CN108855218B - A kind of preparation method of vacuum encapsulated in-situ self-reaction synthesis of multi-modified graphitic carbon nitride supported titanium dioxide - Google Patents
A kind of preparation method of vacuum encapsulated in-situ self-reaction synthesis of multi-modified graphitic carbon nitride supported titanium dioxide Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 6
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical class N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 title claims description 5
- 230000015572 biosynthetic process Effects 0.000 title claims description 4
- 238000003786 synthesis reaction Methods 0.000 title claims description 4
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 14
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010453 quartz Substances 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000009461 vacuum packaging Methods 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 2
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 claims description 2
- 238000004729 solvothermal method Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 8
- 238000001816 cooling Methods 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000001212 derivatisation Methods 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
Description
技术领域technical field
本发明属于光催化技术领域，具体涉及一种真空封装制备改性石墨相氮化碳负载氮掺杂金属有机框架模板衍化二氧化钛方法The invention belongs to the technical field of photocatalysis, and in particular relates to a method for preparing modified graphite phase carbon nitride supported nitrogen-doped metal organic framework template derivatized titanium dioxide by vacuum encapsulation
背景技术Background technique
为了解决人类继续发展过程中，日益提高的能源需求和环境压力，光催化技术因其清洁、廉价和可持续的优点备受科研工作者的关注。然而，单组元的光催化剂难以同时获得较高的可见光吸收率和较强的氧化还原能力，因此难以满足实际生产生活的需要，所以多组元的光催化剂成为光催化材料发展的一个趋势。在多组元光催化剂的设计中，异质结材料可以构建表面自建电场，将光生电子空穴有效分离，有效的降低载流子复合率，成为当前光催化技术研究的热点。In order to solve the increasing energy demand and environmental pressure in the process of human development, photocatalytic technology has attracted the attention of researchers because of its clean, cheap and sustainable advantages. However, it is difficult for single-component photocatalysts to obtain high visible light absorption rate and strong redox ability at the same time, so it is difficult to meet the needs of practical production and life. Therefore, multi-component photocatalysts have become a trend in the development of photocatalytic materials. In the design of multi-component photocatalysts, heterojunction materials can build a surface self-built electric field, effectively separate photo-generated electron holes, and effectively reduce the carrier recombination rate, which has become a hot spot in current photocatalytic technology research.
和其他二元光催化异质结材料相比g-C3N4/TiO2具有以下优点：1.两种组分均有良好的物理化学稳定性及热稳定性，通常不与酸碱发生反应。2.带隙大小及位置合适，能够有效的吸收可见光的部分能量，并在理论上满足产氢、产氧所需要的价带、导带位置。3.储量丰富，价格低廉，有满足实际开发生产的潜力。4.无毒性，可以较为简单的将该种材料普及到日常的生产生活中。Compared with other binary photocatalytic heterojunction materials, gC 3 N 4 /TiO 2 has the following advantages: 1. Both components have good physical and chemical stability and thermal stability, and usually do not react with acids and bases. 2. The size and position of the band gap are suitable, which can effectively absorb part of the energy of visible light, and theoretically meet the valence band and conduction band positions required for hydrogen production and oxygen production. 3. The reserves are abundant and the price is low, and it has the potential to meet the actual development and production. 4. Non-toxic, this material can be popularized into daily production and life relatively simply.
