CN107271488B - Preparation method of gas-sensitive material with nano composite structure - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 29
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 122
- 239000002096 quantum dot Substances 0.000 claims abstract description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 66
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 61
- 239000002071 nanotube Substances 0.000 claims abstract description 58
- 239000002131 composite material Substances 0.000 claims abstract description 37
- 239000002086 nanomaterial Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 239000010408 film Substances 0.000 claims description 49
- 239000006185 dispersion Substances 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 15
- 239000011540 sensing material Substances 0.000 claims description 12
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 238000003795 desorption Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 229910002804 graphite Inorganic materials 0.000 abstract 1
- 239000010439 graphite Substances 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000000231 atomic layer deposition Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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Abstract
本发明公开了一种纳米复合结构气敏材料的制备方法，属于敏感材料技术领域。本方法的制备方法区别于现有采用混合溶液体系制备气敏材料，通过分步制备首先在基片上形成二氧化钛纳米管和氧化石墨烯量子点形成复合纳米结构的薄膜，然后通过激光照射还原氧化石墨烯量子点得到团案化薄膜，在避免石墨烯量子点与二氧化钛纳米管难以混合的缺陷的同时，基于物理膨胀效应使得RGO与二氧化钛纳米管进行有效复合形成具有多维度特征的材料，从而显著增加复合纳米结构的表面积和开放性，有利于气体分子的吸附和脱附，显著提高气敏材料的灵敏度；最后再沉积超薄纳米金属氧化物层，不仅保证复合纳米结构的稳定性，而且提高了材料对气体的选择性。The invention discloses a preparation method of a gas-sensitive material with a nanocomposite structure, belonging to the technical field of sensitive materials. The preparation method of this method is different from the existing mixed solution system to prepare gas-sensitive materials. Firstly, titanium dioxide nanotubes and graphene oxide quantum dots are formed on the substrate to form a composite nanostructure film through step-by-step preparation, and then graphite oxide is reduced by laser irradiation. Graphene quantum dots are obtained into grouped films, while avoiding the defects that graphene quantum dots and titanium dioxide nanotubes are difficult to mix, based on the physical expansion effect, RGO and titanium dioxide nanotubes are effectively combined to form a material with multi-dimensional characteristics, thereby significantly increasing The surface area and openness of the composite nanostructure are conducive to the adsorption and desorption of gas molecules, and significantly improve the sensitivity of gas-sensitive materials; finally, the ultra-thin nano-metal oxide layer is deposited, which not only ensures the stability of the composite nanostructure, but also improves the Material selectivity for gases.
Description
技术领域technical field
本发明属于敏感材料技术领域，特别是涉及一种纳米复合结构气敏材料的制备方法。The invention belongs to the technical field of sensitive materials, and in particular relates to a preparation method of a gas-sensitive material with a nanocomposite structure.
背景技术Background technique
气敏材料涉及敏感材料表面与气体分子间的相互作用，或者引起敏感材料的电学性能发生变化，而产生气敏信号。而气敏信号的产生会涉及到气体在气敏材料表面的吸附以及和气体分子与气敏材料间的电荷转移。在上述过程中较为关键的是提高敏感材料与气体分子之间的作用效果。因此，如何发展出一种新型气敏材料以解决上述问题成为本领域的研究重点。Gas-sensing materials involve the interaction between the surface of the sensitive material and gas molecules, or cause changes in the electrical properties of the sensitive material to generate a gas-sensing signal. The generation of gas-sensing signals involves the adsorption of gas on the surface of the gas-sensing material and the charge transfer between gas molecules and the gas-sensing material. The key point in the above process is to improve the effect of interaction between sensitive materials and gas molecules. Therefore, how to develop a new gas-sensing material to solve the above problems has become the focus of research in this field.
