CN107413355A - A kind of Nb3O7The preparation method of F nano-arrays/graphene heterojunction composite - Google Patents
A kind of Nb3O7The preparation method of F nano-arrays/graphene heterojunction composite Download PDFInfo
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Abstract
本发明公开了一种Nb3O7F纳米阵列/石墨烯异质结复合材料的制备方法，包括如下步骤：配置石墨烯水溶液，搅拌后进行超声剥离，使石墨烯形成均匀分散液；向上述分散液中加入氢氟酸，搅拌并辅以超声，使得剥离的石墨烯表面被充分刻蚀，形成碳氟键；称取NbCl5粉末，加入到上述溶液中，搅拌充分后再添加氢氟酸，继续搅拌充分；将上述溶液转移至特氟龙内衬的反应釜中进行水热反应；反应结束后，将产物离心分离，并用去离子水和无水乙醇清洗，在烘箱中干燥；将干燥的产物热处理，以除去有机物，最终得到Nb3O7F纳米阵列/石墨烯异质结复合材料。本发明过程简单，操作条件易于控制，实现了低温下制备石墨烯基异质结材料。
The invention discloses a preparation method of a Nb 3 O 7 F nano-array/graphene heterojunction composite material, comprising the following steps: configuring an aqueous solution of graphene, performing ultrasonic peeling after stirring, so that the graphene forms a uniform dispersion; Add hydrofluoric acid to the dispersion, stir and supplement with ultrasound, so that the surface of the exfoliated graphene is fully etched to form a carbon-fluorine bond; weigh NbCl 5 powder, add it to the above solution, stir well and then add hydrofluoric acid , continue stirring fully; transfer the above solution to a Teflon-lined reactor for hydrothermal reaction; after the reaction, centrifuge the product, wash it with deionized water and absolute ethanol, and dry it in an oven; The product was heat-treated to remove organic matter, and finally obtained Nb 3 O 7 F nanoarray/graphene heterojunction composite material. The process of the invention is simple, the operating conditions are easy to control, and the preparation of graphene-based heterojunction materials at low temperature is realized.
Description
技术领域technical field
本发明涉及一种石墨烯基异质结材料的制备方法，具体是一种Nb3O7F纳米阵列/石墨烯异质结材料的制备方法。The invention relates to a method for preparing a graphene-based heterojunction material, in particular to a method for preparing a Nb 3 O 7 F nano-array/graphene heterojunction material.
背景技术Background technique
近年来，新型半导体光催化材料的快速发展，为降解有机污染物提供了新的选择方式；同时，一些新型半导体光催化材料能突破传统TiO2光催化材料存在的限制，尤其是载流子复合速率高、光谱响应低等问题，从而引起了学者的广泛关注。最近，Nb3O7F 因与TiO2的电子结构和能带结构相似，结晶性好、物相单一、化学惰性优异、抗氧化能力强、光催化活性高、载流子复合速率低等优点，被认为是一种很有前途的光催化材料。然而，Nb3O7F在光催化应用中存在电荷传输速率慢、量子效率低以及吸附性能差等缺点，致使其光催化效率得不到进一步提升。因此，寻找一种既能优化Nb3O7F的量子效率，又能增加载流子传输速率和吸附性能的途径，是实现其光催化应用的关键。In recent years, the rapid development of new semiconductor photocatalytic materials has provided a new choice for the degradation of organic pollutants; at the same time, some new semiconductor photocatalytic materials can break through the limitations of traditional TiO 2 photocatalytic materials, especially the carrier recombination The problems of high rate and low spectral response have attracted extensive attention of scholars. Recently, Nb 3 O 7 F has the advantages of good crystallinity, single phase, excellent chemical inertness, strong oxidation resistance, high photocatalytic activity, and low carrier recombination rate due to its similar electronic structure and energy band structure to TiO 2 , is considered as a promising photocatalytic material. However, Nb 3 O 7 F has disadvantages such as slow charge transfer rate, low quantum efficiency, and poor adsorption performance in photocatalytic applications, so that its photocatalytic efficiency cannot be further improved. Therefore, finding a way to optimize the quantum efficiency of Nb 3 O 7 F and increase the carrier transport rate and adsorption performance is the key to realize its photocatalytic application.
石墨烯是由单层碳原子组成的二维层状材料，具有优异的导电、导热性能，其较大的比表面积使其具有较强的吸附特性，是一种很好的电子传输材料。石墨烯与半导体材料形成异质结，可优化界面结构，加快半导体的载流子传输速率，减少载流子复合几率，从而提高量子效率，同时还可利用其大的比表面积优势显著增强吸附性能。然而，石墨烯纳米片易于再聚集，不易分散，从而失去石墨烯的特有功能；而且，石墨烯表面惰性强，很难制备理想的石墨烯基异质结材料。尽管人们开始尝试采用不同方法来制备石墨烯基异质结材料，但Nb3O7F纳米阵列/石墨烯异质结的文献或专利还未曾有报道。Graphene is a two-dimensional layered material composed of a single layer of carbon atoms. It has excellent electrical and thermal conductivity, and its large specific surface area makes it have strong adsorption properties. It is a good electron transport material. Graphene and semiconductor materials form a heterojunction, which can optimize the interface structure, accelerate the carrier transport rate of the semiconductor, reduce the probability of carrier recombination, thereby improving the quantum efficiency, and at the same time, it can also use its large specific surface area to significantly enhance the adsorption performance . However, graphene nanosheets are easy to re-aggregate and difficult to disperse, thus losing the unique functions of graphene; moreover, the surface of graphene is highly inert, making it difficult to prepare ideal graphene-based heterojunction materials. Although people have begun to try to use different methods to prepare graphene-based heterojunction materials, there have been no reports or patents on Nb 3 O 7 F nanoarray/graphene heterojunction.
