CN107961816A - 一种WO3/MOF-SO3@Bi4Ti3O12复合光催化剂的制备方法 - Google Patents
一种WO3/MOF-SO3@Bi4Ti3O12复合光催化剂的制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title abstract description 5
- 239000011941 photocatalyst Substances 0.000 title abstract description 5
- 239000010936 titanium Substances 0.000 claims abstract description 61
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 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 claims abstract description 19
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 19
- 239000011734 sodium Substances 0.000 claims abstract description 19
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- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000001103 potassium chloride Substances 0.000 claims abstract description 6
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 6
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- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims abstract description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
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- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical class [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
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- 238000012546 transfer Methods 0.000 claims description 3
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- 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 1
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- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 abstract 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 abstract 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- 230000008859 change Effects 0.000 description 14
- UXAMZEYKWGPDBI-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)Br(C)(C)C Chemical class C(CCCCCCCCCCCCCCC)Br(C)(C)C UXAMZEYKWGPDBI-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- NZSLBYVEIXCMBT-UHFFFAOYSA-N chloro hypochlorite;zirconium Chemical class [Zr].ClOCl NZSLBYVEIXCMBT-UHFFFAOYSA-N 0.000 description 2
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- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical class [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- WGKMWBIFNQLOKM-UHFFFAOYSA-N [O].[Cl] Chemical compound [O].[Cl] WGKMWBIFNQLOKM-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- ARRNBPCNZJXHRJ-UHFFFAOYSA-M hydron;tetrabutylazanium;phosphate Chemical compound OP(O)([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC ARRNBPCNZJXHRJ-UHFFFAOYSA-M 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
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- 150000003624 transition metals Chemical class 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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Abstract
本发明公开了一种WO3/MOF‑SO3@Bi4Ti3O12复合光催化剂制备方法，氧化铋、二氧化钛、氯化钾、氯化钠、N‑N—二甲基乙酰胺、水合氧氯化锆、钨酸钠和2—磺酸对苯二甲酸钠为主要原料，催化剂具备典型三维结构,形貌规则，这种钒酸铋和有机共价化合物组合而成的三维结构,既具有二维片载流子传输效率高的优势,又具有三维结构高比表面积,充足反应位点,高可见光利用率的特点；本发明制备工艺新颖,既具有良好可见光降解效果,又可以降低成本、减少污染,在有机污染物分解方面具有较好的应用前景和经济效益。
Description
技术领域
本发明涉及一种WO3/MOF-SO3@ Bi4Ti3O12复合光催化剂及其制备方法,属于催化剂技术领域。
背景技术
我国工业经济的飞速发展,带来了众多日益严重的新型环境污染问题,工农业废水中以染料废水为代表的含有有机污染物的水污染是急待解决的环境污染问题之一。由于工农业种类繁多,其产生的废水组分非常复杂,而且废水中往往含有一定量的盐浓度,如煤化工、氯碱工业以及农药工业等,其废水中的盐浓度都较高大多在以上。这些高含盐废水中的有机污染物,往往难以应用传统的微生物处理技术进行有效降解,因而不能满足国家对煤化工等行业工业废水的“零排放”要求。光催化技术在这个背景下应运而生，其价格低廉，适用性广，但是传统催化材料光量子效率和光能利用率普遍低，需要发明新型的光催化剂以适应工业需求。
发明内容
本发明的目的在于提供一种WO3/MOF-SO3@ Bi4Ti3O12复合光催化剂及其制备方法，催化剂的稳定性高,对苯具有较高的降解率。
一种WO3/MOF-SO3@ Bi4Ti3O12光催化剂的制备方法，其特征在于该方法包括以下步骤：步骤1、将20g的SPEEK（磺化度62%）,加入3g DMF,溶解形成SPEEK溶液，向上述溶液中加入18g MOF-SO3@ Bi4Ti3O12纳米颗粒,并超声3h而使其分散均匀；
步骤2、将上述分散液小心倾倒于模具中并快速置于60℃烘箱中,保持8h而后,升高温度至80℃,保持8h，在室温下用1mol/L的盐酸酸化48h将纳米颗粒转化为H+型；
