CN102730755B - A kind of rod-shaped N, Ag co-doped TiO2 and its preparation method - Google Patents
A kind of rod-shaped N, Ag co-doped TiO2 and its preparation method Download PDFInfo
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Abstract
本发明公开了一种棒状N、Ag共掺杂TiO2及其制备方法，属于无机纳米材料制备领域。它以可水解钛盐为主要原料，以可溶性氮盐、银盐为氮、银元素的掺杂剂，通过水解、研磨、煅烧等工艺，在烧结的过程中诱导取向，控制其形貌，最终得到了棒状N、Ag共掺杂TiO2。本发明所得纳米粉体具有粒度小、形貌规则、分布均匀、分散性好等特点，该工艺由于合成速度快、成本低、产率高、无污染，具有工业化推广价值。
The invention discloses a rod-shaped N and Ag co-doped TiO 2 and a preparation method thereof, belonging to the field of preparation of inorganic nanometer materials. It uses hydrolyzable titanium salt as the main raw material, and soluble nitrogen salt and silver salt as the dopant of nitrogen and silver elements. Through hydrolysis, grinding, calcination and other processes, the orientation is induced during the sintering process, and its morphology is controlled. Finally, Rod-like N and Ag co-doped TiO 2 was obtained. The nano-powder obtained in the present invention has the characteristics of small particle size, regular shape, uniform distribution, good dispersibility, etc., and the process has the value of industrialization because of fast synthesis speed, low cost, high yield and no pollution.
Description
技术领域 technical field
本发明涉及一种无机纳米材料及其制备，具体涉及一种棒状N、Ag 共掺杂TiO2 及其制备方法。 The invention relates to an inorganic nanometer material and its preparation, in particular to a rod-shaped N and Ag co-doped TiO 2 and its preparation method.
背景技术 Background technique
由于具有对化学和生物的惰性、高稳定性、无毒性和低成本等优点， TiO2 被认为是最具潜在应用价值的半导体光催化剂，同时其在光电池与传感器方面的应用也越来越受到重视。但是TiO2 禁带宽度较宽，且光生电子和空穴容易复合，从而阻碍了其实际应用。 Due to its chemical and biological inertness, high stability, non-toxicity and low cost, TiO 2 is considered to be the semiconductor photocatalyst with the most potential application value, and its application in photovoltaic cells and sensors is also more and more popular Pay attention to. However, the wide bandgap of TiO 2 and the easy recombination of photogenerated electrons and holes hinder its practical application.
众多研究表明，金属与非金属的共掺杂产生的协同效应能够克服纯的TiO2的一些缺陷。现有技术对于N、Ag 共掺杂TiO2 方面的研究参见文献“银和氮共掺杂TiO2 的制备及光催化性能的研究”（沈阳师范大学学报(自然科学版), 2011, 29(2): 252-255) ，通过溶胶凝胶法制备出N、Ag 共掺杂TiO2，并对其性能进行了研究。 Numerous studies have shown that the synergistic effect produced by the co-doping of metals and nonmetals can overcome some defects of pure TiO 2 . For the research on N and Ag co-doped TiO 2 in the prior art, please refer to the literature "Preparation and Photocatalytic Performance of Silver and Nitrogen Co-doped TiO 2 " (Journal of Shenyang Normal University (Natural Science Edition), 2011, 29( 2): 252-255), N, Ag co-doped TiO 2 was prepared by sol-gel method, and its properties were studied.
而相比纳米TiO2 粉体材料，棒状材料有着更明显的优势。首先，棒状材料具有较高的比表面积，可以提高其表面活性；其次，棒状材料中具有较多的非离域态载流子，由于可以在晶体的长度方向自由移动而有可能降低电子空穴的复合率，提高材料的光电性能。 Compared with nano-TiO 2 powder materials, rod-shaped materials have more obvious advantages. Firstly, the rod-shaped material has a higher specific surface area, which can improve its surface activity; secondly, the rod-shaped material has more non-delocalized carriers, which may reduce the electron-hole density because it can move freely in the length direction of the crystal. The recombination rate improves the photoelectric performance of the material.
