CN104148047B - Macro preparation method for carbon doped zinc oxide-based visible-light catalyst - Google Patents
Macro preparation method for carbon doped zinc oxide-based visible-light catalyst Download PDFInfo
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- CN104148047B CN104148047B CN201410435665.5A CN201410435665A CN104148047B CN 104148047 B CN104148047 B CN 104148047B CN 201410435665 A CN201410435665 A CN 201410435665A CN 104148047 B CN104148047 B CN 104148047B
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- Prior art keywords
- zinc oxide
- carbon
- visible light
- doped zinc
- preparation
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 207
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 239000011858 nanopowder Substances 0.000 claims abstract description 11
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- 238000000034 method Methods 0.000 claims description 33
- 239000002243 precursor Substances 0.000 claims description 20
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000011701 zinc Substances 0.000 claims description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 13
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- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 description 4
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- 239000002073 nanorod Substances 0.000 description 4
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
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- 229960000306 zinc gluconate Drugs 0.000 description 4
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- 239000003513 alkali Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000004202 carbamide Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
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- 238000005406 washing Methods 0.000 description 3
- IHXWECHPYNPJRR-UHFFFAOYSA-N 3-hydroxycyclobut-2-en-1-one Chemical compound OC1=CC(=O)C1 IHXWECHPYNPJRR-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
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- NAIUSXBTWBUGMG-UHFFFAOYSA-N [Bi+]=O.[O-2].[Zn+2] Chemical compound [Bi+]=O.[O-2].[Zn+2] NAIUSXBTWBUGMG-UHFFFAOYSA-N 0.000 description 2
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Catalysts (AREA)
Abstract
本发明属于材料化学技术领域，具体涉及一种碳掺杂氧化锌基可见光催化剂的宏量制备方法。本发明采用小分子有机物助燃烧法宏量制备碳掺杂氧化锌基可见光催化剂。其制备原理是利用小分子有机物高温下的燃烧反应热，实现碳元素对氧化锌晶体中的有效沉积、掺杂；同时反应过程中产生大量的气体，能够有效地“破碎”产物，从而获得小尺寸的碳掺杂氧化锌基纳米粒子，实现碳掺杂氧化锌基可见光催化剂的宏量制备。制得的纳米粉体具有分散性好，粒径小且大小分布均匀，可见光催化性能优异，化学稳定性高等优点，在室温为30℃±3℃且太阳光照射下，该可见光催化剂能够在15分钟内将有机染料罗丹明B降解完全，因此，该催化剂可以应用在环境污染物治理等领域。The invention belongs to the technical field of material chemistry, and in particular relates to a macro-preparation method of a carbon-doped zinc oxide-based visible light catalyst. The invention adopts a small-molecular organic substance combustion-assisted combustion method to prepare a carbon-doped zinc oxide-based visible light catalyst in large quantities. Its preparation principle is to use the combustion reaction heat of small molecular organic matter at high temperature to realize the effective deposition and doping of carbon elements in zinc oxide crystals; at the same time, a large amount of gas is generated during the reaction process, which can effectively "break up" the product, thereby obtaining small Large-scale carbon-doped zinc oxide-based nanoparticles to realize the mass preparation of carbon-doped zinc oxide-based visible light catalysts. The prepared nano-powder has the advantages of good dispersion, small particle size and uniform size distribution, excellent visible light catalytic performance and high chemical stability. At a room temperature of 30°C ± 3°C and under sunlight, the visible light catalyst can be used at 15 The organic dye rhodamine B can be completely degraded within minutes, so the catalyst can be applied in fields such as environmental pollutant treatment.
Description
技术领域technical field
本发明属于材料化学领域，具体涉及一种碳掺杂氧化锌基可见光催化剂的宏量制备方法。The invention belongs to the field of material chemistry, and in particular relates to a macro-preparation method of a carbon-doped zinc oxide-based visible light catalyst.
背景技术Background technique
氧化锌是一种应用范围极广的半导体光电材料，其室温下带隙为3.37 eV，激子束缚能高达60 meV。改性后的氧化锌将具有特殊的电学、催化和杀菌等优异性能。比如，掺铝氧化锌是氧化锌与氧化铝形成的置换型固溶体，不仅紫外线吸收性能好、化学稳定性高，而且具有颜色浅、可见光透过率高、导电性好等特性，可以广泛应用于抗静电涂料、橡胶和塑料等领域，有取代导电性好但价格昂贵的ITO（In2O3：Sn）材料的趋势。采用贵金属掺杂的方式，可以获得用于光催降解催化剂的纳米粉体。比如，王李波等采用贵金属来掺杂氧化锌纳米粉体，包括如下步骤：（1）将有机醇溶剂加热至150—190℃；（2）加入乙酸锌-贵金属盐混合物的水溶液，在150—190℃反应5—60min，反应结束后，离心分离，将所得固体样品洗涤；（3）将步骤（2）所得样品干燥，所得贵金属掺杂氧化锌纳米粉体粒径为30-50nm。该发明获得的产物可应用在在光催化处理有机污水领域（CN201410137559）。发明专利CN201110383611公开了钽掺杂氧化锌纳米粉末光催化剂在水处理抗菌中的应用，菌种包括革兰氏阳性菌枯草芽孢杆菌、金黄色葡萄球菌、革兰氏阴性菌大肠杆菌和铜绿假单胞杆菌。研究表明钽掺杂氧化锌纳米粉末能在暗环境及可见光下抑制细菌生长，而且抗菌性优于纯氧化锌纳米粉末，且光催化可以有效降低暗环境下的MIC，更小的加入量就可以达到较高的抑菌效果。Zinc oxide is a semiconductor optoelectronic material with a wide range of applications. It has a band gap of 3.37 eV at room temperature and an exciton binding energy as high as 60 meV. The modified zinc oxide will have special electrical, catalytic and bactericidal properties. For example, aluminum-doped zinc oxide is a replacement solid solution formed by zinc oxide and aluminum oxide. It not only has good ultraviolet absorption performance and high chemical stability, but also has the characteristics of light color, high visible light transmittance and good conductivity. It can be widely used in In the fields of antistatic coatings, rubber and plastics, there is a tendency to replace ITO (In 2 O 3 : Sn) materials with good conductivity but expensive. Nanopowders for photocatalytic degradation catalysts can be obtained by doping noble metals. For example, Wang Libo et al. used noble metals to dope zinc oxide nanopowders, including the following steps: (1) heating the organic alcohol solvent to 150-190°C; Reaction at ℃ for 5-60 minutes. After the reaction, centrifuge and wash the obtained solid sample; (3) dry the sample obtained in step (2), and the particle size of the obtained precious metal-doped zinc oxide nanopowder is 30-50nm. The products obtained by this invention can be applied in the field of photocatalytic treatment of organic sewage (CN201410137559). Invention patent CN201110383611 discloses the application of tantalum-doped zinc oxide nano-powder photocatalyst in water treatment antibacterial, the bacteria include Gram-positive bacteria Bacillus subtilis, Staphylococcus aureus, Gram-negative bacteria Escherichia coli and Pseudomonas aeruginosa bacillus. Studies have shown that tantalum-doped zinc oxide nanopowders can inhibit bacterial growth in dark environments and under visible light, and their antibacterial properties are superior to pure zinc oxide nanopowders, and photocatalysis can effectively reduce the MIC in dark environments, and a smaller amount can be added To achieve a higher antibacterial effect.
