CN1217734C - Method for preparing nano titanium oxynitrides by plasma process - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 19
- 229910052719 titanium Inorganic materials 0.000 title description 4
- 239000010936 titanium Substances 0.000 title description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
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- 230000035484 reaction time Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 229910001873 dinitrogen Inorganic materials 0.000 abstract description 2
- FHKBQTYCGXHYRV-UHFFFAOYSA-N N.[O-2].[Ti+4] Chemical compound N.[O-2].[Ti+4] FHKBQTYCGXHYRV-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
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- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- LGLRLDQPSSWHKG-UHFFFAOYSA-N [N]=O.[Ti] Chemical compound [N]=O.[Ti] LGLRLDQPSSWHKG-UHFFFAOYSA-N 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
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- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 231100000481 chemical toxicant Toxicity 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 241000894006 Bacteria Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种用等离子体法制备纳米氮杂氧化钛的方法。该方法是：将纳米二氧化钛放入微波等离子体发生装置中，抽真空后，通氮气至微波等离子体发生装置内并产生氮等离子体处理纳米二氧化钛，来制备纳米氮杂氧化钛，制得的纳米氮杂氧化钛具有比纳米二氧化钛更好的光催化性能。该方法的特点是反应时间短、反应温度低、无需催化剂。The invention relates to a method for preparing nano-nitride titanium oxide by plasma method. The method is: put nano-titanium dioxide into a microwave plasma generating device, after vacuuming, pass nitrogen gas into the microwave plasma generating device and generate nitrogen plasma to treat nano-titanium dioxide to prepare nano-nitrogen titanium oxide, and the obtained nano-titanium dioxide Titanium oxide nitrogen has better photocatalytic performance than nano-TiO2. The method is characterized by short reaction time, low reaction temperature and no catalyst.
Description
技术领域Technical field
本发明涉及改性纳米材料领域，特别涉及一种用等离子体法制备纳米氮杂氧化钛的方法。The invention relates to the field of modified nano-materials, in particular to a method for preparing nano-nitride titanium oxide by a plasma method.
背景技术 Background technique
锐钛型纳米二氧化钛经紫外光照射可以分解有毒化学品、烟雾残留物、恶臭化学品、脏物、刺激物、细菌等等为无毒、无污染的物质，当紫外光(波长＜388nm)照射时其价带中的电子被激发形成带负电的高活性电子，同时产生带正电的价带空穴，电子与空穴发生分离，迁移到粒子表面的不同位置。空穴和电子分别与表面的水和氧气反应产生高反应活性的羟基自由基和超氧离子自由基，这些自由基能有效地分解有毒化学品。因此，引起人们的极大兴趣，希望利用这种光催化特性解决日益加剧的地球环境污染问题。Anatase nano-titanium dioxide can decompose toxic chemicals, smog residues, odorous chemicals, dirt, irritants, bacteria, etc. into non-toxic and non-polluting substances by ultraviolet light irradiation. When the electrons in the valence band are excited to form negatively charged highly active electrons, positively charged valence band holes are generated at the same time. The electrons and holes are separated and migrate to different positions on the particle surface. The holes and electrons react with water and oxygen on the surface, respectively, to generate highly reactive hydroxyl radicals and superoxide ion radicals, which can efficiently decompose toxic chemicals. Therefore, it has aroused great interest, hoping to use this photocatalytic property to solve the increasing global environmental pollution problem.
锐钛型纳米二氧化钛只有在紫外光照射下才具有催化功能，而自然光中紫外光的含量太少，只占到达地面的太阳光辐射总量的4-6％，且随着时间变化明显，人工产生紫外光耗电量大、还需投入较高设备费，大面积紫外光照射的费用更高甚至难于实现。如果能扩展光催化剂的光谱利用范围，以太阳光作为光源，则可使设备投资和运行成本大大降低，使得在自然环境中去污等成为可能，也为高分子材料作为纳米光催化材料的固载材料创造了条件。为了实现这一宏大目标，很多学者开展了这一领域的研究工作。Anatase nano-titanium dioxide has a catalytic function only under the irradiation of ultraviolet light, and the content of ultraviolet light in natural light is too small, accounting for only 4-6% of the total solar radiation reaching the ground, and it changes significantly with time. Generating ultraviolet light consumes a lot of power and requires high equipment costs. The cost of large-area ultraviolet light irradiation is even higher or even difficult to achieve. If the spectral utilization range of the photocatalyst can be expanded and sunlight is used as the light source, the equipment investment and operating costs can be greatly reduced, making it possible to decontaminate in the natural environment, and it is also possible for polymer materials to be used as nano-photocatalytic materials. Materials create the conditions. In order to achieve this ambitious goal, many scholars have carried out research work in this field.