目前，文献报道的棒状TiO2 的制备方法主要由以下几种：电化学阳极氧化法、水热合成法、模板法、超声法等。文献“银掺杂TiO2 纳米管阵列的制备及可见光光电催化性能的研究”（广西民族大学学报(自然科学版), 2010, 16(3): 75-79）公开了采用电化学阳极氧化法制备Ag 掺杂TiO2纳米管阵列，该方法要进行复杂的预处理步骤，并且在氧化结束后要用大量的去离子水冲洗，不符合现代绿色化学的理念；文献“载Ag 二氧化钛纳米管的制备及其光催化性能”（物理化学学报，2008, 24（8）：1383-1386） 通过水热法合成了载Ag-TiO2纳米管，该方法虽然步骤简单，但是对设备要求较高，同时在制备时加入强碱，后处理时又要通过大量蒸馏水洗涤至中性，不仅增加生产成本，更主要的是所排放水对环境有害。新加坡国立大学的曾华淳等人在文献“Synthesis of single-crystalline TiO2 nanotubes”（Chemistry of Materials, 2002, 14(3): 1391-1397）中报道了利用模板法制备单晶TiO2纳米管的技术，步骤较复杂，同时需要加入盐酸和氨水来调节PH。华中师范大学的夏晓红等人(参见文献：超声法制备TiO2纳米棒及其光催化性质的研究. 电子元件与材料, 2007, 26(1): 20-22) 利用超声法制备了TiO2纳米棒。中国发明专利（CN 101952202A ）公开了一种具有纳米尺寸和可控形状的二氧化钛的制备方法，在装有气泡冷凝器的烧瓶中进行回流制备出二氧化钛纳米棒，但是在过程中要用含苯环的有机溶剂，对人体危害较大。 At present, the preparation methods of rod-shaped TiO 2 reported in the literature mainly include the following methods: electrochemical anodic oxidation, hydrothermal synthesis, template method, ultrasonic method, etc. The document "Preparation of Silver-doped TiO 2 Nanotube Arrays and Research on Visible Light Photoelectrocatalytic Performance" (Journal of Guangxi University for Nationalities (Natural Science Edition), 2010, 16(3): 75-79) discloses the use of electrochemical anodic oxidation method Preparation of Ag-doped TiO 2 nanotube arrays requires complex pretreatment steps and rinses with a large amount of deionized water after oxidation, which does not conform to the concept of modern green chemistry; the literature "Ag-loaded TiO 2 nanotubes Preparation and photocatalytic performance” (Acta Physicochemical Sinica, 2008, 24 (8): 1383-1386) Ag-TiO 2 nanotubes were synthesized by a hydrothermal method. Although the method is simple in steps, it requires high equipment. At the same time, a strong alkali is added during the preparation, and a large amount of distilled water is washed to neutrality during post-treatment, which not only increases the production cost, but more importantly, the discharged water is harmful to the environment. Zeng Huachun and others from the National University of Singapore reported the technology of preparing single-crystal TiO 2 nanotubes by template method in the document "Synthesis of single-crystalline TiO 2 nanotubes" (Chemistry of Materials, 2002, 14(3): 1391-1397) , the steps are more complicated, and hydrochloric acid and ammonia water need to be added to adjust the pH. Xia Xiaohong et al. from Central China Normal University (refer to the literature: Ultrasonic method to prepare TiO 2 nanorods and their photocatalytic properties. Electronic components and materials, 2007, 26(1): 20-22) prepared TiO 2 nanorods by ultrasonic method Great. Chinese invention patent (CN 101952202A ) discloses a method for preparing titanium dioxide with nanometer size and controllable shape. Titanium dioxide nanorods are prepared by reflux in a flask equipped with a bubble condenser, but in the process, titanium dioxide nanorods containing benzene rings are used. Organic solvents are harmful to the human body.
