CN112570010A - 一种TiO2/Cu-ZSM-5分子筛光降解催化剂及降解有机染料废水的应用 - Google Patents
一种TiO2/Cu-ZSM-5分子筛光降解催化剂及降解有机染料废水的应用 Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 68
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 230000000593 degrading effect Effects 0.000 title claims abstract description 10
- 239000002351 wastewater Substances 0.000 title abstract description 8
- 238000001782 photodegradation Methods 0.000 claims abstract description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 23
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000010949 copper Substances 0.000 claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000005342 ion exchange Methods 0.000 claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 4
- 238000003980 solgel method Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical group OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 230000015556 catabolic process Effects 0.000 claims description 5
- 238000006731 degradation reaction Methods 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 24
- 235000019441 ethanol Nutrition 0.000 description 10
- 239000000975 dye Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000987 azo dye Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 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 3
- 229940012189 methyl orange Drugs 0.000 description 3
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000010919 dye waste Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 239000010985 leather Substances 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 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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- 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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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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Abstract
本发明中,本发明提出了一种TiO2/Cu‑ZSM‑5分子筛光降解催化剂及降解有机染料废水的应用,所述光降解催化剂是通过下述方法制备得到:将ZSM‑5分子筛进行铵离子交换,得到铵化分子筛;将铵化分子筛进行铜离子交换,得到铜基分子筛;再通过溶胶凝胶法将钛酸四丁酯在铜基分子筛表面进行水解,干燥,煅烧后,即得到所述光降解催化剂。本发明所述光降解催化剂具有更高效的光催化活性,具有在可见光照射下催化降解有机染料废水的性能。
Description
技术领域
本发明涉及催化剂技术领域,尤其涉及一种TiO2/Cu-ZSM-5分子筛光降解催化剂及降解有机染料废水的应用。
背景技术
偶氮染料是全球制革工业、印染工业中使用的最主要染料,占工业应用染料的50%以上,其化学稳定性高,难以降解,是目前主要的水环境污染源之一。虽然偶氮染料本身并无直接的致癌作用,但其中的一部分经人体内特定酶的作用下分解还原出一些致癌的芳香胺,对人体健康产生巨大威胁。