步骤3、取10g钨酸钠、50g H型MOF-SO3@ Bi4Ti3O12纳米颗粒、0.2g 十六烷基三甲基溴化铵溶于100ml蒸馏水,搅拌后混匀,向所得混合溶液中逐滴滴入浓度为3mol/L的HCl至PH=3，搅拌使之反应完全,离心沉降,用蒸馏水、乙醇反复交替洗涤3次,在100℃鼓风干燥箱中烘干,研磨后得到WO3/MOF-SO3@ Bi4Ti3O12光催化剂。
所述的MOF-SO3@ Bi4Ti3O12纳米颗粒制备方法如下：
步骤1、分别取3.4g氧化铋、7.7g二氧化钛、3.5g氯化钾和10.5g氯化钠于研钵中，研磨均匀后,将得到的淡黄色粉末放置于石英舟中,800℃下锻烧2h,冷却到室温后,将产物水洗烘干,得到纳米Bi4Ti3O12；
步骤2、取15g上述纳米Bi4Ti3O12超声分散在45gN-N—二甲基乙酰胺（DMA）中，而后分别称取50g 水合氧氯化锆和8g 2—磺酸对苯二甲酸钠加入上述分散液中,而后添加11份甲酸,超声分散20min；
步骤3、将其转移至聚四氟乙烯内衬中,盖好盖子并放入反应釜中密封紧密,然后置于150℃的恒温烘箱中持续反应24h,将反应产物通过离心分离出来,先用新鲜的DMF溶剂清洗3次,再用新鲜的乙醇溶剂多次洗涤,离心分离产物最后置于50℃的烘箱中保持6h,即得到MOF-SO3@ Bi4Ti3O12纳米颗粒。
有益效果：本发明制备的WO3/MOF-SO3@ Bi4Ti3O12光催化剂,具备典型三维结构,形貌规则，这种钒酸铋和有机共价化合物组合而成的三维结构,既具有二维片载流子传输效率高的优势,又具有三维结构高比表面积,充足反应位点,高可见光利用率的特点；WO3掺杂能够促进二氧化钛光催化剂由无定型转化为有利于光催化的晶相,且使二氧化钛的带隙中产生中间能级,降低了二氧化钛的禁带宽度,扩展了二氧化钛的吸光范围,过渡金属的掺杂能够取代晶格氧或晶格钛形成二氧化钛表面缺陷或者晶格缺陷,从而抑制电子空穴的表面复合,提高了二氧化钛光催化剂的光催化活性和光生电子和空穴的分离,降低了二氧化钛的禁带宽度,具有较好降解有机污染物的优点。
具体实施方式
实施例1
一种WO3/MOF-SO3@ Bi4Ti3O12光催化剂的制备方法，该方法包括以下步骤：
步骤1、将20g的SPEEK（磺化度62%）,加入3g DMF,溶解形成SPEEK溶液，向上述溶液中加入18g MOF-SO3@ Bi4Ti3O12纳米颗粒,并超声3h而使其分散均匀；
步骤2、将上述分散液小心倾倒于模具中并快速置于60℃烘箱中,保持8h而后,升高温度至80℃,保持8h，在室温下用1mol/L的盐酸酸化48h将纳米颗粒转化为H+型；
步骤3、取10g钨酸钠、50g H型MOF-SO3@ Bi4Ti3O12纳米颗粒、0.2g 十六烷基三甲基溴化铵溶于100ml蒸馏水,搅拌后混匀,向所得混合溶液中逐滴滴入浓度为3mol/L的HCl至PH=3，搅拌使之反应完全,离心沉降,用蒸馏水、乙醇反复交替洗涤3次,在100℃鼓风干燥箱中烘干,研磨后得到WO3/MOF-SO3@ Bi4Ti3O12光催化剂。
所述的MOF-SO3@ Bi4Ti3O12纳米颗粒制备方法如下：
步骤1、分别取3.4g氧化铋、7.7g二氧化钛、3.5g氯化钾和10.5g氯化钠于研钵中，研磨均匀后,将得到的淡黄色粉末放置于石英舟中,800℃下锻烧2h,冷却到室温后,将产物水洗烘干,得到纳米Bi4Ti3O12；
步骤2、取15g上述纳米Bi4Ti3O12超声分散在45gN-N—二甲基乙酰胺（DMA）中，而后分别称取50g 水合氧氯化锆和8g 2—磺酸对苯二甲酸钠加入上述分散液中,而后添加11份甲酸,超声分散20min；
步骤3、将其转移至聚四氟乙烯内衬中,盖好盖子并放入反应釜中密封紧密,然后置于150℃的恒温烘箱中持续反应24h,将反应产物通过离心分离出来,先用新鲜的DMF溶剂清洗3次,再用新鲜的乙醇溶剂多次洗涤,离心分离产物最后置于50℃的烘箱中保持6h,即得到MOF-SO3@ Bi4Ti3O12纳米颗粒；
实施例2
步骤3、取5g钨酸钠、50g H型MOF-SO3@ Bi4Ti3O12纳米颗粒、0.2g 十六烷基三甲基溴化铵溶于100ml蒸馏水,搅拌后混匀,向所得混合溶液中逐滴滴入浓度为3mol/L的HCl至PH=3，搅拌使之反应完全,离心沉降,用蒸馏水、乙醇反复交替洗涤3次,在100℃鼓风干燥箱中烘干,研磨后得到WO3/MOF-SO3@ Bi4Ti3O12光催化剂。其余步骤同实施例1。