由于纳米结构的材料体系具有比表面积大、结构开放的优势，故而在气敏材料领域具有极其重要的应用价值。而纳米结构的复合不仅能够改善材料的形貌与结构，而且各材料之间的协同效应也有望提升气敏材料体系的灵敏度和选择性。故此，如何通过稳定的组装方法使得量子点、纳米线、纳米管等纳米结构实现多维度的纳米结构体系成为了本领域的热点。然而，由于不同纳米结构之间存在表面效应，导致纳米结构材料的堆叠效应严重，故在实现稳定组装还具有较大难度。因此，如何结合有效的制备工艺以获得稳定的纳米复合结构成为本领域亟待解决的问题。Because the nanostructure material system has the advantages of large specific surface area and open structure, it has extremely important application value in the field of gas-sensing materials. The combination of nanostructures can not only improve the morphology and structure of the material, but also the synergistic effect between the various materials is expected to improve the sensitivity and selectivity of the gas-sensing material system. Therefore, how to make nanostructures such as quantum dots, nanowires, and nanotubes realize multi-dimensional nanostructure systems through stable assembly methods has become a hot spot in this field. However, due to the surface effect between different nanostructures, the stacking effect of nanostructure materials is serious, so it is still difficult to achieve stable assembly. Therefore, how to combine an effective preparation process to obtain a stable nanocomposite structure has become an urgent problem to be solved in this field.
发明内容Contents of the invention
本发明解决的技术问题是提供一种制备还原氧化石墨烯量子点与二氧化钛纳米管形成稳定复合结构材料的方法，本发明通过物理膨胀效应，使得RGO与二氧化钛纳米管进行有效复合形成具有多维度特征的材料，从而显著增加复合纳米结构的表面积和开放性，有利于气体分子的吸附和脱附，从而大大提高气体传感器的灵敏度和选择性。The technical problem solved by the present invention is to provide a method for preparing reduced graphene oxide quantum dots and titanium dioxide nanotubes to form a stable composite structure material. The present invention enables effective composite formation of RGO and titanium dioxide nanotubes with multi-dimensional characteristics through the physical expansion effect materials, thereby significantly increasing the surface area and openness of the composite nanostructure, which is conducive to the adsorption and desorption of gas molecules, thereby greatly improving the sensitivity and selectivity of the gas sensor.
为了实现上述目的，本发明提供了以下技术方案：In order to achieve the above object, the present invention provides the following technical solutions:
一种纳米复合结构气敏材料的制备方法，其特征在于，包括：在基片上形成氧化石墨烯量子点和二氧化钛纳米管相复合的薄膜，然后采用激光照射法还原氧化石墨烯量子点，再在制得的还原氧化石墨烯量子点与二氧化钛纳米管的复合结构上形成纳米金属氧化物薄膜，最终制得还原氧化石墨烯量子点、二氧化钛纳米管与纳米金属氧化物薄膜复合纳米结构材料。A method for preparing a gas-sensitive material with a nanocomposite structure, characterized in that it comprises: forming a composite film of graphene oxide quantum dots and titanium dioxide nanotubes on a substrate, then reducing the graphene oxide quantum dots by laser irradiation, and then A nanometer metal oxide film is formed on the composite structure of the prepared reduced graphene oxide quantum dots and titanium dioxide nanotubes, and finally a composite nanostructure material of the reduced graphene oxide quantum dots, titanium dioxide nanotubes and nanometer metal oxide films is obtained.
进一步地，本发明中在基片上形成氧化石墨烯量子点和二氧化钛纳米管相复合的薄膜具体采用如下操作：Further, in the present invention, the composite film of graphene oxide quantum dots and titanium dioxide nanotubes is formed on the substrate by the following operations:
将氧化石墨烯量子点分散液和二氧化钛纳米管分散液这两种分散液采用同时气喷的方式喷涂于基片表面制膜，然后经干燥处理后得到氧化石墨烯量子点和二氧化钛纳米管复合结构的材料。The graphene oxide quantum dot dispersion and titanium dioxide nanotube dispersion are sprayed on the surface of the substrate to form a film by simultaneous air spraying, and then dried to obtain a composite structure of graphene oxide quantum dots and titanium dioxide nanotubes s material.
