CN106492854B - There is the composite nano Ag of photocatalysis performance using two-step method preparation3PO4/TiO2Material and methods and applications - Google Patents
There is the composite nano Ag of photocatalysis performance using two-step method preparation3PO4/TiO2Material and methods and applications Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 25
- 238000007146 photocatalysis Methods 0.000 title abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 158
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 45
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 39
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 82
- 239000004408 titanium dioxide Substances 0.000 claims description 65
- 239000000243 solution Substances 0.000 claims description 51
- 239000002245 particle Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- 239000012153 distilled water Substances 0.000 claims description 21
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 20
- 229910000161 silver phosphate Inorganic materials 0.000 claims description 17
- 229940019931 silver phosphate Drugs 0.000 claims description 16
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 claims description 14
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 3
- 230000002431 foraging effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 11
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 8
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 abstract 1
- 229910000397 disodium phosphate Inorganic materials 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000011246 composite particle Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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Abstract
Description
【技术领域】【Technical field】
本发明属于催化剂制备技术领域，特别涉及一种利用两步水热法制备的对可见光具有光催化性能的复合型纳米Ag3PO4/TiO2材料。The invention belongs to the technical field of catalyst preparation, in particular to a composite nano-Ag 3 PO 4 /TiO 2 material prepared by a two-step hydrothermal method and having photocatalytic performance for visible light.
【背景技术】【Background technique】
随着社会工业化的发展，环境污染却在逐年的加剧。其中，水环境污染的问题尤为严重。然而传统的处理水污染的办法就是在吸附、光催化、厌氧等处理方法。With the development of social industrialization, environmental pollution is increasing year by year. Among them, the problem of water environment pollution is particularly serious. However, the traditional methods to deal with water pollution are adsorption, photocatalysis, anaerobic and other treatment methods.
文献“中国专利CN2014101206604.X”公布了一种磁性纳米磷酸银/二氧化钛复合光催化材料的制备方法，是由四异丙醇、甲醇、硝酸银、硝酸铁、硝酸亚铁、氨水等制成。该材料合成过程简单，其中钛和银两者之间相互掺杂，紧密结合，能有效发挥相互协同作用。The document "Chinese Patent CN2014101206604.X" discloses a preparation method of a magnetic nano-silver phosphate/titanium dioxide composite photocatalytic material, which is made of tetraisopropanol, methanol, silver nitrate, ferric nitrate, ferrous nitrate, ammonia water, and the like. The synthesis process of the material is simple, in which titanium and silver are doped with each other and tightly combined, and can effectively play a synergistic effect.
文献“中国专利CN201410470137.3”公布了一种磷酸银/氧缺陷型二氧化钛复合光催化剂。所述光催化剂是将可见光光催化剂磷酸银负载到氧空穴型二氧化钛上所形成的。磷酸银/氧缺陷型二氧化钛复合可见光催化剂用于光催化降解有机污染物罗丹明B的反应活性较高。The document "Chinese Patent CN201410470137.3" discloses a silver phosphate/oxygen-deficient titanium dioxide composite photocatalyst. The photocatalyst is formed by supporting the visible light photocatalyst silver phosphate on the oxygen hole type titanium dioxide. The silver phosphate/oxygen-deficient titanium dioxide composite visible light catalyst has high reactivity for photocatalytic degradation of the organic pollutant rhodamine B.
文献“中国专利CN02117493.8”公布了一种磷酸银抗菌改性二氧化钛复合光催化剂，是以纳米或亚微米二氧化钛颗粒作为内核，在二氧化钛颗粒表面包覆有二氧化硅和氧化铝层、二氧化硅层或氧化铝层，得到具有多孔性质的二氧化钛复合颗粒，在二氧化钛复合颗粒表面包覆有磷酸银层，得到磷酸银抗菌改性二氧化钛复合光催化剂。该复合颗粒掺杂在涂料、陶瓷、塑料或橡胶材料中作为抗菌材料而被广泛使用。The document "Chinese Patent CN02117493.8" discloses a silver phosphate antibacterial modified titanium dioxide composite photocatalyst, which uses nanometer or submicron titanium dioxide particles as the core, and the surface of the titanium dioxide particles is coated with silicon dioxide and aluminum oxide layers, dioxide A silicon layer or an aluminum oxide layer is used to obtain titanium dioxide composite particles with porous properties, and a silver phosphate layer is coated on the surface of the titanium dioxide composite particles to obtain a silver phosphate antibacterial modified titanium dioxide composite photocatalyst. The composite particles are widely used as antibacterial materials in coatings, ceramics, plastics or rubber materials.
文献“中国专利CN201210487568.1”公布了一种磷酸银/二氧化钛复合材料。其可以有效的避免光生电子与空穴的重新复合，从而有效的促进光催化进程，有效地提高二氧化钛的光催化的活性。并且该复合材料的制备方法比较简单。The document "Chinese Patent CN201210487568.1" discloses a silver phosphate/titanium dioxide composite material. It can effectively avoid the recombination of photogenerated electrons and holes, thereby effectively promoting the photocatalytic process and effectively improving the photocatalytic activity of titanium dioxide. And the preparation method of the composite material is relatively simple.
纳米TiO2是一种N型半导体材料，具有活性高，热稳定性好，无毒，价格便宜等优良特性，近期纳米TiO2的光催化降解有机物的特性在污水处理、空气净化等方面被广泛的应用。然而TiO2在实际中应用只能利用太阳光中的紫外光部分，因此对太阳光的利用率过低，降低了其应用价值。当太阳光对纳米TiO2照射时价带上的电子(e-)就会被激发到导带，在价带上产生相应的空穴(h+)，带负电的电子和带正电的空穴与吸附在半导体表面的H2O、O2发生反应，生成活性基团如·O2，OH-1等，它们有强大的氧化分解能力，从而具有较高的光催化性能。Nano TiO 2 is an N-type semiconductor material with excellent properties such as high activity, good thermal stability, non-toxicity, and low price. Recently, the photocatalytic degradation of organic matter by nano TiO 2 has been widely used in sewage treatment, air purification, etc. Applications. However, the practical application of TiO 2 can only utilize the ultraviolet part of sunlight, so the utilization rate of sunlight is too low, which reduces its application value. When sunlight irradiates nano-TiO 2 , the electrons (e - ) in the valence band will be excited to the conduction band, and corresponding holes (h + ) will be generated in the valence band, negatively charged electrons and positively charged holes The holes react with H 2 O and O 2 adsorbed on the surface of the semiconductor to generate active groups such as ·O 2 , OH -1 , etc., which have strong oxidative decomposition ability and thus have high photocatalytic performance.