文献1(Peifang Wang,Materials Letters,2013,101,41-43)采用溶剂热法，直接将还原氧化石墨烯沉积在TiO2阵列上，并研究了其光催化性能。该方法只是将石墨烯简单地沉积在TiO2阵列上，未形成良好的异质结构，结果光催化性能的提升幅度有限。Document 1 (Peifang Wang, Materials Letters, 2013, 101, 41-43) used a solvothermal method to directly deposit reduced graphene oxide on TiO 2 arrays, and studied its photocatalytic properties. This method simply deposits graphene on the TiO2 array without forming a good heterostructure, resulting in a limited improvement in photocatalytic performance.
文献2(Yu Zhao,Scientific Reports,2016,6,32327)采用水热法直接在还原氧化石墨烯薄膜上生长ZnO纳米棒，从而形成ZnO/石墨烯异质结。该方法操作过程繁琐，成本较高，氧化石墨烯的还原程度较难控制，很难完全还原，极大地影响了产物的性能。Document 2 (Yu Zhao, Scientific Reports, 2016, 6, 32327) uses the hydrothermal method to directly grow ZnO nanorods on the reduced graphene oxide film to form a ZnO/graphene heterojunction. The operation process of this method is cumbersome, the cost is high, the degree of reduction of graphene oxide is difficult to control, and it is difficult to completely reduce it, which greatly affects the performance of the product.
文献3(Qisheng Wang,Advanced Materials,2016,28,6497-6503)采用CVD在高温下将PdS沉积在石墨烯上，制成Graphene/PdS异质结，并研究了其伏安特性。该方法采用物理法，设备昂贵，成本较高，且工艺复杂，制备的异质结均匀性不易控制。Document 3 (Qisheng Wang, Advanced Materials, 2016, 28, 6497-6503) used CVD to deposit PdS on graphene at high temperature to form a Graphene/PdS heterojunction, and studied its volt-ampere characteristics. This method adopts a physical method, and the equipment is expensive, the cost is high, and the process is complicated, and the uniformity of the prepared heterojunction is not easy to control.
文献4(Chemistry-An Asian Journal,2016,11,584-595)采用光致还原法，在还原氧化石墨烯的同时，原位形成Ag3PO4/rGO异质结材料，并研究了其光催化性能。该方法中使用的氧化石墨烯还原程度低，缺陷较多，光催化性能得不到有效提升。Document 4 (Chemistry-An Asian Journal, 2016, 11, 584-595) used the photoreduction method to form Ag 3 PO 4 /rGO heterojunction materials in situ while reducing graphene oxide, and studied its photocatalytic properties . The graphene oxide used in this method has a low degree of reduction and many defects, and the photocatalytic performance cannot be effectively improved.
发明内容Contents of the invention
本发明的目的是提供一种Nb3O7F纳米阵列/石墨烯异质结的制备方法，以解决现有技术中存在的问题，如直接使用石墨烯为基质时其在水溶液中难以稳定分散，表面不易被共价，异质结生长困难的难点；而直接使用氧化石墨烯为基质时其还原程度低，性能无法提升，以及异质结均匀性不好等问题。The purpose of the present invention is to provide a preparation method of Nb 3 O 7 F nano-array/graphene heterojunction to solve the problems in the prior art, such as when graphene is directly used as a matrix, it is difficult to stably disperse in aqueous solution , the surface is not easy to be covalent, and the difficulty of heterojunction growth; when directly using graphene oxide as the substrate, the degree of reduction is low, the performance cannot be improved, and the heterogeneity of the heterojunction is not good.
技术方案：为实现上述目的，本发明采用的技术方案为：Technical scheme: in order to achieve the above object, the technical scheme adopted in the present invention is:
一种Nb3O7F纳米阵列/石墨烯异质结复合材料的制备方法，包括如下步骤：A preparation method of Nb 3 O 7 F nano-array/graphene heterojunction composite material, comprising the steps of:
(1)配置石墨烯水溶液，搅拌后进行超声剥离，使石墨烯形成均匀分散液；(1) Configure graphene aqueous solution, carry out ultrasonic stripping after stirring, graphene is formed uniform dispersion liquid;
(2)向上述分散液中加入氢氟酸，搅拌并辅以超声，使得剥离的石墨烯表面被充分刻蚀，形成碳氟键；(2) adding hydrofluoric acid to the above-mentioned dispersion liquid, stirring and supplemented by ultrasound, so that the surface of the exfoliated graphene is fully etched to form a carbon-fluorine bond;
(3)称取NbCl5粉末，加入到上述溶液中，搅拌充分后再添加氢氟酸，继续搅拌充分；(3) Take NbCl 5 powder, join in the above-mentioned solution, add hydrofluoric acid again after stirring fully, continue to stir fully;
(4)将上述溶液转移至特氟龙内衬的反应釜中进行水热反应；(4) above-mentioned solution is transferred to carry out hydrothermal reaction in the reactor of teflon liner;
(5)反应结束后，将产物离心分离，并用去离子水和无水乙醇清洗，在烘箱中干燥；(5) After the reaction finishes, the product is centrifuged, washed with deionized water and absolute ethanol, and dried in an oven;
(6)将干燥的产物热处理，以除去有机物，最终得到Nb3O7F纳米阵列/石墨烯异质结复合材料。(6) heat-treating the dried product to remove organic matter, and finally obtain a Nb 3 O 7 F nanoarray/graphene heterojunction composite material.