作为优选实施方法，上述氧化石墨烯量子点分散液的浓度为1.5mg/mL～2.0mg/mL，二氧化钛纳米管分散液的浓度为0.5mg/mL～1.0mg/mL。As a preferred implementation method, the concentration of the graphene oxide quantum dot dispersion is 1.5 mg/mL-2.0 mg/mL, and the concentration of the titanium dioxide nanotube dispersion is 0.5 mg/mL-1.0 mg/mL.
进一步地，本发明中制备金属氧化物薄膜的方法包括但不局限于：原子层沉积法、化学气相沉积法以及分子束外延法。Further, the method for preparing the metal oxide thin film in the present invention includes but not limited to: atomic layer deposition method, chemical vapor deposition method and molecular beam epitaxy method.
进一步地，本发明中纳米金属氧化物薄膜的材料为纳米氧化铝、纳米氧化钌、纳米氧化铁、纳米氧化锡、纳米氧化锆或者纳米氧化锌；Further, the material of the nano-metal oxide film in the present invention is nano-alumina, nano-ruthenium oxide, nano-iron oxide, nano-tin oxide, nano-zirconia or nano-zinc oxide;
进一步地，本发明中金属氧化物薄膜的厚度为5～10nm。Further, the thickness of the metal oxide thin film in the present invention is 5-10 nm.
本发明区别于现有采用溶液混合体系制备气敏材料，通过分步制备先在基片上形成氧化石墨烯和二氧化钛纳米管复合结构的薄膜，然后再采用激光照射使得氧化石墨烯量子点还原为还原石墨烯量子点，在激光还原的过程中，量子点产生物理膨胀效应形成凸起结构进而能够与二氧化钛纳米管有效复合，从而显著增加复合纳米结构的表面积和开放性，有利于气体分子的吸附和脱附，提高了气敏材料的选择性和灵敏度；本发明在还原氧化石墨烯量子点与二氧化钛纳米管的复合结构上形成超薄金属氧化物层，保证了形成多维度材料的结构稳定性，并且金属氧化物薄膜同时也改善了复合纳米结构对气体分子的选择性。The present invention is different from the existing solution mixing system for preparing gas-sensitive materials, and first forms a film with a composite structure of graphene oxide and titanium dioxide nanotubes on the substrate through step-by-step preparation, and then uses laser irradiation to reduce the graphene oxide quantum dots to a reduced Graphene quantum dots, in the process of laser reduction, the quantum dots produce a physical expansion effect to form a raised structure and can be effectively composited with titanium dioxide nanotubes, thereby significantly increasing the surface area and openness of the composite nanostructure, which is conducive to the adsorption and absorption of gas molecules. Desorption improves the selectivity and sensitivity of gas-sensing materials; the invention forms an ultra-thin metal oxide layer on the composite structure of reduced graphene oxide quantum dots and titanium dioxide nanotubes, ensuring the structural stability of the multi-dimensional material, And the metal oxide thin film also improves the selectivity of the composite nanostructure to gas molecules.
相比现有技术，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
(1).本发明采用同时气喷氧化石墨烯量子点与二氧化钛纳米管再激光还原氧化石墨烯量子点的技术手段，有效避免了石墨烯量子点与二氧化钛纳米管难以混合的缺陷，同时，在激光还原过程中，由于物理膨胀效应使得量子点与纳米管有效复合，从而显著增加复合纳米结构的表面积和开放性，有利于气体分子的吸附和脱附，提高了气敏材料的选择性和灵敏度。(1). The present invention adopts the technical means of gas spraying graphene oxide quantum dots and titanium dioxide nanotubes and then laser reducing graphene oxide quantum dots at the same time, effectively avoiding the defect that graphene quantum dots and titanium dioxide nanotubes are difficult to mix, and at the same time, During the laser reduction process, due to the physical expansion effect, the quantum dots and nanotubes are effectively recombined, thereby significantly increasing the surface area and openness of the composite nanostructure, which is conducive to the adsorption and desorption of gas molecules, and improves the selectivity and sensitivity of gas-sensing materials. .