实施例3
步骤3、取1g钨酸钠、50g H型MOF-SO3@ Bi4Ti3O12纳米颗粒、0.2g 十六烷基三甲基溴化铵溶于100ml蒸馏水,搅拌后混匀,向所得混合溶液中逐滴滴入浓度为3mol/L的HCl至PH=3，搅拌使之反应完全,离心沉降,用蒸馏水、乙醇反复交替洗涤3次,在100℃鼓风干燥箱中烘干,研磨后得到WO3/MOF-SO3@ Bi4Ti3O12光催化剂。其余步骤同实施例1。
实施例4
步骤3、取0.1g钨酸钠、50g H型MOF-SO3@ Bi4Ti3O12纳米颗粒、0.2g 十六烷基三甲基溴化铵溶于100ml蒸馏水,搅拌后混匀,向所得混合溶液中逐滴滴入浓度为3mol/L的HCl至PH=3，搅拌使之反应完全,离心沉降,用蒸馏水、乙醇反复交替洗涤3次,在100℃鼓风干燥箱中烘干,研磨后得到WO3/MOF-SO3@ Bi4Ti3O12光催化剂。其余步骤同实施例1。
实施例5
步骤3、取10g钨酸钠、25g H型MOF-SO3@ Bi4Ti3O12纳米颗粒、0.2g 十六烷基三甲基溴化铵溶于100ml蒸馏水,搅拌后混匀,向所得混合溶液中逐滴滴入浓度为3mol/L的HCl至PH=3，搅拌使之反应完全,离心沉降,用蒸馏水、乙醇反复交替洗涤3次,在100℃鼓风干燥箱中烘干,研磨后得到WO3/MOF-SO3@ Bi4Ti3O12光催化剂。其余步骤同实施例1。
实施例6
步骤3、取10g钨酸钠、10g H型MOF-SO3@ Bi4Ti3O12纳米颗粒、0.2g 十六烷基三甲基溴化铵溶于100ml蒸馏水,搅拌后混匀,向所得混合溶液中逐滴滴入浓度为3mol/L的HCl至PH=3，搅拌使之反应完全,离心沉降,用蒸馏水、乙醇反复交替洗涤3次,在100℃鼓风干燥箱中烘干,研磨后得到WO3/MOF-SO3@ Bi4Ti3O12光催化剂。其余步骤同实施例1。
实施例7
步骤3、取10g钨酸钠、75g H型MOF-SO3@ Bi4Ti3O12纳米颗粒、0.2g 十六烷基三甲基溴化铵溶于100ml蒸馏水,搅拌后混匀,向所得混合溶液中逐滴滴入浓度为3mol/L的HCl至PH=3，搅拌使之反应完全,离心沉降,用蒸馏水、乙醇反复交替洗涤3次,在100℃鼓风干燥箱中烘干,研磨后得到WO3/MOF-SO3@ Bi4Ti3O12光催化剂。其余步骤同实施例1。
实施例8
步骤3、取10g钨酸钠、100g H型MOF-SO3@ Bi4Ti3O12纳米颗粒、0.2g 十六烷基三甲基溴化铵溶于100ml蒸馏水,搅拌后混匀,向所得混合溶液中逐滴滴入浓度为3mol/L的HCl至PH=3，搅拌使之反应完全,离心沉降,用蒸馏水、乙醇反复交替洗涤3次,在100℃鼓风干燥箱中烘干,研磨后得到WO3/MOF-SO3@ Bi4Ti3O12光催化剂。其余步骤同实施例1。
实施例9
步骤3、取10g钨酸钠、150g H型MOF-SO3@ Bi4Ti3O12纳米颗粒、0.2g 十六烷基三甲基溴化铵溶于100ml蒸馏水,搅拌后混匀,向所得混合溶液中逐滴滴入浓度为3mol/L的HCl至PH=3，搅拌使之反应完全,离心沉降,用蒸馏水、乙醇反复交替洗涤3次,在100℃鼓风干燥箱中烘干,研磨后得到WO3/MOF-SO3@ Bi4Ti3O12光催化剂。其余步骤同实施例1。
实施例10
步骤3、取10g钨酸钠、200g H型MOF-SO3@ Bi4Ti3O12纳米颗粒、0.2g 十六烷基三甲基溴化铵溶于100ml蒸馏水,搅拌后混匀,向所得混合溶液中逐滴滴入浓度为3mol/L的HCl至PH=3，搅拌使之反应完全,离心沉降,用蒸馏水、乙醇反复交替洗涤3次,在100℃鼓风干燥箱中烘干,研磨后得到WO3/MOF-SO3@ Bi4Ti3O12光催化剂。其余步骤同实施例1。
实施例11
步骤3、取10g钨酸钠、20gCu-MOF多孔纳米材料、50g H型MOF-SO3@ Bi4Ti3O12纳米颗粒、0.2g 十六烷基三甲基溴化铵溶于100ml蒸馏水,搅拌后混匀,向所得混合溶液中逐滴滴入浓度为3mol/L的HCl至PH=3，搅拌使之反应完全,离心沉降,用蒸馏水、乙醇反复交替洗涤3次,在100℃鼓风干燥箱中烘干,研磨后得到WO3/MOF-SO3@ Bi4Ti3O12光催化剂。其余步骤同实施例1。