发明内容 Contents of the invention
本发明的目的在于克服现有技术存在的不足，提供一种形貌可控，制备工艺简单、绿色环保，适于工业化生产的棒状N、Ag 共掺杂TiO2及其制备方法。 The purpose of the present invention is to overcome the deficiencies of the prior art and provide a rod-shaped N and Ag co-doped TiO 2 and its preparation method with controllable shape, simple preparation process, green and environmental protection, and suitable for industrial production.
实现本发明目的的技术方案是提供一种棒状N、Ag 共掺杂TiO2 的制备方法，包括如下步骤： The technical solution for realizing the object of the present invention is to provide a kind of rod-shaped N, Ag co-doped TiO 2 preparation method, comprising the steps:
（1）称取一定量的含氮物质加入到体积比为1:2～9 的钛酸酯与无水乙醇的混合溶液中，N 和Ti 的摩尔比为1～5：100，混合均匀后得到微黄色透明混合液体；所述的含氮物质为硫酸铵、碳酸铵、碳酸氢铵、高氯酸铵、硝酸铵、尿素和氨基酸中的一种或几种； (1) Weigh a certain amount of nitrogen-containing substances and add them to the mixed solution of titanate and absolute ethanol with a volume ratio of 1:2~9, the molar ratio of N and Ti is 1~5:100, and mix well A light yellow transparent mixed liquid is obtained; the nitrogen-containing substance is one or more of ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium perchlorate, ammonium nitrate, urea and amino acids;
（2）在搅拌条件下，将含有水蒸气的空气输送到混合液体中,待微黄色透明混合液体变成白色乳液，停止反应； (2) Under the condition of stirring, the air containing water vapor is transported into the mixed liquid, and the light yellow transparent mixed liquid turns into a white emulsion, and the reaction is stopped;
（3）减压蒸馏后将得到的白色粉末置于鼓风烘箱中，再在40～60℃的温度条件下静置8～12 h，干燥后得到白色粉末状的纳米颗粒； (3) Place the obtained white powder in a blast oven after vacuum distillation, and then let it stand at a temperature of 40-60°C for 8-12 hours, and obtain white powdery nanoparticles after drying;
（4）将硝酸银溶于一定量的无水乙醇中，Ag 和Ti 的摩尔比为1～5：100，加入步骤（3）得到的纳米颗粒，研磨至干后置于鼓风烘箱中，在40～80℃ 的温度条件下干燥处理2～3 h； (4) Dissolve silver nitrate in a certain amount of absolute ethanol, the molar ratio of Ag to Ti is 1-5:100, add the nanoparticles obtained in step (3), grind until dry and place in a blast oven, Drying treatment at 40-80°C for 2-3 hours;
（5）在500～600 ℃ 的温度条件下煅烧1～3h，自然冷却后得到一种棒状N、Ag 共掺杂 TiO2。 (5) Calcining at a temperature of 500-600 ℃ for 1-3 hours, and cooling naturally to obtain a rod-shaped N and Ag co-doped TiO 2 .
所述的钛酸酯为钛酸丁酯、钛酸异丙酯、钛酸乙酯中的一种或几种。 The titanate is one or more of butyl titanate, isopropyl titanate and ethyl titanate. the
所述的含有水蒸气的空气输送到混合液体中，其输送速率为30～50L·min-1,输送水蒸汽的质量为2.5～3.5g·L-1。 The air containing water vapor is transported into the mixed liquid at a transport rate of 30-50L·min -1 , and the mass of transported water vapor is 2.5-3.5g·L -1 .
本发明技术方案还包括提供一种按上述制备方法得到的棒状N、Ag 共掺杂TiO2。 The technical solution of the present invention also includes providing a rod-shaped N and Ag co-doped TiO 2 obtained by the above-mentioned preparation method.