所述步骤(1)中，配置石墨烯水溶液所采用的石墨烯为纳米片结构，石墨烯的添加量，是按质量百分比，以Nb3O7F为基准，添加量为0.5～3.0wt.％。In the step (1), the graphene used in configuring the graphene aqueous solution has a nanosheet structure, and the amount of graphene added is by mass percentage, based on Nb3O7F , and the added amount is 0.5 to 3.0wt. %.
所述步骤(1)中，搅拌时间为1～3h，超声剥离时间为5～10h。In the step (1), the stirring time is 1-3 hours, and the ultrasonic stripping time is 5-10 hours.
所述步骤(1)中，石墨烯水溶液中添加有表面活性剂，所述表面活性剂为三嵌段表面活性剂，表面活性剂在步骤(4)的反应溶液中的浓度控制在0～40g/L。In the step (1), a surfactant is added to the graphene aqueous solution, the surfactant is a three-block surfactant, and the concentration of the surfactant in the reaction solution of the step (4) is controlled at 0～40g /L.
所述步骤(1)中，石墨烯水溶液中添加有络合剂，所述络合剂为一水合柠檬酸，络合剂在步骤(4)的反应溶液中的浓度控制在0～40g/L。In the step (1), a complexing agent is added to the graphene aqueous solution, the complexing agent is citric acid monohydrate, and the concentration of the complexing agent in the reaction solution of the step (4) is controlled at 0～40g/L .
本发明中，氢氟酸采用两次添加，第一次添加在步骤(2)中，目的是为了石墨烯的表面刻蚀，从而形成碳氟键，第二次添加在步骤(3)中，目的是为了合成Nb3O7F纳米阵列；所述步骤(2)中，加入氢氟酸后的溶液中，氢氟酸的浓度控制在0.1～0.15mol/L，搅拌时间为5～15min，超声剥离时间为10～30min；步骤(3)中，再次加入氢氟酸的溶液中，最终氢氟酸浓度控制在0.3～0.4mol/L，搅拌时间为2～6min。In the present invention, hydrofluoric acid is added twice, the first time is added in step (2), the purpose is for the surface etching of graphene, thereby forming carbon-fluorine bond, the second time is added in step (3), The purpose is to synthesize Nb 3 O 7 F nano-arrays; in the step (2), in the solution after adding hydrofluoric acid, the concentration of hydrofluoric acid is controlled at 0.1-0.15mol/L, and the stirring time is 5-15min. The ultrasonic peeling time is 10-30 min; in step (3), add hydrofluoric acid solution again, the final hydrofluoric acid concentration is controlled at 0.3-0.4 mol/L, and the stirring time is 2-6 min.
所述步骤(4)中，水热温度为120～200℃，水热时间为12～48h。In the step (4), the hydrothermal temperature is 120-200°C, and the hydrothermal time is 12-48h.
所述步骤(5)中，去离子水清洗为常温清洗，洗涤次数为3～5次，目的是除去杂质离子，提高产物纯度；乙醇清洗为常温清洗，洗涤次数为1～3次，目的是除去有机杂质；干燥温度为60～80℃，干燥时间大于5h。In the step (5), cleaning with deionized water is normal temperature cleaning, and the number of washings is 3 to 5 times, the purpose is to remove impurity ions and improve product purity; cleaning with ethanol is normal temperature cleaning, and the number of washings is 1 to 3 times, the purpose is to Remove organic impurities; the drying temperature is 60-80°C, and the drying time is more than 5 hours.
所述步骤(6)中，热处理温度为400℃，热处理时间为2～4h。In the step (6), the heat treatment temperature is 400° C., and the heat treatment time is 2 to 4 hours.
有益效果：Beneficial effect:
本发明通过合理地选取原材料，充分利用原材料的物化性质，利用石墨烯表面的酸刻蚀及功能化作用，采用水热/刻蚀法在低温条件下成功制备Nb3O7F纳米阵列/石墨烯异质结材料。本发明制备过程简单，易于操作，适于放大生产。本发明所要解决的关键问题是：1)石墨烯在水溶液中的分散性和稳定性，即石墨烯在水溶液中能够长时间稳定分散，以便下一步的均匀异质成核；2)石墨烯的表面功能化，即在石墨烯表面引入氟原子，形成表面缺陷；3)含铌前驱体与石墨烯相互作用，以保证Nb3O7F在石墨烯面上异质生长；4)Nb3O7F形貌结构的控制，通过添加表面活性剂，以改变结构的微观形貌，最终获得不同形态的阵列结构。The present invention selects raw materials reasonably, makes full use of the physical and chemical properties of the raw materials, utilizes the acid etching and functionalization of the graphene surface, and successfully prepares Nb 3 O 7 F nanometer arrays/graphite under low temperature conditions by using a hydrothermal/etching method ene heterojunction materials. The preparation process of the invention is simple, easy to operate and suitable for scale-up production. The key problem to be solved by the present invention is: 1) dispersibility and stability of graphene in aqueous solution, that is, graphene can be dispersed stably for a long time in aqueous solution, so that the uniform heterogeneous nucleation of next step; 2) the dispersibility of graphene Surface functionalization, that is, the introduction of fluorine atoms on the surface of graphene to form surface defects; 3) the interaction between niobium-containing precursors and graphene to ensure the heterogeneous growth of Nb 3 O 7 F on the graphene surface; 4) Nb 3 O The control of the morphology of 7 F is to change the microscopic morphology of the structure by adding surfactants, and finally obtain array structures of different shapes.