Wang C M，Choi，Anpo等尝试采用过渡金属掺杂TiO2制备光催化材料，明显提高了紫外光催化效率，但是没有实现可见光催化功能。Wang CM, Choi, Anpo et al. tried to prepare photocatalytic materials by doping TiO 2 with transition metals, which significantly improved the efficiency of ultraviolet photocatalysis, but did not realize the catalytic function of visible light.
Asahi(Science，2001，293(5528)：269)采用30％的N2/Ar混合气体处理锐钛型纳米二氧化钛TiO2薄膜或采用67％的NH3/Ar混合气体处理锐钛型TiO2纳米微粉4小时，分别制备了氮杂氧化钛TiO2-xNx纳米薄膜和纳米微粉。这种纳米材料在可见光即波长＜500nm的光照射下使乙醛等分解为二氧化碳和水。但是该方法反应时间长，并且还需要氩气，因而成本太高。Asahi (Science, 2001, 293 (5528): 269) used 30% N 2 /Ar mixed gas to treat anatase nano-titanium dioxide TiO 2 film or 67% NH 3 /Ar mixed gas to treat anatase TiO 2 nanometer Micropowder for 4 hours, respectively prepared titanium nitrogen oxide TiO 2-x N x nano-film and nano-powder. The nanometer material decomposes acetaldehyde and the like into carbon dioxide and water under the irradiation of visible light, that is, light with a wavelength less than 500nm. But this method takes a long time to react and also needs argon, so the cost is too high.
等离子体是指由电子、正离子和中性粒子组成的混合体，通常又称为物质的第四种状态。处于等离子态的各种活性种的能量相当高，当分子暴露于等离子体的环境中时，这种能量足以引起化学键的断裂，采用等离子体技术可以制备通常方法难于制备的材料，例如，通过氮等离子体可以进行氮化钛TiN的合成和金属离子的氮化。Plasma refers to a mixture of electrons, positive ions, and neutral particles, often referred to as the fourth state of matter. The energy of various active species in the plasma state is quite high. When the molecules are exposed to the plasma environment, this energy is enough to cause the breaking of chemical bonds. Using plasma technology, materials that are difficult to prepare by conventional methods can be prepared, for example, through nitrogen The plasma can carry out the synthesis of titanium nitride TiN and the nitriding of metal ions.
发明内容Contents of the invention
本发明的目的是针对现有技术的存在的反应时间长及制造成本高的不足，利用等离子体技术的优势，而提供一种用等离子体法制备纳米氮杂氧化钛的方法。该方法的特点是：①反应时间短，小于1小时；②反应温度低，小于500℃；③无需催化剂；④制备的纳米氮杂氧化钛具有比纳米二氧化钛更好的光催化性能。The object of the present invention is to provide a method for preparing nano-nitrided titanium oxide by plasma method in view of the disadvantages of long reaction time and high manufacturing cost in the prior art, and utilizing the advantages of plasma technology. The characteristics of this method are: ①short reaction time, less than 1 hour; ②low reaction temperature, less than 500°C; ③no catalyst required; ④prepared nano aza-titanium oxide has better photocatalytic performance than nano-titanium dioxide.
本发明的目的是采用以下技术措施实现的：The purpose of the present invention is to adopt the following technical measures to achieve:
将纳米二氧化钛放入微波等离子体发生装置中，抽真空至真空度小于50毫米汞柱后，通氮气至微波等离子体发生装置内，调节氮气流速1-60立方厘米/分、微波功率300-1000W、温度200-500℃、辐照处理1-60分钟，即得纳米氮杂氧化钛。Put nano-titanium dioxide into the microwave plasma generator, evacuate until the vacuum degree is less than 50 mmHg, then pass nitrogen gas into the microwave plasma generator, adjust the nitrogen flow rate to 1-60 cubic centimeters per minute, and the microwave power to 300-1000W , temperature 200-500°C, and irradiation treatment for 1-60 minutes to obtain nano-titanium nitrogen oxide.