目前对氧化锌进行掺杂修饰以提高或者改善其光催化、杀菌等性能，已经是近年来环境材料领域研究的热点之一。按照掺杂物质类别的不同，氧化锌基材料的掺杂可以分为如下几类：At present, the doping modification of zinc oxide to improve or improve its photocatalytic and bactericidal properties has become one of the research hotspots in the field of environmental materials in recent years. According to the different types of doping substances, the doping of zinc oxide-based materials can be divided into the following categories:
1，金属原子掺杂 中国发明专利CN201310636925公开了一种具有可见光催化活性的镍掺杂氧化锌分级结构光催化纳米材料及其制备方法，该材料组分为：Zn1-xNixO，式中x=0.5–10mol%。该方法是：将锌盐、镍盐及碱溶解于醇溶剂或醇/水混合溶剂中得到前驱体溶液，金属离子总浓度为0.0625–0.25mol/L，碱的摩尔浓度为0.0625–2.5mol/L；置于高压反应釜中密封反应；冷却后乙醇洗涤，空气中干燥，制得具有纳米粒状、空心球、二十面体、六棱柱或类球型等多种分级结构光催化纳米材料。发明专利CN201310122285涉及一种竹炭负载氧化锌掺铜复合催化剂材料的制备及其应用。采用溶胶-凝胶法制备负载于竹炭上的氧化锌掺铜催化剂前驱物，经高温焙烧后制备具有光催化活性的复合催化剂材料。发明专利CN201210106093公开了一种掺杂纳米氧化锌粉体及其制备方法，利用共沉淀-煅烧一步法合成硅铝共掺杂的纳米氧化锌粉体，掺杂元素铝、掺杂元素硅各自与氧化锌的摩尔比均为0.03∶1～0.18∶1。CN201010275787公开了具有可见光催化活性的过渡金属掺杂氧化锌介孔材料及其制备方法。本发明的过渡金属掺杂ZnO介孔材料组分为：Zn1-xRexO(其中Re＝Mn，Fe，Co，Cu；x＝0.1mol～6mol％)。将锌盐、尿素以及用于掺杂的金属盐溶解于蒸馏水中搅拌得到前驱体溶液，金属离子总浓度控制为0.05mol/L-0.2mol/L，尿素与金属离子的摩尔之比控制为5-15；置于高压反应釜中密封反应；冷却，去离子水洗涤，真空干燥；然后焙烧，制得的过渡金属掺杂氧化锌介孔材料。CN201010104899涉及一种醇热法制备钴掺杂氧化锌CoxZn1-xO多功能磁性纳米粉体的方法，包括：(1)在室温下，将可溶性钴盐和锌盐溶于乙二醇中，机械搅拌，加入无水乙酸钠和聚乙二醇，超声分散得到反应溶液；(2)将反应溶液进行醇热反应，反应温度为180℃～220℃，反应10～14小时，自然冷却至室温；(3)将上述产物离心分离，洗涤，干燥得到CoxZn1-xO多功能磁性纳米粉体。CN200810021689公开了一种钽掺杂氧化锌纳米粉末光催化剂，其制备方法及应用。该催化剂制备方法是将可溶性锌盐溶于去离子水中形成锌盐溶液，加入适量的柠檬酸得到透明溶液A；再取适量钽前体溶液，加入适量乙二醇形成溶液B；将两种溶液混合，在搅拌过程中加入PVP和硝酸，搅拌0.5～1小时，得到透明溶液；将透明溶液加热，蒸发至原质量的50～70％，再加入为分散剂和稳定剂，搅拌后置于空气中，老化、烘干，形成粉末前体；再进行退火处理，得到样品。CN200510095053涉及掺杂银、稀土金属的纳米氧化锌制备方法及其光催化降解有机物和抗菌的应用，该发明通过有机络合法在纳米氧化锌中掺入银Ag、稀土金属(镧La、铈Ce、镨Pr、钕Nd、钐Sm、铕Eu、钆Gd、镝Dy、铒Er、钇Y)等，来改善纳米氧化锌的光催化活性。1. Metal atom doping Chinese invention patent CN201310636925 discloses a nickel-doped zinc oxide hierarchical structure photocatalytic nanomaterial with visible light catalytic activity and its preparation method. The material component is: Zn 1-x Ni x O, formula Where x=0.5–10mol%. The method is: dissolving zinc salt, nickel salt and alkali in alcohol solvent or alcohol/water mixed solvent to obtain precursor solution, the total concentration of metal ions is 0.0625-0.25mol/L, and the molar concentration of alkali is 0.0625-2.5mol/L L; placed in a high-pressure reactor to seal the reaction; after cooling, washing with ethanol and drying in the air, photocatalytic nanomaterials with various hierarchical structures such as nanoparticles, hollow spheres, icosahedrons, hexagonal prisms or spheroids were prepared. The invention patent CN201310122285 relates to the preparation and application of a bamboo charcoal-supported zinc oxide-doped copper composite catalyst material. The zinc oxide-doped copper catalyst precursor supported on bamboo charcoal was prepared by sol-gel method, and the composite catalyst material with photocatalytic activity was prepared after high-temperature calcination. Invention patent CN201210106093 discloses a doped nano-zinc oxide powder and its preparation method. A co-precipitation-calcination one-step method is used to synthesize silicon-aluminum co-doped nano-zinc oxide powder. The doped element aluminum and the doped element silicon are respectively mixed with The molar ratio of zinc oxide is 0.03:1-0.18:1. CN201010275787 discloses a transition metal-doped zinc oxide mesoporous material with visible light catalytic activity and a preparation method thereof. The composition of the transition metal-doped ZnO mesoporous material of the present invention is: Zn 1-x Re x O (wherein Re=Mn, Fe, Co, Cu; x=0.1mol˜6mol%). Dissolve zinc salt, urea and metal salt for doping in distilled water and stir to obtain a precursor solution. The total concentration of metal ions is controlled at 0.05mol/L-0.2mol/L, and the molar ratio of urea to metal ions is controlled at 5 -15; placed in a high-pressure reactor to seal the reaction; cooled, washed with deionized water, and vacuum-dried; then roasted to obtain the transition metal-doped zinc oxide mesoporous material. CN201010104899 relates to a method for preparing cobalt-doped zinc oxide Co x Zn 1-x O multifunctional magnetic nanopowder by alcohol thermal method, comprising: (1) at room temperature, dissolving soluble cobalt salt and zinc salt in ethylene glycol In the process, stir mechanically, add anhydrous sodium acetate and polyethylene glycol, and ultrasonically disperse to obtain a reaction solution; (2) The reaction solution is subjected to alcohol thermal reaction at a reaction temperature of 180°C to 220°C for 10 to 14 hours, and then cooled naturally to room temperature; (3) centrifuging the above product, washing and drying to obtain Co x Zn 1-x O multifunctional magnetic nanopowder. CN200810021689 discloses a tantalum-doped zinc oxide nano-powder photocatalyst, its preparation method and application. The preparation method of the catalyst is to dissolve soluble zinc salt in deionized water to form a zinc salt solution, add an appropriate amount of citric acid to obtain a transparent solution A; then take an appropriate amount of tantalum precursor solution, add an appropriate amount of ethylene glycol to form a solution B; mix the two solutions Mix, add PVP and nitric acid during the stirring process, stir for 0.5 to 1 hour to obtain a transparent solution; heat the transparent solution to evaporate to 50 to 70% of the original mass, then add it as a dispersant and stabilizer, and place it in the air after stirring , aged and dried to form a powder precursor; then annealed to obtain a sample. CN200510095053 relates to the preparation method of nano-zinc oxide doped with silver and rare earth metals and its photocatalytic degradation of organic matter and antibacterial applications. The invention incorporates silver Ag and rare earth metals (lanthanum La, cerium Ce) into nano-zinc oxide by organic complexation , Praseodymium Pr, Neodymium Nd, Samarium Sm, Europium Eu, Gadolinium Gd, Dysprosium Dy, Erbium Er, Yttrium Y), etc., to improve the photocatalytic activity of nano-zinc oxide.