(2).本发明在还原氧化石墨烯量子点与二氧化钛纳米管的复合结构上形成超薄纳米金属氧化物层，不仅保证了量子点与纳米管相复合表面结构的稳定性，而且金属氧化物的引入有利于增强复合气敏材料对于气体的选择性。(2). The present invention forms an ultra-thin nanometer metal oxide layer on the composite structure of reduced graphene oxide quantum dots and titanium dioxide nanotubes, which not only ensures the stability of the composite surface structure of quantum dots and nanotubes, but also The introduction of is beneficial to enhance the selectivity of composite gas-sensing materials for gases.
(3).运用本发明制备方法具有简单可控、环保的优势，激光还原工序能够实现复合纳米结构的图案化，并且有利于实现器件的直接组装。(3). The preparation method of the present invention has the advantages of being simple, controllable, and environmentally friendly. The laser reduction process can realize the patterning of composite nanostructures, and is conducive to the direct assembly of devices.
具体实施方式Detailed ways
以下结合具体实施例对本发明工艺流程进行详细说明：Process flow of the present invention is described in detail below in conjunction with specific embodiment:
实施例1：Example 1:
步骤1：step 1:
称取石墨烯量子点15mg溶解于9.8ml去离子水中，配制得到10mL浓度为1.5mg/mL的氧化石墨烯量子点分散液；称取二氧化钛纳米管10mg溶解于9.6ml乙醇中，配制得到10mL浓度为1.0mg/mL的二氧化钛纳米管分散液；Weigh 15mg of graphene quantum dots and dissolve them in 9.8ml of deionized water to prepare 10mL of graphene oxide quantum dot dispersion with a concentration of 1.5mg/mL; weigh 10mg of titanium dioxide nanotubes and dissolve them in 9.6ml of ethanol to prepare 10mL of concentration 1.0 mg/mL titanium dioxide nanotube dispersion;
步骤2：Step 2:
分别量取氧化石墨烯量子点分散液和二氧化钛纳米管分散液各2ml，加入气喷设备腔体中，采用同时气喷的方式将氧化石墨烯量子点和二氧化钛纳米管沉积于经过亲水处理的叉指电极表面，然后置于温度为60℃的真空干燥箱中干燥2小时，得到氧化石墨烯量子点与二氧化钛纳米管形成复合纳米结构的薄膜；Measure 2ml each of graphene oxide quantum dot dispersion liquid and titanium dioxide nanotube dispersion liquid respectively, add them into the cavity of the air-spray equipment, and deposit graphene oxide quantum dots and titanium dioxide nanotubes on the hydrophilic treated surface by means of simultaneous air spraying. The surface of the interdigitated electrode is then placed in a vacuum drying oven at a temperature of 60 ° C for 2 hours to obtain a film of composite nanostructure formed by graphene oxide quantum dots and titanium dioxide nanotubes;
步骤3：Step 3:
将步骤2制得叉指电极表面薄膜置于激光光束下，调整功率为100mW，激光头步进速率为15mm/min，使得氧化石墨烯量子点还原为还原氧化石墨烯量子点，最终得到图案化薄膜；Put the interdigitated electrode surface film prepared in step 2 under the laser beam, adjust the power to 100mW, and the laser head step rate to 15mm/min, so that the graphene oxide quantum dots are reduced to reduced graphene oxide quantum dots, and finally the patterned film;
步骤4：Step 4:
将步骤3制得叉指电极表面薄膜置于原子层沉积设备中，在薄膜表面沉积一层厚度为5nm的纳米氧化锌层，最终在叉指电极表面制得还原氧化石墨烯量子点、二氧化钛纳米管和纳米氧化锌形成复合纳米结构的薄膜。Place the film on the surface of the interdigitated electrode prepared in step 3 in an atomic layer deposition device, deposit a nano-zinc oxide layer with a thickness of 5 nm on the surface of the film, and finally prepare reduced graphene oxide quantum dots and titanium dioxide nanometers on the surface of the interdigitated electrode. tubes and ZnO nanoparticles to form composite nanostructured films.