本发明的水热/刻蚀法制备Nb3O7F纳米阵列/石墨烯异质结材料的基本原理为：制备工艺通过分散剂调节溶液的黏度，使得超声剥离的石墨烯纳米片能够在水溶液中长时间稳定分散；利用氢氟酸刻蚀石墨烯，在石墨烯面上引入氟原子，形成碳氟键的表面缺陷；通过键合作用含铌前驱体，使得Nb3O7F在面缺陷处成核生长；最后，通过非离子表面活性剂大分子的位阻效应，减缓了Nb3O7F的生长速度，并调整Nb3O7F的生长方向，最终导致不同纳米阵列在石墨烯表面的生长。The basic principle of preparing Nb 3 O 7 F nanoarray/graphene heterojunction material by the hydrothermal/etching method of the present invention is: the preparation process adjusts the viscosity of the solution through the dispersant, so that the graphene nanosheets exfoliated by ultrasonic can be dissolved in the aqueous solution. Stable dispersion for a medium and long time; use hydrofluoric acid to etch graphene, introduce fluorine atoms on the graphene surface, and form surface defects of carbon-fluorine bonds; through bonding with niobium-containing precursors, make Nb 3 O 7 F surface defects nucleation and growth; finally, through the steric hindrance effect of non-ionic surfactant macromolecules, the growth rate of Nb 3 O 7 F is slowed down, and the growth direction of Nb 3 O 7 F is adjusted, finally resulting in different nano-arrays in graphene surface growth.
由于采用了上述方案，本发明与前述的背景技术相比，具有如下优点：Owing to having adopted above-mentioned scheme, the present invention has following advantages compared with aforementioned background technology:
1)石墨烯的功能化方式不同，本发明是基于石墨烯的刻蚀作用，并在表面形成碳氟键，从而使石墨烯表面功能化。1) The functionalization mode of graphene is different, and the present invention is based on the etching action of graphene, and forms carbon-fluorine bond on the surface, thereby makes graphene surface functionalization.
2)通过低温水热的方法，首次合成Nb3O7F纳米阵列/石墨烯异质结材料，特殊的材料结构导致了良好的光电性能。2) The Nb 3 O 7 F nanoarray/graphene heterojunction material was synthesized for the first time by a low-temperature hydrothermal method, and the special material structure led to good photoelectric performance.
3)整个制备过程简单，操作条件易于控制，既适用于实验室研究的少量制备，又可用于大批量生产。3) The whole preparation process is simple, and the operating conditions are easy to control, which is suitable for both small-scale preparation for laboratory research and mass production.
4)在石墨烯水溶液中添加了表面活性剂或/和络合剂，添加表面活性剂石墨烯分散性更好，结果阵列效果更好，添加络合剂可以改变阵列形貌。4) Surfactants or/and complexing agents are added to the graphene aqueous solution. Adding surfactants has better dispersion of graphene, resulting in better array effects. Adding complexing agents can change the array morphology.
附图说明Description of drawings
图1为本发明制备的刻蚀石墨烯的EDS图；Fig. 1 is the EDS figure of the etched graphene prepared by the present invention;
图2为本发明制备的刻蚀石墨烯的XPS图；Fig. 2 is the XPS figure of the etched graphene prepared by the present invention;
图3为本发明制备的Nb3O7F纳米柱阵列/石墨烯异质结材料的SEM图；Fig. 3 is the SEM picture of the Nb 3 O 7 F nanocolumn array/graphene heterojunction material prepared by the present invention;
图4为本发明制备的Nb3O7F纳米柱阵列/石墨烯异质结材料的TEM图；Fig. 4 is the TEM picture of the Nb 3 O 7 F nanocolumn array/graphene heterojunction material prepared by the present invention;
图5为本发明制备的Nb3O7F纳米柱阵列/石墨烯异质结材料的XRD图；Fig. 5 is the XRD diagram of the Nb 3 O 7 F nanocolumn array/graphene heterojunction material prepared by the present invention;
图6为本发明制备的Nb3O7F草坪阵列/石墨烯异质结材料的SEM图。Fig. 6 is a SEM image of the Nb 3 O 7 F lawn array/graphene heterojunction material prepared by the present invention.
具体实施方式detailed description
下面结合具体实施例对本发明作更进一步的说明。The present invention will be further described below in conjunction with specific examples.
