔纳米带材料与Li~+离子复合，我们研究了该复合材料对孔雀石绿的光催化降解效果。实验结果表明，Li~+离子与二氧化钛介孔纳米带的复合未明显改变纳米带的形貌和晶相组成，但会通过置换Ti~(4+)离子破坏纳米带的晶体结构，同时提高复合材料的电负性，对其光催化降解性能有正反双重作用。
(2)相比于一维的纳米线、纳米管、纳米带等结构，三维二氧化钛微纳米结构更加复杂，其制备工艺、晶体生长机理和光学性能目前缺乏深入的研究。在强酸性条件下，以硫酸钾为形貌控制剂，通过缓慢氧化氯化亚钛制备了具有复杂形貌、可响应整个可见光区的二氧化钛混晶材料。通过控制硫酸钾的浓度可实现对二氧化钛晶体生长方向和生长速率的控制，一步合成具有典型的放射形方柱状结构的金红石型二氧化钛、八面体结构的锐钛矿型二氧化钛，以及二者共存的混晶结构。所得样品的微观形貌和晶粒尺寸对样品的光学吸收性能有明显影响，这些对可见光有强烈吸收的二氧化钛材料在太阳能电池、光催化等领域有重要的应用价值。
(3)半导体耦合是扩展二氧化钛光谱响应区间的有效手段，三维二氧化钛基微纳米材料的半导体耦合方法目前鲜有研究。以刺棒状硫化镉为基础，通过水热法一步制备了三维硫化镉/钛酸盐复合材料，该复合材料由玫瑰花状结构和纳米线结构组成。实验表明，主要原料P25的用量对于玫瑰花状微纳米结构的形成至关重要：足量P25可保证二氧化钛在参与化学反应时能有效与S2-离子竞争，抑制硫化镉的自由生长，并以其为成核和生长的基点，最终形成玫瑰花状纳米结构；当P25用量不足时，样品最终形貌则呈现多样性，如颗粒状、不规则柱状及纤维状等。S~(2-)离子的形成和释放速度从动力学上决定了硫化镉成核和生长的速度，对最终反应产物的形貌有决定性作用。从动力学角度寻求材料制备过程中可能的速率控制步骤是制备具有特定形貌、特定性能纳米材料的有效途径。
（4）为了探究二氧化钛混晶的晶体生长机制，通过计算机模拟软件MaterialsStudio的CASTEP模块对金红石型二氧化钛(110)面吸附硫酸进行了第一性原理计算分析，从热力学角度确定了主要的吸附模式。计算结果表明，在强酸性条件下硫酸钾对二氧化钛生长基元[TiO_6]八面体的螯合作用主要是通过H+HSO_4分子片段来实现的，其次是以H_2SO_4分子形式，而之前研究者提出的硫酸根螯合二氧化钛的机制是不正确的。该螯合作用改变了[TiO_6]八面体彼此之间结合的方式和结合速率，形成了锐钛矿型二氧化钛和金红石型二氧化钛共存的特殊结构。
As one of the most promising semiconductor materials, titanium dioxide hasaroused keen interest of researchers in the fields of solar cells, photocatalyticdegradation of pollutants and hydrogen production by water-splitting. In the microand nano scales, titanium dioxide shows a variety of morphology (such asnanoparticles, nanowires, nanorods, nanotubes, micro-nano-balls, etc.) and crystalstructure (such as amorphous, rutile, anatase, mixed crystal type). Many studies haveindicated that the microscopic morphologies and crystal structures of titanium dioxidebased micro-nano material have significant impacts on the UV-Vis light absorptionand photocatalytic properties; however, there are very limited researches investigatingthe morphology diversity, formation mechanism or the optical properties of titaniumdioxide based micro-nano material with complex morphologies. Such researches havepositive practical significance in promoting the development of new energy andenvironmental governance.