与现有技术相比，本发明的突出优点是： Compared with prior art, outstanding advantage of the present invention is:
1、TiO2 的形貌控制是制备棒状N、Ag 共掺杂TiO2 过程中的关键。本发明通过Ag 元素的掺杂，能够在对N 掺杂TiO2 的前驱体进行煅烧的时候诱导其晶粒发生取向，从而使晶粒进行规则的排列、生长，得到棒状N、Ag 共掺杂 TiO2 。这种通过掺杂就能实现对TiO2 进行诱导取向从而达到形貌控制的方法在国内外相关领域的研究还是空白。 1. The shape control of TiO 2 is the key to the preparation of rod-like N and Ag co-doped TiO 2 . The present invention can induce the orientation of the crystal grains of the N-doped TiO2 precursor when the N-doped TiO2 precursor is calcined through the doping of the Ag element, so that the crystal grains can be arranged and grown regularly, and a rod-shaped N and Ag co-doped TiO 2 . This method of inducing orientation of TiO 2 through doping to achieve shape control is still blank in related fields at home and abroad.
2、本发明在进行棒状TiO2 形貌控制的同时，完成了对TiO2 的Ag、N共掺杂。通过Ag、N 元素的协同效应，以克服纯TiO2 的不足之处，从而使TiO2 的性能更加优异。使其不仅适用于光催化材料，也适用于涉及用于转化太阳能和产生氢的光伏电池，特别是染料敏化太阳能电池等的应用。 2. The present invention completes Ag and N co-doping of TiO 2 while controlling the shape of rod-shaped TiO 2 . Through the synergistic effect of Ag and N elements, the shortcomings of pure TiO 2 are overcome, so that the performance of TiO 2 is more excellent. This makes it suitable not only for photocatalytic materials, but also for applications involving photovoltaic cells for converting solar energy and generating hydrogen, especially dye-sensitized solar cells.
3、本发明工艺简单，前驱体制备中所用的溶剂乙醇可通过减压蒸馏的方式回收再利用，整个制备过程不需要酸调节，减小了制备过程中对环境的污染，达到节能减排的要求，适合连续化生产。 3. The process of the present invention is simple, and the solvent ethanol used in the preparation of the precursor can be recycled and reused through vacuum distillation. The whole preparation process does not require acid adjustment, which reduces the pollution to the environment during the preparation process and achieves energy saving and emission reduction. requirements, suitable for continuous production. the
附图说明 Description of drawings
图1是本发明实施例制备的棒状N、Ag 共掺杂 TiO2 的X射线衍射图谱； Fig. 1 is rod-shaped N, Ag co-doped TiO prepared by the embodiment of the present invention The X-ray diffraction spectrum;
图2是本发明实施例制备的棒状N、Ag 共掺杂 TiO2 的扫描电镜图； Fig. 2 is the scanning electron micrograph of rod-shaped N, Ag co-doped TiO prepared by the embodiment of the present invention;
图3是本发明实施例制备的棒状N、Ag 共掺杂 TiO2 的X射线光电子能谱分析图。 Fig. 3 is an X-ray photoelectron spectroscopy analysis diagram of rod-shaped N and Ag co-doped TiO2 prepared in the embodiment of the present invention.