纳米Ag3PO4是一种重要的抗菌剂、催化剂，可以吸收波长小于530nm的太阳光，在可见光下的量子产率高达90％，并且在可见光照射下表现出更大的氧化能力等，因此被作为一种高效可见光响应剂。纳米Ag3PO4能迅速在可见光下对有机染料分子进行降解，因此在处理水污染等方面具有巨大的应用前景，从而受到大家的广泛关注。Nano-Ag 3 PO 4 is an important antibacterial agent and catalyst, which can absorb sunlight with a wavelength of less than 530nm, the quantum yield under visible light is as high as 90%, and it shows greater oxidation ability under visible light irradiation, etc., so as a highly efficient visible light responsive agent. Nano-Ag 3 PO 4 can rapidly degrade organic dye molecules under visible light, so it has great application prospects in the treatment of water pollution and so on, which has attracted widespread attention.
【发明内容】[Content of the invention]
本发明的目的在于提供利用两步法制备具有光催化性能的复合型纳米Ag3PO4/TiO2材料，该制备方法先利用热法的优点制备出稳定性好、光催化降解能力优异的复合型纳米 Ag3PO4/TiO2材料。该操作简单，需要的设备简单，产物产率高、产物结晶良好。The purpose of the present invention is to provide a composite nano-Ag 3 PO 4 /TiO 2 material with photocatalytic performance prepared by a two-step method. The preparation method first utilizes the advantages of a thermal method to prepare a composite material with good stability and excellent photocatalytic degradation ability. Type nano-Ag 3 PO 4 /TiO 2 material. The operation is simple, the required equipment is simple, the product yield is high, and the product crystallization is good.
为达到上述目的，本发明采用的技术方案是：To achieve the above object, the technical scheme adopted in the present invention is:
一种利用两步法制备具有光催化性能的复合型纳米Ag3PO4/TiO2材料的方法，先利用水热法将制备出棒状二氧化钛后，再次利用水热法将纳米磷酸银颗粒负载到棒状二氧化钛上，所述二氧化钛与硝酸银的摩尔比为1：(1～3)，可溶性银盐中银离子与磷酸盐的摩尔比为3:1。A method for preparing a composite nano-Ag 3 PO 4 /TiO 2 material with photocatalytic performance by a two-step method, firstly using a hydrothermal method to prepare rod-shaped titanium dioxide, and then using a hydrothermal method to load the nano-silver phosphate particles into the On the rod-shaped titanium dioxide, the molar ratio of the titanium dioxide to the silver nitrate is 1:(1-3), and the molar ratio of the silver ion to the phosphate in the soluble silver salt is 3:1.
作为本发明的进一步改进，所述的复合型纳米Ag3PO4/TiO2材料磷酸银的颗粒粒径为 10-20nm。As a further improvement of the present invention, the particle size of the composite nano-Ag 3 PO 4 /TiO 2 material silver phosphate is 10-20 nm.
作为本发明的进一步改进，具体包括以下步骤：As a further improvement of the present invention, it specifically comprises the following steps:
步骤1：将二氧化钛(P25)加入NaOH溶液中，并在反应釜中于150～170℃反应14～16h，反应完成后待其自然冷却至室温静置后洗至中性后，放入干燥箱干燥；将干燥后的样品加入到酸性溶液中陈化，过滤后洗涤至中性，80℃下干燥8h后在马弗炉中进行煅烧，煅烧温度400～450℃，煅烧时间5～7h，制成棒状二氧化钛。Step 1: Add titanium dioxide (P25) into the NaOH solution, and react in the reaction kettle at 150-170 ° C for 14-16 hours. After the reaction is completed, let it cool to room temperature naturally and then wash to neutrality, then put it in a drying oven Drying; add the dried sample to an acidic solution for aging, filter and wash to neutrality, dry at 80 °C for 8 hours, and then calcinate in a muffle furnace at a calcination temperature of 400 to 450 °C and a calcination time of 5 to 7 hours. into rod-shaped titanium dioxide.
步骤2：将用水热法制备的棒状二氧化钛108g加入25ml蒸馏水中，进行超声分散15min，再加入可溶性盐，然后滴加少量氨水搅拌均匀后，最后加入磷酸盐，继续充分搅拌反应后可得到纳米Ag3PO4/TiO2溶液；二氧化钛与硝酸银的摩尔比为1：(1～3)，可溶性银盐中银离子与磷酸银的摩尔比为3:1；Step 2: Add 108 g of rod-shaped titanium dioxide prepared by hydrothermal method into 25 ml of distilled water, carry out ultrasonic dispersion for 15 minutes, then add soluble salt, then add a small amount of ammonia water and stir evenly, finally add phosphate, and continue to fully stir the reaction to obtain nano-Ag 3 PO 4 /TiO 2 solution; the molar ratio of titanium dioxide to silver nitrate is 1:(1-3), and the molar ratio of silver ion to silver phosphate in the soluble silver salt is 3:1;
步骤3：将制备的纳米Ag3PO4/TiO2溶液放入反应釜，在100～160℃进行二次水热反应，反应完全后进行过滤、洗涤、80℃下干燥6h即可得到复合型纳米Ag3PO4/TiO2材料。Step 3: Put the prepared nano Ag 3 PO 4 /TiO 2 solution into the reaction kettle, conduct secondary hydrothermal reaction at 100-160°C, filter, wash and dry at 80°C for 6 hours after the reaction is complete to obtain the composite type Nano Ag 3 PO 4 /TiO 2 material.
作为本发明的进一步改进，步骤1)中，利用水热法制备棒状二氧化钛，NaOH溶液的浓度为2～10mol/L，所用二氧化钛为市售P25，锐钛矿和金红石的重量比为71：29。As a further improvement of the present invention, in step 1), the rod-shaped titanium dioxide is prepared by a hydrothermal method, the concentration of the NaOH solution is 2-10 mol/L, the titanium dioxide used is commercially available P25, and the weight ratio of anatase and rutile is 71:29 .
