CN103896338A - Method for preparing tungsten trioxide with regular hexagonal flaky morphology by using template method and application thereof - Google Patents
Method for preparing tungsten trioxide with regular hexagonal flaky morphology by using template method and application thereof Download PDFInfo
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Abstract
本发明涉及一种利用模板法制备具有规则六方片状形貌的三氧化钨的方法。该材料对硫化氢（H2S）气体表现出优良的气敏特性。属敏感材料及气体传感器技术领域。本发明以具有规则六方片状形貌的氨基功能化NH2-SBA-15为模板，制备出具有规则形貌的六方片状三氧化钨。所制备出的片状三氧化钨对硫化氢（H2S）气体表现出优良的气敏特性，所制得的硫化氢传感器具有灵敏度高，选择性好，响应/恢复时间短，重复性好等优点。同时利用多酸组成的可调变性，这种方法还可能被用来制备其他规则形貌的纳米金属氧化物，对于控制纳米材料生长具有积极意义。
The invention relates to a method for preparing tungsten trioxide with a regular hexagonal sheet shape by using a template method. The material exhibits excellent gas-sensing properties to hydrogen sulfide (H 2 S) gas. It belongs to the technical field of sensitive materials and gas sensors. The invention uses the amino-functionalized NH 2 -SBA-15 with the regular hexagonal sheet shape as a template to prepare the hexagonal sheet-like tungsten trioxide with the regular shape. The prepared flaky tungsten trioxide exhibits excellent gas-sensing properties for hydrogen sulfide (H 2 S) gas, and the prepared hydrogen sulfide sensor has high sensitivity, good selectivity, short response/recovery time and good repeatability Etc. At the same time, taking advantage of the tunable denaturation of the polyacid composition, this method may also be used to prepare nano-metal oxides with other regular shapes, which is of positive significance for controlling the growth of nano-materials.
Description
技术领域 technical field
本发明涉及一种利用模板法制备具有规则六方片状形貌的三氧化钨的方法。该材料对硫化氢（H2S）气体表现出优良的气敏特性。属敏感材料及气体传感器技术领域。 The invention relates to a method for preparing tungsten trioxide with a regular hexagonal sheet shape by using a template method. The material exhibits excellent gas-sensing properties to hydrogen sulfide (H 2 S) gas. It belongs to the technical field of sensitive materials and gas sensors.
技术背景 technical background
纳米材料的可控生长，尤其是对于特殊形貌纳米材料的制备和组装，是近年来纳米材料研究的热点和难点。由于其特定的形态和尺寸，使得它们具有独特的催化、非线性光学、半导体和磁性性能，在各种应用中表现出独特的优势。因此，合成特定尺寸与形貌的纳米晶材料无论是在基础科学还是应用研究方面都有着重要的意义。作为重要的宽带隙半导体，三氧化钨（WO3）因其独特的物理性质和化学性质，适用于气体传感器，电致变色器件，光催化和光电器件等应用，受到广泛的关注。WO3本身结构复杂，物相繁多，对纳米级WO3可控合成的研究引起了人们广泛兴趣，时至今日，诸如纳米线、纳米棒，纳米管等各种形貌的WO3都已被合成出来。制备特殊形貌的WO3纳米材料的的方法很多，如化学气相沉积、电化学沉积、电化学阳极氧化、溶胶凝胶和模板法等。模板法是一种重要的纳米材料组装方法，其主要思路是采用具有一定的形貌或孔道结构的材料作为模板，将目标材料的纳米粒子或前驱体通过与模板发生一定的相互作用覆盖于模板的表面或填入模板内部形成主客体复合材料，在一定条件下，纳米粒子或前体发生相互交联，形成连续相后去除模板，从而获得具有复制模板的形貌或孔道结构的目标材料。模板法作为一种制备纳米材料的有效方法，其主要特点是模板法不管是在液相中或是气相中发生的化学反应，其反应都是在有效控制的区域内进行的，这就是模板法与普通方法的主要区别。模板法合成纳米材料与直接合成相比具有诸多优点，主要表现在：①以模板为载体精确控制纳米材料的尺寸和形状、结构和性质；②实现纳米材料合成与组装一体化，同时可以解决纳米材料的分散稳定性问题；③合成过程相对简单，很多方法适合批量生产[16]。利用纳米介孔材料规整排列的孔道用为“微反应器”和载体，在合成形态各异的纳米球、饼、线及块体材料方面具有独特的优势。 