2，非金属原子掺杂 比如，发明专利CN201110164917涉及一种膨胀石墨氧化锌复合光催化剂及其制备方法，复合光催化剂组成包括：按重量百分比，10％～99％的膨胀石墨和1％～90％的氧化锌。制备方法包括：(1)向氢氧化钠溶液中按质量体积比1～2g∶100ml加入膨胀石墨，室温下搅拌0.5～3小时，得反应液；(2)将与氢氧化钠摩尔比为1∶0.1～5的乙酸锌溶液加入上述反应液中，在50℃～90℃下反应2～6小时，将混合液真空抽滤，滤渣在60℃～120℃下烘干即得。中国发明专利CN201310589707公开了一种制备具有多级结构碳掺杂氧化锌微球的方法，将葡萄糖酸锌溶解在水中，得到葡萄糖酸锌溶液；将葡萄糖酸锌溶液的pH值调节后进行超声处理；再将葡萄糖酸锌溶液放入微波水热合成仪中，进行合成反应，反应结束后自然冷却到室温，得到中间产物；将中间产物进行离心分离，得到固体，将固体煅烧，得到具有多级结构碳掺杂氧化锌微球。发明专利CN201210015819公开了一种溶剂热法合成氧化锌/石墨烯复合材料的方法，方法是采用氧化石墨、溶剂和锌源混合而成，得到混合溶液；采用溶剂热处理方法处理混合溶液，最后真空烘干，即得氧化锌/石墨烯复合材料。CN201010294546涉及一种F-掺杂的ZnO多孔棱柱阵列薄膜及其制备方法，该薄膜以一种低温化学浴与后续热处理相结合的方法制备。该方法采用简单的Zn(NO3)2和NH4F的混合水溶液，在70℃的低温水浴条件下，直接在导电玻璃基底上制备出棱柱状的Zn(OH)F前驱体阵列膜，再经500℃的热处理，得到纳米多孔结构的ZnO-F棱柱阵列膜。CN200410099023提供了一种制备具有光催化活性的碳纳米管/氧化锌复合粉体的方法。主要特征是以阴离子表面活性剂为分散剂在碳纳米管表面成功引入负电性的活性基团，而不改变碳纳米管的结构。再以锌盐、氢氧化锂为合成氧化锌的原料，在乙醇介质中利用反应离子与活性基团的静电作用以及反应离子之间的化学反应，即可得到氧化锌纳米晶覆盖于碳纳米管表面的复合粉体，晶粒直径约为5～10nm。2. Doping of non-metal atoms For example, the invention patent CN201110164917 relates to an expanded graphite zinc oxide composite photocatalyst and its preparation method. The composition of the composite photocatalyst includes: by weight percentage, 10% to 99% of expanded graphite and 1% to 90% % zinc oxide. The preparation method comprises: (1) adding expanded graphite to sodium hydroxide solution at a mass volume ratio of 1-2 g: 100 ml, and stirring at room temperature for 0.5-3 hours to obtain a reaction liquid; : Add 0.1-5 zinc acetate solution into the above reaction solution, react at 50°C-90°C for 2-6 hours, vacuum filter the mixed solution, and dry the filter residue at 60°C-120°C. Chinese invention patent CN201310589707 discloses a method for preparing carbon-doped zinc oxide microspheres with a multi-level structure, dissolving zinc gluconate in water to obtain a zinc gluconate solution; adjusting the pH value of the zinc gluconate solution and performing ultrasonic treatment ; put the zinc gluconate solution into a microwave hydrothermal synthesizer to carry out a synthesis reaction, and naturally cool to room temperature after the reaction to obtain an intermediate product; the intermediate product is centrifuged to obtain a solid, and the solid is calcined to obtain a multi-stage Structural carbon-doped zinc oxide microspheres. Invention patent CN201210015819 discloses a method for synthesizing zinc oxide/graphene composite material by solvothermal method. The method is to mix graphite oxide, solvent and zinc source to obtain a mixed solution; use solvothermal treatment to process the mixed solution, and finally vacuum-dry dry to obtain the zinc oxide/graphene composite material. CN201010294546 relates to an F-doped ZnO porous prism array film and its preparation method. The film is prepared by combining a low-temperature chemical bath with subsequent heat treatment. This method uses a simple mixed aqueous solution of Zn(NO 3 ) 2 and NH 4 F to directly prepare a prismatic Zn(OH)F precursor array film on a conductive glass substrate under a low-temperature water bath at 70°C, and then After heat treatment at 500°C, a ZnO-F prism array film with nanoporous structure is obtained. CN200410099023 provides a method for preparing carbon nanotube/zinc oxide composite powder with photocatalytic activity. The main feature is that the anionic surfactant is used as a dispersant to successfully introduce negatively charged active groups on the surface of the carbon nanotube without changing the structure of the carbon nanotube. Then use zinc salt and lithium hydroxide as raw materials for synthesizing zinc oxide, and use the electrostatic interaction between reactive ions and active groups and the chemical reaction between reactive ions in an ethanol medium to obtain zinc oxide nanocrystals covering carbon nanotubes. The composite powder on the surface has a grain diameter of about 5-10nm.