作为本发明的进一步改进，步骤2)中，可溶性银盐为硝酸银。As a further improvement of the present invention, in step 2), the soluble silver salt is silver nitrate.
作为本发明的进一步改进，步骤2)中，磷酸盐为：Na2HPO4·12H2O、Na3PO4、NaH2PO4。As a further improvement of the present invention, in step 2), the phosphates are: Na 2 HPO 4 ·12H 2 O, Na 3 PO 4 , NaH 2 PO 4 .
作为本发明的进一步改进，步骤3)中，利用水热法制备复合型纳米Ag3PO4/TiO2材料，水热反应的时间为2～4h。As a further improvement of the present invention, in step 3), the composite nano-Ag 3 PO 4 /TiO 2 material is prepared by a hydrothermal method, and the hydrothermal reaction time is 2-4 hours.
一种利用两步水热法制备的在可见光下具有光催化性能的复合型纳米Ag3PO4/TiO2材料，是由上述的方法制得。A composite nano-Ag 3 PO 4 /TiO 2 material with photocatalytic performance under visible light prepared by a two-step hydrothermal method is prepared by the above method.
一种利用两步水热法制备的在可见光下具有光催化性能的复合型纳米Ag3PO4/TiO2材料在光催化降解中应用。A composite nano-Ag 3 PO 4 /TiO 2 material with photocatalytic performance under visible light prepared by a two-step hydrothermal method is applied in photocatalytic degradation.
本发明的有益效果在于：The beneficial effects of the present invention are:
本发明将稳定性优良的宽禁带半导体材料二氧化钛与纳米磷酸银复合，得到一种新型的可见光催化剂；将纳米磷酸银颗粒负载在棒状二氧化钛表面形成异质结构，有效地促进光生电子和空穴的快速输运和分离，解决了单一磷酸银光催化剂成本较高、光腐蚀现象严重、稳定性较差等问题；复合材料的制备方法简单，操作简便，有利于大规模生产。In the invention, the wide band gap semiconductor material titanium dioxide with excellent stability is compounded with nanometer silver phosphate to obtain a new type of visible light catalyst; the nanometer silver phosphate particles are loaded on the surface of rod-shaped titanium dioxide to form a heterostructure, which effectively promotes photogenerated electrons and holes The rapid transportation and separation of the composite material solves the problems of high cost, serious photocorrosion phenomenon and poor stability of a single silver phosphate photocatalyst; the preparation method of the composite material is simple, the operation is simple, and it is conducive to large-scale production.
尤其是，本发明先制备棒状的TiO2，然后向棒状的TiO2的水溶液中依次加入硝酸银、氨水、Na2HPO4·12H2O，再通过水热法制备纳米Ag3PO4/TiO2复合材料。本发明的关键步骤为棒状的TiO2、硝酸银、氨水和Na2HPO4·12H2O的加料顺序及水热法的制备工艺，硝酸银中的银离子和氨水容易形成络合物，然后加入Na2HPO4·12H2O，其中的硝酸根能够和络合的银离子进行反应生产纳米Ag3PO4/TiO2；加入采用棒状的TiO2可以增加负载的比表面积，使更多的 Ag3PO4负载在TiO2上面，促使电子与空穴的分离效率增大；用水热法制备的磷酸银相对其他方法制备的比表面积更大，从而导致光催化效率提高。利用纳米Ag3PO4在可见光照射下具有优异的催化降解有机染料的能力，因此利用水热法将Ag3PO4负载在棒状二氧化钛上。In particular, the present invention first prepares rod-shaped TiO 2 , and then adds silver nitrate, ammonia water, Na 2 HPO 4 ·12H 2 O to the aqueous solution of rod-shaped TiO 2 in sequence, and then prepares nano-Ag 3 PO 4 /TiO by hydrothermal method. 2 composite materials. The key steps of the present invention are the feeding sequence of rod-shaped TiO 2 , silver nitrate, ammonia water and Na 2 HPO 4 ·12H 2 O and the preparation process of hydrothermal method. Adding Na 2 HPO 4 ·12H 2 O, the nitrate can react with the complexed silver ions to produce nano-Ag 3 PO 4 /TiO 2 ; adding rod-shaped TiO 2 can increase the specific surface area of the load and make more Ag 3 PO 4 is loaded on TiO 2 to increase the separation efficiency of electrons and holes; the silver phosphate prepared by hydrothermal method has a larger specific surface area than those prepared by other methods, which leads to the improvement of photocatalytic efficiency. Using nano-Ag 3 PO 4 to have an excellent ability to catalyze the degradation of organic dyes under visible light irradiation, Ag 3 PO 4 was supported on rod-shaped titania by hydrothermal method.
进一步，利用市售P25的优点(二氧化钛纳锐钛矿相为主，包含少量的金红石相，该混合相二氧化钛与纯锐钛矿型或纯金红石型二氧化钛相比可显示出更优异的光催化性)；利用水热法合成的二氧化钛具有较大的比表面积优异的光催化性能。Further, using the advantages of commercially available P25 (titanium dioxide is mainly nanoanatase phase, including a small amount of rutile phase, this mixed phase titanium dioxide can show more excellent photocatalytic activity compared with pure anatase type or pure rutile type titanium dioxide. ); TiO2 synthesized by hydrothermal method has large specific surface area and excellent photocatalytic performance.
在光催化降解中应用，试验表明Ag3PO4/TiO2对亚甲基蓝的光催化降解效果已经达到了 90％以上。因此制备的纳米Ag3PO4/TiO2催化剂在可见光下对亚甲基蓝具有较高的催化降解能力。Applied in photocatalytic degradation, the test shows that the photocatalytic degradation effect of Ag 3 PO 4 /TiO 2 on methylene blue has reached more than 90%. Therefore, the prepared nano-Ag 3 PO 4 /TiO 2 catalyst has high catalytic degradation ability to methylene blue under visible light.