目前,已有人尝试用物理吸附法、混凝沉淀法、电化学法、高级氧化法、湿式过氧化氢氧化法、超声波氧化法、生物法等处理有机染料废水。光催化氧化技术以其低耗能、易操作,能使几乎所有有机污染物降解到CO2、H2O和其它无机物,不产生二次污染等优点,在水处理领域引起广泛关注。
在众多的光催化剂中,TiO2因其优异的光催化性能和成本相对低廉,成为当前研究光催化降解有机染料废水的主流材料。但是由于纳米TiO2的带隙较宽,只有在紫外线照射下,才能激发价带电子跃迁到导带,形成光生电子和空穴,因此,极大地限制了TiO2在环境工程领域的应用。
发明内容
基于背景技术存在的技术问题,本发明提出了一种TiO2/Cu-ZSM-5分子筛光降解催化剂及降解有机染料废水的应用,该光降解催化剂具有更高效的光催化活性,具有在可见光照射下催化降解有机染料废水的性能。
本发明提出的一种TiO2/Cu-ZSM-5分子筛光降解催化剂,所述光降解催化剂是通过下述方法制备得到:
将ZSM-5分子筛进行铵离子交换,得到铵化分子筛;将铵化分子筛进行铜离子交换,得到铜基分子筛;再通过溶胶凝胶法将钛酸四丁酯在铜基分子筛表面进行水解,干燥,煅烧后,即得到所述光降解催化剂。
优选地,所述铵离子交换具体包括:将ZSM-5分子筛加入到铵盐溶液中,80-100℃搅拌反应1-3h,过滤,水洗,干燥,即得到所述铵化分子筛。
优选地,所述铵盐为硝酸铵和/或氯化铵。
优选地,所述铜离子交换具体包括:将铵化分子筛加入到铜盐溶液中,室温下搅拌反应4-6h,过滤,水洗,干燥,得到铜基分子筛。
优选地,所述铜盐为硝酸铜、硫酸铜和/或醋酸铜;
优选地,所述铜盐溶液的浓度为0.05-0.5mol/L。
优选地,所述水解具体包括:将钛酸四丁酯与无水乙醇混合后,加入铜基分子筛搅拌均匀,再加入酸性添加剂调节pH值为2-5,搅拌,陈化,完成水解。
优选地,所述钛酸四丁酯和铜基分子筛的质量比为2-5:1。
优选地,所述干燥温度为100-120℃,时间为12-16h。
优选地,所述煅烧温度为500-600℃,时间为2-4h。
本发明还提出一种上述光降解催化剂在降解有机染料废水中的应用。
本发明所述光降解催化剂,通过将分子筛预先与铵盐进行离子交换,如此在分子筛阳离子位上负载NH4+,以得到铵化分子筛;此后将铵化分子筛与铜盐进行离子交换,使得Cu2+定向交换到分子筛上NH4+交换位上,有利于活性金属Cu的均匀分布,以此得到了铜基分子筛;最后通过溶胶-凝胶法,使得钛酸四丁酯优先在Cu2+交换位(酸性位)上进行水解,再经过煅烧,即可以将生成的TiO2定向固载在分子筛上,一方面,有利于TiO2的均匀分布和纳米级的形貌控制,另一方面使得TiO2和Cu2+形成有效掺杂,从而使得TiO2激发波长红移至可见光区,最终使所述光降解催化剂的催化活性在TiO2基础上有了显著的提升,实现在可见光照射下有机染料废水的高效降解。
具体实施方式
下面,通过具体实施例对本发明的技术方案进行详细说明,但是应该明确提出这些实施例用于举例说明,但是不解释为限制本发明的范围。
实施例1
一种TiO2/Cu-ZSM-5分子筛光降解催化剂,其制备方法包括:
(1)、将5gZSM-5分子筛加入到50mL硝酸铵溶液(1.5mol/L)中,90℃下搅拌反应2h,过滤并用去离子水洗涤,100℃下干燥10h,得到铵化分子筛;
(2)、将5g铵化分子筛加入到50mL硝酸铜溶液(0.2mol/L)中,常温下搅拌反应5h,过滤并用去离子水洗涤,100℃下干燥10h,得到铜基分子筛;
(3)、将10mL钛酸四丁酯加入到30mL无水乙醇中搅拌混匀得到钛酸四丁酯乙醇溶液;在搅拌条件下将3g铜基分子筛加入到所述钛酸四丁酯乙醇溶液中,搅拌0.5h后,在频率为45KHz条件下超声处理1h;再在搅拌条件下逐滴加入硝酸溶液(0.5mol/L)搅拌0.5h,调节pH值为3,继续搅拌1h后密闭陈化20h,在110℃下干燥14h,再在550℃下煅烧3h,即得到所述TiO2/Cu-ZSM-5分子筛光降解催化剂。
实施例2
一种TiO2/Cu-ZSM-5分子筛光降解催化剂,其制备方法包括:
(1)、将5gZSM-5分子筛加入到50mL硝酸铵溶液(1.5mol/L)中,80℃下搅拌反应3h,过滤并用去离子水洗涤,100℃下干燥10h,得到铵化分子筛;
(2)、将5g铵化分子筛加入到50mL硝酸铜溶液(0.05mol/L)中,常温下搅拌反应6h,过滤并用去离子水洗涤,100℃下干燥10h,得到铜基分子筛;
(3)、将10mL钛酸四丁酯加入到30mL无水乙醇中搅拌混匀得到钛酸四丁酯乙醇溶液;在搅拌条件下将5g铜基分子筛加入到所述钛酸四丁酯乙醇溶液中,搅拌0.5h后,在频率为45KHz条件下超声处理1h;再在搅拌条件下逐滴加入硝酸溶液(0.5mol/L)搅拌0.5h,调节pH值为3,继续搅拌1h后密闭陈化20h,在100℃下干燥16h,再在600℃下煅烧2h,即得到所述TiO2/Cu-ZSM-5分子筛光降解催化剂。
实施例3
一种TiO2/Cu-ZSM-5分子筛光降解催化剂,其制备方法包括:
(1)、将5gZSM-5分子筛加入到50mL硝酸铵溶液(1.5mol/L)中,100℃下搅拌反应1h,过滤并用去离子水洗涤,100℃下干燥10h,得到铵化分子筛;
(2)、将5g铵化分子筛加入到50mL硝酸铜溶液(0.5mol/L)中,常温下搅拌反应4h,过滤并用去离子水洗涤,100℃下干燥10h,得到铜基分子筛;
