CN101816943B - High-efficiency nano silver/silver bromide sunshine photocatalytic material and preparation method thereof - Google Patents
High-efficiency nano silver/silver bromide sunshine photocatalytic material and preparation method thereof Download PDFInfo
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- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 title claims abstract description 94
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 17
- 235000019253 formic acid Nutrition 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- -1 softex kw Chemical compound 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
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- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000001954 sterilising effect Effects 0.000 abstract description 2
- 230000003247 decreasing effect Effects 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 18
- 239000004332 silver Substances 0.000 description 13
- 229910052709 silver Inorganic materials 0.000 description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 7
- 101710134784 Agnoprotein Proteins 0.000 description 6
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- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
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- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
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- 238000006722 reduction reaction Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
技术领域：Technical field:
本发明属于太阳光光催化材料及其制备方法，特别属于净化水中污染物和杀菌的纳米银/溴化银太阳光光催化材料及其制备方法。The invention belongs to solar photocatalytic materials and a preparation method thereof, in particular to a nano-silver/silver bromide solar photocatalytic material for purifying water pollutants and sterilizing bacteria and a preparation method thereof.
技术背景：technical background:
人们正面临着水资源短缺、污染严重的挑战。经调查，仅自来水中的化学污染物就达数千种之多，直接威胁着人类的健康。在世界范围内的能源危机的背景下，为寻求有效低耗的净化途径，太阳能因其来源丰富且绿色清洁引起科学家们的广泛关注。太阳能对人类可以说是取之不尽用之不竭的能源，一年到达地球的总能量约是全世界现在一年消耗能量的一万倍。但是遗憾的是，太阳能的利用率极低，这使太阳能的利用得到极大地限制，同时，像光解水制氢气，光降解空气及水中的污染物等诱人的技术领域很多仍只能停留在低水平层次上。因此，制备能高效地利用太阳光的光催化材料成了解决问题的关键，近年来也得到了许多化学家的关注和研究。People are facing challenges of water shortage and serious pollution. According to investigations, there are thousands of chemical pollutants in tap water alone, directly threatening human health. In the context of the worldwide energy crisis, in order to seek effective and low-consumption purification methods, solar energy has attracted widespread attention of scientists because of its abundant sources and green cleanliness. Solar energy can be said to be an inexhaustible source of energy for human beings. The total energy that reaches the earth in a year is about 10,000 times that of the current annual energy consumption in the world. But unfortunately, the utilization rate of solar energy is extremely low, which greatly limits the utilization of solar energy. At the same time, many attractive technical fields such as photolysis of water to produce hydrogen, photodegradation of pollutants in air and water, etc. can only stay at a low level. Therefore, the preparation of photocatalytic materials that can efficiently utilize sunlight has become the key to solving the problem, and has also attracted the attention and research of many chemists in recent years.
当前，研究最多的光催化材料是二氧化钛，其中锐钛矿和金红石结构是常用的光催化材料，市售的主要为P25型。当前用于解释二氧化钛的光催化反应原理的理论为半导体的能带理论：当用能量等于或大于禁带宽度(Eg)的光照射半导体时，半导体价带上的电子可被激发跃迁到导带，同时在价带产生相应的空穴，这就在半导体内部生成电子(e-)-空穴(h+)对，在电场的作用下，电子(e-)-空穴(h+)对发生分离，迁移到粒子表面，与吸附在催化剂粒子表面的物质发生还原或者氧化反应，从而实现光解水或污染物的降解。At present, the most studied photocatalytic material is titanium dioxide, among which anatase and rutile structures are commonly used photocatalytic materials, and the commercially available one is mainly P25 type. The theory currently used to explain the photocatalytic reaction principle of titanium dioxide is the energy band theory of semiconductors: when the semiconductor is irradiated with light with energy equal to or greater than the forbidden band width (Eg), electrons on the valence band of the semiconductor can be excited to transition to the conduction band , and corresponding holes are generated in the valence band, which generates electron (e - )-hole (h + ) pairs inside the semiconductor. Under the action of the electric field, the electron (e - )-hole (h + ) pair Separation occurs, migrates to the surface of the particle, and undergoes a reduction or oxidation reaction with the substance adsorbed on the surface of the catalyst particle, thereby realizing the photolysis of water or the degradation of pollutants.