In this thesis, a series of titanium dioxide based micro-nano materials areprepared by hydrothermal or solvothermal method, and the morphology, crystalstructure, optical absorption and photocatalytic properties are studied exhaustively.The results are helpful to analyse the influencing factors of morphology evolution oftitanium dioxide within the range of the micro-nano scale, to synthetize titaniumdioxide with good visible light response for new energy and environmental protectionapplications, and to further study the relationship between the complex morphology oftitanium dioxide and its performance. The thermodynamic calculations by CASTEPmodule from Materials Studio are used to futher elaborate the mechanism of crystalgrowth of titanium dioxide. The main study contents and results of this paper aredescribed in detail as follows:
(1)By improving the traditional hydrothermal method for the synthesis oftitanium dioxide nanowires or nanotubes, a solvothermal process for the synthesis oftitanium dioxide mesoporous nanobelts is developed. Different volume ratio mixturesof ethanol and10mol/L sodium hydroxide solution are used as the reaction mediumto prepare titanium dioxide nanobelts with different morphologies, when the volumeratio is1:1, the nanobelts with structured and uniform geometric morphology isobtained. When soaked in hydrochloric acid solution (pH <3) for24hours andcalcined at400℃for2hours, the titanium dioxide nanobelts will change intomesoporous structure, the size of the pore is about5-7nm and the number of thesepores has a slight increase when pH decreases. The experimental results show that thereaction pressure has great impact on the morphology of the titanium dioxide: thegreater the pressure, it is the more beneficial to the formation of nanobelts. Comparedwith other systhesis methods for nanobelt, the solvothermal process can significantlyreduce the amount of sodium hydroxide and hydrothermal reaction time, and thuslower costs and energy consumption. The specific surface area of nano titaniumdioxide is further improved by maintaining the lamellar Titanate in this solvothermalprocess.
The visible light photocatalytic activity of mesoporous Li-doped titaniumdioxide nanobelts is studied. The doping of Li~+ion does not change the crystallinephase but decompose the lattice of titanium dioxide nanobelts and enhance theelectronegativity by replacing Ti~(4+)ion. The lattice breaking and the electronegativityhave important but contradictory influences on the photocatalytic activity of themesoporous Li-doped TiO_2nanobelts.
(2) Compared to the one-dimensional nanowire, nanotube and nanobeltstructures, three-dimensional titanium dioxide micro-nano structures are morecomplex, while their synthesis technology, crystal growth mechanism or opticalproperties are lack of in-depth research.Titanium dioxide mixed crystals, havingcomplex morphologies and responsing to the whole visible region, are prepared under strong acidic conditions by hydrothermal method. The potassium sulfate is believed tochelate with the octahedral growth unit [TiO_6], which will change the crystal growthdirection and the growth rate of titanium dioxide. As a result, morphology control canbe achieved through the concentration control of potassium sulfate. Rutile with atypical radial prismatic structure, anatase with an octahedral structure, as well asrutile-anatase coexistence structures is synthesized. Both the morphology and grainsize of the samples have significant effects on the optical absorption properties oftitanium dioxide. These materials with visible light response have importantapplications prospects in solar cells, photocatalysis and other fields.
(3) The semiconductor coupling is an effective means to extend the visible lightresponse range; however, there are few researches involving the coupling methods forthere-dimensional titanium dioxide based mirco-nano materials. Based on the thornyrod-like CdS, CdS/titanate composite nanostructure, consisting of nanoroses andnanowires, is prepared by hydrothermal method. The amount of P25is vital for theformation of rose-like nanostructure: a sufficient amount of titanium dioxide caneffectively compete with S2-ion in all related reactions, inhibit the free growth of CdSand make the transition from nanoparticle to nanoroses; inadequate amount oftitanium dioxide, however, gaves rise to diverse morphologies, such as particles,irregular columns and fibres. The formation and release rate of S~(2-)ion determines thenucleation and growth rate of CdS dynamically, which has a decisive role on themorphology of the final products. From the kinetic point of view, the rate controllingstep of chemical reactions is the key to prepare nanomaterials with specificmorphologies and properties.
(4) The interaction of sulfuric acid with rutile titanium dioxide (110) surfacefrom density functional theory calculations is carried on the CASTEP module ofMaterials Studio to determine the major adsorption mode from a thermodynamicpoint of view. The results show that, under strong acidic conditions, the chelationeffect between the potassium sulfate and [TiO_6] is mainly achieved by H+HSO_4 molecular fragment, partly by H_2SO_4molecular, but unlikely by2H+SO_4; the resultsfurther elaborate the crystal growth mechanism of titanium dioxide mixed crystalsfrom the energy point of view.
引文
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