实施例2：Example 2:
步骤1：step 1:
称取石墨烯量子点20mg溶解于9.6ml去离子水中，配制得到10mL浓度为2.0mg/mL的氧化石墨烯量子点分散液；称取二氧化钛纳米管10mg溶解于9.6ml乙醇中，配制得到10mL浓度为1.0mg/mL的二氧化钛纳米管分散液；Weigh 20 mg of graphene quantum dots and dissolve them in 9.6 ml of deionized water to prepare 10 mL of graphene oxide quantum dot dispersions with a concentration of 2.0 mg/mL; weigh 10 mg of titanium dioxide nanotubes and dissolve them in 9.6 ml of ethanol to prepare 10 mL of 1.0 mg/mL titanium dioxide nanotube dispersion;
步骤2：Step 2:
分别量取氧化石墨烯量子点分散液和二氧化钛纳米管分散液各2ml，加入气喷设备腔体中，采用同时气喷的方式将氧化石墨烯量子点和二氧化钛纳米管沉积于经过亲水处理的叉指电极表面，然后置于温度为60℃的真空干燥箱中干燥2小时，得到氧化石墨烯量子点与二氧化钛纳米管形成复合纳米结构的薄膜；Measure 2ml each of graphene oxide quantum dot dispersion liquid and titanium dioxide nanotube dispersion liquid respectively, add them into the cavity of the air-spray equipment, and deposit graphene oxide quantum dots and titanium dioxide nanotubes on the hydrophilic treated surface by means of simultaneous air spraying. The surface of the interdigitated electrode is then placed in a vacuum drying oven at a temperature of 60 ° C for 2 hours to obtain a film of composite nanostructure formed by graphene oxide quantum dots and titanium dioxide nanotubes;
步骤3：Step 3:
将步骤2制得叉指电极表面薄膜置于激光光束下，调整功率为100mW，激光头步进速率为15mm/min，使得氧化石墨烯量子点还原为还原氧化石墨烯量子点，最终得到图案化薄膜；Put the interdigitated electrode surface film prepared in step 2 under the laser beam, adjust the power to 100mW, and the laser head step rate to 15mm/min, so that the graphene oxide quantum dots are reduced to reduced graphene oxide quantum dots, and finally the patterned film;
步骤4：Step 4:
将步骤3制得叉指电极表面薄膜置于原子层沉积设备中，在薄膜表面沉积一层厚度为5nm的纳米氧化锆层，最终在叉指电极表面制得还原氧化石墨烯量子点、二氧化钛纳米管和纳米氧化锆形成复合纳米结构的薄膜。Place the film on the surface of the interdigitated electrode prepared in step 3 in an atomic layer deposition device, deposit a layer of nano-zirconia layer with a thickness of 5 nm on the surface of the film, and finally prepare reduced graphene oxide quantum dots and titanium dioxide nanometers on the surface of the interdigitated electrode. tubes and nanozirconia to form composite nanostructured films.