本发明采用水热/刻蚀的方法，通过一系列化学反应，在石墨烯纳米片上生长Nb3O7F 纳米阵列，步骤如下：The present invention adopts a hydrothermal/etching method to grow Nb 3 O 7 F nano-arrays on graphene nano-sheets through a series of chemical reactions, and the steps are as follows:
1)选取石墨烯纳米片作为基底，以NbCl5作为铌源，以强腐蚀性氢氟酸作为氟源，以表面活性剂和络合剂为分散剂；1) Select graphene nanosheets as the substrate, use NbCl 5 as the niobium source, use highly corrosive hydrofluoric acid as the fluorine source, and use surfactants and complexing agents as dispersants;
2)配置石墨烯水溶液，搅拌后进行超声剥离，使石墨烯形成均匀分散液；2) configure the graphene aqueous solution, carry out ultrasonic stripping after stirring, so that the graphene forms a uniform dispersion;
配置石墨烯水溶液所采用的石墨烯为纳米片结构，石墨烯的添加量，是按质量百分比，以Nb3O7F为基准，添加量为0.5～3.0wt.％；其中Nb3O7F的质量通过NbCl5换算；The graphene used to configure the graphene aqueous solution is a nanosheet structure, and the amount of graphene added is based on mass percentage, based on Nb 3 O 7 F, and the amount added is 0.5 to 3.0wt.%; wherein Nb 3 O 7 F The quality of is converted by NbCl 5 ;
搅拌时间为1～3h，超声剥离时间为4～8hStirring time is 1~3h, ultrasonic peeling time is 4~8h
3)向上述均匀分散液中加入强腐蚀性氢氟酸，搅拌并辅以超声，使得石墨烯表面被充分刻蚀，形成碳氟键；3) Add strong corrosive hydrofluoric acid to the above-mentioned uniform dispersion, stir and supplement with ultrasound, so that the graphene surface is fully etched to form a carbon-fluorine bond;
所述搅拌时间为5～15min，超声剥离时间为10～20min；The stirring time is 5-15 min, and the ultrasonic stripping time is 10-20 min;
4)称取NbCl5粉末，加入到上述溶液中，搅拌充分后再适量添加强腐蚀性氢氟酸，继续搅拌充分；4) Weigh the NbCl 5 powder and add it to the above solution, after stirring fully, add strong corrosive hydrofluoric acid in an appropriate amount, and continue stirring fully;
所述搅拌时间为2～6min；The stirring time is 2～6min;
5)将上述溶液转移至特氟龙内衬的反应釜中进行水热反应；水热温度为120～200℃，水热时间为12～48h；5) Transfer the above solution to a Teflon-lined reactor for hydrothermal reaction; the hydrothermal temperature is 120-200°C, and the hydrothermal time is 12-48h;
6)反应结束后，将产物离心分离，并用去离子水和无水乙醇清洗，在烘箱中干燥；6) After the reaction, the product was centrifuged, washed with deionized water and absolute ethanol, and dried in an oven;
其中，去离子水清洗为常温清洗，洗涤次数为3～5次，除去杂质离子，提高产物纯度；乙醇清洗为常温清洗，洗涤次数为1～3次，除去有机杂质；干燥温度为60～80℃，干燥时间大于5h；Among them, deionized water cleaning is normal temperature cleaning, and the number of washings is 3 to 5 times to remove impurity ions and improve product purity; ethanol cleaning is normal temperature cleaning, and the number of washings is 1 to 3 times to remove organic impurities; the drying temperature is 60 to 80 ℃, the drying time is greater than 5h;
7)将干燥的产物在400℃热处理2～4h，以除去有机物，最终得到Nb3O7F纳米阵列/石墨烯异质结材料。7) heat-treating the dried product at 400° C. for 2-4 hours to remove organic matter, and finally obtain a Nb 3 O 7 F nanoarray/graphene heterojunction material.
步骤2)中，可在配制好的石墨烯水溶液中添加表面活性剂或络合剂，或者两者都添加；In step 2), surfactant or complexing agent can be added in the prepared graphene aqueous solution, or both can be added;
表面活性剂为三嵌段表面活性剂，表面活性剂在步骤5)的反应溶液中的浓度控制在0～40g/L。其中，三嵌段表面活性剂为P123或F127；The surfactant is a three-block surfactant, and the concentration of the surfactant in the reaction solution in step 5) is controlled at 0-40 g/L. Among them, the triblock surfactant is P123 or F127;
络合剂为一水合柠檬酸，络合剂在步骤5)的反应溶液中的浓度控制在0～40g/L。The complexing agent is citric acid monohydrate, and the concentration of the complexing agent in the reaction solution in step 5) is controlled at 0-40 g/L.
本发明所采用的原材料包括石墨烯粉末(纯度为99.95％)，NbCl5粉末(纯度为99.99％)，氢氟酸(浓度为40％)，非离子表面活性剂和柠檬酸，原材料均为分析纯；The raw material that the present invention adopts comprises graphene powder (purity is 99.95%), NbCl5 powder (purity is 99.99%), hydrofluoric acid (concentration is 40%), nonionic surfactant and citric acid, and raw material is analysis pure;
本发明中，氢氟酸采用两次添加，第一次添加在步骤(2)中，目的是为了石墨烯的表面刻蚀，从而形成碳氟键，第二次添加在步骤(3)中，目的是为了合成Nb3O7F纳米阵列；所述步骤(2)中，加入氢氟酸后的溶液中，氢氟酸的浓度控制在0.1～0.15mol/L；步骤(3)中，再次加入氢氟酸的溶液中，最终氢氟酸浓度控制在0.3～0.4mol/L。In the present invention, hydrofluoric acid is added twice, the first time is added in step (2), the purpose is for the surface etching of graphene, thereby forming carbon-fluorine bond, the second time is added in step (3), The purpose is to synthesize Nb 3 O 7 F nanometer arrays; in the step (2), in the solution after adding hydrofluoric acid, the concentration of the hydrofluoric acid is controlled at 0.1～0.15mol/L; in the step (3), again Add hydrofluoric acid to the solution, and the final concentration of hydrofluoric acid is controlled at 0.3-0.4mol/L.