【附图说明】【Description of drawings】
图1(a)是二氧化钛载体的照片，图1(b)是纳米Ag3PO4/TiO2的照片。Fig. 1(a) is a photograph of a titanium dioxide support, and Fig. 1(b) is a photograph of nano-Ag 3 PO 4 /TiO 2 .
图2为Ag3PO4、TiO2、Ag3PO4/TiO2的XRD谱图。FIG. 2 is the XRD patterns of Ag 3 PO 4 , TiO 2 and Ag 3 PO 4 /TiO 2 .
图3是纳米Ag3PO4/TiO2对亚甲基蓝溶液的光催化降解效果。Figure 3 is the photocatalytic degradation effect of nano-Ag 3 PO 4 /TiO 2 on methylene blue solution.
【具体实施方式】【Detailed ways】
下面结合具体实施例，对本发明的具体实施方式进行详细阐述，但本发明不限于该实施例。The specific embodiments of the present invention will be described in detail below with reference to specific examples, but the present invention is not limited to the examples.
(一)合成(1) Synthesis
本发明利用两步水热法制备在可见光下具有光催化性能的复合型纳米Ag3PO4/TiO2材料的方法为：The present invention utilizes a two-step hydrothermal method to prepare the composite nano-Ag 3 PO 4 /TiO 2 material with photocatalytic performance under visible light as follows:
1)棒状二氧化钛：1) rod-shaped titanium dioxide:
将0.25g市售二氧化钛P25加入NaOH溶液中，并在反应釜中于150～170℃反应14～16h，反应完成后待其自然冷却至室温静置后洗至中性后，放入干燥箱干燥；将干燥后的样品加入到HCI溶液中陈化，过滤后洗涤至中性，然后在马弗炉中进行煅烧，煅烧温度400～450℃，煅烧时间5～7h，制成棒状二氧化钛。NaOH溶液的浓度为2～10mol/L。Add 0.25g of commercially available titanium dioxide P25 to the NaOH solution, and react in the reaction kettle at 150-170 ° C for 14-16 hours. After the reaction is completed, let it cool to room temperature naturally and then wash to neutrality, then put it in a drying box to dry ; Add the dried sample to the HCI solution for aging, filter and wash to neutrality, and then calcinate in a muffle furnace at a calcination temperature of 400-450°C and a calcination time of 5-7h to make rod-shaped titanium dioxide. The concentration of the NaOH solution is 2 to 10 mol/L.
2)纳米Ag3PO4/TiO2的制备2) Preparation of nano-Ag 3 PO 4 /TiO 2
将1)中制备的棒状二氧化钛加入蒸馏水中，进行超声分散处理，再加入硝酸银，然后滴加少量氨水搅拌均匀后，最后加入Na2HPO4·12H2O，继续充分搅拌2.5h后可得到纳米Ag3PO4/TiO2溶液；二氧化钛与硝酸银的摩尔比为1：(1～3)，硝酸银与Na2HPO4·12H2O的摩尔比为3:1；Add the rod-shaped titanium dioxide prepared in 1) into distilled water, carry out ultrasonic dispersion treatment, then add silver nitrate, then dropwise add a small amount of ammonia water and stir evenly, finally add Na 2 HPO 4 ·12H 2 O, and continue to fully stir for 2.5h to obtain Nano Ag 3 PO 4 /TiO 2 solution; the molar ratio of titanium dioxide to silver nitrate is 1:(1-3), and the molar ratio of silver nitrate to Na 2 HPO 4 ·12H 2 O is 3:1;
3)将2)制备的纳米Ag3PO4/TiO2溶液放入反应釜进行水热反应后，在100～160℃进行水热反应，水热反应的时间为2～4h后，进行过滤、洗涤、干燥(80～100℃)即可得到纳米Ag3PO4/TiO2颗粒。3) After the nano-Ag 3 PO 4 /TiO 2 solution prepared in 2) is put into the reaction kettle to carry out the hydrothermal reaction, the hydrothermal reaction is carried out at 100～160° C. After the hydrothermal reaction time is 2～4h, filtration, After washing and drying (80-100°C), nano-Ag 3 PO 4 /TiO 2 particles can be obtained.
为了使公众对本发明有彻底的了解，在以下本发明优选施例中详细说明具体的细节。In order to provide the public with a thorough understanding of the present invention, specific details are set forth in the following preferred embodiments of the present invention.
实施例1Example 1
(1)将0.25g市售二氧化钛P25颗粒超声分散于30mL 10mol/L NaOH溶液中，15min后将溶液置于聚四氟乙烯内衬的高压反应釜中，进行水热反应16h。待其自然冷却至室温静置后用蒸馏水和酒精洗至中性后，放入干燥箱，在80℃下干燥10h。将干燥好的样品加入到0.1 mol/L HCI中陈化6h，过滤后洗涤至中性，在干燥箱中80℃干燥10h后于马弗炉450℃进行煅烧6h，制成棒状二氧化钛颗粒。(1) ultrasonically disperse 0.25 g of commercially available titanium dioxide P25 particles in 30 mL of 10 mol/L NaOH solution, and after 15 min, place the solution in a polytetrafluoroethylene-lined autoclave for hydrothermal reaction for 16 h. After it was naturally cooled to room temperature, it was washed with distilled water and alcohol until it became neutral, and then it was placed in a drying oven and dried at 80 °C for 10 hours. The dried samples were added to 0.1 mol/L HCI for 6 h, filtered and washed to neutrality, dried in a drying oven at 80 °C for 10 h, and then calcined in a muffle furnace at 450 °C for 6 h to obtain rod-shaped titanium dioxide particles.
(2)将1)制备的72mg棒状二氧化钛超声分散于25mL蒸馏水中，再加入236mg硝酸银，3-4滴NH3·H2O搅拌30min，再加入161mg Na2HPO4·12H2O颗粒继续搅拌2.5小时即可得到纳米Ag3PO4/TiO2溶液。(2) ultrasonically disperse 72 mg of rod-shaped titanium dioxide prepared in 1) in 25 mL of distilled water, then add 236 mg of silver nitrate, stir 3-4 drops of NH 3 ·H 2 O for 30 minutes, and then add 161 mg of Na 2 HPO 4 ·12H 2 O particles to continue After stirring for 2.5 hours, the nano Ag 3 PO 4 /TiO 2 solution can be obtained.