但是，锐钛矿和金红石结构的二氧化钛的带隙宽度分别为3.2eV和3.0eV，只能利用仅占太阳光4％的紫外光，而占太阳光中43％的丰富的可见光资源却无用武之地。掺杂的二氧化钛的改性光催化材料能有效地将吸收范围扩展至可见光区域，但阳离子的改性显著降低光量子的转化效率，或用于敏化的染料分子会在使用过程中逐步降解而失活。因此，二氧化钛的光催化性能只能是低水平的。However, titanium dioxide with anatase and rutile structures has band gap widths of 3.2eV and 3.0eV, respectively, and can only use ultraviolet light, which accounts for only 4% of sunlight, while the abundant visible light resources, which account for 43% of sunlight, are useless. land. The modified photocatalytic material doped with titanium dioxide can effectively extend the absorption range to the visible light region, but the modification of cations significantly reduces the conversion efficiency of photons, or the dye molecules used for sensitization will gradually degrade during use and lose live. Therefore, the photocatalytic performance of titanium dioxide can only be at a low level.
鉴于二氧化钛的上述缺点，对光十分敏感的卤化银引起了很多科研工作者的关注。但是，卤化银只有在紫外波段有强吸收，在可见光区域基本无吸收，且卤化银不稳定，易分解。后来研究发现，卤化银与单质银或三氧化钨等复合后，在可见光区域有强吸收，有希望取代二氧化钛成为新一代的高效光催化材料。In view of the above shortcomings of titanium dioxide, silver halide, which is very sensitive to light, has attracted the attention of many researchers. However, silver halide has strong absorption only in the ultraviolet band, basically no absorption in the visible light region, and silver halide is unstable and easy to decompose. Later research found that silver halide, after compounding with simple silver or tungsten trioxide, has strong absorption in the visible light region, and is expected to replace titanium dioxide as a new generation of high-efficiency photocatalytic materials.
最近，山东大学的王朋等制备了一些基于氯化银或溴化银的复合光催化材料，在专利申请号为200810016610.5，200810016611.X，200810016609.2，200810016612.4中作了介绍，在此统称“王氏催化剂”，其效果远好于当前普遍使用的光催化材料P25。但其制备方法和过程繁杂，且光催化实验是在300w氙灯(滤去400nm以下的光)下进行的，波段和强度都和太阳光有较大区别，不能真实地反映直接太阳光下的光催化效果。Recently, Wang Peng from Shandong University prepared some composite photocatalytic materials based on silver chloride or silver bromide, which were introduced in patent application numbers 200810016610.5, 200810016611. Catalyst", its effect is much better than the commonly used photocatalytic material P25. However, its preparation method and process are complicated, and the photocatalytic experiment is carried out under a 300w xenon lamp (filtering light below 400nm), the wavelength band and intensity are quite different from sunlight, and it cannot truly reflect the light under direct sunlight. catalytic effect.
发明内容：Invention content:
本发明针对P25光催化材料对太阳能的利用率低和“王氏催化剂”制备方法繁杂，且效果不十分理想等问题，提供一种更高效且制备工艺非常简便的直接太阳光光催化材料及其制备方法。The present invention aims at the problems that the P25 photocatalytic material has a low utilization rate of solar energy and the preparation method of "Wang's catalyst" is complicated, and the effect is not very ideal, and provides a more efficient direct sunlight photocatalytic material and its preparation process is very simple. Preparation.
本发明的纳米银/溴化银太阳光光催化材料，由纳米银和微米级的溴化银构成，化学式是Ag/AgBr，纳米银均匀地分布在溴化银表面，溴化银的粒径为1-3μm，纳米银的粒径为8-14nm。The nano-silver/silver bromide solar photocatalytic material of the present invention is composed of nano-silver and micron-sized silver bromide. The particle size of nano silver is 8-14nm.
