CN116408109A - Method for preparing photocatalyst by utilizing graphite purification waste liquid - Google Patents
Method for preparing photocatalyst by utilizing graphite purification waste liquid Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 35
- 239000010439 graphite Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000002699 waste material Substances 0.000 title claims abstract description 28
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 26
- 238000000746 purification Methods 0.000 title claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 32
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 28
- IPNGSXQUQIUWKO-UHFFFAOYSA-N bismuth;fluoro hypofluorite Chemical group [Bi].FOF IPNGSXQUQIUWKO-UHFFFAOYSA-N 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims 1
- 239000013078 crystal Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- -1 fluoride ions Chemical class 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J27/06—Halogens; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
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Abstract
本发明涉及提纯石墨废液合成光催化剂的制备方法，一种利用提纯石墨废液制备光催化剂的方法，其主要步骤是，将提纯石墨过程中废弃的含氢氟酸法废液静置、离心处理得到无固体物质的清液，将硝酸铋与清液混合，再用氢氧化钠溶液中和后得到得到光催化剂。本发明提供的合成光催化剂制备方法具有生产效率高、能耗低，充分利用提纯石墨废液降低提纯石墨产生废液的无害化处理成本，同时也降低了光催化剂的制备成本，利于大规模工业化生产。The invention relates to a method for preparing a photocatalyst from purified graphite waste liquid, a method for preparing a photocatalyst by using purified graphite waste liquid. Treat the clear liquid without solid matter, mix the bismuth nitrate with the clear liquid, and then neutralize it with sodium hydroxide solution to obtain the photocatalyst. The synthetic photocatalyst preparation method provided by the present invention has high production efficiency and low energy consumption, fully utilizes the purified graphite waste liquid to reduce the harmless treatment cost of the purified graphite waste liquid, and also reduces the preparation cost of the photocatalyst, which is beneficial to large-scale Industrial production.
Description
技术领域technical field
本发明涉及提纯石墨废液合成光催化剂。The invention relates to the synthesis of photocatalyst by purifying graphite waste liquid.
背景技术Background technique
近年来,利用半导体技术进行光催化法治理环境受到了广泛的重视。以工业原料制取二氧化钛、卤氧化铋等所需光催化剂已经被广泛研究。石墨中含有钾、钒、铬、钠、铁、钙、铝等硅酸盐杂质，对石墨的进一步提纯就是采取有效手段去除这部分杂质，目前国内外提纯石墨的方法主要有氢氟酸法、浮选法、碱酸法、氯化焙烧法，高温法等。氢氟酸法属于化学提纯法，氢氟酸法的原理是利用任何硅酸盐矿物都可以和氢氟酸反应生成能溶于水的盐和气体，通过过滤洗涤而得到高纯度石墨。例如中国专利CN109065884A中公开了酸洗法提纯电阻料人造石墨造孔负极材料的制法及材料，提纯石墨所用酸含有氢氟酸。中国专利CN107895657A中公开了一种使用球形微晶石墨材料的锂离子电容器的制备方法，所使用的酸溶液为含40％的氢氟酸溶液。中国专利CN105460923B中公开了一种高纯氟化石墨的连续制备方法，所使用的氢氟酸质量浓度为10～30％。氢氟酸法中使用的酸液在100-150℃下，液体中的F-离子能够游离并浸染在石墨鳞片中。此法主要步骤：1.将筛分好的物料和混合酸依次加入反应容器内，搅拌并加热，待反应结束后放料，将物料放入离心机内脱酸，再用大量的清水洗涤，最后用纯水洗涤、脱水、卸料。而如何解决提纯石墨过程的产生的氢氟酸成为制约企业提升环保水平和生产成本的关键因素。In recent years, the use of semiconductor technology for photocatalytic environmental governance has received extensive attention. The photocatalysts required to prepare titanium dioxide, bismuth oxyhalide, etc. from industrial raw materials have been extensively studied. Graphite contains silicate impurities such as potassium, vanadium, chromium, sodium, iron, calcium, aluminum, etc. The further purification of graphite is to take effective means to remove these impurities. At present, the methods for purifying graphite at home and abroad mainly include hydrofluoric acid method, Flotation method, alkali-acid method, chlorination roasting method, high temperature method, etc. The hydrofluoric acid method belongs to the chemical purification method. The principle of the hydrofluoric acid method is to use any silicate mineral to react with hydrofluoric acid to generate water-soluble salt and gas, and obtain high-purity graphite through filtration and washing. For example, Chinese patent CN109065884A discloses the preparation method and materials of the artificial graphite pore-forming negative electrode material purified by pickling method, and the acid used for the purification of graphite contains hydrofluoric acid. Chinese patent CN107895657A discloses a preparation method of a lithium ion capacitor using a spherical microcrystalline graphite material, and the acid solution used is a 40% hydrofluoric acid solution. Chinese patent CN105460923B discloses a continuous preparation method of high-purity fluorinated graphite, and the mass concentration of hydrofluoric acid used is 10-30%. When the acid liquid used in the hydrofluoric acid method is at 100-150°C, the F - ions in the liquid can be dissociated and impregnated in the graphite flakes. The main steps of this method: 1. Put the screened material and mixed acid into the reaction vessel in turn, stir and heat, discharge the material after the reaction is completed, put the material into the centrifuge for deacidification, and then wash with a large amount of water. Finally, wash with pure water, dehydrate and unload. How to solve the hydrofluoric acid produced in the graphite purification process has become a key factor that restricts enterprises from improving environmental protection and production costs.