3，有机物掺杂 发明专利CN201310064916公开了一种氧化锌/聚苯胺复合材料光催化剂的制备方法。采用直接沉淀法和水热法，分别制备出纳米氧化锌，用硅烷偶联剂对所得纳米氧化锌进行表面化学改性，通过乳液聚合法使其与聚苯胺（PANI）复合得到不同形貌的纳米氧化锌/聚苯胺复合材料光催化剂。发明专利CN201310013813公开了一种方酸菁染料敏化的氧化锌可见光催化剂的制备方法，将Zn(Ac)22H2O和葡萄糖溶于去离子水中，超声形成澄清溶液，将溶液转入聚四氟乙烯高压釜内胆中后，140～180℃的水热反应12～24h，冷却至室温后，将得到的黑色粉体分别用去离子水和无水乙醇进行离心洗涤，在60℃条件下干燥得到氧化锌和碳的复合前驱体，将前驱体置于马弗炉中400～600℃煅烧3h即得氧化锌微球，氧化锌微球与方酸菁染料和有机溶剂混合，在30～50℃的温度下，将上述混合物超声处理0.5～2小时，然后将有机溶剂在减压条件下去除，最后将得到的固体物在60℃下烘干，即可获得方酸菁染料敏化的氧化锌可见光催化剂。CN201010513013采用细乳液聚合的方法将乙烯基单体和有机硅氧烷进行共聚制备表面带有活性硅羟基的聚合物微球；再通过有机胺碱源与所述聚合物微球表面的活性硅羟基作用在聚合物微球表面原位生成纳米ZnO，制得聚合物/ZnO纳米复合微球。3. Organic doping invention patent CN201310064916 discloses a method for preparing a zinc oxide/polyaniline composite photocatalyst. Nano-zinc oxide was prepared by direct precipitation method and hydrothermal method, and the surface of the obtained nano-zinc oxide was chemically modified by silane coupling agent, and it was compounded with polyaniline (PANI) by emulsion polymerization to obtain polyaniline (PANI) with different shapes. Nano ZnO/polyaniline composite photocatalyst. Invention patent CN201310013813 discloses a preparation method of squaraine dye-sensitized zinc oxide visible light catalyst, dissolving Zn(Ac) 2 2H 2 O and glucose in deionized water, ultrasonically forming a clear solution, and transferring the solution to polytetrafluoroethylene After being placed in the inner liner of vinyl fluoride autoclave, hydrothermal reaction at 140-180°C for 12-24 hours, after cooling to room temperature, the obtained black powder was centrifugally washed with deionized water and absolute ethanol respectively, and heated at 60°C Dry to obtain a composite precursor of zinc oxide and carbon, place the precursor in a muffle furnace and calcinate at 400-600°C for 3 hours to obtain zinc oxide microspheres, mix the zinc oxide microspheres with squarylium dye and an organic solvent, At a temperature of 50°C, ultrasonically treat the above mixture for 0.5 to 2 hours, then remove the organic solvent under reduced pressure, and finally dry the obtained solid at 60°C to obtain squaraine dye-sensitized Zinc oxide visible light catalyst. CN201010513013 adopts the method of miniemulsion polymerization to carry out copolymerization of vinyl monomer and organosiloxane to prepare polymer microspheres with active silanol on the surface; Nano-ZnO is generated in situ on the surface of polymer microspheres to prepare polymer/ZnO nanocomposite microspheres.
4，金属氧化物掺杂 比如，发明专利CN201110352185提出一种氧化锌/二氧化钛复合纳米棒的制备方法，其特征在于包括如下步骤在搅拌过程中，把碱溶液和乙二胺分别加入至锌离子溶液中；搅拌均匀后，向混合溶液中加入二氧化钛粉体搅拌混合均匀后，将悬浮液放入聚四氟乙烯衬里的不锈钢高压釜中，进行水热反应；将制得沉淀产物用去离子水洗涤干燥，得到氧化锌/二氧化钛复合纳米棒材料。中国发明专利CN201410081116公开了α-Fe2O3纳米粒修饰ZnO复合光催化体系其制备方法包括两步：（1）锌盐的醇/水溶液置于高压反应釜中，140–180℃反应1.5–9h；产物用乙醇洗涤，60℃干燥2–6h，得到海胆状ZnO微球。（2）利用浸渍-沉淀法，将海胆状ZnO超声分散于铁盐溶液中，其中铁盐与ZnO的质量比为0.05–0.2，40℃搅拌条件下滴加氨水反应1–12h；收集固体并在350℃下焙烧2h得到最终产物。发明专利CN201210258435公开了一种氧化锌/二氧化锡复合微球的制备方法，该方法是利用湿化学法，在有机溶剂中以嵌段聚合物为模板，以水溶性的锌盐和锡盐前驱体，通过模板介观尺寸的有序结构以及亲水、亲油等特征来控制颗粒的大小、形状，然后脱除模板从而得到金属氧化物微球。发明专利CN201210246994公开了一种氧化锌/氧化亚铜异质结的制备方法，技术方案是超声清洗柔性ITO衬底，称量Zn(NO3)2·6H2O和六亚甲基四胺，溶于去离子水中配成电解液，在电化学工作站上进行电化学沉积，柔性ITO衬底为工作电极，铂片为对电极，控制沉积温度40-70℃，横电位-1.3～-1.6V，得到ZnO纳米棒阵列，冲洗、烘干，采用CuSO4和柠檬酸配制电解液，在电化学工作站上进行电化学沉积，柔性ITO衬底为工作电极，铂片为对电极，控制沉积温度在40-70℃，沉积电位为-0.5～-0.6V，在ZnO纳米棒上沉积Cu2O，得到ZnO/Cu2O异质结。发明专利CN201210004993公开了一种可见光响应的氧化锌-氧化铋复合光催化剂及其制备方法。该复合物由质量比为1∶0.05～1∶0～2的纳米氧化锌、氧化铋和氧化石墨烯复合而成。步骤如下：水溶性锌盐、铋盐和尿素分别加入到水溶液中，共沉淀反应后，产物经离心、洗涤、干燥和煅烧后，将反应产物置于超声分散后的氧化石墨烯水溶液中加热搅拌进行反应，反应结束后，产物经离心、洗涤和干燥后，获得氧化锌-氧化铋复合光催化剂。发明专利CN201110153091涉及基于氧化亚铜量子点修饰的氧化锌纳米线阵列光催化材料及其制备方法和应用。该发明是将牢固生长于导电基底上的氧化锌纳米线阵列作为工作电极，以铂电极作为对电极，以饱和甘汞电极作为参比电极，以硝酸铜的二甲基亚砜溶液作为电解液，通过电化学循环伏安法制备得到了氧化亚铜量子点修饰的氧化锌纳米线阵列光催化材料。CN200910014385提供了一种氧化锌/氧化铟纳米异质结光催化材料及其制备方法。该光催化材料的化学式为ZnO/In2O3，硝酸锌和硝酸铟的摩尔比为1∶5－5∶1。其制备方法是(1)将摩尔比为1∶5－5∶1的硝酸锌和硝酸铟混合，完全溶解于去离子水中形成透明溶液，将氨水滴加到该透明溶液中，使溶液的pH值调解到9，陈化24小时，将硝酸锌和硝酸铟充分沉淀；(2)用去离子水过滤洗涤、沉淀三次后，在95℃将沉淀物蒸干，再在600℃～1000℃退火。CN200710039531涉及一种核/壳结构的氧化锌/二氧化钛复合光催化剂、制备方法及应用，其特征在于核/壳结构中的核层为四足或多足状的氧化锌，壳层为均匀包覆在四足或多足状的氧化锌核层表面的二氧化钛层，单个核/壳结构的复合光催化剂颗粒内相邻足末端的距离大于10微米。以四足或多足状氧化锌为载体，通过气相水解的方法将二氧化钛的纳米颗粒固定在氧化锌的表面，氧化钛层的厚度为5纳米到数百纳米，可根据钛原料的用量来调节。4. Metal oxide doping For example, the invention patent CN201110352185 proposes a method for preparing zinc oxide/titanium dioxide composite nanorods, which is characterized in that it includes the following steps: adding alkali solution and ethylenediamine to the zinc ion solution during the stirring process medium; after stirring evenly, add titanium dioxide powder to the mixed solution, stir and mix evenly, put the suspension into a stainless steel autoclave lined with polytetrafluoroethylene, and carry out hydrothermal reaction; wash the precipitated product with deionized water After drying, the zinc oxide/titanium dioxide composite nanorod material is obtained. Chinese invention patent CN201410081116 discloses α-Fe 2 O 3 nanoparticles modified ZnO composite photocatalytic system. The preparation method includes two steps: (1) Alcohol/water solution of zinc salt is placed in a high-pressure reactor, and reacted