实施例3：Example 3:
步骤1：step 1:
称取石墨烯量子点15mg溶解于9.8ml去离子水中，配制得到10mL浓度为1.5mg/mL的氧化石墨烯量子点分散液；称取二氧化钛纳米管5.0mg溶解于9.8ml乙醇中，配制得到10mL浓度为0.5mg/mL的二氧化钛纳米管分散液；Weigh 15mg of graphene quantum dots and dissolve them in 9.8ml of deionized water to prepare 10mL of graphene oxide quantum dot dispersion with a concentration of 1.5mg/mL; weigh 5.0mg of titanium dioxide nanotubes and dissolve them in 9.8ml of ethanol to prepare 10mL Concentration is the titanium dioxide nanotube dispersion liquid of 0.5mg/mL;
步骤2：Step 2:
分别量取氧化石墨烯量子点分散液和二氧化钛纳米管分散液各2ml，加入气喷设备腔体中，采用同时气喷的方式将氧化石墨烯量子点和二氧化钛纳米管沉积于经过亲水处理的叉指电极表面，然后置于温度为60℃的真空干燥箱中干燥2小时，得到氧化石墨烯量子点与二氧化钛纳米管形成复合纳米结构的薄膜；Measure 2ml each of graphene oxide quantum dot dispersion liquid and titanium dioxide nanotube dispersion liquid respectively, add them into the cavity of the air-spray equipment, and deposit graphene oxide quantum dots and titanium dioxide nanotubes on the hydrophilic treated surface by means of simultaneous air spraying. The surface of the interdigitated electrode is then placed in a vacuum drying oven at a temperature of 60 ° C for 2 hours to obtain a film of composite nanostructure formed by graphene oxide quantum dots and titanium dioxide nanotubes;
步骤3：Step 3:
将步骤2制得叉指电极表面薄膜置于激光光束下，调整功率为100mW，激光头步进速率为15mm/min，使得氧化石墨烯量子点还原为还原氧化石墨烯量子点，最终得到图案化薄膜；Put the interdigitated electrode surface film prepared in step 2 under the laser beam, adjust the power to 100mW, and the laser head step rate to 15mm/min, so that the graphene oxide quantum dots are reduced to reduced graphene oxide quantum dots, and finally the patterned film;
步骤4：Step 4:
将步骤3制得叉指电极表面薄膜置于原子层沉积设备中，在薄膜表面沉积一层厚度为5nm的纳米氧化铝层，最终在叉指电极表面制得还原氧化石墨烯量子点、二氧化钛纳米管和纳米氧化铝形成复合纳米结构的薄膜。Place the film on the surface of the interdigitated electrode prepared in step 3 in an atomic layer deposition device, deposit a layer of nano-alumina layer with a thickness of 5 nm on the surface of the film, and finally prepare reduced graphene oxide quantum dots and titanium dioxide nanometers on the surface of the interdigitated electrode. tubes and nano-alumina to form composite nanostructured films.
实施例4：Example 4:
步骤1：step 1:
称取石墨烯量子点15mg溶解于9.8ml去离子水中，配制得到10mL浓度为1.5mg/mL的氧化石墨烯量子点分散液；称取二氧化钛纳米管10mg溶解于9.6ml乙醇中，配制得到10mL浓度为1.0mg/mL的二氧化钛纳米管分散液；Weigh 15mg of graphene quantum dots and dissolve them in 9.8ml of deionized water to prepare 10mL of graphene oxide quantum dot dispersion with a concentration of 1.5mg/mL; weigh 10mg of titanium dioxide nanotubes and dissolve them in 9.6ml of ethanol to prepare 10mL of concentration 1.0 mg/mL titanium dioxide nanotube dispersion;
步骤2：Step 2:
分别量取氧化石墨烯量子点分散液和二氧化钛纳米管分散液各2ml，加入气喷设备腔体中，采用同时气喷的方式将氧化石墨烯量子点和二氧化钛纳米管沉积于经过亲水处理的叉指电极表面，然后置于温度为60℃的真空干燥箱中干燥2小时，得到氧化石墨烯量子点与二氧化钛纳米管形成复合纳米结构的薄膜；Measure 2ml each of graphene oxide quantum dot dispersion liquid and titanium dioxide nanotube dispersion liquid respectively, add them into the cavity of the air-spray equipment, and deposit graphene oxide quantum dots and titanium dioxide nanotubes on the hydrophilic treated surface by means of simultaneous air spraying. The surface of the interdigitated electrode is then placed in a vacuum drying oven at a temperature of 60 ° C for 2 hours to obtain a film of composite nanostructure formed by graphene oxide quantum dots and titanium dioxide nanotubes;