本发明的纳米银/溴化银太阳光光催化材料的制备包括下列步骤：The preparation of nano silver/silver bromide sunlight photocatalytic material of the present invention comprises the following steps:
(1)制备微米级的溴化银：在硝酸银溶液中加入十六烷基三甲基溴化铵(CTAB)，搅拌5-10min后，依次加入甲酸和氨水，然后转移至高压釜中100-130℃反应2-8小时，分离、洗涤，即得到淡黄色的微米级的溴化银，硝酸银、十六烷基三甲基溴化铵、甲酸、氨水的摩尔比为1∶3-5∶750-1100∶80-110；(1) Preparation of micron-sized silver bromide: add cetyltrimethylammonium bromide (CTAB) to the silver nitrate solution, after stirring for 5-10min, add formic acid and ammonia water successively, then transfer to the autoclave for 100 React at -130°C for 2-8 hours, separate and wash to obtain light yellow micron-sized silver bromide. The molar ratio of silver nitrate, hexadecyltrimethylammonium bromide, formic acid and ammonia water is 1:3- 5:750-1100:80-110;
(2)制备纳米银/溴化银太阳光光催化材料：将步骤(1)中所得的淡黄色溴化银分散在足够量的水或无水乙醇中，暴露在室内光下1-5小时，淡黄色转化为灰色，溴化银部分分解成银单质，均匀地分布在溴化银表面，然后将产物分离干燥，即得纳米银/溴化银太阳光光催化材料。(2) Preparation of nano-silver/silver bromide sunlight photocatalytic material: disperse the light yellow silver bromide obtained in step (1) in a sufficient amount of water or absolute ethanol, and expose to indoor light for 1-5 hours , the light yellow turns into gray, and the silver bromide is partially decomposed into silver element, which is evenly distributed on the surface of the silver bromide, and then the product is separated and dried, and the nano-silver/silver bromide solar photocatalytic material is obtained.
所述的甲酸的重量浓度大于88％；The weight concentration of described formic acid is greater than 88%;
所述的氨水的重量浓度为25％-28％；The weight concentration of the ammonia water is 25%-28%;
所述的步骤(2)中，优选的暴光时间为2小时。In the described step (2), the preferred exposure time is 2 hours.
本发明的纳米银/溴化银太阳光光催化材料，由于表面纳米银的等离子体效应，表面只要有小部分纳米银产生溴化银就停止继续分解，在太阳光净化时是稳定的，同时在可见光区域有强吸收。The nano-silver/silver bromide sunlight photocatalytic material of the present invention, due to the plasma effect of nano-silver on the surface, as long as a small part of nano-silver produces silver bromide on the surface, it will stop decomposing, and it is stable during sunlight purification, and at the same time It has strong absorption in the visible region.
由于银的最好的金属导体，电子可以快速转移至催化剂表面，与吸附在催化剂表面的污染物发生反应，光催化速率和效率得到大大提高。Because silver is the best metal conductor, electrons can be quickly transferred to the surface of the catalyst to react with the pollutants adsorbed on the surface of the catalyst, and the photocatalytic rate and efficiency are greatly improved.
本发明与现有技术相比，所制备的纳米银/溴化银太阳光光催化材料可用于净化水中污染物及杀菌，其效果远好于当前普遍使用的光催化材料P25和最近开发的“王氏催化剂”，可以直接高效的利用太阳能，而且多次循环使用后光催化能力基本不下降。同时，本发明的纳米银/溴化银太阳光光催化材料的制备工艺非常简便，成本低廉，适合工业生产。Compared with the prior art, the prepared nano-silver/silver bromide sunlight photocatalytic material can be used to purify pollutants in water and sterilize bacteria, and its effect is much better than the currently commonly used photocatalytic material P25 and the recently developed " "Wang's Catalyst" can directly and efficiently utilize solar energy, and the photocatalytic ability will not decrease after repeated use. At the same time, the preparation process of the nano-silver/silver bromide sunlight photocatalytic material of the present invention is very simple and low in cost, and is suitable for industrial production.
附图说明：Description of drawings:
图1：实施例1所制的高效纳米银/溴化银太阳光光催化材料光催化能力示意图。Figure 1: A schematic diagram of the photocatalytic capacity of the high-efficiency nano-silver/silver bromide solar photocatalytic material prepared in Example 1.
图2：实施例2所制的高效纳米银/溴化银太阳光光催化材料光催化稳定性示意图。Figure 2: Schematic diagram of the photocatalytic stability of the high-efficiency nano-silver/silver bromide solar photocatalytic material prepared in Example 2.
在图2中，11为本发明所制的催化剂、12为市售的P25催化剂。In Fig. 2, 11 is the catalyst prepared by the present invention, and 12 is the commercially available P25 catalyst.