本发明使用氢氟酸法提纯石墨所产生的废液制备氟氧化铋光催化剂，能够变废为宝，一方面降低石墨提纯企业的废液处理成本，另一方面也降低了氟氧化铋光催化剂的制备成本，本发明的制备方法完全符合目前提倡的绿色发展理念。The present invention prepares bismuth oxyfluoride photocatalyst by using the waste liquid produced by the purification of graphite by hydrofluoric acid method, which can turn waste into treasure, reduce the waste liquid treatment cost of graphite purification enterprises on the one hand, and reduce the cost of bismuth oxyfluoride photocatalyst on the other hand. preparation cost, the preparation method of the present invention fully complies with the concept of green development advocated at present.
发明内容Contents of the invention
本发明是要解决现有的石墨提纯方法存在的污染环境，能耗高，工艺复杂，成本较高的问题，提供一种利用石墨提纯废液制备光催化剂的方法。The invention aims to solve the problems of polluted environment, high energy consumption, complex process and high cost in the existing graphite purification method, and provides a method for preparing photocatalyst by using graphite purification waste liquid.
本发明一种利用石墨提纯废液制备光催化剂的方法，按以下步骤进行：A kind of method that utilizes graphite purification waste liquid of the present invention to prepare photocatalyst, carries out according to the following steps:
步骤一，将提纯石墨过程中废弃的含氢氟酸法废液静置一定时间后，取上层液体以一定速度离心处理后得到无固体物质的清液；Step 1, after the hydrofluoric acid-containing waste liquid discarded in the graphite purification process is left to stand for a certain period of time, the upper layer liquid is centrifuged at a certain speed to obtain a clear liquid without solid matter;
步骤二，将硝酸铋加入到步骤一中离心分离得到的清液中；In step 2, bismuth nitrate is added to the supernatant obtained by centrifugal separation in step 1;
步骤三，再用氢氧化钠溶液中和步骤二中得到的溶液，得到含有沉淀的悬浊液；In step 3, neutralize the solution obtained in step 2 with sodium hydroxide solution to obtain a suspension containing precipitate;
步骤四，将步骤三中得到的悬浊液加入到反应釜中，在一定温度下水热反应一段时间后，得到灰色沉淀，将其清洗、干燥后得到光催化剂。Step 4: Add the suspension obtained in Step 3 into the reaction kettle, and after hydrothermal reaction at a certain temperature for a period of time, a gray precipitate is obtained, which is washed and dried to obtain a photocatalyst.
优选地，步骤一中，所述静置时间为3～6小时，离心速度为6000～10000r/min，离心分离时间为3～5min。Preferably, in step 1, the standing time is 3-6 hours, the centrifugation speed is 6000-10000 r/min, and the centrifugation time is 3-5 minutes.
优选地，步骤二中，所述硝酸铋的的摩尔加入量为10-pH×V，其中V为步骤一中得到上层清液的体积，pH为步骤一中得到清液的酸碱度。Preferably, in step 2, the molar addition of the bismuth nitrate is 10 -pH ×V, where V is the volume of the supernatant obtained in step 1, and pH is the pH of the supernatant obtained in step 1.
优选地，步骤三中，所述氢氧化钠溶液的浓度为4～6摩尔/升，用氢氧化钠溶液调节步骤二中获得溶液的pH值至4～6。Preferably, in step three, the concentration of the sodium hydroxide solution is 4-6 mol/liter, and the pH value of the solution obtained in step two is adjusted to 4-6 with sodium hydroxide solution.
优选地，步骤四中，所述水热温度为160～180摄氏度，水热反应时间为6～18小时。Preferably, in step 4, the hydrothermal temperature is 160-180 degrees Celsius, and the hydrothermal reaction time is 6-18 hours.
本发明原理如下：Principle of the present invention is as follows:
利用提纯石墨废液中含有较高浓度的氟离子作为制备氟氧化铋的一种主要原料，再将硝酸铋加入到含有氟离子的废液中，通过加入氢氧化钠中和提纯石墨废液中的氢离子，而后逐步形成氟氧化铋前驱体物质，通过一定温度下的水热反应将前驱体转换为氟氧化铋。在形成氟氧化铋的过程中，由于提纯石墨中将石墨中的钒、铬、钠、铁等溶解在废液中，因此在用氢氧化钠中和的过程中，也会将上述离子沉淀出来，导致获得的沉淀为灰色。Utilize the fluoride ions in the purified graphite waste liquid with a higher concentration as a main raw material for preparing bismuth oxyfluoride, then add bismuth nitrate to the waste liquid containing fluorine ions, and neutralize the purified graphite waste liquid by adding sodium hydroxide hydrogen ions, and then gradually form the precursor of bismuth oxyfluoride, and convert the precursor into bismuth oxyfluoride through a hydrothermal reaction at a certain temperature. In the process of forming bismuth oxyfluoride, since the vanadium, chromium, sodium, iron, etc. in graphite are dissolved in the waste liquid in the purification of graphite, the above ions will also be precipitated in the process of neutralization with sodium hydroxide , resulting in the obtained precipitate being gray.