但是g-C3N4/TiO2这种光催化材料也有一些缺点：1.在可见光区域的吸收有待提高，光吸收主要受到带隙大小的限制，块状的g-C3N4的带隙约为2.7eV，无改性的TiO2带隙约为3.2eV。2.比表面积比较小，块状g-C3N4比表面积大小仅为7m2/g，以此为基体负载得到的异质结材料比表面积也难以提高。3.电子空穴对的复合率高，g-C3N4/TiO2的简单复合在可见光区仅能实现简单的电子传输，并不能有效发挥异质结结构的优势，这些方面限制了复合材料的光催化制氢性能。However, the photocatalytic material gC 3 N 4 /TiO 2 also has some disadvantages: 1. The absorption in the visible light region needs to be improved, and the light absorption is mainly limited by the size of the band gap. The band gap of bulk gC 3 N 4 is about 2.7 eV, the band gap of unmodified TiO is about 3.2 eV. 2. The specific surface area is relatively small, the specific surface area of bulk gC 3 N 4 is only 7m 2 /g, and the specific surface area of the heterojunction material obtained by using this as the substrate is also difficult to improve. 3. The recombination rate of electron-hole pairs is high, and the simple recombination of gC 3 N 4 /TiO 2 can only achieve simple electron transport in the visible light region, and cannot effectively take advantage of the heterojunction structure. These aspects limit the performance of the composite material. Photocatalytic hydrogen production performance.
大量文献证明，研究者对g-C3N4/TiO2的改性手段主要集中在：设计和改性g-C3N4的纳米结构，引入合适的官能团；设计和改性TiO2的纳米结构，进行其他元素掺杂；设计合理的界面。设计和改性g-C3N4或TiO2的纳米结构主要就是为了增大比表面积来暴露出更多的活性位点，在g-C3N4纳米结构设计方面主要通过二次煅烧的方式制备g-C3N4纳米片和使用软、硬模板制备g-C3N4核壳结构或者三维孔结构，也有通过外通氨气或混入氨水的方式制备氨气改性的大比表面积的g-C3N4；在TiO2的结构设计方面。主要通过溶胶凝胶法、静电纺丝法、金属有机框架衍化法等方法制备。在g-C3N4上引入合适的官能团，可以使有效官能团被引入到g-C3N4的边缘后促进载流子分离和提高光吸收。进行其他元素掺杂，可以调控半导体材料的能带结构，设计合理的界面能够更有效的实现载流子的传输与分离。 A large number of literatures have proved that the modification methods of gC3N4 / TiO2 by researchers mainly focus on : designing and modifying the nanostructure of gC3N4 , introducing suitable functional groups; designing and modifying the nanostructure of TiO2 , carrying out Doping with other elements; well-designed interface. The main purpose of designing and modifying the nanostructure of gC 3 N 4 or TiO 2 is to increase the specific surface area to expose more active sites. In the design of gC 3 N 4 nanostructures, gC 3 is mainly prepared by secondary calcination. N 4 nanosheets and gC 3 N 4 core-shell structure or three-dimensional pore structure prepared by soft and hard templates, and gC 3 N 4 with large specific surface area modified by ammonia gas is also prepared by externally passing ammonia gas or mixing ammonia water; Structural design aspects of TiO2 . It is mainly prepared by sol-gel method, electrospinning method, metal organic framework derivatization method and other methods. Introducing suitable functional groups on gC 3 N 4 can make effective functional groups introduced into the edge of gC 3 N 4 to promote carrier separation and improve light absorption. Doping with other elements can control the energy band structure of semiconductor materials, and a reasonable interface design can more effectively realize the transport and separation of carriers.
前文提到的对g-C3N4/TiO2改性的研究通常只注重某一方面，不同改性方式之间并不相互适用，同时多步骤的改性通常会造成无意义的浪费，提高成本。因此如何通过设计合适的工艺，用简单的步骤，实现g-C3N4/TiO2复合材料的整体改性，以更加适用于实际的生产生活，一直是人们努力的方向。The research on gC 3 N 4 /TiO 2 modification mentioned above usually only focuses on one aspect, and different modification methods are not applicable to each other. At the same time, multi-step modification usually causes meaningless waste and increases costs. . Therefore, how to realize the overall modification of gC 3 N 4 /TiO 2 composite material by designing a suitable process and using simple steps, so as to be more suitable for practical production and life, has always been the direction of people's efforts.