具体实施方式：Detailed ways:
下面是本发明非限定制备实施例，通过这些实施例对本发明作进一步描述。The following are non-limiting preparation examples of the present invention, through which the present invention will be further described.
实施例1：Example 1:
(1)制备微米级的溴化银：在10mL 0.015mol/L的硝酸银(AgNO3)溶液中加入0.2g的CTAB，搅拌5min后，依次加入4mL甲酸(重量浓度大于88％)；所述的甲酸的；和2.5mL氨水(重量浓度为25％-28％)，然后转移至高压釜中100℃反应2小时，最后将产物分离洗涤即得到淡黄色的微米级的溴化银(AgBr)。(1) Preparation of micron-sized silver bromide: add 0.2 g of CTAB to 10 mL of 0.015 mol/L silver nitrate (AgNO 3 ) solution, stir for 5 min, then add 4 mL of formic acid (weight concentration greater than 88%); and 2.5mL of ammonia water (weight concentration is 25%-28%), then transferred to an autoclave at 100 ° C for 2 hours, and finally the product was separated and washed to obtain light yellow micron-sized silver bromide (AgBr) .
(2)制备纳米银/溴化银太阳光光催化材料：将步骤(1)中所得的淡黄色溴化银分散在水中，暴露在室内光下1小时，淡黄色转化为灰色，溴化银部分分解成银单质，均匀地分布在溴化银表面。然后将产物分离干燥，即得纳米银/溴化银太阳光光催化材料。溴化银的粒径为1-3μm，纳米银的粒径为8-14nm。(2) Preparation of nano-silver/silver bromide sunlight photocatalytic material: disperse the light yellow silver bromide obtained in step (1) in water, expose it to indoor light for 1 hour, the light yellow turns into gray, and the silver bromide Partially decomposes into simple silver, which is evenly distributed on the surface of silver bromide. Then the product is separated and dried to obtain the nano-silver/silver bromide solar photocatalytic material. The particle size of the silver bromide is 1-3 μm, and the particle size of the nano-silver is 8-14 nm.
实施例2：Example 2:
(1)制备微米级的溴化银：在10mL 0.02mol/L的AgNO3溶液中加入0.25g的CTAB，搅拌8min后，依次加入5mL HCOOH和3mL NH3·H2O，然后转移至高压釜中120℃反应5小时，最后将产物分离洗涤即得到淡黄色的微米级的AgBr。(1) Preparation of micron-sized silver bromide: Add 0.25 g of CTAB to 10 mL of 0.02 mol/L AgNO 3 solution, stir for 8 minutes, then add 5 mL of HCOOH and 3 mL of NH 3 ·H 2 O in sequence, and then transfer to an autoclave React at 120°C for 5 hours, and finally separate and wash the product to obtain light yellow micron-sized AgBr.
(2)制备纳米银/溴化银太阳光光催化材料：将步骤(1)中所得的淡黄色溴化银分散在无水乙醇中，暴露在室内光下1小时，淡黄色转化为灰色，溴化银部分分解成银单质，均匀地分布在溴化银表面。然后将产物分离干燥，即得纳米银/溴化银太阳光光催化材料。溴化银的粒径为1-3μm，纳米银的粒径为8-14nm。(2) Preparation of nano-silver/silver bromide sunlight photocatalytic material: the light yellow silver bromide obtained in step (1) is dispersed in absolute ethanol, exposed to indoor light for 1 hour, the light yellow is converted into gray, Silver bromide is partially decomposed into silver element, which is evenly distributed on the surface of silver bromide. Then the product is separated and dried to obtain the nano-silver/silver bromide solar photocatalytic material. The particle size of the silver bromide is 1-3 μm, and the particle size of the nano-silver is 8-14 nm.
实施例3：Example 3:
(1)制备微米级的溴化银：在10mL 0.025mol/L的AgNO3溶液中加入0.3g的CTAB，搅拌10min后，依次加入6mL HCOOH和3.5mL NH3·H2O，然后转移至高压釜中130℃反应2小时，最后将产物分离洗涤即得到淡黄色的微米级的AgBr。(1) Preparation of micron-sized silver bromide: Add 0.3g of CTAB to 10mL of 0.025mol/L AgNO 3 solution, stir for 10min, then add 6mL of HCOOH and 3.5mL of NH 3 ·H 2 O, then transfer to high pressure React in the kettle at 130°C for 2 hours, and finally separate and wash the product to obtain light yellow micron-sized AgBr.