at 140–180°C for 1.5– 9h; the product was washed with ethanol and dried at 60°C for 2–6h to obtain sea urchin-like ZnO microspheres. (2) Using the impregnation-precipitation method, the sea urchin-like ZnO was ultrasonically dispersed in the iron salt solution, where the mass ratio of iron salt to ZnO was 0.05–0.2, and ammonia water was added dropwise under stirring at 40°C for 1–12 h; the solid was collected and Calcined at 350°C for 2h to obtain the final product. Invention patent CN201210258435 discloses a preparation method of zinc oxide/tin dioxide composite microspheres. The method uses a wet chemical method, using a block polymer as a template in an organic solvent, and using a water-soluble zinc salt and tin salt as a precursor The size and shape of the particles are controlled by the ordered structure of the mesoscopic size of the template and the characteristics of hydrophilicity and lipophilicity, and then the template is removed to obtain metal oxide microspheres. Invention patent CN201210246994 discloses a preparation method of zinc oxide/cuprous oxide heterojunction. The technical solution is to ultrasonically clean the flexible ITO substrate, weigh Zn(NO 3 ) 2 6H 2 O and hexamethylenetetramine, It is dissolved in deionized water to make electrolyte, and electrochemical deposition is carried out on the electrochemical workstation. The flexible ITO substrate is used as the working electrode, and the platinum sheet is used as the counter electrode. , get the ZnO nanorod array, wash and dry, use CuSO 4 and citric acid to prepare the electrolyte, and carry out electrochemical deposition on the electrochemical workstation, the flexible ITO substrate is the working electrode, the platinum sheet is the counter electrode, and the deposition temperature is controlled at Cu 2 O is deposited on the ZnO nanorods at 40-70° C. and the deposition potential is -0.5-0.6 V to obtain a ZnO/Cu 2 O heterojunction. Invention patent CN201210004993 discloses a visible light-responsive zinc oxide-bismuth oxide composite photocatalyst and its preparation method. The composite is composed of nanometer zinc oxide, bismuth oxide and graphene oxide with a mass ratio of 1:0.05-1:0-2. The steps are as follows: water-soluble zinc salt, bismuth salt and urea are respectively added to the aqueous solution, after the co-precipitation reaction, the product is centrifuged, washed, dried and calcined, and the reaction product is heated and stirred in the graphene oxide aqueous solution after ultrasonic dispersion The reaction is carried out, and after the reaction is completed, the product is centrifuged, washed and dried to obtain the zinc oxide-bismuth oxide composite photocatalyst. Invention patent CN201110153091 relates to a zinc oxide nanowire array photocatalytic material based on cuprous oxide quantum dot modification and its preparation method and application. In this invention, the zinc oxide nanowire array firmly grown on the conductive substrate is used as the working electrode, the platinum electrode is used as the counter electrode, the saturated calomel electrode is used as the reference electrode, and the dimethyl sulfoxide solution of copper nitrate is used as the electrolyte , A photocatalytic material of ZnO nanowire arrays decorated with cuprous oxide quantum dots was prepared by electrochemical cyclic voltammetry. CN200910014385 provides a zinc oxide/indium oxide nano-heterojunction photocatalytic material and a preparation method thereof. The chemical formula of the photocatalytic material is ZnO/In 2 O 3 , and the molar ratio of zinc nitrate and indium nitrate is 1:5-5:1. Its preparation method is (1) mix zinc nitrate and indium nitrate with a molar ratio of 1:5-5:1, completely dissolve in deionized water to form a transparent solution, add ammonia water dropwise to the transparent solution, and make the pH of the solution Adjust the value to 9, age for 24 hours, and fully precipitate zinc nitrate and indium nitrate; (2) filter, wash and precipitate three times with deionized water, evaporate the precipitate to dryness at 95 ° C, and then anneal at 600 ° C ~ 1000 ° C . CN200710039531 relates to a zinc oxide/titanium dioxide composite photocatalyst with core/shell structure, preparation method and application, characterized in that the core layer in the core/shell structure is tetrapod or multi-pod zinc oxide, and the shell layer is evenly coated On the titanium dioxide layer on the surface of the four-legged or multi-legged zinc oxide core layer, the distance between the ends of adjacent legs in the composite photocatalyst particles with a single core/shell structure is greater than 10 microns. Using tetrapod or multipod zinc oxide as a carrier, titanium dioxide nanoparticles are fixed on the surface of zinc oxide by gas phase hydrolysis. The thickness of the titanium oxide layer is from 5 nanometers to hundreds of nanometers, which can be adjusted according to the amount of titanium raw materials. .