发明内容SUMMARY OF THE INVENTION
本发明的目的是提供一种真空封装原位自反应合成多改性的石墨相氮化碳负载二氧化钛的制备方法。本发明通过真空封装的工艺，将前驱体(双氰胺、金属有机框架模板衍化二氧化钛)封入真空石英管中进行煅烧，一步制备出改性石墨相氮化碳负载氮掺杂金属有机框架模板衍化二氧化钛复合材料，制备出复合材料的过程中，双氰胺热诱导聚合生成g-C3N4，释放出副产物氨气被保留在石英管中，提供压力和高浓度的氨气环境，使得同时实现g-C3N4结晶性增强，比表面积增大，原位氮掺杂TiO2多种改性。该工艺实现了多目的材料设计的工艺简化和副产物的有效利用，得到的复合材料具有较高的光催化水分解制氢能力，并且适用于可见光照射和无助催化剂条件。本发明的技术方案如下：The purpose of the present invention is to provide a method for preparing multi-modified graphitic phase carbon nitride supported titanium dioxide by in-situ self-reaction synthesis of vacuum packaging. In the present invention, the precursor (dicyandiamide, metal organic framework template derivatized titanium dioxide) is sealed in a vacuum quartz tube for calcination through a vacuum packaging process, and a modified graphite phase carbon nitride supported nitrogen-doped metal organic framework template derivatization is prepared in one step. Titanium dioxide composite material, in the process of preparing the composite material, dicyandiamide thermally induces polymerization to generate gC 3 N 4 , and the released by-product ammonia gas is retained in the quartz tube, providing pressure and a high-concentration ammonia gas environment, so that the simultaneous realization of The crystallinity of gC 3 N 4 is enhanced, the specific surface area is increased, and the in-situ nitrogen-doped TiO 2 is variously modified. This process realizes the process simplification of multi-purpose material design and the effective utilization of by-products, and the obtained composite material has high photocatalytic water splitting ability to produce hydrogen, and is suitable for visible light irradiation and no cocatalyst conditions. The technical scheme of the present invention is as follows:
一种真空封装原位自反应合成多改性的石墨相氮化碳负载二氧化钛的制备方法，包括下列步骤：A method for preparing multi-modified graphitic carbon nitride-supported titanium dioxide by in-situ self-reaction synthesis of vacuum packaging, comprising the following steps:
1)通过溶剂热的方式制备MIL-125金属有机框架材料：将质量比为100：(50-60)的钛酸异丙酯与对二苯甲酸溶于体积比为1：(8-10)的无水甲醇和N，N-二甲基甲酰胺DMF溶液中，溶液浓度在(60-70)mg/ml范围内，搅拌后转移到水热釜中，将水热釜置于鼓风烘箱中，150℃保温24h，反应后经离心得到的白色粉末，用无水甲醇和DMF溶液分别清洗三次后，在60℃恒温烘干，得到的白色粉末即为MIL-125金属有机框架材料；1) Preparation of MIL-125 metal-organic framework material by solvothermal method: dissolving isopropyl titanate and terephthalic acid in a mass ratio of 100:(50-60) in a volume ratio of 1:(8-10) In the anhydrous methanol and N,N-dimethylformamide DMF solution, the solution concentration is in the range of (60-70) mg/ml, and after stirring, it is transferred to the hydrothermal kettle, and the hydrothermal kettle is placed in a blast oven The white powder obtained by centrifugation after the reaction was washed three times with anhydrous methanol and DMF solution, and then dried at a constant temperature of 60 °C, and the obtained white powder was MIL-125 metal organic framework material;
2)通过煅烧MIL-125制备多孔二氧化钛材料：将制备的MIL-125在箱式炉中进行煅烧，工艺参数为2℃/min升温至400℃，保温5h，随炉降温，得到暗白色粉末即为多孔二氧化钛材料；2) Preparation of porous titanium dioxide material by calcining MIL-125: The prepared MIL-125 was calcined in a box furnace, and the process parameters were 2 °C/min to heat up to 400 °C, hold for 5 hours, and cool down with the furnace to obtain a dark white powder that is It is a porous titanium dioxide material;
3)将制备好的多孔二氧化钛溶于去离子水中，再按照多孔二氧化钛与双氰胺1：(50-400)的质量配比，加入双氰胺，60℃水浴加热搅拌干燥；3) Dissolving the prepared porous titanium dioxide in deionized water, then adding dicyandiamide according to the mass ratio of porous titanium dioxide and dicyandiamide 1: (50-400), heating, stirring and drying in a water bath at 60°C;
4)将适量干燥后的粉末以真空封装的方式封入真空石英管后，置于箱式炉中，5℃/min升温至550℃，保温2h，随炉降温，得到黄色粉末即为多改性的石墨相氮化碳负载二氧化钛复合材料。4) After an appropriate amount of dried powder is sealed in a vacuum quartz tube by vacuum packaging, it is placed in a box furnace, heated to 550 °C at 5 °C/min, kept for 2 hours, and cooled with the furnace to obtain yellow powder, which is multi-modified Graphitic phase carbon nitride supported titania composites.