(2)制备纳米银/溴化银太阳光光催化材料：将步骤(1)中所得的淡黄色溴化银分散在水中，暴露在室内光下5小时，淡黄色转化为灰色，溴化银部分分解成银单质，均匀地分布在溴化银表面。然后将产物分离干燥，即得纳米银/溴化银太阳光光催化材料。溴化银的粒径为1-3μm，纳米银的粒径为8-14nm。(2) Preparation of nano-silver/silver bromide sunlight photocatalytic material: disperse the light yellow silver bromide obtained in step (1) in water, expose to indoor light for 5 hours, the light yellow is converted into gray, silver bromide Partially decomposes into simple silver, which is evenly distributed on the surface of silver bromide. Then the product is separated and dried to obtain the nano-silver/silver bromide solar photocatalytic material. The particle size of the silver bromide is 1-3 μm, and the particle size of the nano-silver is 8-14 nm.
实施例4：Example 4:
(1)制备微米级的溴化银：在10mL 0.02mol/L的AgNO3溶液中加入0.2g的CTAB，搅拌10min后，依次加入5mL HCOOH和3mL NH3·H2O，然后转移至高压釜中120℃反应5小时，最后将产物分离洗涤即得到淡黄色的微米级的AgBr。(1) Preparation of micron-sized silver bromide: Add 0.2 g of CTAB to 10 mL of 0.02 mol/L AgNO 3 solution, stir for 10 min, then add 5 mL of HCOOH and 3 mL of NH 3 ·H 2 O in turn, then transfer to an autoclave React at 120°C for 5 hours, and finally separate and wash the product to obtain light yellow micron-sized AgBr.
(2)制备纳米银/溴化银太阳光光催化材料：将步骤(1)中所得的淡黄色溴化银分散在无水乙醇中，暴露在室内光下1小时，淡黄色转化为灰色，溴化银部分分解成银单质，均匀地分布在溴化银表面。然后将产物分离干燥，即得纳米银/溴化银太阳光光催化材料。溴化银的粒径为1-3μm，纳米银的粒径为8-14nm。(2) Preparation of nano-silver/silver bromide sunlight photocatalytic material: the light yellow silver bromide obtained in step (1) is dispersed in absolute ethanol, exposed to indoor light for 1 hour, the light yellow is converted into gray, Silver bromide is partially decomposed into silver element, which is evenly distributed on the surface of silver bromide. Then the product is separated and dried to obtain the nano-silver/silver bromide solar photocatalytic material. The particle size of the silver bromide is 1-3 μm, and the particle size of the nano-silver is 8-14 nm.
实施例5：Example 5:
(1)制备微米级的溴化银：在10mL 0.02mol/L的AgNO3溶液中加入0.2g的CTAB，搅拌10min后，依次加入5mL HCOOH和3mL NH3·H2O，然后转移至高压釜中130℃反应8小时，最后将产物分离洗涤即得到淡黄色的微米级的AgBr。(1) Preparation of micron-sized silver bromide: Add 0.2 g of CTAB to 10 mL of 0.02 mol/L AgNO 3 solution, stir for 10 min, then add 5 mL of HCOOH and 3 mL of NH 3 ·H 2 O in turn, then transfer to an autoclave React at 130°C for 8 hours, and finally separate and wash the product to obtain light yellow micron-sized AgBr.
(2)制备纳米银/溴化银太阳光光催化材料：将步骤(1)中所得的淡黄色溴化银分散在水中，暴露在室内光下1小时，淡黄色转化为灰色，溴化银部分分解成银单质，均匀地分布在溴化银表面。然后将产物分离干燥，即得纳米银/溴化银太阳光光催化材料。溴化银的粒径为1-3μm，纳米银的粒径为8-14nm。(2) Preparation of nano-silver/silver bromide sunlight photocatalytic material: disperse the light yellow silver bromide obtained in step (1) in water, expose it to indoor light for 1 hour, the light yellow turns into gray, and the silver bromide Partially decomposes into simple silver, which is evenly distributed on the surface of silver bromide. Then the product is separated and dried to obtain the nano-silver/silver bromide solar photocatalytic material. The particle size of the silver bromide is 1-3 μm, and the particle size of the nano-silver is 8-14 nm.