(3)、将10mL钛酸四丁酯加入到30mL无水乙醇中搅拌混匀得到钛酸四丁酯乙醇溶液;在搅拌条件下将2g铜基分子筛加入到所述钛酸四丁酯乙醇溶液中,搅拌0.5h后,在频率为45KHz条件下超声处理1h;再在搅拌条件下逐滴加入硝酸溶液(0.5mol/L)搅拌0.5h,调节pH值为3,继续搅拌1h后密闭陈化20h,在120℃下干燥12h,再在500℃下煅烧4h,即得到所述TiO2/Cu-ZSM-5分子筛光降解催化剂。
对比例1
一种光降解催化剂,其制备方法包括:
将10mL钛酸四丁酯加入到30mL无水乙醇中搅拌混匀得到钛酸四丁酯乙醇溶液;在搅拌条件下将3gZSM-5分子筛加入到所述钛酸四丁酯乙醇溶液中,搅拌0.5h后,在频率为45KHz条件下超声处理1h;再在搅拌条件下逐滴加入硝酸溶液(0.5mol/L)搅拌0.5h,调节pH值为3,继续搅拌1h后密闭陈化20h,在110℃下干燥14h,再在550℃下煅烧3h,即得到所述光降解催化剂。
对比例2
一种光降解催化剂,其制备方法包括:
(1)、将5g铵化分子筛加入到50mL硝酸铜溶液(0.2mol/L)中,常温下搅拌反应5h,过滤并用去离子水洗涤,100℃下干燥10h,550℃下煅烧3h,得到铜基分子筛;
(2)、将10mL钛酸四丁酯加入到30mL无水乙醇中搅拌混匀得到钛酸四丁酯乙醇溶液;在搅拌条件下将3g铜基分子筛加入到所述钛酸四丁酯乙醇溶液中,搅拌0.5h后,在频率为45KHz条件下超声处理1h;再在搅拌条件下逐滴加入硝酸溶液(0.5mol/L)搅拌0.5h,调节pH值为3,继续搅拌1h后密闭陈化20h,在110℃下干燥14h,再在550℃下煅烧3h,即得到所述光降解催化剂。
采用降解甲基橙溶液对实施例和对比例的光降解催化剂进行光催化活性评价。将100mg上述光催化材料加入到200mL浓度为50mg/L的甲基橙溶液中,可见光源(300W氙灯用滤光片滤去420nm以下的光)对该甲基橙溶液光照2h以实现降解处理,用紫外-可见分光光度计测出甲基橙的浓度变化,从而计算出降解率,结果如下表1所示:
表1实施例和对比例的光催化评价效果
催化剂 | 甲基橙的降解率(%) |
实施例1 | 98.6 |
实施例2 | 97.2 |
实施例3 | 98.1 |
对比例1 | 43.5 |
对比例2 | 70.9 |
从上表数据可以看出,本发明方法所获得的光降解催化剂,其甲基橙的可见光降解效率得到了有效提高。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种TiO2/Cu-ZSM-5分子筛光降解催化剂,其特征在于,所述光降解催化剂是通过下述方法制备得到:
将ZSM-5分子筛进行铵离子交换,得到铵化分子筛;将铵化分子筛进行铜离子交换,得到铜基分子筛;再通过溶胶凝胶法将钛酸四丁酯在铜基分子筛表面进行水解,干燥,煅烧后,即得到所述光降解催化剂。
2.根据权利要求1所述TiO2/Cu-ZSM-5分子筛光降解催化剂,其特征在于,所述铵离子交换具体包括:将ZSM-5分子筛加入到铵盐溶液中,80-100℃搅拌反应1-3h,过滤,水洗,干燥,即得到所述铵化分子筛。
3.根据权利要求2所述TiO2/Cu-ZSM-5分子筛光降解催化剂,其特征在于,所述铵盐为硝酸铵和/或氯化铵。
4.根据权利要求1-3任一项所述TiO2/Cu-ZSM-5分子筛光降解催化剂,其特征在于,所述铜离子交换具体包括:将铵化分子筛加入到铜盐溶液中,室温下搅拌反应4-6h,过滤,水洗,干燥,得到铜基分子筛。
5.根据权利要求4所述TiO2/Cu-ZSM-5分子筛光降解催化剂,其特征在于,所述铜盐为硝酸铜、硫酸铜和/或醋酸铜;
优选地,所述铜盐溶液的浓度为0.05-0.5mol/L。
6.根据权利要求1-5任一项所述TiO2/Cu-ZSM-5分子筛光降解催化剂,其特征在于,所述水解具体包括:将钛酸四丁酯与无水乙醇混合后,加入铜基分子筛搅拌均匀,再加入酸性添加剂调节pH值为2-5,搅拌,陈化,完成水解。
7.根据权利要求6所述TiO2/Cu-ZSM-5分子筛光降解催化剂,其特征在于,所述钛酸四丁酯和铜基分子筛的质量比为2-5:1。
8.根据权利要求1-7任一项所述TiO2/Cu-ZSM-5分子筛光降解催化剂,其特征在于,所述干燥温度为100-120℃,时间为12-16h。
9.根据权利要求1-8任一项所述TiO2/Cu-ZSM-5分子筛光降解催化剂,其特征在于,所述煅烧温度为500-600℃,时间为2-4h。
10.一种权利要求1-9任一项所述TiO2/Cu-ZSM-5分子筛光降解催化剂在降解中的应用。
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CN116099568A (zh) * | 2022-12-30 | 2023-05-12 | 重庆市畜牧科学院 | 一种Cu/ZSM-5/TiO2复合光催化材料及其制备方法和应用 |
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CN116099568A (zh) * | 2022-12-30 | 2023-05-12 | 重庆市畜牧科学院 | 一种Cu/ZSM-5/TiO2复合光催化材料及其制备方法和应用 |
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