与现有的技术相比，本发明的优点在于：Compared with the prior art, the advantages of the present invention are:
(1)本发明制备的多改性石墨相氮化碳负载氮掺杂金属有机框架模板衍化二氧化钛，从结晶性，比表面积和元素掺杂三个方面***整体的改性了g-C3N4/TiO2复合材料，实现了多功能的协同作用，显著的提高了复合材料的光催化水分解制氢性能，并且在降解污染物方面也表现出良好的性能。。(1) The multi-modified graphitic phase carbon nitride supported nitrogen-doped metal organic framework template derivatized titanium dioxide prepared by the present invention systematically modified the gC 3 N 4 / The TiO2 composite material achieves a multifunctional synergistic effect, significantly improves the photocatalytic water splitting performance of the composite material for hydrogen production, and also exhibits good performance in degrading pollutants. .
(2)本发明制备的多改性石墨相氮化碳负载氮掺杂金属有机框架模板衍化二氧化钛，是通过在反应过程中，对前驱体双氰胺热聚合的副产物氨气的有效利用制备得到的。以此种工艺制备得到的材料成本更低，环境更友好。(2) The multi-modified graphitic phase carbon nitride supported nitrogen-doped metal organic framework template derivatized titanium dioxide prepared by the present invention is prepared by effectively utilizing ammonia gas, a by-product of the thermal polymerization of the precursor dicyandiamide, during the reaction process. owned. Materials prepared by this process have lower cost and are more environmentally friendly.
(3)本发明制备设备简单，工艺简便。(3) The preparation equipment of the present invention is simple and the process is simple.
(4)本发明可靠性高，无毒无害，有良好的应用前景。(4) The present invention has high reliability, is non-toxic and harmless, and has good application prospects.
附图说明Description of drawings
图1为本发明实施例1所制备的改性石墨相氮化碳负载氮掺杂金属有机框架模板衍化二氧化钛的XRD图谱1 is the XRD pattern of the modified graphitic carbon nitride supported nitrogen-doped metal organic framework template derivatized titanium dioxide prepared in Example 1 of the present invention
图2为本发明实施例1所制备的改性石墨相氮化碳负载氮掺杂金属有机框架模板衍化二氧化钛的SEM图。2 is a SEM image of the modified graphitic carbon nitride supported nitrogen-doped metal organic framework template derivatized titanium dioxide prepared in Example 1 of the present invention.
图3为本发明实施例1所制备的改性石墨相氮化碳负载氮掺杂金属有机框架模板衍化二氧化钛的TEM图。3 is a TEM image of the modified graphitic carbon nitride supported nitrogen-doped metal organic framework template derivatized titanium dioxide prepared in Example 1 of the present invention.
本发明未述及之处适用于现有技术。What is not described in the present invention applies to the prior art.
具体实施方式Detailed ways
以下给出本发明制备方法的具体实施例。这些实施例仅用于详细说明本发明制备方法，并不限制本申请权利要求的保护范围。Specific examples of the preparation method of the present invention are given below. These examples are only used to illustrate the preparation method of the present invention in detail, and do not limit the protection scope of the claims of the present application.