5，无机盐掺杂 发明专利CN201310429225公开了一种磷酸银/氧化锌复合光催化材料及其制备方法。其具体步骤如下：将氧化锌在去离子水中超声分散得到氧化锌分散液；将硝酸银溶于去离子水中，在磁力搅拌条件下滴加到上述氧化锌分散液中，得到混合溶液，搅拌一段时间后；将配置好的磷酸盐溶液缓慢滴加到氧化锌和硝酸银的混合溶液中继续搅拌一段时间，滴加完毕后得到的混合溶液继续搅拌，产物抽滤后用无水乙醇和去离子水反复洗涤多次后真空干燥，得到磷酸银/氧化锌复合光催化材料。发明专利CN201310400890公开了一种氧化锌/溴化银纳米复合物的制备方法，方法是先将蒸馏水加热到一定温度并保持恒温，再加入锌源前驱物、硼氢化物和表面活性剂，反应一段时间，随后加入银源前驱物，继续反应一定时间。所得样品经几次离心洗涤后烘干得到产物。5. Inorganic salt doping Invention patent CN201310429225 discloses a silver phosphate/zinc oxide composite photocatalytic material and its preparation method. The specific steps are as follows: ultrasonically disperse zinc oxide in deionized water to obtain a zinc oxide dispersion; dissolve silver nitrate in deionized water, and add it dropwise to the above zinc oxide dispersion under magnetic stirring conditions to obtain a mixed solution, and stir for a period of time. After a period of time; slowly add the prepared phosphate solution dropwise to the mixed solution of zinc oxide and silver nitrate and continue to stir for a period of time. After the dropwise addition, the obtained mixed solution continues to stir. Washing repeatedly with water and then drying in vacuum to obtain a silver phosphate/zinc oxide composite photocatalytic material. Invention patent CN201310400890 discloses a preparation method of zinc oxide/silver bromide nanocomposites. The method is to heat distilled water to a certain temperature and maintain a constant temperature, then add zinc source precursors, borohydrides and surfactants, and react for a period of time. Time, then add the silver source precursor, and continue to react for a certain period of time. The obtained samples were centrifuged several times and then dried to obtain the product.
通过分析对比发现，现有关于氧化锌掺杂碳的制备技术，采用的工艺过程相对复杂，且不适合进行大规模生产，而碳掺杂氧化锌基可见光催化剂在环境领域应用潜力巨大，因此，探索其宏量制备技术，具有现实意义。Through analysis and comparison, it is found that the existing preparation technology of zinc oxide doped with carbon is relatively complicated and not suitable for large-scale production, and carbon doped zinc oxide-based visible light catalyst has great potential in the environmental field. Therefore, It is of practical significance to explore its macro-preparation technology.
本发明是针对现有碳掺杂氧化锌基可见光催化剂粉体材料的制备现状的不足，创造性地提出了一种新的制备碳掺杂氧化锌基可见光催化剂纳米粉体材料的方法，即小分子物质助燃烧法。本发明着眼于提高碳掺杂氧化锌基可见光催化剂粉体的可见光催化活性，利用小分子物质的自燃烧实现前驱物分子水平上的扩散混合，使碳掺杂氧化锌基可见光催化剂晶体中碳的掺杂更加均匀有序，促进稳定固溶体的形成；同时，小分子物质的加入克服了粉体间的团聚，有效控制了产物的粒径尺寸，提高了产物的分散性。另外，本发明探索出的制备技术注重对工艺条件的控制，其一是采用远高于体系沸点的温度下干燥前驱物，以加速分子间的流动，实现体系更为有效的掺杂；其二是煅烧后的产物采用快速冷却的方式，与现有技术采用的自然冷却相比，可保留更多的催化活性位。因此，利用本发明小分子物质自燃烧法获得的碳掺杂氧化锌基可见光催化剂不仅分散性好，粒径大小均一，而且可见光催化性能非常优异，同现有技术相比，表现出制备技术和产物可见光催化性能两个方面上的优势。The present invention aims at the shortcomings of the current preparation status of carbon-doped zinc oxide-based visible light catalyst powder materials, and creatively proposes a new method for preparing carbon-doped zinc oxide-based visible light catalyst nano-powder materials, that is, small molecule Substance-assisted combustion method. The present invention focuses on improving the visible light catalytic activity of carbon-doped zinc oxide-based visible light catalyst powder, and utilizes the self-combustion of small molecular substances to realize the diffusion and mixing at the molecular level of the precursor, so that the carbon in the carbon-doped zinc oxide-based visible light catalyst crystal The doping is more uniform and orderly, which promotes the formation of a stable solid solution; at the same time, the addition of small molecular substances overcomes the agglomeration between powders, effectively controls the particle size of the product, and improves the dispersibility of the product. In addition, the preparation technology explored by the present invention focuses on the control of process conditions. One is to dry the precursor at a temperature much higher than the boiling point of the system to accelerate the flow between molecules and achieve more effective doping of the system; The calcined product adopts a rapid cooling method, which can retain more catalytic active sites compared with the natural cooling adopted in the prior art. Therefore, the carbon-doped zinc oxide-based visible light catalyst obtained by the self-combustion method of the small molecule substance of the present invention not only has good dispersibility and uniform particle size, but also has excellent visible light catalytic performance. Compared with the prior art, it shows that the preparation technology and The product has two advantages in visible photocatalytic performance.
本发明采用小分子有机物助燃烧法宏量制备碳修饰氧化锌可见光催化剂。其制备原理是利用小分子有机物高温下的燃烧反应热，实现碳元素对氧化锌晶体中的有效沉积、掺杂；同时反应过程中产生大量的气体，能够有效地“破碎”产物，从而获得小尺寸的碳掺杂氧化锌纳米粒子，实现碳掺杂氧化锌基可见光催化剂的宏量制备。The invention adopts a small-molecule organic substance combustion-assisted combustion method to prepare a carbon-modified zinc oxide visible light catalyst in large quantities. Its preparation principle is to use the combustion reaction heat of small molecular organic matter at high temperature to realize the effective deposition and doping of carbon elements in zinc oxide crystals; at the same time, a large amount of gas is generated during the reaction process, which can effectively "break up" the product, thereby obtaining small Large-scale carbon-doped ZnO nanoparticles to realize the mass preparation of carbon-doped ZnO-based visible light catalysts.
该方法在碳掺杂氧化锌基可见光催化剂制备领域尚无人采纳，相关文献也无直接借鉴价值，因此，该发明对于从事碳掺杂氧化锌基可见光催化剂制备的技术人员具有重要的启发作用。由于本发明采用的制备方法具有设备简单、合成效率高、生产成本低、产物分散性和可见光催化效率高等特点，因此，具有很强的工业可行性。This method has not yet been adopted in the field of preparation of carbon-doped zinc oxide-based visible light catalysts, and the relevant literature has no direct reference value. Therefore, this invention has an important inspiration for technicians engaged in the preparation of carbon-doped zinc oxide-based visible light catalysts. Since the preparation method adopted in the present invention has the characteristics of simple equipment, high synthesis efficiency, low production cost, product dispersion and high visible light catalytic efficiency, it has strong industrial feasibility.
发明内容Contents of the invention
本发明的目的在于提出一种碳掺杂氧化锌基可见光催化剂的宏量制备方法，获得粒径均匀、可见光催化性能优异的纳米粉体，降低碳掺杂氧化锌基可见光催化剂的生产成本，更好地实现产物粒径大小及分布的均匀可控。The purpose of the present invention is to propose a macro-preparation method of a carbon-doped zinc oxide-based visible light catalyst to obtain nano-powders with uniform particle size and excellent visible light catalytic performance, reduce the production cost of carbon-doped zinc oxide-based visible light catalysts, and more To achieve a uniform and controllable particle size and distribution of the product.