下面结合具体实施例对本发明做进一步说明。The present invention will be further described below in conjunction with specific embodiments.
实施例1：Example 1:
(1)称取16.9mg石墨烯加入塑料烧杯中，添加40mL H2O，配制成石墨烯水溶液，搅拌后进行超声剥离，使石墨烯形成均匀分散液；(1) Weigh 16.9 mg of graphene and add it to a plastic beaker, add 40 mL of H 2 O to prepare a graphene aqueous solution, and perform ultrasonic peeling after stirring to form a uniform dispersion of graphene;
(2)然后向上述分散液添加0.5mL HF，搅拌并辅以超声6h，使得剥离的石墨烯表面被充分刻蚀，形成碳氟键；(2) Then add 0.5mL HF to the above-mentioned dispersion liquid, stir and supplement with ultrasound for 6h, so that the surface of the exfoliated graphene is fully etched to form a carbon-fluorine bond;
(3)将1.623g NbCl5加入上述溶液中，室温下磁力搅拌30min，并添加0.65mL HF和40mL H2O，搅拌30s；(3) Add 1.623g NbCl 5 into the above solution, stir magnetically for 30min at room temperature, add 0.65mL HF and 40mL H 2 O, and stir for 30s;
(4)将上述溶液转移至100mL聚四氟乙烯内衬中，然后将聚四氟乙烯内衬置入微型反应釜中，密封好；将反应釜放入烘箱中，在120℃下加热反应24h，然后随炉冷却；(4) Transfer the above solution to a 100mL polytetrafluoroethylene liner, then put the polytetrafluoroethylene liner into a micro-reactor and seal it; put the reactor into an oven, and heat the reaction at 120°C for 24h , and then cooled with the furnace;
(5)将沉淀离心分离，用常温的去离子水清洗5次，用无水乙醇清洗3次；产物在70℃的真空烘箱中干燥6h。(5) Centrifuge the precipitate, wash it with normal temperature deionized water for 5 times, and wash it with absolute ethanol for 3 times; the product is dried in a vacuum oven at 70° C. for 6 hours.
(6)将干燥后的产物在400℃的空气中热处理2h，即得到最终产物。(6) heat-treating the dried product in air at 400° C. for 2 hours to obtain the final product.
实施例2：Example 2:
(1)称取16.9mg石墨烯加入烧杯中，添加40mL H2O，配制成石墨烯水溶液，然后添加2g P123，在70℃下水浴搅拌30min，使P123完全溶解；然后进行超声剥离，使石墨烯形成均匀分散液；(1) Weigh 16.9mg of graphene into a beaker, add 40mL of H 2 O to prepare a graphene aqueous solution, then add 2g of P123, stir in a water bath at 70°C for 30 minutes to completely dissolve P123; then perform ultrasonic stripping to make graphite Alkenes form a homogeneous dispersion;
(2)然后向上述分散液添加0.5mL HF，搅拌并辅以超声6h，使得剥离的石墨烯表面被充分刻蚀，形成碳氟键；(2) Then add 0.5mL HF to the above-mentioned dispersion liquid, stir and supplement with ultrasound for 6h, so that the surface of the exfoliated graphene is fully etched to form a carbon-fluorine bond;
(3)称取1.623g NbCl5加入上述溶液中，室温下磁力搅拌1h；并添加0.65mL HF 和40mL H2O，搅拌30s；(3) Weigh 1.623g NbCl 5 into the above solution, stir magnetically at room temperature for 1h; add 0.65mL HF and 40mL H 2 O, and stir for 30s;
(4)将搅拌后的混合溶液转移至100mL聚四氟乙烯内衬中，然后将聚四氟乙烯内衬置入微型反应釜中，密封好；将反应釜转移至烘箱中，在120℃下加热反应24h，然后随炉冷却；(4) Transfer the stirred mixed solution to a 100mL polytetrafluoroethylene lining, then put the polytetrafluoroethylene lining into a micro-reactor and seal it well; Heating and reacting for 24h, then cooling with the furnace;
(5)将沉淀离心分离，用去离子水清洗5次，用无水乙醇清洗3次；将产物在70℃的真空烘箱中干燥6h；(5) Centrifuge the precipitate, wash it 5 times with deionized water, and wash it 3 times with absolute ethanol; dry the product in a vacuum oven at 70° C. for 6 hours;
(6)最后，将干燥后的产物在400℃的空气中进行热处理3h，即得最终产物。(6) Finally, heat-treat the dried product in air at 400° C. for 3 hours to obtain the final product.