实施例1Example 1
将1.56ml的钛酸异丙酯与3g对二苯甲酸溶于70ml的体积比为1：9的无水甲醇和DMF溶液中，搅拌后转移到水热釜中。将水热釜置于鼓风烘箱中，150℃保温24h。反应后用无水甲醇和DMF溶液分别清洗三次后，在60℃恒温烘箱中烘干过夜，得到白色粉末在箱式炉中进行煅烧，工艺参数为2℃/min升温至400℃，保温5h，随炉降温。得到暗白色多孔二氧化钛。取10mg多孔二氧化钛溶于去离子水中，超声2h后，与双氰胺粉末混合，质量比约为1：100，60℃水浴加热搅拌干燥后，将得到的混合粉末，以真空封装的方式封入直径1cm，长度20cm的真空石英管后，置于箱式炉中，5℃/min升温至550℃，保温2h，随炉降温，得到黄色粉末。Dissolve 1.56ml of isopropyl titanate and 3g of terephthalic acid in 70ml of anhydrous methanol and DMF solution with a volume ratio of 1:9, stir and transfer to a hydrothermal kettle. The hydrothermal kettle was placed in a blast oven and kept at 150°C for 24h. After the reaction, it was washed with anhydrous methanol and DMF solution for three times, and dried in a constant temperature oven at 60 °C overnight to obtain a white powder, which was calcined in a box furnace. Cool down with the oven. Dark white porous titanium dioxide was obtained. Dissolve 10 mg of porous titanium dioxide in deionized water, and after sonicating for 2 hours, mix with dicyandiamide powder in a mass ratio of about 1:100. After heating, stirring and drying in a water bath at 60 °C, the obtained mixed powder is sealed in a vacuum package. After the vacuum quartz tube with a length of 1 cm and a length of 20 cm was placed in a box furnace, the temperature was raised to 550 ° C at 5 ° C/min, kept for 2 h, and cooled with the furnace to obtain yellow powder.
实施例2Example 2
将1.56ml的钛酸异丙酯与3g对二苯甲酸溶于70ml的体积比为1：9的无水甲醇和DMF溶液中，搅拌后转移到水热釜中。将水热釜置于鼓风烘箱中，150℃保温24h。反应后用无水甲醇和DMF溶液分别清洗三次后，在60℃恒温烘箱中烘干过夜，得到白色粉末在箱式炉中进行煅烧，工艺参数为2℃/min升温至400℃，保温5h，随炉降温。得到暗白色多孔二氧化钛。取10mg多孔二氧化钛溶于去离子水中，超声2h后，与双氰胺粉末混合，质量比约为1：200，60℃水浴加热搅拌干燥后，将得到的混合粉末，以真空封装的方式封入直径1cm，长度20cm的真空石英管后，置于箱式炉中，5℃/min升温至550℃，保温2h，随炉降温，得到黄色粉末。Dissolve 1.56ml of isopropyl titanate and 3g of terephthalic acid in 70ml of anhydrous methanol and DMF solution with a volume ratio of 1:9, stir and transfer to a hydrothermal kettle. The hydrothermal kettle was placed in a blast oven and kept at 150°C for 24h. After the reaction, it was washed with anhydrous methanol and DMF solution for three times, and dried in a constant temperature oven at 60 °C overnight to obtain a white powder, which was calcined in a box furnace. Cool down with the oven. Dark white porous titanium dioxide was obtained. Dissolve 10 mg of porous titanium dioxide in deionized water, and after sonicating for 2 hours, mix with dicyandiamide powder in a mass ratio of about 1:200. After heating, stirring and drying in a water bath at 60 °C, the obtained mixed powder is sealed in a vacuum package. After the vacuum quartz tube with a length of 1 cm and a length of 20 cm was placed in a box furnace, the temperature was raised to 550 ° C at 5 ° C/min, kept for 2 h, and cooled with the furnace to obtain yellow powder.