The controllable growth of nanomaterials, especially the preparation and assembly of nanomaterials with special morphology, is a hot and difficult point in nanomaterials research in recent years. Due to their specific morphology and size, they possess unique catalytic, nonlinear optical, semiconducting, and magnetic properties, showing unique advantages in various applications. Therefore, the synthesis of nanocrystalline materials with specific sizes and shapes is of great significance in both basic science and applied research. As an important wide-bandgap semiconductor, tungsten trioxide (WO 3 ) has attracted extensive attention due to its unique physical and chemical properties, which are suitable for applications such as gas sensors, electrochromic devices, photocatalytic and optoelectronic devices. WO 3 itself has a complex structure and various phases. The research on the controllable synthesis of nanoscale WO 3 has aroused widespread interest. Up to now, WO 3 with various shapes such as nanowires, nanorods, and nanotubes have been produced. synthesized. There are many methods for preparing WO 3 nanomaterials with special morphology, such as chemical vapor deposition, electrochemical deposition, electrochemical anodic oxidation, sol-gel and template methods. The template method is an important nanomaterial assembly method. The main idea is to use a material with a certain morphology or pore structure as a template, and cover the nanoparticles or precursors of the target material on the template through a certain interaction with the template. Under certain conditions, the nanoparticles or precursors cross-link with each other to form a continuous phase and then remove the template, so as to obtain the target material with the morphology or pore structure of the replicated template. The template method is an effective method for preparing nanomaterials. Its main feature is that the template method, whether it is a chemical reaction in the liquid phase or in the gas phase, the reaction is carried out in an effectively controlled area. This is the template method. The main difference from the normal method. Synthesis of nanomaterials by template method has many advantages compared with direct synthesis, which are mainly manifested in: ① use template as carrier to precisely control the size, shape, structure and properties of nanomaterials; ② realize the integration of synthesis and assembly of nanomaterials, and can solve the problem of Dispersion stability of materials; ③ The synthesis process is relatively simple, and many methods are suitable for mass production [16]. The regularly arranged pores of nano-mesoporous materials are used as "micro-reactors" and carriers, and have unique advantages in the synthesis of nano-spheres, cakes, wires and bulk materials of various shapes.
基于上述思想，我们以具有规则六方片状形貌的氨基功能化NH2-SBA-15为模板，制备出具有规则形貌的六方片状三氧化钨。所制备出的片状三氧化钨对硫化氢（H2S）气体表现出优良的气敏特性，所制得的硫化氢传感器具有灵敏度高，选择性好，响应/恢复时间短，重复性好等优点。同时利用多酸组成的可调变性，这种方法还可能被用来制备其他规则形貌的纳米金属氧化物，对于控制纳米材料生长具有积极意义。 Based on the above ideas, we used amino-functionalized NH 2 -SBA-15 with regular hexagonal sheet morphology as a template to prepare hexagonal sheet-like tungsten trioxide with regular morphology. The prepared flaky tungsten trioxide exhibits excellent gas-sensing properties for hydrogen sulfide (H 2 S) gas, and the prepared hydrogen sulfide sensor has high sensitivity, good selectivity, short response/recovery time and good repeatability Etc. At the same time, taking advantage of the tunable denaturation of the polyacid composition, this method may also be used to prepare nano-metal oxides with other regular shapes, which is of positive significance for controlling the growth of nano-materials.