(3)将(2)制备的纳米Ag3PO4/TiO2溶液放入反应釜140℃进行水热反应2h后，过滤后进行洗涤，并在80℃下干燥6h即可得到复合型纳米Ag3PO4/TiO2材料。(3) Put the nano-Ag 3 PO 4 /TiO 2 solution prepared in (2) into a reactor at 140°C for hydrothermal reaction for 2h, filter, wash, and dry at 80°C for 6h to obtain composite nano-Ag 3 PO 4 /TiO 2 material.
分析：从图1(a)中可以看出，已经成功的制备出棒状TiO2，图1(b)可以看出粒径较小的纳米Ag3PO4颗粒已经成功的负载在棒状TiO2上面。Analysis: It can be seen from Figure 1(a) that rod-shaped TiO 2 has been successfully prepared, and Figure 1(b) shows that nano-sized Ag 3 PO 4 particles with smaller particle size have been successfully supported on rod-shaped TiO 2 .
图2为Ag3PO4、TiO2、Ag3PO4/TiO2的XRD谱图。由上面的图出峰位置可以判断TiO2主要以锐钛矿形式存在。在2θ＝35，39都出现了明显的衍射峰，根据Ag3PO4的标准卡片(JCPDS file no.06-0505)可以检索到为Ag3PO4的(110)，(200)，(210)，(211)，(320)，(321)晶面。说明Ag3PO4纳米颗粒已经成功的负载到了棒状TiO2。FIG. 2 is the XRD patterns of Ag 3 PO 4 , TiO 2 and Ag 3 PO 4 /TiO 2 . From the peak positions in the above figure, it can be judged that TiO2 mainly exists in the form of anatase. There are obvious diffraction peaks at 2θ=35 and 39. According to the standard card of Ag3PO4 (JCPDS file no.06-0505 ), it can be retrieved as (110), (200), (210), ( 211), (320), (321) crystal planes. It shows that Ag 3 PO 4 nanoparticles have been successfully loaded into rod-shaped TiO 2 .
从图3可以看出，制备的Ag3PO4/TiO2复合催化剂催化性能远远高于单一的TiO2，并且 Ag3PO4/TiO2对亚甲基蓝的光催化降解效果已经达到了90％以上。It can be seen from Figure 3 that the catalytic performance of the prepared Ag 3 PO 4 /TiO 2 composite catalyst is much higher than that of single TiO 2 , and the photocatalytic degradation effect of Ag 3 PO 4 /TiO 2 on methylene blue has reached more than 90%. .
实施例2Example 2
(1)将0.25g市售二氧化钛P25颗粒超声分散于30mL 10mol/L NaOH溶液中，15min后将溶液置于聚四氟乙烯内衬的高压反应釜中，进行水热反应16h。待其自然冷却至室温静置后用蒸馏水和酒精洗至中性后，放入干燥箱，在80℃下干燥10h。将干燥好的样品加入到0.1 mol/L HCI中陈化6h，过滤后洗涤至中性，在干燥箱中80℃干燥10h后于马弗炉450℃进行煅烧6h，制成棒状二氧化钛颗粒。(1) ultrasonically disperse 0.25 g of commercially available titanium dioxide P25 particles in 30 mL of 10 mol/L NaOH solution, and after 15 min, place the solution in a polytetrafluoroethylene-lined autoclave for hydrothermal reaction for 16 h. After it was naturally cooled to room temperature, it was washed with distilled water and alcohol until it became neutral, and then it was placed in a drying oven and dried at 80 °C for 10 hours. The dried samples were added to 0.1 mol/L HCI for 6 h, filtered and washed to neutrality, dried in a drying oven at 80 °C for 10 h, and then calcined in a muffle furnace at 450 °C for 6 h to obtain rod-shaped titanium dioxide particles.
(2)将(1)制备的108mg棒状二氧化钛超声分散于25mL蒸馏水中，再加入236mg硝酸银，3-4滴NH3·H2O搅拌30min，再加入161mg Na2HPO4·12H2O颗粒继续搅拌2.5小时即可得到纳米Ag3PO4/TiO2溶液。(2) 108 mg of rod-shaped titanium dioxide prepared in (1) was ultrasonically dispersed in 25 mL of distilled water, 236 mg of silver nitrate was added, 3-4 drops of NH 3 ·H 2 O were stirred for 30 min, and 161 mg of Na 2 HPO 4 ·12H 2 O particles were added Continue stirring for 2.5 hours to obtain nano-Ag 3 PO 4 /TiO 2 solution.
(3)将(2)制备的纳米Ag3PO4/TiO2溶液放入反应釜100℃进行水热反应3h后，过滤后进行洗涤，并在80℃下干燥6h即可得到复合型纳米Ag3PO4/TiO2材料。(3) Put the nano-Ag 3 PO 4 /TiO 2 solution prepared in (2) into the reactor at 100°C for hydrothermal reaction for 3h, filter, wash, and dry at 80°C for 6h to obtain composite nano-Ag 3 PO 4 /TiO 2 material.
实施例3Example 3
(1)将0.25g市售二氧化钛P25颗粒超声分散于30mL 10mol/L NaOH溶液中，15min后将溶液置于聚四氟乙烯内衬的高压反应釜中，进行水热反应16h。待其自然冷却至室温静置后用蒸馏水和酒精洗至中性后，放入干燥箱，在80℃下干燥10h。将干燥好的样品加入到0.1 mol/L HCI中陈化6h，过滤后洗涤至中性，在干燥箱中80℃干燥10h后于马弗炉450℃进行煅烧6h，制成棒状二氧化钛颗粒。(1) ultrasonically disperse 0.25 g of commercially available titanium dioxide P25 particles in 30 mL of 10 mol/L NaOH solution, and after 15 min, place the solution in a polytetrafluoroethylene-lined autoclave for hydrothermal reaction for 16 h. After it was naturally cooled to room temperature, it was washed with distilled water and alcohol until it became neutral, and then it was placed in a drying oven and dried at 80 °C for 10 hours. The dried samples were added to 0.1 mol/L HCI for 6 h, filtered and washed to neutrality, dried in a drying oven at 80 °C for 10 h, and then calcined in a muffle furnace at 450 °C for 6 h to obtain rod-shaped titanium dioxide particles.