本发明按照一定比例称取小分子有机物质与锌源置于研钵中，充分研磨至体系呈现粘稠透明状，然后将透明液体转移到坩埚中，并于一定条件下干燥至没有水蒸气放出。最后将得到的褐色蓬松的物质再煅烧，煅烧结束后快速冷却，得到浅色的碳掺杂氧化锌基可见光催化剂纳米粉体。The present invention weighs small molecular organic substances and zinc sources according to a certain ratio and puts them in a mortar, grinds them sufficiently until the system appears viscous and transparent, then transfers the transparent liquid to a crucible, and dries under certain conditions until no water vapor is released. . Finally, the obtained brown fluffy material is calcined again, and after the calcining is completed, it is rapidly cooled to obtain a light-colored carbon-doped zinc oxide-based visible photocatalyst nanopowder.
具体制备条件为：The specific preparation conditions are:
小分子有机物质和锌源的物质的量之比为2~5：1；The ratio of small molecular organic substances to zinc source substances is 2~5:1;
前驱物干燥温度为180~220℃，干燥时间为2~6 h；The drying temperature of the precursor is 180~220℃, and the drying time is 2~6 h;
前驱物煅烧温度为500~800℃，煅烧时间1~5 h。The precursor calcination temperature is 500~800℃, and the calcination time is 1~5 h.
本发明中的碳掺杂氧化锌基可见光催化剂的制备方法，锌源为硝酸锌。In the preparation method of the carbon-doped zinc oxide-based visible light catalyst in the present invention, the zinc source is zinc nitrate.
本发明中的碳掺杂氧化锌基可见光催化剂的制备方法，小分子有机物为甘氨酸或者草酸或者柠檬酸之一种。In the preparation method of the carbon-doped zinc oxide-based visible light catalyst in the present invention, the small molecule organic substance is one of glycine, oxalic acid or citric acid.
本发明中，研磨是为了使反应原料能够混合均匀；In the present invention, grinding is to make the reaction raw materials can be mixed evenly;
本发明中，烘干是在高于沸点条件下进行，一方面是为了蒸去混合物中游离的自由水分子，以便于后续操作；另一方面，能够加速分子间的扩散，从而实现有效掺杂。In the present invention, the drying is carried out under the condition of higher than the boiling point. On the one hand, it is to evaporate free free water molecules in the mixture to facilitate subsequent operations; on the other hand, it can accelerate the diffusion between molecules, so as to achieve effective doping .
本发明中，由于所得的前驱物在分解过程中会产生大量的气体，使反应体系疏松，有效地防止了产物团聚现象的发生。In the present invention, since the obtained precursor produces a large amount of gas during the decomposition process, the reaction system is loosened, and the occurrence of product agglomeration is effectively prevented.
本发明经过煅烧后快速冷却，为了使产物结构中保留尽可能多的催化活性位，使其具有更高的可见光催化效率。得到的产物颜色为很淡的粉体，粒径达到纳米量级，并具有良好的分散性。The present invention is rapidly cooled after calcination, in order to retain as many catalytic active sites as possible in the product structure, so that it has higher visible light catalytic efficiency. The color of the obtained product is very light powder, the particle size reaches nanometer level, and has good dispersibility.
本发明具有如下优点：The present invention has the following advantages:
1、首次提出小分子有机物质助燃烧法来制备碳掺杂氧化锌基可见光催化剂粉体。小分子有机物质的加入，在分解过程中膨胀并产生大量气体，使反应体系疏松，有效防止了团聚现象的发生。1. For the first time, a small molecule organic substance combustion-assisted method was proposed to prepare carbon-doped zinc oxide-based visible light catalyst powder. The addition of small molecular organic substances expands and produces a large amount of gas during the decomposition process, making the reaction system loose and effectively preventing the occurrence of agglomeration.
2、本发明所用的原材料来源丰富而且廉价，制备工艺简单，生产过程中不产生废水、废渣等工业污染。2. The source of raw materials used in the present invention is abundant and cheap, the preparation process is simple, and industrial pollution such as waste water and waste residues are not generated during the production process.
3、利用本发明制备的产物同其他技术相比，制备的碳掺杂氧化锌基可见光催化剂不仅具有纯度高、颜色浅、粒径小且粒径大小均一、无团聚现象、易于分散等优点，而且其可见光催化效率高于利用现有制备技术获得的产物。3. Compared with other technologies, compared with other technologies, the carbon-doped zinc oxide-based visible light catalyst not only has the advantages of high purity, light color, small and uniform particle size, no agglomeration phenomenon, and easy dispersion. Moreover, its visible light catalytic efficiency is higher than that of products obtained by using existing preparation technologies.
4、本发明探索出的制备技术注重对工艺条件的控制，采用远高于体系沸点的温度下干燥前驱物，以加速分子间的流动，实现体系更为有效的掺杂；其二是煅烧后的产物采用快速冷却的方式，与现有技术采用的自然冷却相比，可保留更多的催化活性位。4. The preparation technology explored by the present invention focuses on the control of process conditions, and uses a temperature much higher than the boiling point of the system to dry the precursor to accelerate the flow between molecules and achieve more effective doping of the system; the second is after calcination The product adopts a rapid cooling method, which can retain more catalytic active sites compared with the natural cooling adopted by the prior art.
5、利用本发明提出的小分子有机物质助燃烧法制备碳掺杂氧化锌基可见光催化剂粉体，直接以太阳光为光源，能够快速高效地降解有机染料，可见光利用率高，工业应用前景大。5. The carbon-doped zinc oxide-based visible light catalyst powder is prepared by using the small-molecule organic substance combustion-assisted method proposed by the present invention, directly using sunlight as the light source, which can quickly and efficiently degrade organic dyes, has a high utilization rate of visible light, and has great industrial application prospects.
实施例：Example:
下面通过具体实施例对本发明作进一步的说明。The present invention will be further described below by specific examples.
实施例1：Example 1:
按照小分子有机物甘氨酸与硝酸锌的摩尔比例为2:1称取原料置于研钵中，充分研磨至体系呈现粘稠透明状，然后将透明液体转移到坩埚中，并于200℃条件下干燥6h至没有水蒸气放出。最后将得到的褐色蓬松的物质在600℃条件下煅烧2h后，快速冷却，得到淡粉色粉末。通过透射电子显微镜观察产物的粒径约为65 nm，产物具有很好的分散性。取0.1g该碳掺杂氧化锌基可见光催化剂粉体加入到30 mL 2×10-5 摩尔/升的罗丹明B溶液中进行催化。在室温为30℃±3℃且太阳光照射下，可在15分钟将有机染料罗丹明B降解完全。Weigh the raw materials according to the molar ratio of the small molecule organic compound glycine and zinc nitrate as 2:1, place them in a mortar, grind them thoroughly until the system becomes viscous and transparent, then transfer the transparent liquid to a crucible, and dry it at 200°C 6h until no water vapor is released. Finally, the obtained brown fluffy substance was calcined at 600° C. for 2 h, and then rapidly cooled to obtain a pale pink powder. The particle size of the product observed by a transmission electron microscope is about 65 nm, and the product has good dispersibility. 0.1 g of the carbon-doped zinc oxide-based visible light catalyst powder was added to 30 mL of 2×10 −5 mol/liter rhodamine B solution for catalysis. The organic dye rhodamine B can be completely degraded within 15 minutes at a room temperature of 30°C±3°C and sunlight irradiation.