实施例6：Embodiment 6:
(1)制备微米级的溴化银：在10mL 0.02mol/L的AgNO3溶液中加入0.2g的CTAB，搅拌10min后，依次加入5mL HCOOH和3mL NH3·H2O，然后转移至高压釜中100℃反应8小时，最后将产物分离洗涤即得到淡黄色的微米级的AgBr。(1) Preparation of micron-sized silver bromide: Add 0.2 g of CTAB to 10 mL of 0.02 mol/L AgNO 3 solution, stir for 10 min, then add 5 mL of HCOOH and 3 mL of NH 3 ·H 2 O in turn, then transfer to an autoclave React at 100°C for 8 hours, and finally separate and wash the product to obtain light yellow micron-sized AgBr.
(2)制备纳米银/溴化银太阳光光催化材料：将步骤(1)中所得的淡黄色溴化银分散在无水乙醇中，暴露在室内光下3小时，淡黄色转化为灰色，溴化银部分分解成银单质，均匀地分布在溴化银表面。然后将产物分离干燥，即得纳米银/溴化银太阳光光催化材料。溴化银的粒径为1-3μm，纳米银的粒径为8-14nm。(2) Preparation of nano-silver/silver bromide sunlight photocatalytic material: the light yellow silver bromide obtained in step (1) is dispersed in absolute ethanol, exposed to room light for 3 hours, the light yellow is transformed into gray, Silver bromide is partially decomposed into silver element, which is evenly distributed on the surface of silver bromide. Then the product is separated and dried to obtain the nano-silver/silver bromide solar photocatalytic material. The particle size of the silver bromide is 1-3 μm, and the particle size of the nano-silver is 8-14 nm.
本发明的纳米银/溴化银太阳光光催化材料光催化性能的评价方式：The method for evaluating the photocatalytic performance of the nano-silver/silver bromide sunlight photocatalytic material of the present invention:
(1)光催化能力：(1) Photocatalytic ability:
配制20mL反应液，其中甲基橙浓度为10mg/L，加入20mg本发明实施例1所制的的纳米银/溴化银太阳光光催化材料，分散后直接放在太阳光照下进行降解实验，对不同反应阶段离去催化剂后液体进行紫外—可见光谱跟踪。其结果如图1所示，1min即可降解86％，5min基本降解完全。Prepare 20mL reaction solution, wherein the concentration of methyl orange is 10mg/L, add 20mg of the nano-silver/silver bromide solar photocatalytic material prepared in Example 1 of the present invention, and directly place it under sunlight for degradation experiments after dispersion, Ultraviolet-visible spectrum tracking is carried out on the liquid after leaving the catalyst in different reaction stages. The result is shown in Figure 1, 86% of the degradation can be achieved in 1 minute, and the degradation is basically complete in 5 minutes.
(2)光催化稳定性：(2) Photocatalytic stability:
采用循环催化实验来评价：配制五份20mL反应液，其中甲基橙浓度均为10mg/L。在第一份反应液中加入20mg实施例2所制的纳米银/溴化银太阳光光催化材料，分散后直接放在太阳光照下进行降解实验，5min后对反应液进行紫外—可见光谱表征，分离出催化材料，用使用过的光催化材料分别对第二、三、四、五份反应液在相同条件下进行降解，依次用紫外—可见光谱进行表征。其结果如图2所示，经过5次循环使用，本发明的纳米银/溴化银太阳光光催化材料的催化能力基本不下降，均保持很高的光催化水平。Evaluation was carried out by cyclic catalytic experiment: five 20mL reaction solutions were prepared, in which the concentration of methyl orange was 10mg/L. Add 20mg of the nano-silver/silver bromide solar photocatalytic material prepared in Example 2 to the first reaction solution, and put it directly under sunlight for degradation experiments after dispersion, and perform ultraviolet-visible spectrum characterization on the reaction solution after 5 minutes , separate the catalytic material, use the used photocatalytic material to degrade the second, third, fourth, and fifth reaction solutions under the same conditions, and then use ultraviolet-visible spectroscopy to characterize. As a result, as shown in FIG. 2 , after 5 cycles of use, the catalytic ability of the nano-silver/silver bromide solar photocatalytic material of the present invention basically does not decrease, and both maintain a high photocatalytic level.
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