发明内容 Contents of the invention
本发明的目的在于提供一种利用模板法制备具有规则六方片状形貌的三氧化钨的方法。本发明的另一目的是提供一种对硫化氢（H2S）气体表现出优良的气敏特性的敏感材料。 The object of the present invention is to provide a method for preparing tungsten trioxide with a regular hexagonal sheet shape by using a template method. Another object of the present invention is to provide a sensitive material exhibiting excellent gas sensing characteristics to hydrogen sulfide ( H₂S ) gas.
本发明是一种基于模板法制备具有规则六方片状形貌的三氧化钨的方法，其特征在于具有以下的工艺过程和步骤： The present invention is a method for preparing tungsten trioxide with a regular hexagonal sheet shape based on a template method, which is characterized in that it has the following process and steps:
a．六方片状WO3前驱体的制备：煅烧后的六方片状介孔材料二氧化硅SBA-15在180 ℃抽真空加热3 h， 然后将1 ～ 5mg 上述SBA-15分散在15 ml浓度为2-5% 的γ-氨丙基三甲氧基硅烷（APTMS）的无水甲苯溶液中，回流24 h后将样品取出，抽滤，用无水甲苯或乙醇溶剂洗涤，然后在烘箱中60 ～ 85 ℃放置1 ～ 3 h，干燥后备用，该样品记为APTMS/SBA-15；在10 ～ 20 mg APTMS/SBA-15 中加入1 ～ 5 ml 含有0.1 × 10-3 mol H3PW12O40 （磷钼酸）的醇溶液，在60 ℃持续搅拌后抽滤，并用大量乙醇洗涤三次，然后在50 ℃干燥 30 h，得到H3PW12O40/APTMS/SBA-15； a. Preparation of the hexagonal flaky WO 3 precursor: the calcined hexagonal flaky mesoporous material silica SBA-15 was heated at 180 °C for 3 h under vacuum, and then 1–5 mg of the above SBA-15 was dispersed in 15 ml at a concentration of 2 -5% γ-Aminopropyltrimethoxysilane (APTMS) in anhydrous toluene solution, reflux for 24 h, take out the sample, filter with suction, wash with anhydrous toluene or ethanol solvent, and then place in an oven for 60 to 85 Store at ℃ for 1-3 h, dry and set aside, this sample is recorded as APTMS/SBA-15; add 1-5 ml to 10-20 mg APTMS/SBA-15 containing 0.1 × 10 -3 mol H 3 PW 12 O 40 (Phosphomolybdic acid) alcohol solution, suction filtered after continuous stirring at 60 °C, washed with a large amount of ethanol three times, and then dried at 50 °C for 30 h to obtain H 3 PW 12 O 40 /APTMS/SBA-15;
b．六方片状WO3材料的制备：将上述反应得到的H3PW12O40/APTMS/SBA-15，在马弗炉中从室温以程序升温加热到500 ℃，并500 ℃ 空气中保持3 h，所获样品记为WO3 /SBA-15；将WO3/SBA-15在HF水溶液中溶解，除去SBA-15氧化硅得到纯的呈浅绿色的WO3。 b. Preparation of hexagonal flake-shaped WO 3 material: Heating H 3 PW 12 O 40 /APTMS/SBA-15 obtained from the above reaction in a muffle furnace from room temperature to 500 °C by temperature programming, and kept at 500 °C in air for 3 h , the obtained sample was recorded as WO 3 /SBA-15; WO 3 /SBA-15 was dissolved in HF aqueous solution, and the SBA-15 silicon oxide was removed to obtain pure light green WO 3 .