实施例2Example 2
按照小分子有机物草酸与硝酸锌的摩尔比例为2:1称取原料置于研钵中，充分研磨至体系呈现粘稠透明状，然后将透明液体转移到坩埚中，并于180℃条件下干燥5h至没有水蒸气放出。最后将得到的褐色蓬松的物质在600℃条件下煅烧2h后，快速冷却，得到淡粉色粉末。通过透射电子显微镜观察产物的粒径约为75 nm，产物具有很好的分散性。取0.1g该碳掺杂氧化锌基可见光催化剂粉体加入到30 mL 2×10-5 摩尔/升的罗丹明B溶液中进行催化。在室温为30℃±3℃且太阳光照射下，可在25分钟将有机染料罗丹明B降解完全。Weigh the raw materials according to the molar ratio of oxalic acid and zinc nitrate, a small molecule organic compound, and put them in a mortar, grind them thoroughly until the system becomes viscous and transparent, then transfer the transparent liquid to a crucible, and dry it at 180°C 5h until no water vapor is released. Finally, the obtained brown fluffy substance was calcined at 600° C. for 2 h, and then rapidly cooled to obtain a pale pink powder. The particle size of the product observed by a transmission electron microscope is about 75 nm, and the product has good dispersibility. 0.1 g of the carbon-doped zinc oxide-based visible light catalyst powder was added to 30 mL of 2×10 −5 mol/liter rhodamine B solution for catalysis. The organic dye rhodamine B can be completely degraded within 25 minutes at a room temperature of 30°C±3°C and sunlight irradiation.
实施例3Example 3
按照小分子有机物柠檬酸与硝酸锌的摩尔比例为5:1称取原料置于研钵中，充分研磨至体系呈现粘稠透明状，然后将透明液体转移到坩埚中，并于200℃条件下干燥6h至没有水蒸气放出。最后将得到的褐色蓬松的物质在800℃条件下煅烧2h后，快速冷却，得到淡粉色粉末。通过透射电子显微镜观察产物的粒径约为50 nm，产物具有很好的分散性。取0.1g该碳掺杂氧化锌基可见光催化剂粉体加入到30 mL 2×10-5 摩尔/升的罗丹明B溶液中进行催化。在室温为30℃±3℃且太阳光照射下，可在40分钟将有机染料罗丹明B降解完全。Weigh the raw materials according to the molar ratio of citric acid and zinc nitrate of the small molecular organic matter to be 5:1, place them in a mortar, grind them thoroughly until the system becomes viscous and transparent, then transfer the transparent liquid to a crucible, and put it under the condition of 200°C Dry for 6h until no water vapor is released. Finally, the obtained brown fluffy substance was calcined at 800° C. for 2 h, and then rapidly cooled to obtain a pale pink powder. The particle size of the product observed by a transmission electron microscope is about 50 nm, and the product has good dispersibility. 0.1 g of the carbon-doped zinc oxide-based visible light catalyst powder was added to 30 mL of 2×10 −5 mol/liter rhodamine B solution for catalysis. The organic dye Rhodamine B can be completely degraded within 40 minutes at a room temperature of 30°C±3°C and under sunlight.
实施例4Example 4
按照小分子有机物草酸与硝酸锌的摩尔比例为4:1称取原料置于研钵中，充分研磨至体系呈现粘稠透明状，然后将透明液体转移到坩埚中，并于220℃条件下干燥2h至没有水蒸气放出。最后将得到的褐色蓬松的物质在600℃条件下煅烧5h后，快速冷却，得到淡粉色粉末。通过透射电子显微镜观察产物的粒径约为55 nm，产物具有很好的分散性。取0.1g该碳掺杂氧化锌基可见光催化剂粉体加入到30 mL 2×10-5 摩尔/升的罗丹明B溶液中进行催化。在室温为30℃±3℃且太阳光照射下，可在30分钟将有机染料罗丹明B降解完全。According to the molar ratio of small molecule organic compound oxalic acid to zinc nitrate is 4:1, weigh the raw materials and place them in a mortar, grind them thoroughly until the system becomes viscous and transparent, then transfer the transparent liquid to a crucible and dry it at 220°C 2h until no water vapor is released. Finally, the obtained brown fluffy substance was calcined at 600° C. for 5 h, and then rapidly cooled to obtain a pale pink powder. The particle size of the product observed by a transmission electron microscope is about 55 nm, and the product has good dispersibility. 0.1 g of the carbon-doped zinc oxide-based visible light catalyst powder was added to 30 mL of 2×10 −5 mol/liter rhodamine B solution for catalysis. The organic dye rhodamine B can be completely degraded within 30 minutes at a room temperature of 30°C±3°C under sunlight irradiation.
实施例5Example 5
按照小分子有机物柠檬酸与硝酸锌的摩尔比例为2:1称取原料置于研钵中，充分研磨至体系呈现粘稠透明状，然后将透明液体转移到坩埚中，并于200℃条件下干燥5h至没有水蒸气放出。最后将得到的褐色蓬松的物质在700℃条件下煅烧2h后，快速冷却，得到淡粉色粉末。通过透射电子显微镜观察产物的粒径约为70 nm，产物具有很好的分散性。取0.1g该碳掺杂氧化锌基可见光催化剂粉体加入到30 mL 2×10-5 摩尔/升的罗丹明B溶液中进行催化。在室温为30℃±3℃且太阳光照射下，可在35分钟将有机染料罗丹明B降解完全。Weigh the raw materials according to the molar ratio of citric acid and zinc nitrate of the small molecular organic matter to be 2:1, place them in a mortar, grind them thoroughly until the system becomes viscous and transparent, then transfer the transparent liquid to a crucible, and put it under the condition of 200°C Dry for 5h until no water vapor is released. Finally, the obtained brown fluffy substance was calcined at 700° C. for 2 h, and then rapidly cooled to obtain a pale pink powder. The particle size of the product observed by a transmission electron microscope is about 70 nm, and the product has good dispersibility. 0.1 g of the carbon-doped zinc oxide-based visible light catalyst powder was added to 30 mL of 2×10 −5 mol/liter rhodamine B solution for catalysis. The organic dye rhodamine B can be completely degraded within 35 minutes at a room temperature of 30°C±3°C and under sunlight irradiation.
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