具体实施方式 Detailed ways
下面通过实施例并结合附图，对本发明的技术方案作进一步的阐述。 The technical solutions of the present invention will be further described below through the embodiments and in conjunction with the accompanying drawings. the
实施例一 Embodiment one
（1）称取0.007g 尿素(N 和Ti 的摩尔比为1：100)，8 mL钛酸丁酯与32 mL 无水乙醇，倒入同一个三口烧瓶，打开磁力搅拌，使之混合均匀，配成溶液； (1) Weigh 0.007g of urea (the molar ratio of N and Ti is 1:100), 8 mL of butyl titanate and 32 mL of absolute ethanol, pour them into the same three-necked flask, turn on the magnetic stirring, and mix them evenly. dubbed into a solution;
（2）5 min后打开空气泵开关，以40 L·min-1 的速率将空气输送到密闭容器的水中，通过容器上的另一个接口，输送水蒸汽的质量为2.5～3.5g·L-1，将含有水份的气体输入到钛酸丁酯与乙醇的混合溶液中，在机械搅拌条件下，混合溶液由微黄色透明液体逐渐变浑浊，最后变成白色乳液，停止输入空气，反应30min 后停止； (2) After 5 minutes, turn on the air pump switch to deliver air to the water in the closed container at a rate of 40 L·min -1 , and through another port on the container, the mass of water vapor delivered is 2.5-3.5g·L - 1. Input the gas containing water into the mixed solution of butyl titanate and ethanol. Under the condition of mechanical stirring, the mixed solution gradually becomes turbid from light yellow transparent liquid, and finally turns into white emulsion. Stop inputting air and react for 30 minutes. after stop;
（3）将装有白色乳液的三口烧瓶减压蒸馏，收集无水乙醇，以便重复利用；收集白色粉末，放入鼓风干燥箱，40 ℃ 下静置12 h，得到干燥的白色粉末状纳米颗粒； (3) Distill the three-necked flask containing the white emulsion under reduced pressure to collect absolute ethanol for reuse; collect the white powder, put it in a blast drying oven, and let it stand at 40°C for 12 hours to obtain a dry white powder nano particles;
（4） 称取0.04 g 硝酸银(Ag 和Ti 的摩尔比为1：100)溶于5mL 无水乙醇中，与步骤3 所得纳米颗粒在玛瑙研钵中研磨至干，放入鼓风烘箱，在温度为50 ℃ 的条件下进行干燥处理2 h，得到纳米粉末； (4) Weigh 0.04 g of silver nitrate (the molar ratio of Ag to Ti is 1:100) and dissolve it in 5 mL of absolute ethanol, grind it with the nanoparticles obtained in step 3 in an agate mortar until dry, and put it in a blast oven. Drying treatment was carried out for 2 h at a temperature of 50 °C to obtain nanopowder;
（5） 将步骤4 所得纳米粉末在氮气气氛保护中于500 ℃ 煅烧2 h，得到氮气保护下500 ℃ 煅烧的棒状N、Ag 共掺杂 TiO2。标记为PNAT-1-500，其X射线衍射图参见附图1的曲线a，扫描电镜图参见附图2的图（a）。 (5) The nanopowder obtained in step 4 was calcined at 500 °C for 2 h in a nitrogen atmosphere to obtain rod-shaped N, Ag co-doped TiO 2 calcined at 500 °C under a nitrogen atmosphere. It is marked as PNAT-1-500, its X-ray diffraction diagram is shown in the curve a of the attached drawing 1, and the scanning electron micrograph is shown in the drawing (a) of the attached drawing 2.
实施例二 Example two
按实施例1的技术方案，将在步骤（4）中得到的纳米粉末在500 ℃ 的温度条件下煅烧2 h，得到无氮气保护的500 ℃ 煅烧的棒状N、Ag 共掺杂 TiO2，标记为NAT-1-500，其X射线衍射图参见附图1的曲线b，扫描电镜图参见附图2的图（b）。 According to the technical scheme of Example 1, the nanopowder obtained in step (4) was calcined at 500 °C for 2 h to obtain rod-shaped N, Ag co-doped TiO 2 calcined at 500 °C without nitrogen protection, marked It is NAT-1-500, its X-ray diffraction pattern is shown in the curve b of the attached drawing 1, and the scanning electron microscope picture is shown in the drawing (b) of the attached drawing 2.