本发明一种模板法制备具有规则的六方片状WO3的用途及其应用—制造H2S气敏元件；其制造方法如下：在玛瑙研钵中置入少许上述制备的WO3纳米片，然后滴入少量黏合剂，调成糊状后均匀涂于气敏元件的陶瓷管外面，将涂有WO3敏感材料的陶瓷管放在红外灯下烘干后，于马弗炉中300 °C煅烧3 h，自然冷却后备用。最后将其4个电极丝焊接在底座上，将焊好的元件置于专用的老化台上，老化240 h, 制成H2S气敏元件。 The use and application of a template method in the present invention to prepare regular hexagonal sheet-shaped WO 3 - manufacture of H 2 S gas sensor; the manufacturing method is as follows: put a little of the above-prepared WO 3 nanosheets in an agate mortar, Then drop a small amount of adhesive, adjust it into a paste, and apply it evenly on the outside of the ceramic tube of the gas sensor. After drying the ceramic tube coated with WO 3 sensitive material under an infrared lamp, place it in a muffle furnace at 300 °C. Calcined for 3 h, cooled naturally for later use. Finally, the 4 electrode wires are welded on the base, and the welded components are placed on a special aging table, aged for 240 h, and the H 2 S gas sensor is made.
本发明方法制得的石英晶体微天平甲醛传感器的优点和特点如下所述： The advantages and characteristics of the quartz crystal microbalance formaldehyde sensor that the inventive method makes are as follows:
（1）使用六方片状SBA-15作为主体材料，进行氨基功能化修饰，利于客体材料APTMS在孔道内的扩散和传输，避免了成客体材料在孔道内分布不均匀、嫁接量过低的问题。基于氨基功能化材料表面的氨基可以和多酸结合形成强的离子键。因此可以通过多酸与氨基的作用强相互作用固定合成WO3的前驱体H3PW12O40，这样就能够实现前驱体在载体上的均匀分散，合成结构规则的纳米结构打下良好的基础。本实验过程中所用的模板剂NH2-SBA-15具有规则的形貌和均匀的孔道，使得WO3纳米颗粒生长受到一定的限制并沿着一定的方向生长，最终在热分解过程中形成了六方片状的WO3。利用多酸组成的可调变性，这种方法还可能被用来制备其他规则形貌的纳米金属氧化物。 (1) Using hexagonal flake SBA-15 as the main material for amino functional modification is conducive to the diffusion and transmission of the guest material APTMS in the channel, avoiding the problem of uneven distribution of the guest material in the channel and too low grafting amount . Amino groups based on the surface of amino-functionalized materials can combine with polyacids to form strong ionic bonds. Therefore, the precursor H 3 PW 12 O 40 for the synthesis of WO 3 can be immobilized through the strong interaction between the polyacid and the amino group, so that the uniform dispersion of the precursor on the carrier can be achieved, and a good foundation for the synthesis of a regular nanostructure can be laid. The templating agent NH 2 -SBA-15 used in this experiment has regular morphology and uniform pores, so that the growth of WO 3 nanoparticles is limited and grows along a certain direction, and finally formed during the thermal decomposition process. Hexagonal sheet of WO 3 . Utilizing the tunable denaturation of the polyacid composition, this method may also be used to prepare other nanometer metal oxides with regular shapes.
（2）所制备出的片状三氧化钨对硫化氢（H2S）气体表现出优良的气敏特性，所制得的硫化氢传感器具有灵敏度高，选择性好，响应/恢复时间短，重复性好等优点。 (2) The prepared flake tungsten trioxide exhibits excellent gas-sensing properties for hydrogen sulfide (H 2 S) gas, and the prepared hydrogen sulfide sensor has high sensitivity, good selectivity, short response/recovery time, Good repeatability and other advantages.