步骤3：Step 3:
将步骤2制得叉指电极表面薄膜置于激光光束下，调整功率为100mW，激光头步进速率为15mm/min，使得氧化石墨烯量子点还原为还原氧化石墨烯量子点，最终得到图案化薄膜；Put the interdigitated electrode surface film prepared in step 2 under the laser beam, adjust the power to 100mW, and the laser head step rate to 15mm/min, so that the graphene oxide quantum dots are reduced to reduced graphene oxide quantum dots, and finally the patterned film;
步骤4：Step 4:
将步骤3制得叉指电极表面薄膜置于原子层沉积设备中，在薄膜表面沉积一层厚度为5nm的纳米氧化钌层，最终在叉指电极表面制得还原氧化石墨烯量子点、二氧化钛纳米管和纳米氧化钌形成复合纳米结构的薄膜。Place the film on the surface of the interdigitated electrode prepared in step 3 in an atomic layer deposition device, deposit a layer of nanometer ruthenium oxide layer with a thickness of 5 nm on the surface of the film, and finally prepare reduced graphene oxide quantum dots and titanium dioxide nanometers on the surface of the interdigitated electrode. Tubes and nano-ruthenium oxide form composite nanostructured films.
实施例5：Example 5:
步骤1：step 1:
称取石墨烯量子点15mg溶解于9.8ml去离子水中，配制得到10mL浓度为1.5mg/mL的氧化石墨烯量子点分散液；称取二氧化钛纳米管10mg溶解于9.6ml乙醇中，配制得到10mL浓度为1.0mg/mL的二氧化钛纳米管分散液；Weigh 15mg of graphene quantum dots and dissolve them in 9.8ml of deionized water to prepare 10mL of graphene oxide quantum dot dispersion with a concentration of 1.5mg/mL; weigh 10mg of titanium dioxide nanotubes and dissolve them in 9.6ml of ethanol to prepare 10mL of concentration 1.0 mg/mL titanium dioxide nanotube dispersion;
步骤2：Step 2:
分别量取氧化石墨烯量子点分散液和二氧化钛纳米管分散液各2ml，加入气喷设备腔体中，采用同时气喷的方式将氧化石墨烯量子点和二氧化钛纳米管沉积于经过亲水处理的叉指电极表面，然后置于温度为60℃的真空干燥箱中干燥2小时，得到氧化石墨烯量子点与二氧化钛纳米管形成复合纳米结构的薄膜；Measure 2ml each of graphene oxide quantum dot dispersion liquid and titanium dioxide nanotube dispersion liquid respectively, add them into the cavity of the air-spray equipment, and deposit graphene oxide quantum dots and titanium dioxide nanotubes on the hydrophilic treated surface by means of simultaneous air spraying. The surface of the interdigitated electrode is then placed in a vacuum drying oven at a temperature of 60 ° C for 2 hours to obtain a film of composite nanostructure formed by graphene oxide quantum dots and titanium dioxide nanotubes;
步骤3：Step 3:
将步骤2制得叉指电极表面薄膜置于激光光束下，调整功率为100mW，激光头步进速率为15mm/min，使得氧化石墨烯量子点还原为还原氧化石墨烯量子点，最终得到图案化薄膜；Put the interdigitated electrode surface film prepared in step 2 under the laser beam, adjust the power to 100mW, and the laser head step rate to 15mm/min, so that the graphene oxide quantum dots are reduced to reduced graphene oxide quantum dots, and finally the patterned film;
步骤4：Step 4:
将步骤3制得叉指电极表面薄膜置于原子层沉积设备中，在薄膜表面沉积一层厚度为5nm的纳米氧化铁层，最终在叉指电极表面制得还原氧化石墨烯量子点、二氧化钛纳米管和纳米氧化铁形成复合纳米结构的薄膜。Place the film on the surface of the interdigitated electrode prepared in step 3 in an atomic layer deposition device, deposit a layer of nano-iron oxide layer with a thickness of 5 nm on the surface of the film, and finally prepare reduced graphene oxide quantum dots and titanium dioxide nanometers on the surface of the interdigitated electrode. tubes and nano-iron oxides form composite nanostructured films.