实施例三 Embodiment three
（1）称取0.007 g 尿素和0.009 g硝酸铵 ( N 和Ti 的摩尔比为2：100) 溶于8 mL钛酸丁酯与32 mL 无水乙醇；倒入同一个三口烧瓶，打开磁力搅拌，使之混合均匀，配成溶液； (1) Weigh 0.007 g urea and 0.009 g ammonium nitrate (the molar ratio of N and Ti is 2:100) and dissolve them in 8 mL butyl titanate and 32 mL absolute ethanol; pour them into the same three-necked flask and turn on the magnetic stirring , make it evenly mixed, and make a solution;
（2）5 min后打开空气泵开关，以40 L·min-1 的速率将空气输送到装有少量水的密闭容器的水中，通过容器上的另一个接口，输出含有水份的空气，输送水蒸汽的质量为2.5～3.5g·L-1，将含有水份的气体输入到钛酸丁酯与乙醇的混合溶液中，进行机械搅拌，混合溶液由微黄色透明液体逐渐变浑浊，最后变成白色乳液，停止输入空气，反应30min 后停止； (2) After 5 minutes, turn on the air pump switch, and deliver the air to the water in a closed container with a small amount of water at a rate of 40 L·min -1 , and output the air containing moisture through another port on the container, and deliver The mass of water vapor is 2.5～3.5g·L -1 , the gas containing water is input into the mixed solution of butyl titanate and ethanol, and mechanically stirred, the mixed solution gradually becomes turbid from light yellow transparent liquid, and finally becomes Turn into a white emulsion, stop inputting air, and stop after 30 minutes of reaction;
（3）将装有白色乳液的三口烧瓶减压蒸馏，收集无水乙醇，以便重复利用；收集白色粉末，放入鼓风干燥箱，40 ℃ 下静置12 h，得到干燥的白色粉末； (3) Distill the three-neck flask containing the white emulsion under reduced pressure to collect absolute ethanol for reuse; collect the white powder, put it in a blast drying oven, and let it stand at 40°C for 12 hours to obtain a dry white powder;
（4）称取0.08 g 硝酸银(Ag 和Ti 的摩尔比为2：100)溶于5mL 无水乙醇，与步骤3 所得纳米颗粒在玛瑙研钵中研磨至干，得到纳米粉末； (4) Weigh 0.08 g of silver nitrate (the molar ratio of Ag to Ti is 2:100) and dissolve it in 5 mL of absolute ethanol, and grind it with the nanoparticles obtained in step 3 in an agate mortar until dry to obtain nanopowder;
（5） 将步骤4 所得纳米粉末放入鼓风烘箱，50 ℃ 下进行干燥2 h后，在氮气气氛保护中于500 ℃ 煅烧2 h，得到氮气保护下500 ℃ 煅烧的棒状N、Ag 共掺杂 TiO2，标记为PNAT-2-500，其X射线衍射图参见附图1的曲线c，扫描电镜图参见附图2的图（c）。 (5) Put the nano-powder obtained in step 4 into a blast oven, dry at 50 °C for 2 h, and then calcinate at 500 °C for 2 h in a nitrogen atmosphere to obtain a rod-shaped N, Ag co-doped at 500 °C under a nitrogen atmosphere Doped TiO 2 , marked as PNAT-2-500, its X-ray diffraction diagram is shown in the curve c of the attached drawing 1, and its scanning electron microscopic picture is shown in the drawing (c) of the attached drawing 2.
实施例四 Embodiment four
按实施例1的技术方案，将在步骤（4）中得到的纳米粉末在氮气气氛保护中于600℃ 煅烧2 h，得到氮气保护下600℃ 煅烧的棒状N、Ag 共掺杂 TiO2。标记为PNAT-1-600，其X射线衍射图参见附图1的曲线d，扫描电镜图参见附图2的图（d）。 According to the technical scheme of Example 1, the nanopowder obtained in step (4) was calcined at 600°C for 2 h in a nitrogen atmosphere to obtain rod-shaped N, Ag co-doped TiO 2 calcined at 600°C under a nitrogen atmosphere. It is marked as PNAT-1-600, its X-ray diffraction pattern is shown in the curve d of the attached drawing 1, and the scanning electron microscope picture is shown in the drawing (d) of the attached drawing 2.