用等离子体法制备纳米氮杂氧化钛的方法中所述纳米二氧化钛可以为纳米二氧化钛粉体、纳米二氧化钛薄膜或二氧化钛多孔材料。The nano-titanium dioxide mentioned in the method for preparing nano-nitrogen titanium oxide by plasma method can be nano-titanium dioxide powder, nano-titanium dioxide film or titanium dioxide porous material.
本发明具有如下优点：(1)反应时间短，小于1小时；(2)反应温度低，小于500℃；(3)无需催化剂；(4)制备的纳米氮杂氧化钛具有很好的光催化性能，含0.5克纳米氮杂氧化钛的10毫升1％的甲基橙溶液，经太阳光照射下30-50min，其颜色退至无色。The present invention has the following advantages: (1) the reaction time is short, less than 1 hour; (2) the reaction temperature is low, less than 500°C; (3) no catalyst is needed; (4) the prepared nano aza titanium oxide has good photocatalysis Properties: 10 ml of 1% methyl orange solution containing 0.5 g of nano azoxy titanium will fade to colorless after being irradiated by sunlight for 30-50 min.
铬酸根光催化降解率实验表明，采用本发明制备的氮杂氧化钛比未改性的二氧化钛具有很好的光催化性能(见下表)，吸光度越小，体系中铬酸根浓度越少，被降解的铬酸根越多，光催化性能越好。称取0.5g氮杂氧化钛于50mL烧杯中，滴加1.6mLCr2O7 2-溶液(Cr(VI)含量0.08g/L)后，萤光高压汞灯照射8min，后取出并冷却，然后加水15mL并摇匀，离心沉降，取10mL上层清液转入25mL比色管，加入0.3mL H2SO4(1∶1)和2mLH3PO4，摇匀静置，再加入0.5mL二苯胺基脲(DCPI)，迅速用水稀至25mL，立即摇匀，静置5min后放入721型分光光度计中，在波长540nm处测定溶液的吸光度；未改性的二氧化钛采用以上方法进行同样的实验以作比较。其吸光度数据列如下表。The photocatalytic degradation rate experiment of chromate shows that the titanium nitrogen oxide prepared by the present invention has better photocatalytic performance than unmodified titanium dioxide (see the table below), the smaller the absorbance, the less the chromate concentration in the system, and the The more degraded chromate, the better the photocatalytic performance. Weigh 0.5g titanium azaoxide into a 50mL beaker, add 1.6mL Cr 2 O 7 2- solution (Cr(VI) content 0.08g/L) dropwise, irradiate with a fluorescent high-pressure mercury lamp for 8min, take it out and cool it, then Add 15mL of water and shake well, centrifuge to settle, take 10mL supernatant and transfer to 25mL colorimetric tube, add 0.3mL H 2 SO 4 (1:1) and 2mL H 3 PO 4 , shake well and let stand, then add 0.5mL diphenylamine Dilute urea (DCPI) with water to 25mL quickly, shake it up immediately, put it into a 721-type spectrophotometer after standing for 5min, and measure the absorbance of the solution at a wavelength of 540nm; the unmodified titanium dioxide uses the above method to carry out the same experiment for comparison. The absorbance data are listed in the table below.
氮杂氧化钛和未改性的二氧化钛光催化实验数据
实施例1Example 1
将粒度为20纳米的二氧化钛粉体放入微波等离子体化学气相沉淀装置中，抽真空至真空度45毫米汞柱后，调节氮气流量为50立方厘米/分钟，温度500℃，微波功率为450W，反应30分钟即得产物。产物呈淡黄色，用元素分析表明，氮元素含量为0.35％，称取这种粉体0.2克于10毫升1％的甲基橙溶液中，用太阳光照射下30min，其颜色退至无色。Put the titanium dioxide powder with a particle size of 20 nanometers into a microwave plasma chemical vapor deposition device, and after vacuuming to a vacuum degree of 45 mm Hg, adjust the nitrogen flow rate to 50 cubic centimeters per minute, the temperature at 500 ° C, and the microwave power at 450 W. The product was obtained after 30 minutes of reaction. The product is pale yellow, and elemental analysis shows that the nitrogen content is 0.35%. Weigh 0.2 grams of this powder in 10 ml of 1% methyl orange solution, and irradiate it with sunlight for 30 minutes, and its color fades to colorless. .