本发明的有益效果：Beneficial effects of the present invention:
1、本发明突破了传统光催化的主要制备方法，本发明采用了提纯石墨废液合成光催化剂，一方面降低石墨提纯企业的废液处理成本，另一方面也降低了氟氧化铋光催化剂的制备成本。1. The present invention breaks through the main preparation method of traditional photocatalysis. The present invention uses purified graphite waste liquid to synthesize photocatalyst. On the one hand, it reduces the waste liquid treatment cost of graphite purification enterprises, and on the other hand, it also reduces the cost of bismuth oxyfluoride photocatalyst. preparation cost.
2、本发明方法易于操作，能耗低，利于大规模工业化生产。2. The method of the present invention is easy to operate, has low energy consumption, and is beneficial to large-scale industrial production.
附图说明Description of drawings
图1为本发明实施例1中获得光催化剂的XRD图。FIG. 1 is an XRD pattern of the photocatalyst obtained in Example 1 of the present invention.
图2为本发明实施例1中获得光催化剂的SEM图。FIG. 2 is an SEM image of the photocatalyst obtained in Example 1 of the present invention.
具体实施方式Detailed ways
本发明技术方案不局限于以下所列举具体实施方式，还包括各具体实施方式间的任意组合。为验证本发明的有益效果进行以下实验。The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments. Carry out following experiment for verifying beneficial effect of the present invention.
实施例1Example 1
将提纯石墨过程中产生的含氢氟酸法废液静置5小时后，取上层液体以6000/min离心处理5min后得到无固体物质的500mL清液，pH值为1.3。After the hydrofluoric acid-containing waste liquid generated in the graphite purification process was left to stand for 5 hours, the upper layer liquid was centrifuged at 6000/min for 5 minutes to obtain 500 mL of clear liquid without solid matter, and the pH value was 1.3.
将硝酸铋加入到无固体物质的清液中，生成浑浊液，其中硝酸铋的的摩尔加入量为0.025摩尔，再用浓度为4摩尔/升的氢氧化钠溶液中和得到的浑浊液，调节到pH值为7。Bismuth nitrate is added in the clear liquid without solid matter, generates turbid liquid, wherein the molar addition of bismuth nitrate is 0.025 mole, and then with the concentration of 4 mol/liter of sodium hydroxide solution and the turbid liquid that obtains, adjust to a pH of 7.
将pH值为7的浑浊液加入到反应釜中，在160摄氏度下水热反应10小时后，得到灰色沉淀，将其清洗、干燥后得到光催化剂。The turbid liquid with a pH value of 7 was added into the reaction kettle, and after hydrothermal reaction at 160 degrees Celsius for 10 hours, a gray precipitate was obtained, which was washed and dried to obtain a photocatalyst.
实施例2Example 2
将提纯石墨过程中产生的含氢氟酸法废液静置5小时后，取上层液体以8000/min离心处理4min后得到无固体物质的500mL清液，pH值为1.3。After the hydrofluoric acid-containing waste liquid produced in the graphite purification process was left to stand for 5 hours, the upper layer liquid was centrifuged at 8000/min for 4 minutes to obtain 500 mL of clear liquid without solid matter, and the pH value was 1.3.
将硝酸铋加入到无固体物质的清液中，生成浑浊液，其中硝酸铋的的摩尔加入量为0.399摩尔，再用浓度为5摩尔/升的氢氧化钠溶液中和得到的浑浊液，调节到pH值为6。Bismuth nitrate is added in the clear liquid without solid matter, generates turbid liquid, and wherein the molar addition of bismuth nitrate is 0.399 mole, then use the sodium hydroxide solution that concentration is 5 mol/liter to neutralize the turbid liquid that obtains, adjust to a pH of 6.
将pH值为6的浑浊液加入到反应釜中，在180摄氏度下水热反应8小时后，得到灰色沉淀，将其清洗、干燥后得到光催化剂。The turbid solution with a pH value of 6 was added into the reactor, and after a hydrothermal reaction at 180 degrees Celsius for 8 hours, a gray precipitate was obtained, which was washed and dried to obtain a photocatalyst.
以上实施方式仅用于说明本发明，而非对本发明的限制。通过阅读本发明说明书而对本发明技术方案采取的任何等效的变换，只要不脱离本发明技术方案的精神和范围，均应涵盖在本发明的权利要求范围当中。The above embodiments are only used to illustrate the present invention, but not to limit the present invention. Any equivalent transformation of the technical solution of the present invention adopted by reading the description of the present invention, as long as it does not deviate from the spirit and scope of the technical solution of the present invention, shall be included in the claims of the present invention.
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