参见附图1,它是本发明实施例1、2、3、4所制备的棒状N、Ag 共掺杂 TiO2的X射线衍射图谱，分析结果显示：图谱上均未出现N、Ag 的峰，说明N 和Ag 的掺杂不改变TiO2的晶型。与PNAT-1-500（曲线a）不同的是，NAT-1-500（曲线b）在2θ位于27.4°的位置出现了较为明显的特征峰，由此可知，在煅烧过程中采用氮气保护能一定程度地抑制二氧化钛由锐钛矿相向金红石相的转变。PNAT-2-500（曲线c）样品的峰强较弱，这说明，随着N、Ag 掺杂量的增加，样品的结晶度随之下降。PNAT-1-600（曲线d）样品的2θ位于25.3°和27.4°的位置都出现了特征峰，表明产物为锐钛矿和金红石型TiO2 的混合体。 Referring to accompanying drawing 1, it is the X-ray diffraction spectrum of the rod-shaped N, Ag co-doped TiO prepared by Examples 1, 2, 3 , and 4 of the present invention. The analysis results show that no peaks of N and Ag appear on the spectrum. , indicating that the doping of N and Ag does not change the crystal form of TiO2 . Different from PNAT-1-500 (curve a), NAT-1-500 (curve b) has a more obvious characteristic peak at the position of 2θ at 27.4°. To a certain extent, the transformation of titanium dioxide from anatase phase to rutile phase is inhibited. The peak intensity of the PNAT-2-500 (curve c) sample is weak, which indicates that the crystallinity of the sample decreases with the increase of N and Ag doping amounts. The 2θ of the PNAT-1-600 (curve d) sample has characteristic peaks at 25.3° and 27.4°, indicating that the product is a mixture of anatase and rutile TiO 2 .
参见附图2：它是本发明实施例1、2、3和4所制备的棒状N、Ag 共掺杂 TiO2的扫描电镜图，实施例样品分别对应为图（a）标记为PNAT-1-500、（b）标记为NAT-1-500、（c）标记为PNAT-2-500和（d）标记为PNAT-1-600，结果显示：实施例1～4 都成功制备出了棒状N、Ag 共掺杂 TiO2，其形貌较为规则，棒的直径为100nm～2um，其长径比较大。 See accompanying drawing 2: it is the scanning electron microscope picture of rod-like N, Ag co-doped TiO 2 prepared in Examples 1, 2, 3 and 4 of the present invention, and the samples of the examples correspond to Figure (a) marked as PNAT-1 -500, (b) marked as NAT-1-500, (c) marked as PNAT-2-500 and (d) marked as PNAT-1-600, the results show that the rod-shaped N, Ag co-doped TiO 2 , its shape is relatively regular, the diameter of the rod is 100nm-2um, and its long diameter is relatively large.
参见附图3，它是按实施例1 制备方法制得的棒状N、Ag 共掺杂 TiO2的X射线光电子能谱（XPS）图，其中，图(a) 为全扫描谱图 ；图(b)为Ag 的3d 谱图；图(c)为N 的1s 谱图，由图3分析结果显示：棒状N、Ag 共掺杂 TiO2的样品所含元素为N、Ti、O、Ag、C。而Ag 在3d5/2 和3d3/2 的结合能分别为367.9eV 和374.2eV，在Ag 离子对应的3d5/2 和3d3/2 分别为370.0 eV 和376.0 eV 处并没有发现明显的特征峰，这表明Ag 是以单质的形式存在。由N1s 的XPS 图谱可以看出，仅在400 eV 处出现了较明显的特征峰，归属于O-Ti-N 中的N，表明N 元素已经掺入晶格。 Referring to accompanying drawing 3, it is the X-ray photoelectron energy spectrum (XPS) figure of the rod-shaped N, Ag co-doped TiO2 that is made by the preparation method of embodiment 1, and wherein, figure (a) is full-scan spectrogram; Figure ( b) is the 3d spectrum of Ag; Figure (c) is the 1s spectrum of N. The analysis results in Figure 3 show that the elements contained in the sample of rod-shaped N and Ag co-doped TiO 2 are N, Ti, O, Ag, c. However, the binding energies of Ag in 3d 5/2 and 3d 3/2 are 367.9 eV and 374.2 eV, respectively, and there is no obvious binding energy at 370.0 eV and 376.0 eV in 3d 5/2 and 3d 3/2 corresponding to Ag ions. Characteristic peaks, indicating that Ag exists in the form of simple substance. From the XPS spectrum of N1s, it can be seen that there is only a more obvious characteristic peak at 400 eV, which belongs to N in O-Ti-N, indicating that N element has been incorporated into the lattice.
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