附图说明 Description of drawings
图1为实施例1所用的六方片状介孔材料SBA-15的的透射电子显微镜的TEM照片； Fig. 1 is the TEM photograph of the transmission electron microscope of the hexagonal sheet mesoporous material SBA-15 used in embodiment 1;
图2为按实施例1中用到的介孔材料SBA-15以及修饰后SBA-15的氮气吸附脱附曲线； Fig. 2 is the nitrogen adsorption-desorption curve of the mesoporous material SBA-15 used in Example 1 and SBA-15 after modification;
图3为按实施例1中所用的介孔材料SBA-15以及修饰后红外图谱； Fig. 3 is according to the mesoporous material SBA-15 used in the embodiment 1 and the infrared spectrum after modification;
图4为按下述实施例1中制备得到的六方片状WO3的透射电子显微镜的照片和扫描电子显微镜的照片； Fig. 4 is the photo of the transmission electron microscope and the photo of the scanning electron microscope of the hexagonal flake WO 3 prepared in the following example 1;
图5为实施例1中制备得到的六方片状WO3敏感材料在硫化氢不同浓度下的循环曲线图。 FIG. 5 is a cycle curve diagram of the hexagonal flake-shaped WO 3 sensitive material prepared in Example 1 under different concentrations of hydrogen sulfide.
具体实施方式 Detailed ways
本发明的具体实施例如下所示。 Specific examples of the present invention are shown below.
实施例一 Embodiment one
六方片状WO3及其气敏传感器的的制备方法，其过程和步骤如下： The preparation method of hexagonal sheet WO 3 and its gas sensor, its process and steps are as follows:
（1）六方片状WO3的制备：煅烧后的六方片状SBA-15在180 ℃抽真空加热1 h除去其中吸附的水分，然后在其表面修饰γ-氨丙基三甲氧基硅烷（APTMS）；将5 mg SBA-15分散在15ml (浓度为2-5%的APTMS) 的无水甲苯溶液中，回流24 h 后将样品取出，抽滤，用无水乙醇溶剂洗涤，然后在烘箱中70 ℃放置2 h，待干燥后备用，该样品记为APTMS/SBA-15； 在10 mg APTMS/SBA-15 中加入2ml 含有0.1 × 10-3 mol H3PW12O40 （磷钼酸）的醇溶液，在60 ℃持续搅拌28 h，倾出并抽滤，并用大量醇洗涤三次，除去未嫁接的多酸，然后在50 ℃干燥 30 h，得到H3PW12O40/APTMS/SBA-15。（2）六方片状WO3材料的制备：将反应得到的H3PW12O40/APTMS/SBA-15，在马弗炉中从室温以程序升温加热到500 ℃，并保持3 h，所获样品记为WO3 /SBA-15；将WO3/SBA-15在5 ml HF水溶液中溶解，除去SBA-15氧化硅得到纯的WO3。充分溶解后离心分离，用大量甲醇和去离子水清洗，最后得到纯的呈浅绿色的WO3。 (1) Preparation of hexagonal sheet-shaped WO 3 : the calcined hexagonal sheet-shaped SBA-15 was heated at 180 °C for 1 h to remove the adsorbed moisture, and then the surface was modified with γ-aminopropyltrimethoxysilane (APTMS ); Disperse 5 mg of SBA-15 in 15ml (concentration of 2-5% APTMS) in anhydrous toluene solution, take out the sample after reflux for 24 h, filter with suction, wash with absolute ethanol solvent, and then in the oven Put it at 70 ℃ for 2 hours, and wait for it to dry before use. This sample is recorded as APTMS/SBA-15; add 2ml of 0.1 × 10 -3 mol H 3 PW 12 O 40 (phosphomolybdic acid) to 10 mg APTMS/SBA-15 The alcohol solution was continuously stirred at 60 ℃ for 28 h, decanted and suction filtered, washed three times with a large amount of alcohol to remove ungrafted polyacids, and then dried at 50 ℃ for 30 h to obtain H 3 PW 12 O 40 /APTMS/SBA -15. (2) Preparation of hexagonal flake-shaped WO 3 material: The H 3 PW 12 O 40 /APTMS/SBA-15 obtained by the reaction was heated from room temperature to 500 ℃ in a muffle furnace with a temperature program and kept for 3 h. The obtained sample was recorded as WO 3 /SBA-15; WO 3 /SBA-15 was dissolved in 5 ml of HF aqueous solution, and the silicon oxide of SBA-15 was removed to obtain pure WO 3 . After fully dissolving, it was centrifuged and washed with a large amount of methanol and deionized water to finally obtain pure light green WO 3 .