实施例6：Embodiment 6:
步骤1：step 1:
称取石墨烯量子点15mg溶解于9.8ml去离子水中，配制得到10mL浓度为1.5mg/mL的氧化石墨烯量子点分散液；称取二氧化钛纳米管10mg溶解于9.6ml乙醇中，配制得到10mL浓度为1.0mg/mL的二氧化钛纳米管分散液；Weigh 15mg of graphene quantum dots and dissolve them in 9.8ml of deionized water to prepare 10mL of graphene oxide quantum dot dispersion with a concentration of 1.5mg/mL; weigh 10mg of titanium dioxide nanotubes and dissolve them in 9.6ml of ethanol to prepare 10mL of concentration 1.0 mg/mL titanium dioxide nanotube dispersion;
步骤2：Step 2:
分别量取氧化石墨烯量子点分散液和二氧化钛纳米管分散液各2ml，加入气喷设备腔体中，采用同时气喷的方式将氧化石墨烯量子点和二氧化钛纳米管沉积于经过亲水处理的叉指电极表面，然后置于温度为60℃的真空干燥箱中干燥2小时，得到氧化石墨烯量子点与二氧化钛纳米管形成复合纳米结构的薄膜；Measure 2ml each of graphene oxide quantum dot dispersion liquid and titanium dioxide nanotube dispersion liquid respectively, add them into the cavity of the air-spray equipment, and deposit graphene oxide quantum dots and titanium dioxide nanotubes on the hydrophilic treated surface by means of simultaneous air spraying. The surface of the interdigitated electrode is then placed in a vacuum drying oven at a temperature of 60 ° C for 2 hours to obtain a film of composite nanostructure formed by graphene oxide quantum dots and titanium dioxide nanotubes;
步骤3：Step 3:
将步骤2制得叉指电极表面薄膜置于激光光束下，调整功率为100mW，激光头步进速率为15mm/min，使得氧化石墨烯量子点还原为还原氧化石墨烯量子点，最终得到图案化薄膜；Put the interdigitated electrode surface film prepared in step 2 under the laser beam, adjust the power to 100mW, and the laser head step rate to 15mm/min, so that the graphene oxide quantum dots are reduced to reduced graphene oxide quantum dots, and finally the patterned film;
步骤4：Step 4:
将步骤3制得叉指电极表面薄膜置于原子层沉积设备中，在薄膜表面沉积一层厚度为5nm的纳米氧化锡层，最终在叉指电极表面制得还原氧化石墨烯量子点、二氧化钛纳米管和纳米氧化锡形成复合纳米结构的薄膜。Place the film on the surface of the interdigitated electrode prepared in step 3 in an atomic layer deposition device, deposit a layer of nano-tin oxide layer with a thickness of 5 nm on the surface of the film, and finally prepare reduced graphene oxide quantum dots and titanium dioxide nanometers on the surface of the interdigitated electrode. tubes and nano-tin oxide form composite nanostructured films.
上述具体实施方式仅仅是示意性的，而不是限制性的，尽管已阐述了本发明的优选实施例，但本领域内的技术人员一旦得知了基本创造性概念，即可对上述实施例作出另外的变更和修改。因此本发明的权利要求的范围应涵盖优选实施例以及落入本发明范围的所有变更和修改。The above-mentioned specific embodiments are only illustrative, rather than restrictive. Although the preferred embodiments of the present invention have been described, those skilled in the art can make additional changes to the above-mentioned embodiments once they understand the basic creative concepts. changes and modifications. Therefore, the scope of the claims of the present invention shall cover the preferred embodiment and all changes and modifications falling within the scope of the present invention.
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