(2)将(1)制备的36mg棒状二氧化钛超声分散于25mL蒸馏水中，再加入236mg硝酸银，3-4滴NH3·H2O搅拌30min，再加入161mg Na2HPO4·12H2O颗粒继续搅拌2.5小时即可得到纳米Ag3PO4/TiO2溶液。(2) ultrasonically disperse 36 mg of rod-shaped titanium dioxide prepared in (1) in 25 mL of distilled water, add 236 mg of silver nitrate, stir 3-4 drops of NH 3 ·H 2 O for 30 min, and then add 161 mg of Na 2 HPO 4 ·12H 2 O particles Continue stirring for 2.5 hours to obtain nano-Ag 3 PO 4 /TiO 2 solution.
(3)将(2)制备的纳米Ag3PO4/TiO2溶液放入反应釜140℃进行水热反应3h后，过滤后进行洗涤，并在80℃下干燥6h即可得到复合型纳米Ag3PO4/TiO2材料。(3) Put the nano-Ag 3 PO 4 /TiO 2 solution prepared in (2) into the reactor at 140°C for hydrothermal reaction for 3h, filter, wash, and dry at 80°C for 6h to obtain composite nano-Ag 3 PO 4 /TiO 2 material.
实施例4Example 4
(1)将0.3g市售二氧化钛P25颗粒超声分散于30mL 10mol/L NaOH溶液中，15min后将溶液置于聚四氟乙烯内衬的高压反应釜中，进行水热反应16h。待其自然冷却至室温静置后用蒸馏水和酒精洗至中性后，放入干燥箱，在80℃下干燥10h。将干燥好的样品加入到0.1mol/L HCI中陈化6h，过滤后洗涤至中性，在干燥箱中80℃干燥10h后于马弗炉450℃进行煅烧6h，制成棒状二氧化钛颗粒。(1) 0.3g of commercially available titanium dioxide P25 particles were ultrasonically dispersed in 30mL of 10mol/L NaOH solution, and after 15min, the solution was placed in a polytetrafluoroethylene-lined autoclave for hydrothermal reaction for 16h. After it was naturally cooled to room temperature, it was washed with distilled water and alcohol until it became neutral, and then it was placed in a drying oven and dried at 80 °C for 10 hours. The dried samples were added to 0.1 mol/L HCI for 6 h, filtered and washed to neutrality, dried in a drying oven at 80 °C for 10 h, and then calcined in a muffle furnace at 450 °C for 6 h to obtain rod-shaped titanium dioxide particles.
(2)将(1)制备的36mg棒状二氧化钛超声分散于25mL蒸馏水中，再加入236mg硝酸银，3-4滴NH3·H2O搅拌30min，再加入161mg Na2HPO4·12H2O颗粒继续搅拌2.5小时即可得到纳米Ag3PO4/TiO2溶液。(2) ultrasonically disperse 36 mg of rod-shaped titanium dioxide prepared in (1) in 25 mL of distilled water, add 236 mg of silver nitrate, stir 3-4 drops of NH 3 ·H 2 O for 30 min, and then add 161 mg of Na 2 HPO 4 ·12H 2 O particles Continue stirring for 2.5 hours to obtain nano-Ag 3 PO 4 /TiO 2 solution.
(3)将(2)制备的纳米Ag3PO4/TiO2溶液放入反应釜120℃进行水热反应2h后，过滤后进行洗涤，并在80℃下干燥6h即可得到复合型纳米Ag3PO4/TiO2材料。(3) Put the nano-Ag 3 PO 4 /TiO 2 solution prepared in (2) into the reactor at 120°C for hydrothermal reaction for 2h, filter, wash, and dry at 80°C for 6h to obtain composite nano-Ag 3 PO 4 /TiO 2 material.
实施例5Example 5
(1)将0.2g市售二氧化钛P25颗粒超声分散于30mL 2mol/L NaOH溶液中，15min后将溶液置于聚四氟乙烯内衬的高压反应釜中，进行水热反应14h。待其自然冷却至室温静置后用蒸馏水和酒精洗至中性后，放入干燥箱，在85℃下干燥10h。将干燥好的样品加入到0.1mol/LHCI中陈化5h，过滤后洗涤至中性，在干燥箱中85℃干燥8h后于马弗炉400℃进行煅烧5h，制成棒状二氧化钛颗粒。(1) 0.2g of commercially available titanium dioxide P25 particles were ultrasonically dispersed in 30mL of 2mol/L NaOH solution, and after 15min, the solution was placed in a polytetrafluoroethylene-lined autoclave for hydrothermal reaction for 14h. After it was naturally cooled to room temperature, it was washed with distilled water and alcohol until it became neutral, and then it was put into a drying oven and dried at 85 °C for 10 hours. The dried samples were added to 0.1 mol/L HCl for 5 h, filtered and washed to neutrality, dried in a drying oven at 85 °C for 8 h, and then calcined in a muffle furnace at 400 °C for 5 h to obtain rod-shaped titanium dioxide particles.
(2)将(1)制备的72mg棒状二氧化钛超声分散于25mL蒸馏水中，再加入236mg硝酸银，3-4滴NH3·H2O搅拌30min，再加入161mg Na2HPO4·12H2O颗粒继续搅拌2小时即可得到纳米Ag3PO4/TiO2溶液。(2) ultrasonically disperse 72 mg of rod-shaped titanium dioxide prepared in (1) in 25 mL of distilled water, add 236 mg of silver nitrate, 3-4 drops of NH 3 ·H 2 O, stir for 30 min, and then add 161 mg of Na 2 HPO 4 ·12H 2 O particles Continue to stir for 2 hours to obtain nano Ag 3 PO 4 /TiO 2 solution.
(3)将(2)制备的纳米Ag3PO4/TiO2溶液放入反应釜140℃进行水热反应3h后，过滤后进行洗涤，并在100℃下干燥7h即可得到复合型纳米Ag3PO4/TiO2材料。(3) Put the nano-Ag 3 PO 4 /TiO 2 solution prepared in (2) into the reactor at 140°C for hydrothermal reaction for 3h, filter, wash, and dry at 100°C for 7h to obtain composite nano-Ag 3 PO 4 /TiO 2 material.