所述的Cu-MOF多孔纳米材料制备如下：
步骤1、将24份体积分数为66.7%的乙醇溶液、1.75份有机配体H3BTC和2份支持电解质TBAP加入到烧杯中,超声10min,超声功率为100W,使之分散溶解均匀,制成电解质溶液；
步骤2、将金属Cu棒（纯度为99.98%）作为阳极,采用石墨棒作为阴极,将所述阳极、阴极和电解质溶液连接成电解反应电路,保证阳极和阴极之间的距离为5cm,在电路电压为30V的条件下反应3h，将所得的产物用乙醇和水分别洗涤3次,并将其在100℃下干燥24h，随后在120℃的静态真空条件下处理12h，得到Cu-MOF纳米晶体材料。
对照例1
与实施例1不同点在于：光催化剂制备的步骤1中，将10g的SPEEK（磺化度62%）,加入3gDMF,溶解形成SPEEK溶液，其余步骤与实施例1完全相同。
对照例2
与实施例1不同点在于：光催化剂制备的步骤1中，将40g的SPEEK（磺化度62%）,加入3gDMF,溶解形成SPEEK溶液，其余步骤与实施例1完全相同。
对照例3
与实施例1不同点在于：光催化剂制备的步骤3中，逐滴滴入浓度为0.3mol/L的NaOH至PH=10，其余步骤与实施例1完全相同。
对照例4
与实施例1不同点在于：光催化剂制备的步骤3中，逐滴滴入浓度为0.3mol/L的醋酸至PH=6，其余步骤与实施例1完全相同。
对照例5
与实施例1不同点在于：MOF-SO3@ Bi4Ti3O12纳米颗粒制备的步骤1中，分别取1.7g氧化铋、3.7g二氧化钛、5.0g氯化钾和10.5g氯化钠于研钵中，其余步骤与实施例1完全相同。
对照例6
与实施例1不同点在于：MOF-SO3@ Bi4Ti3O12纳米颗粒制备的步骤1中，分别取6.8g氧化铋、1.7g二氧化钛、0.5g氯化钾和1.5g氯化钠于研钵中，其余步骤与实施例1完全相同。
对照例7
与实施例1不同点在于：MOF-SO3@ Bi4Ti3O12纳米颗粒制备步骤2中，取5g上述纳米Bi4Ti3O12超声分散在45gN-N—二甲基乙酰胺（DMA）中，其余步骤与实施例1完全相同。
对照例8
与实施例1不同点在于：MOF-SO3@ Bi4Ti3O12纳米颗粒制备步骤2中，取30g上述纳米Bi4Ti3O12超声分散在45gN-N—二甲基乙酰胺（DMA）中，其余步骤与实施例1完全相同。
对照例9
与实施例1不同点在于：MOF-SO3@ Bi4Ti3O12纳米颗粒制备步骤2中，分散液中不再加入水合氧氯化锆，其余步骤与实施例1完全相同。
对照例10
与实施例1不同点在于：MOF-SO3@ Bi4Ti3O12纳米颗粒制备步骤2中，分散液中不再加入2—磺酸对苯二甲酸钠，其余步骤与实施例1完全相同。
使用实施例和对照例制备的光催化剂对有机污染物苯进行降解：气相降解反应在连续反应装置上进行,采用苯（吹扫发生）做为模拟反应物,流速均设为20ml/min,浓度调为200ppm。催化剂在石英反应器的装填量约为0.85g,以泊菲莱PLS-XE300C为光源,灯口与反应器距离固定为10cm左右。反应物和产物由气相色谱在线监测。吸附饱和后开灯,并每隔30min自动进样分析,有机污染物和产物的浓度采用外标法标定，测定苯的降解率。
结果如表所示。
实验结果表明光催化剂对有机污染物苯分解反应具有良好的降解效果，在反应条件一定时，苯降解率越高，催化性能越好，反之越差；在钨酸钠、H型MOF-SO3@ Bi4Ti3O12纳米颗粒比质量为1:5时，其他配料固定，催化效果最好，与实施例1不同点在于，实施例2至实施例10分别改变光催化剂主要原料钨酸钠、H型MOF-SO3@ Bi4Ti3O12纳米颗粒的用量和配比，对光催化剂的分解性能有不同的影响，值得注意的是实施例11加入了Cu-MOF纳米晶体材料，苯分解率明显提高，说明Cu-MOF纳米晶体材料对光催化材料的结构活性有更好的优化作用；对照例1至对照例 2 改变SPEEK溶液SPEEK和DMF用量，其他步骤完全相同，导致催化剂的纳米颗粒活性发生变化，苯降解率明显降低；对照例3至对照例4用氢氧化钠和醋酸改变混合液PH，纳米颗粒酸性发生变化，分解效果明显变差；对照例5至对照例6，MOF-SO3@ Bi4Ti3O12纳米颗粒主要原料的配比改变，导致材料结构发生变化，降解效果依然不好；对照例7至对照例10，改变N-N—二甲基乙酰胺（DMA）的用量和分散液的组分，效果明显变差，说明水合氧氯化锆和2—磺酸对苯二甲酸钠对纳米颗粒的合成很重要；因此使用本发明制备的光催化剂对有机污染物苯的分解具有优异的效果。