实施例3：Example 3:
(1)称取16.9mg石墨烯加入烧杯中，添加40mL H2O，配制成石墨烯水溶液，然后添加2g柠檬酸，在70℃下水浴搅拌30min，使柠檬酸完全溶解；然后进行超声剥离，使石墨烯形成均匀分散液；(1) Weigh 16.9 mg of graphene and add it to a beaker, add 40 mL of H 2 O to prepare a graphene aqueous solution, then add 2 g of citric acid, stir in a water bath at 70 ° C for 30 min to completely dissolve the citric acid; then perform ultrasonic stripping, Make graphene form a uniform dispersion;
(2)然后向上述分散液添加0.5mL HF，搅拌并辅以超声5h，使得剥离的石墨烯表面被充分刻蚀，形成碳氟键；(2) Then add 0.5mL HF to the above-mentioned dispersion liquid, stir and supplement with ultrasonic 5h, make the graphene surface of exfoliation be fully etched, form carbon-fluorine bond;
(3)称取1.623g NbCl5加入上述溶液中，室温下磁力搅拌1h；并添加0.65mL HF 和40mL H2O，搅拌30s；(3) Weigh 1.623g NbCl 5 into the above solution, stir magnetically at room temperature for 1h; add 0.65mL HF and 40mL H 2 O, and stir for 30s;
(4)将搅拌后的混合溶液转移至100mL聚四氟乙烯内衬中，然后将聚四氟乙烯内衬置入微型反应釜中，密封好；将反应釜转移至烘箱中，在120℃下加热反应24h，然后随炉冷却；(4) Transfer the stirred mixed solution to a 100mL polytetrafluoroethylene lining, then put the polytetrafluoroethylene lining into a micro-reactor and seal it well; Heating and reacting for 24h, then cooling with the furnace;
(5)将沉淀离心分离，用去离子水清洗5次，用无水乙醇清洗3次；将产物在70℃的真空烘箱中干燥6h；(5) Centrifuge the precipitate, wash it 5 times with deionized water, and wash it 3 times with absolute ethanol; dry the product in a vacuum oven at 70° C. for 6 hours;
(6)最后，将干燥后的产物在400℃的空气中进行热处理3h，即得最终产物。(6) Finally, heat-treat the dried product in air at 400° C. for 3 hours to obtain the final product.
实施例4：Example 4:
(1)称取16.9mg石墨烯加入烧杯中，添加40mL H2O，配制成石墨烯水溶液，然后添加2g F127和2g柠檬酸，在70℃下水浴搅拌30min，使柠檬酸完全溶解；然后进行超声剥离，使石墨烯形成均匀分散液；(1) Weigh 16.9mg of graphene into a beaker, add 40mL of H 2 O to prepare a graphene aqueous solution, then add 2g of F127 and 2g of citric acid, and stir in a water bath at 70°C for 30min to completely dissolve the citric acid; then Ultrasonic stripping to make graphene form a uniform dispersion;
(2)然后向上述分散液添加0.5mL HF，搅拌并辅以超声5h，使得剥离的石墨烯表面被充分刻蚀，形成碳氟键；(2) Then add 0.5mL HF to the above-mentioned dispersion liquid, stir and supplement with ultrasonic 5h, make the graphene surface of exfoliation be fully etched, form carbon-fluorine bond;
(3)称取1.623g NbCl5加入上述溶液中，室温下磁力搅拌1h；并添加0.65mL HF 和40mL H2O，搅拌30s；(3) Weigh 1.623g NbCl 5 into the above solution, stir magnetically at room temperature for 1h; add 0.65mL HF and 40mL H 2 O, and stir for 30s;
(4)将搅拌后的混合溶液转移至100mL聚四氟乙烯内衬中，然后将聚四氟乙烯内衬置入微型反应釜中，密封好；将反应釜转移至烘箱中，在120℃下加热反应24h，然后随炉冷却；(4) Transfer the stirred mixed solution to a 100mL polytetrafluoroethylene lining, then put the polytetrafluoroethylene lining into a micro-reactor and seal it well; Heating and reacting for 24h, then cooling with the furnace;
(5)将沉淀离心分离，用去离子水清洗5次，用无水乙醇清洗3次；将产物在70℃的真空烘箱中干燥6h；(5) Centrifuge the precipitate, wash it 5 times with deionized water, and wash it 3 times with absolute ethanol; dry the product in a vacuum oven at 70° C. for 6 hours;
(6)最后，将干燥后的产物在400℃的空气中进行热处理4h，即得最终产物。(6) Finally, heat-treat the dried product in air at 400° C. for 4 hours to obtain the final product.
图1为本发明制备的刻蚀石墨烯的EDS图，从图中可以知道，刻蚀后的石墨烯含有碳元素和氟元素，且氟元素在石墨烯上均匀分布。Fig. 1 is the EDS diagram of the etched graphene prepared by the present invention, it can be known from the figure that the etched graphene contains carbon elements and fluorine elements, and the fluorine elements are evenly distributed on the graphene.
图2为本发明制备的刻蚀石墨烯的XPS图，从图中可以知道，刻蚀前后的石墨烯最大的变化就是刻蚀后石墨烯表面形成了碳氟键。Fig. 2 is the XPS diagram of the etched graphene prepared by the present invention, as can be known from the figure, the biggest change of the graphene before and after etching is that the carbon-fluorine bond is formed on the graphene surface after etching.
图3为本发明制备的Nb3O7F纳米柱阵列/石墨烯异质结材料的SEM图，从图中可以看出产物为纳米柱阵列。Fig. 3 is an SEM image of the Nb 3 O 7 F nanocolumn array/graphene heterojunction material prepared by the present invention, from which it can be seen that the product is a nanocolumn array.
图4为本发明制备的Nb3O7F纳米柱阵列/石墨烯异质结材料的TEM图，从图中可以看出超声后纳米柱阵破碎，纳米柱直径在20～50nm范围内。Fig. 4 is a TEM image of the Nb 3 O 7 F nanocolumn array/graphene heterojunction material prepared by the present invention. It can be seen from the figure that the nanocolumn array is broken after ultrasound, and the diameter of the nanocolumn is in the range of 20-50nm.