本发明产物的应用—H2S气敏元件的制备 Application of the product of the present invention—preparation of H 2 S gas sensor
在玛瑙研钵中置入实施例1制备的WO3纳米片，研磨均匀后滴入少量黏合剂，调成糊状后用竹签均匀涂于带Pt引线的陶瓷管外面，涂有WO3敏感材料的陶瓷管立于陶瓷方舟内放在红外灯下烘干后，于马弗炉中300 °C煅烧1 ～ 6 h，以除去材料中所用的黏合剂，自然冷却后备用。将涂有敏感材料的陶瓷管的4个电极丝焊接在底座上，然后将加热丝从陶瓷管中穿过并将其两端也焊接在底座上，制成气敏元件。为了改善器件的性能，增加元件的稳定性，将焊好的元件置于专用的老化台上，老化240 h。 Put the WO 3 nanosheet prepared in Example 1 into the agate mortar, grind it evenly, add a small amount of adhesive, adjust it into a paste, and apply it evenly on the outside of the ceramic tube with Pt lead wire with a bamboo stick, coated with WO 3 sensitive The ceramic tube of the material was placed in a ceramic ark and dried under an infrared lamp, then calcined in a muffle furnace at 300 °C for 1–6 h to remove the binder used in the material, and cooled naturally for later use. The four electrode wires of the ceramic tube coated with sensitive materials are welded on the base, and then the heating wire is passed through the ceramic tube and its two ends are also welded on the base to make a gas sensor. In order to improve the performance of the device and increase the stability of the components, the soldered components were placed on a special aging table and aged for 240 h.
对上述实施例中所得样品的检测及实验的结果参见附图中的图1～5。 For the detection and experimental results of the samples obtained in the above examples, please refer to Figures 1-5 in the accompanying drawings.
参见图1，图1为本发明所用六方片状形貌的SBA-15的透射电子显微镜照片，从TEM可以看出本实验中用到的SBA-15全部具有六方片状规则形貌，且晶粒大小均匀。高分辨的TEM结果表明该样品具有均匀规则的六方孔道结构。 Referring to Fig. 1, Fig. 1 is the transmission electron micrograph of the SBA-15 of hexagonal flake morphology used in the present invention, from TEM it can be seen that the SBA-15 used in this experiment all has hexagonal flake regular morphology, and crystal The particle size is uniform. High-resolution TEM results show that the sample has a uniform and regular hexagonal channel structure.
参见附图2，从图中可以看出修饰前后的SBA-15均具有Ⅳ型吸附曲线，证明该材料具有典型的直线型孔结构、说明所用的介孔材料SBA-15具有均一有序的孔道，且修饰前后介孔材料的孔道保持良好，只是其孔径和比表面积变小。 Referring to accompanying drawing 2, it can be seen from the figure that SBA-15 before and after modification has a type IV adsorption curve, which proves that the material has a typical linear pore structure, indicating that the mesoporous material SBA-15 used has uniform and orderly channels , and the pores of the mesoporous materials before and after modification remain good, but the pore diameter and specific surface area become smaller.