实施例6Example 6
(1)将0.3g市售二氧化钛P25颗粒超声分散于30mL 8mol/L NaOH溶液中，15min后将溶液置于聚四氟乙烯内衬的高压反应釜中，进行水热反应16h。待其自然冷却至室温静置后用蒸馏水和酒精洗至中性后，放入干燥箱，在80℃下干燥10h。将干燥好的样品加入到0.1mol/LHCI中陈化6h，过滤后洗涤至中性，在干燥箱中80℃干燥10h后于马弗炉450℃进行煅烧6h，制成棒状二氧化钛颗粒。(1) ultrasonically disperse 0.3 g of commercially available titanium dioxide P25 particles in 30 mL of 8 mol/L NaOH solution, and after 15 min, place the solution in a polytetrafluoroethylene-lined autoclave for hydrothermal reaction for 16 h. After it was naturally cooled to room temperature, it was washed with distilled water and alcohol until it became neutral, and then it was placed in a drying oven and dried at 80 °C for 10 hours. The dried samples were added to 0.1 mol/L HCl for 6 h, filtered and washed to neutrality, dried in a drying oven at 80 °C for 10 h, and then calcined in a muffle furnace at 450 °C for 6 h to obtain rod-shaped titanium dioxide particles.
(2)将(1)制备的36mg棒状二氧化钛超声分散于25mL蒸馏水中，再加入236mg硝酸银，3-4滴NH3·H2O搅拌30min，再加入161mg Na2HPO4·12H2O颗粒继续搅拌2.5小时即可得到纳米Ag3PO4/TiO2溶液。(2) ultrasonically disperse 36 mg of rod-shaped titanium dioxide prepared in (1) in 25 mL of distilled water, add 236 mg of silver nitrate, stir 3-4 drops of NH 3 ·H 2 O for 30 min, and then add 161 mg of Na 2 HPO 4 ·12H 2 O particles Continue stirring for 2.5 hours to obtain nano-Ag 3 PO 4 /TiO 2 solution.
(3)将(2)制备的纳米Ag3PO4/TiO2溶液放入反应釜150℃进行水热反应3h后，过滤后进行洗涤，并在80℃下干燥6h即可得到复合型纳米Ag3PO4/TiO2材料。(3) Put the nano-Ag 3 PO 4 /TiO 2 solution prepared in (2) into the reactor at 150°C for hydrothermal reaction for 3h, filter, wash, and dry at 80°C for 6h to obtain composite nano-Ag 3 PO 4 /TiO 2 material.
实施例7Example 7
(1)将0.3g市售二氧化钛P25颗粒超声分散于30mL 6mol/L NaOH溶液中，15min后将溶液置于聚四氟乙烯内衬的高压反应釜中，进行水热反应16h。待其自然冷却至室温静置后用蒸馏水和酒精洗至中性后，放入干燥箱，在90℃下干燥11h。将干燥好的样品加入到0.1mol/L HCI中陈化7h，过滤后洗涤至中性，在干燥箱中90℃干燥7h后于马弗炉430℃进行煅烧7h，制成棒状二氧化钛颗粒。(1) ultrasonically disperse 0.3 g of commercially available titanium dioxide P25 particles in 30 mL of 6 mol/L NaOH solution, and after 15 min, place the solution in a polytetrafluoroethylene-lined autoclave for hydrothermal reaction for 16 h. After it was naturally cooled to room temperature, it was washed with distilled water and alcohol until it became neutral, and then it was placed in a drying oven and dried at 90 °C for 11 hours. The dried samples were added to 0.1 mol/L HCI for 7 h, filtered and washed to neutrality, dried in a drying oven at 90 °C for 7 h, and then calcined in a muffle furnace at 430 °C for 7 h to obtain rod-shaped titanium dioxide particles.
(2)将(1)制备的72mg棒状二氧化钛超声分散于25mL蒸馏水中，再加入236mg硝酸银，3-4滴NH3·H2O搅拌30min，再加入161mg Na2HPO4·12H2O颗粒继续搅拌3小时即可得到纳米Ag3PO4/TiO2溶液。(2) ultrasonically disperse 72 mg of rod-shaped titanium dioxide prepared in (1) in 25 mL of distilled water, add 236 mg of silver nitrate, 3-4 drops of NH 3 ·H 2 O, stir for 30 min, and then add 161 mg of Na 2 HPO 4 ·12H 2 O particles Continue stirring for 3 hours to obtain nano Ag 3 PO 4 /TiO 2 solution.
(3)将(2)制备的纳米Ag3PO4/TiO2溶液放入反应釜160℃进行水热反应4h后，过滤后进行洗涤，并在90℃下干燥6.5h即可得到复合型纳米Ag3PO4/TiO2材料。(3) Put the nano-Ag 3 PO 4 /TiO 2 solution prepared in (2) into the reactor at 160°C for hydrothermal reaction for 4h, filter, wash, and dry at 90°C for 6.5h to obtain composite nanometers. Ag 3 PO 4 /TiO 2 material.
以下分别针对步骤(2)中加入的氨水替换成聚乙二醇或水，进行对比试验：The following are respectively replaced with polyethylene glycol or water for the ammoniacal liquor added in step (2), and a comparative test is carried out:
对比例1Comparative Example 1
(1)将0.25g市售二氧化钛P25颗粒超声分散于30mL 10mol/L NaOH溶液中，15min后将溶液置于聚四氟乙烯内衬的高压反应釜中，进行水热反应16h。待其自然冷却至室温静置后用蒸馏水和酒精洗至中性后，放入干燥箱，在80℃下干燥10h。将干燥好的样品加入到0.1 mol/LHCI中陈化6h，过滤后洗涤至中性，在干燥箱中80℃干燥10h后于马弗炉450℃进行煅烧6h，制成棒状二氧化钛颗粒。(1) ultrasonically disperse 0.25 g of commercially available titanium dioxide P25 particles in 30 mL of 10 mol/L NaOH solution, and after 15 min, place the solution in a polytetrafluoroethylene-lined autoclave for hydrothermal reaction for 16 h. After it was naturally cooled to room temperature, it was washed with distilled water and alcohol until it became neutral, and then it was placed in a drying oven and dried at 80 °C for 10 hours. The dried samples were added to 0.1 mol/L HCl for 6 h, filtered and washed to neutrality, dried in a drying oven at 80 °C for 10 h, and then calcined in a muffle furnace at 450 °C for 6 h to obtain rod-shaped titanium dioxide particles.