实施例3Example 3
将1.56ml的钛酸异丙酯与3g对二苯甲酸溶于70ml的体积比为1：9的无水甲醇和DMF溶液中，搅拌后转移到水热釜中。将水热釜置于鼓风烘箱中，150℃保温24h。反应后用无水甲醇和DMF溶液分别清洗三次后，在60℃恒温烘箱中烘干过夜，得到白色粉末在箱式炉中进行煅烧，工艺参数为2℃/min升温至400℃，保温5h，随炉降温。得到暗白色多孔二氧化钛。取10mg多孔二氧化钛溶于去离子水中，超声2h后，与双氰胺粉末混合，质量比约为1：400，60℃水浴加热搅拌干燥后，将得到的混合粉末，以真空封装的方式封入直径1cm，长度20cm的真空石英管后，置于箱式炉中，5℃/min升温至550℃，保温2h，随炉降温，得到黄色粉末。Dissolve 1.56ml of isopropyl titanate and 3g of terephthalic acid in 70ml of anhydrous methanol and DMF solution with a volume ratio of 1:9, stir and transfer to a hydrothermal kettle. The hydrothermal kettle was placed in a blast oven and kept at 150°C for 24h. After the reaction, it was washed with anhydrous methanol and DMF solution for three times, and dried in a constant temperature oven at 60 °C overnight to obtain a white powder, which was calcined in a box furnace. Cool down with the oven. Dark white porous titanium dioxide was obtained. Dissolve 10 mg of porous titanium dioxide in deionized water. After sonicating for 2 hours, mix with dicyandiamide powder in a mass ratio of about 1:400. After heating, stirring and drying in a water bath at 60 °C, the obtained mixed powder is sealed in a vacuum package. After the vacuum quartz tube with a length of 1 cm and a length of 20 cm was placed in a box furnace, the temperature was raised to 550 ° C at 5 ° C/min, kept for 2 h, and cooled with the furnace to obtain yellow powder.
实施例4Example 4
将1.56ml的钛酸异丙酯与3g对二苯甲酸溶于70ml的体积比为1：9的无水甲醇和DMF溶液中，搅拌后转移到水热釜中。将水热釜置于鼓风烘箱中，150℃保温24h。反应后用无水甲醇和DMF溶液分别清洗三次后，在60℃恒温烘箱中烘干过夜，得到白色粉末在箱式炉中进行煅烧，工艺参数为2℃/min升温至400℃，保温5h，随炉降温。得到暗白色多孔二氧化钛。取10mg多孔二氧化钛溶于去离子水中，超声2h后，与双氰胺粉末混合，质量比约为1：50，60℃水浴加热搅拌干燥后，将得到的混合粉末，以真空封装的方式封入直径1cm，长度20cm的真空石英管后，置于箱式炉中，5℃/min升温至550℃，保温2h，随炉降温，得到黄色粉末。Dissolve 1.56ml of isopropyl titanate and 3g of terephthalic acid in 70ml of anhydrous methanol and DMF solution with a volume ratio of 1:9, stir and transfer to a hydrothermal kettle. The hydrothermal kettle was placed in a blast oven and kept at 150°C for 24h. After the reaction, it was washed with anhydrous methanol and DMF solution for three times, and dried in a constant temperature oven at 60 °C overnight to obtain a white powder, which was calcined in a box furnace. Cool down with the oven. Dark white porous titanium dioxide was obtained. Dissolve 10 mg of porous titanium dioxide in deionized water. After ultrasonication for 2 hours, mix with dicyandiamide powder in a mass ratio of about 1:50. After heating, stirring and drying in a water bath at 60 °C, the obtained mixed powder is sealed in a vacuum package. After the vacuum quartz tube with a length of 1 cm and a length of 20 cm was placed in a box furnace, the temperature was raised to 550 ° C at 5 ° C/min, kept for 2 h, and cooled with the furnace to obtain yellow powder.
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