参见附图3，是SBA-15, APTMS/SBA-15和WO3/SBA-15的红外谱图。从图中可以看出胺基功能化后，如图所示，1076 cm-1和803 cm-1 处的吸收峰是由SBA-15骨架的Si-O-Si键的伸缩振动引起的，460 cm-1处的吸收峰对应Si-O-Si键的弯曲振动，939 cm-1处的吸收峰是由端羟基Si-OH的伸缩振动引起的。样品中C-H键的吸收峰出现在2927 cm-1处，-NH2官能团的吸收峰出现在1590 cm-1和1480 cm-1处。以上结果表明APTMS成功的嫁接到介孔材料SBA-15上。在WO3/SBA-15的红外谱图中在600 ~ 1000 cm-1出现了对应于W-O-W的吸收峰，与此同时，在1590 cm-1和1480 cm-1处对应于-NH2官能团的吸收峰消失，说明磷钨酸在煅烧过程中在SBA-15模板上形成了WO3。 Referring to accompanying drawing 3, it is the infrared spectrogram of SBA-15, APTMS/SBA-15 and WO 3 /SBA-15. It can be seen from the figure that after the functionalization of the amine group, as shown in the figure, the absorption peaks at 1076 cm -1 and 803 cm -1 are caused by the stretching vibration of the Si-O-Si bond of the SBA-15 skeleton, and the 460 The absorption peak at cm -1 corresponds to the bending vibration of the Si-O-Si bond, and the absorption peak at 939 cm -1 is caused by the stretching vibration of the terminal hydroxyl Si-OH. The absorption peak of the CH bond in the sample appeared at 2927 cm -1 , and the absorption peaks of the -NH2 functional group appeared at 1590 cm -1 and 1480 cm -1 . The above results indicated that APTMS was successfully grafted onto the mesoporous material SBA-15. In the infrared spectrum of WO 3 /SBA-15, the absorption peaks corresponding to WOW appeared at 600 ~ 1000 cm -1 , at the same time, corresponding to -NH 2 functional groups at 1590 cm -1 and 1480 cm -1 The absorption peak disappeared, indicating that phosphotungstic acid formed WO 3 on the SBA-15 template during the calcination process.
参见附图4，是合成样品的TEM照片和XRD图谱，从图中可以看出，从图中可以看出本实验中得到的WO3和所用的模板氨基功能化SBA-15一样具有规则的六方片状行貌，且晶粒大小均匀。图中所标出的所有XRD衍射峰与标准图谱(JCPDS No. 46-1096, a = 7.521Å)的峰完全相一致属于立方相的WO3。图中无明显其他杂质峰出现，说明样品是单一的WO3相。 See accompanying drawing 4, it is the TEM picture and XRD spectrum of synthetic sample, can be seen from the picture, can see from the picture that WO 3 obtained in this experiment has the same regular hexagonal structure as the template amino-functionalized SBA-15 used. Flaky appearance with uniform grain size. All the XRD diffraction peaks marked in the figure are completely consistent with the peaks of the standard spectrum (JCPDS No. 46-1096, a = 7.521Å), which belongs to the cubic phase of WO 3 . No other obvious impurity peaks appear in the figure, indicating that the sample is a single WO 3 phase.
参见附图5，为WO3纳米片制备的气敏元件的电压随硫化氢浓度变化的关系图。由图可知基于WO3纳米片制备的气敏元件的电压随硫化氢浓度增加而增大，即WO3纳米片对酒精的响应随着硫化氢浓度的增加而升高，几乎呈线性关系。并且从图中还可以看出，WO3纳米片对硫化氢响应的重复性也比较好，响应-恢复时间也很短。其响应和恢复时间分别为8 s和11 s。 Referring to accompanying drawing 5, it is a graph showing the relationship between the voltage of the gas sensor prepared by WO 3 nanosheets and the concentration of hydrogen sulfide. It can be seen from the figure that the voltage of the gas sensor based on WO 3 nanosheets increases with the increase of hydrogen sulfide concentration, that is, the response of WO 3 nanosheets to alcohol increases with the increase of hydrogen sulfide concentration, almost in a linear relationship. And it can also be seen from the figure that the repeatability of the response of WO 3 nanosheets to hydrogen sulfide is relatively good, and the response-recovery time is also very short. Its response and recovery time are 8 s and 11 s, respectively.
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