实施例2Example 2
将厚度80纳米的二氧化钛薄膜放入微波等离子体化学气相沉淀装置中，抽真空至真空度45毫米汞柱后，调节氮气流量为1立方厘米/分钟，温度200℃，微波功率为1000W，反应60分钟即得产物。产物呈淡黄色，用元素分析表明，氮元素含量为0.10％，称取这种薄膜0.2克于10毫升1％的甲基橙溶液中，用太阳光照射50min，其颜色退至无色。Put a titanium dioxide film with a thickness of 80 nanometers into a microwave plasma chemical vapor deposition device, vacuumize to a vacuum of 45 mm Hg, adjust the nitrogen flow rate to 1 cubic centimeter per minute, the temperature is 200 ° C, the microwave power is 1000 W, and the reaction time is 60 The product is available in minutes. The product is pale yellow, and elemental analysis shows that the nitrogen content is 0.10%. Take 0.2 grams of this film in 10 ml of 1% methyl orange solution, and irradiate it with sunlight for 50 minutes, and its color fades to colorless.
实施例3Example 3
将多孔二氧化钛放入微波等离子体化学气相沉淀装置中，抽真空至真空度45毫米汞柱后，调节氮气流量为30立方厘米/分钟，温度300℃，微波功率为300W，反应20分钟即得产物。产物呈淡黄色，用元素分析表明，氮元素含量为0.10％，称取这种产物0.2克于10毫升1％的甲基橙溶液中，用太阳光照射50min，其颜色退至无色。Put porous titanium dioxide into a microwave plasma chemical vapor deposition device, vacuumize to a vacuum of 45 mm Hg, adjust the nitrogen flow rate to 30 cubic centimeters per minute, temperature 300 ° C, microwave power 300 W, and react for 20 minutes to obtain the product . The product is light yellow, and elemental analysis shows that the nitrogen content is 0.10%. Weigh 0.2 grams of this product in 10 ml of 1% methyl orange solution, and irradiate it with sunlight for 50 minutes, and its color fades to colorless.
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| CN1304114C (en) * | 2004-02-06 | 2007-03-14 | 华东理工大学 | Method for preparing nanometer TiO(2-x)N(x) photocatalyst and fluidized bed reactor |
| CN100360425C (en) * | 2005-11-15 | 2008-01-09 | 武汉化工学院 | Method for preparing nanometer aza-titanium oxide by using micro-wave radiation |
| US7967891B2 (en) * | 2006-06-01 | 2011-06-28 | Inco Limited | Method producing metal nanopowders by decompositon of metal carbonyl using an induction plasma torch |
| CN100463861C (en) * | 2007-01-18 | 2009-02-25 | 武汉工程大学 | A kind of method for preparing ordered porous nitrogen heterotitanium oxide micropowder |
| CN100441289C (en) * | 2007-04-24 | 2008-12-10 | 武汉工程大学 | Preparation of Titanium Nitroxide/Fluoropolymer Core-Shell Composite Porous Microspheres |
| CN102974378A (en) * | 2012-10-22 | 2013-03-20 | 复旦大学 | Preparation method for high-efficiency nitrogen-doped strontium titanate photocatalyst |
| CN104174391A (en) * | 2014-08-21 | 2014-12-03 | 华中科技大学 | Nanometer titania photocatalyst for degrading VOC and preparation method of nanometer titania photocatalyst for degrading VOC |
| CN108355470A (en) * | 2018-03-30 | 2018-08-03 | 华南农业大学 | A kind of Ag-TiO2/Ti(NO2)/ITO optoelectronic poles, electrical enhanced photocatalysis reaction unit and its application |
| CN108371954A (en) * | 2018-03-30 | 2018-08-07 | 华南农业大学 | A kind of support type Ag-TiO2/Ti(NO2) film catalyst and its fruit storage in application |
| CN112582626B (en) * | 2020-12-22 | 2022-03-25 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | Method for improving electrocatalytic activity of perovskite oxide and substance thereof |
| CN120329803A (en) * | 2025-06-17 | 2025-07-18 | 鑫隆涂环保科技(大连)有限公司 | A photocatalytic self-cleaning water-based coating and preparation method thereof |
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