Claims (2)
1.一种WO3/MOF-SO3@ Bi4Ti3O12光催化剂的制备方法，其特征在于该方法包括以下步骤：
步骤1、将20g的SPEEK,加入3g DMF,溶解形成SPEEK溶液，向上述溶液中加入18g MOF-SO3@ Bi4Ti3O12纳米颗粒,并超声3h而使其分散均匀；
步骤2、将上述分散液小心倾倒于模具中并快速置于60℃烘箱中,保持8h而后,升高温度至80℃,保持8h，在室温下用1mol/L的盐酸酸化48h将纳米颗粒转化为H+型；
步骤3、取10g钨酸钠、50g H型MOF-SO3@ Bi4Ti3O12纳米颗粒、0.2g 十六烷基三甲基溴化铵溶于100ml蒸馏水,搅拌后混匀,向所得混合溶液中逐滴滴入浓度为3mol/L的HCl至PH=3，搅拌使之反应完全,离心沉降,用蒸馏水、乙醇反复交替洗涤3次,在100℃鼓风干燥箱中烘干,研磨后得到WO3/MOF-SO3@ Bi4Ti3O12光催化剂。
2.权利要求1所述一种WO3/MOF-SO3@ Bi4Ti3O12光催化剂的制备方法，其特征在于，
所述的MOF-SO3@ Bi4Ti3O12纳米颗粒制备方法如下：
步骤1、分别取3.4g氧化铋、7.7g二氧化钛、3.5g氯化钾和10.5g氯化钠于研钵中，研磨均匀后,将得到的淡黄色粉末放置于石英舟中,800℃下锻烧2h,冷却到室温后,将产物水洗烘干,得到纳米Bi4Ti3O12；
步骤2、取15g上述纳米Bi4Ti3O12超声分散在45gN-N—二甲基乙酰胺中，而后分别称取50g 水合氧氯化锆和8g 2—磺酸对苯二甲酸钠加入上述分散液中,而后添加11份甲酸,超声分散20min；
步骤3、将其转移至聚四氟乙烯内衬中,盖好盖子并放入反应釜中密封紧密,然后置于150℃的恒温烘箱中持续反应24h,将反应产物通过离心分离出来,先用新鲜的DMF溶剂清洗3次,再用新鲜的乙醇溶剂多次洗涤,离心分离产物最后置于50℃的烘箱中保持6h,即得到MOF-SO3@ Bi4Ti3O12纳米颗粒。
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| US20120149560A1 (en) * | 2010-12-08 | 2012-06-14 | Electronics And Telecommunications Research Institute | Method of manufacturing porous metal oxide |
| CN106964338A (zh) * | 2017-03-28 | 2017-07-21 | 辽宁大学 | 一种wo3/钛酸盐复合光催化剂及其制备方法和应用 |
| CN107008248A (zh) * | 2017-05-18 | 2017-08-04 | 江苏大学 | 一种黑色Bi4Ti3O12光催化剂的制备方法 |
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2017
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| US20120149560A1 (en) * | 2010-12-08 | 2012-06-14 | Electronics And Telecommunications Research Institute | Method of manufacturing porous metal oxide |
| CN106964338A (zh) * | 2017-03-28 | 2017-07-21 | 辽宁大学 | 一种wo3/钛酸盐复合光催化剂及其制备方法和应用 |
| CN107008248A (zh) * | 2017-05-18 | 2017-08-04 | 江苏大学 | 一种黑色Bi4Ti3O12光催化剂的制备方法 |
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