(2)将1)制备的108mg棒状二氧化钛超声分散于25mL蒸馏水中，再加入236mg硝酸银，3-4滴聚乙二醇搅拌30min，再加入161mg Na2HPO4·12H2O颗粒继续搅拌2.5小时即可得到纳米Ag3PO4/TiO2溶液。(2) ultrasonically disperse 108 mg of rod-shaped titanium dioxide prepared in 1) in 25 mL of distilled water, then add 236 mg of silver nitrate, stir 3-4 drops of polyethylene glycol for 30 min, and then add 161 mg of Na 2 HPO 4 ·12H 2 O particles and continue to stir for 2.5 Within hours, nano-Ag 3 PO 4 /TiO 2 solution can be obtained.
(3)将(2)制备的纳米Ag3PO4/TiO2溶液放入反应釜120℃进行水热反应3h后，进行洗涤、过滤、并在80℃下干燥8h即可得到复合型纳米Ag3PO4/TiO2材料。(3) Put the nano-Ag 3 PO 4 /TiO 2 solution prepared in (2) into the reactor at 120°C for hydrothermal reaction for 3h, wash, filter, and dry at 80°C for 8h to obtain composite nano-Ag 3 PO 4 /TiO 2 material.
对比例2Comparative Example 2
(1)将0.25g市售二氧化钛P25颗粒超声分散于30mL 10mol/L NaOH溶液中，15min后将溶液置于聚四氟乙烯内衬的高压反应釜中，进行水热反应16h。待其自然冷却至室温静置后用蒸馏水和酒精洗至中性后，放入干燥箱，在80℃下干燥10h。将干燥好的样品加入到0.1 mol/LHCI中陈化6h，过滤后洗涤至中性，在干燥箱中80℃干燥10h后于马弗炉450℃进行煅烧6h，制成棒状二氧化钛颗粒。(1) ultrasonically disperse 0.25 g of commercially available titanium dioxide P25 particles in 30 mL of 10 mol/L NaOH solution, and after 15 min, place the solution in a polytetrafluoroethylene-lined autoclave for hydrothermal reaction for 16 h. After it was naturally cooled to room temperature, it was washed with distilled water and alcohol until it became neutral, and then it was placed in a drying oven and dried at 80 °C for 10 hours. The dried samples were added to 0.1 mol/L HCl for 6 h, filtered and washed to neutrality, dried in a drying oven at 80 °C for 10 h, and then calcined in a muffle furnace at 450 °C for 6 h to obtain rod-shaped titanium dioxide particles.
(2)将1)制备的36mg棒状二氧化钛超声分散于25mL蒸馏水中，再加入236mg硝酸银，3-4滴水搅拌30min，再加入161mg Na2HPO4·12H2O颗粒继续搅拌2.5小时即可得到纳米Ag3PO4/TiO2溶液。(2) ultrasonically disperse 36 mg of rod-shaped titanium dioxide prepared in 1) in 25 mL of distilled water, add 236 mg of silver nitrate, stir with 3-4 drops of water for 30 min, and then add 161 mg of Na 2 HPO 4 ·12H 2 O particles and continue to stir for 2.5 hours to obtain Nano Ag 3 PO 4 /TiO 2 solution.
(3)将(2)制备的纳米Ag3PO4/TiO2溶液放入反应釜140℃进行水热反应4h后，进行洗涤、过滤、并在80℃下干燥8h即可得到复合型纳米Ag3PO4/TiO2材料。(3) Put the nano-Ag 3 PO 4 /TiO 2 solution prepared in (2) into the reactor at 140°C for hydrothermal reaction for 4h, wash, filter, and dry at 80°C for 8h to obtain composite nano-Ag 3 PO 4 /TiO 2 material.
(二)应用(2) Application
所制备的纳米Ag3PO4/TiO2催化剂，经测试其在可见光下具有优异的光催化降解性能。The prepared nano-Ag 3 PO 4 /TiO 2 catalyst has excellent photocatalytic degradation performance under visible light.
对负载纳米Ag3PO4的棒状纳米TiO2材料的光催化性能采取降解亚甲基蓝的方法进行了测试，分别将实施例1、对比例1和对比例2制备的纳米Ag3PO4/TiO2复合材料放入50mL浓度10mg/L的亚甲基蓝溶液中，先在暗室下反应30min后，再在可见光灯下照射1h后分离测其吸光度，计算亚甲基蓝的降解率可知，实施例1降解达到90％以上，对比例1降解达到50％以上，对比例2降解达60％以上。由此可以见，实施例1制备的纳米Ag3PO4/TiO2催化剂在可见光下对亚甲基蓝具有较高的催化降解能力。The photocatalytic performance of the rod-shaped nano-TiO 2 material loaded with nano-Ag 3 PO 4 was tested by the method of degrading methylene blue. The nano-Ag 3 PO 4 /TiO 2 prepared in Example 1, Comparative Example 1 and Comparative Example 2 were composited The material was put into 50 mL of methylene blue solution with a concentration of 10 mg/L, first reacted in a dark room for 30 min, then irradiated under a visible light lamp for 1 h, and then separated and measured for its absorbance, and the degradation rate of methylene blue was calculated. The degradation of Comparative Example 1 reached more than 50%, and the degradation of Comparative Example 2 reached more than 60%. It can be seen that the nano-Ag 3 PO 4 /TiO 2 catalyst prepared in Example 1 has a high catalytic degradation ability to methylene blue under visible light.
以上，仅为本发明的较佳实施例，并非仅限于本发明的实施范围，凡依本发明范围的内容所做的等效变化和修饰，都应为本发明的技术范畴。The above are only preferred embodiments of the present invention, and are not limited to the scope of implementation of the present invention. All equivalent changes and modifications made according to the content of the scope of the present invention shall fall within the technical scope of the present invention.
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