图5为本发明制备的Nb3O7F纳米柱阵列/石墨烯异质结材料的XRD图，从图中可以看出产物的主要物相为Nb3O7F(JCPDS No.18-0915)，这主要源自于石墨烯含量比较低的缘故。Fig. 5 is the XRD pattern of the Nb 3 O 7 F nanocolumn array/graphene heterojunction material prepared by the present invention, as can be seen from the figure that the main phase of the product is Nb 3 O 7 F (JCPDS No.18-0915 ), which is mainly due to the relatively low content of graphene.
图6为本发明制备的Nb3O7F草坪阵列/石墨烯异质结材料的SEM图，从图中可以看出产物为草坪阵列。Fig. 6 is an SEM image of the Nb 3 O 7 F lawn array/graphene heterojunction material prepared by the present invention, from which it can be seen that the product is a lawn array.
上述列举出了本发明的四种实施方式，但本发明的上述实施方案都只是对本发明的说明而不能限制本发明，权利要求书指出本发明的范围。因此，在不违背本发明基本思想的情况下，只要利用HF对石墨烯进行表面刻蚀，形成碳氟键，并利用这种表面缺陷形成Nb3O7F/石墨烯异质结材料都应是落入本发明的保护范围内。本发明各原材料的上下限、区间取值，以及工艺参数(如温度、时间等)的上下限、区间取值都能实现本发明，在此不一一列举。The above lists four embodiments of the present invention, but the above embodiments of the present invention are only descriptions of the present invention and cannot limit the present invention, and the claims point out the scope of the present invention. Therefore, without violating the basic idea of the present invention, as long as HF is used to etch the surface of graphene to form carbon-fluorine bonds, and to use this surface defect to form Nb 3 O 7 F/graphene heterojunction materials should be fall within the protection scope of the present invention. The upper and lower limits and interval values of each raw material of the present invention, and the upper and lower limits and interval values of process parameters (such as temperature, time, etc.) can realize the present invention, and are not listed one by one here.
Claims (10)
- A kind of 1. Nb3O7The preparation method of F nano-arrays/graphene heterojunction composite, it is characterized in that：Comprise the following steps：(1) graphene aqueous solution is configured, ultrasonic stripping is carried out after stirring, graphene is formed uniform dispersion；(2) hydrofluoric acid is added into above-mentioned dispersion liquid, stirs and be aided with ultrasound so that the graphenic surface of stripping is fully carved Erosion, form carbon-fluorine bond；(3) NbCl is weighed5Powder, it is added in above-mentioned solution, hydrofluoric acid is added again after stirring fully, it is abundant continues stirring；(4) above-mentioned solution is transferred in the reactor of Teflon liner and carries out hydro-thermal reaction；(5) after reaction terminates, product is centrifuged, and with deionized water and washes of absolute alcohol, dried in an oven；(6) dry product is heat-treated, to remove organic matter, finally gives Nb3O7F nano-arrays/graphene hetero-junctions is compound Material.
- 2. Nb according to claim 13O7The preparation method of F nano-arrays/graphene heterojunction composite, its feature It is：In the step (1), graphene is nanometer chip architecture used by configuring graphene aqueous solution, the addition of graphene, is By mass percentage, with Nb3O7On the basis of F, addition is 0.5~3.0wt.%.
- 3. Nb according to claim 13O7The preparation method of F nano-arrays/graphene heterojunction composite, its feature It is：In the step (1), mixing time is 1~3h, and ultrasonic splitting time is 5~10h.
- 4. Nb according to claim 13O7The preparation method of F nano-arrays/graphene heterojunction composite, its feature It is：In the step (1), surfactant is added with graphene aqueous solution, the surfactant is lived for three block surface Property agent, concentration of the surfactant in the reaction solution of step (4) controlled in 0~40g/L.
- 5. the Nb according to claim 1 or 43O7The preparation method of F nano-arrays/graphene heterojunction composite, it is special Sign is：In the step (1), complexing agent is added with graphene aqueous solution, the complexing agent is monohydrate potassium, complexing agent Concentration in the reaction solution of step (4) is controlled in 0~40g/L.
- 6. Nb according to claim 13O7The preparation method of F nano-arrays/graphene heterojunction composite, its feature It is：In the step (2), add in the solution after hydrofluoric acid, the concentration of hydrofluoric acid is controlled in 0.1~0.15mol/L；The step Suddenly in (3), hydrofluoric acid is added again into solution, and final hydrofluoric acid concentration control is in 0.3~0.4mol/L.
- 7. Nb according to claim 13O7The preparation method of F nano-arrays/graphene heterojunction composite, its feature It is：In the step (2), mixing time is 5~15min, and ultrasonic splitting time is 10~30min；In the step (3), stir It is 2~6min to mix the time.
- 8. Nb according to claim 13O7The preparation method of F nano-arrays/graphene heterojunction composite, its feature It is：In the step (4), hydrothermal temperature is 120~200 DEG C, and the hydro-thermal time is 12~48h.
- 9. Nb according to claim 13O7The preparation method of F nano-arrays/graphene heterojunction composite, its feature It is：In the step (5), deionized water cleaning is cleaned for normal temperature, and washing times are 3~5 times；Ethanol cleaning is cleaned for normal temperature, Washing times are 1~3 time；Drying temperature is 60~80 DEG C, and drying time is more than 5h.
- 10. Nb according to claim 13O7The preparation method of F nano-arrays/graphene heterojunction composite, its feature It is：In the step (6), heat treatment temperature is 400 DEG C, and heat treatment time is 2~4h.
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