CN109499604A - 一步法合成介孔wo3/sba-15的方法 - Google Patents
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- 238000003786 synthesis reaction Methods 0.000 title description 5
- 230000015572 biosynthetic process Effects 0.000 title description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 239000010937 tungsten Substances 0.000 claims abstract description 9
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
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- 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 1
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- 238000003756 stirring Methods 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
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- 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 5
- 229940043267 rhodamine b Drugs 0.000 description 5
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- 230000000694 effects Effects 0.000 description 4
- 239000013335 mesoporous material Substances 0.000 description 4
- WPZFLQRLSGVIAA-UHFFFAOYSA-N sodium tungstate dihydrate Chemical compound O.O.[Na+].[Na+].[O-][W]([O-])(=O)=O WPZFLQRLSGVIAA-UHFFFAOYSA-N 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
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- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
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- 238000006243 chemical reaction Methods 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
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- 239000010936 titanium Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- DCLMSQHLMMBQNX-UHFFFAOYSA-H [W].Cl[W](Cl)(Cl)(Cl)(Cl)Cl Chemical compound [W].Cl[W](Cl)(Cl)(Cl)(Cl)Cl DCLMSQHLMMBQNX-UHFFFAOYSA-H 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
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- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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Classifications
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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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- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
本发明涉及一种一步法制备介孔WO3/SBA‑15分子筛，属于无机纳米材料技术领域。制备步骤如下：以聚乙二醇一聚丙二醇一聚乙二醇三嵌段高分子表面活性剂为模板剂，加入钨源形成共模板剂，再加入硅源，晶化后煅烧形成介孔结构。本发明的介孔WO3/SBA‑15分子筛具有如下优点：(1)本发明的溶剂只有水，没有其他溶剂，因此不会产生副产物，是环境友好型的；(2)采用一步法合成介孔WO3/SBA‑15，操作简单，制备时间短，节约制备成本，且介孔结构较好，重复性高；(3)本发明的介孔WO3/SBA‑15分子筛具有良好的光催化性能。
Description
技术领域：
本发明涉及一种介孔WO3/SBA-15分子筛的制备方法，属于无机纳米材料技术领域。
技术背景：
目前，工业废水已经成为亟待解决的环境问题，尤其是染料废水，由于其排放量大，浓度高，难脱色等特点，造成了很大的环境污染。光催化材料因其可以对染料废水进行降解处理而具有很好的应用前景。
然而很多对染料有较好的光催化性能的材料都只能在紫外光下进行光降解，而紫外光只占太阳光的一小部分，这限制了光催化材料的应用范围。
CN104229924A报道了将稀土元素引入到石墨烯中的合成方法，从而在汞灯下作为光催化染料的催化剂。
CN104229924A报道了在紫外照射下，所合成的高能面暴露的二氧化钛对罗丹明B有着很好的光降解效果。
CN104229924A报道了合成的WO3复合涂料具有在室外光降解甲醛的应用。
由此可见，WO3能在可见光下进行光降解，具有良好的实际应用效果。
介孔材料具有纳米级均一孔道结构和大表面积的一种新型材料，是一种良好的催化剂载体，通过负载或直接合成将活性组分引入介孔载体，可以提供催化反应所需要的活性位。与常规载体相比，介孔材料上的活性组分分散度更好，反应物与活性中心的接触更为充分，尤其适合大流量、高空速的反应体系。
US5672556报道了将一系列过渡金属物种引入到MCM-41介孔材料骨架中的合成方法，这些过渡金属物种包括Ti,V,Sn,Zr,Zn,Cu,Co,Cr等。
US6391278报道了以电中性伯胺或二胺为模板剂室温下合成含过渡金属物种的HMS系列介孔材料，这些过渡金属物种包括Ti,V,Sn,Zr,Zn,Cu,Cr等。
到目前为止，一步法合成的介孔WO3/SBA-15为光催化材料未见报道。
发明内容：
本发明所要解决的技术问题是以往技术中未涉及一步法制备骨架中含钨的介孔二氧化硅分子筛WO3/SBA-15的问题，提供一种新的介孔WO3/SBA-15分子筛的制备方法。该方法制备的分子筛具有较大的比表面积，钨的分散性能好和分散容量大，用于光催化反应，反应活性较高。为解决上述技术问题，本发明采用的技术方案如下:一种介孔WO3/SBA-15分子筛的制备方法，以聚乙二醇一聚丙二醇一聚乙二醇三嵌段聚合物M为模板剂，以选自正硅酸四乙酯、硅溶胶、水玻璃或白炭黑为硅源，以选自偏钨酸铵、仲钨酸铵、钨酸钠或六氯化钨为钨源，在酸性条件下，原料摩尔配比如下:
1SiO2:0.01～0.03M:3～10H+:50～200H2O:0.03～0.25WO3
在晶化温度为20～170℃，压力为凝胶混合物的自生压力下，水热晶化6～120小时获得所需的WO3/SBA-15分子筛；
上述技术方案中硅源优选方案选自正硅酸乙酷；钨源优选方案选自钨酸钠。模板剂聚乙二醇—聚丙二醇—聚乙二醇三嵌段聚合物M分子式为H(-OCH2-CH2-)x[-OCH(CH3)CH2-]y(OCH2CH2-)zOH平均分子量为5800，简称P123。制备方法优选方案为在晶化之前，在20～60℃下先将模板剂M溶于酸性水溶液中，然后加入钨源形成共模板，再加入硅源的溶液。晶化温度优选范围为100℃；水热晶化时间优选范围为24小时。
上述技术方案中合成的含钨的SBA-15需经焙烧脱除模板剂处理，焙烧处理可选取在马弗炉或在管式炉中进行；焙烧升温方式可选在惰性气氛下程序升温，升温速度在1～10℃，焙烧温度可选取350℃～800℃，优选500℃～750℃。焙烧时间为氧化气氛1～20小时，优选为3～9小时；惰性气氛1～10小时，优选为3～6小时。本发明通过将钨引入介孔SBA-15分子筛的骨架，使催化剂比表面积大大提高，增加了的钨的分散度，从而提高了光催化反应性能，取得了较好的技术效果。
下面通过实施例对本发明作进一步阐述。
具体实施方式：
实例一
2.0g P123溶于65ml去离子水中室温搅拌3h，加入10ml 2mol·L-1的盐酸溶液于40℃剧烈搅拌1h，分别将0.36g(m(WO3):m(SiO2)＝20％，下同)二水合钨酸钠溶于10ml去离子水后加入上述体系中，搅拌1h后形成澄清溶液，缓慢滴加4.5g正硅酸四乙酯，于40℃搅拌24h。将溶液转移至水热釜中，100℃静置陈化24h，取出，依次用去离子水，乙醇洗涤三次，60℃干燥8h，550℃煅烧6h。准确量取100mL10mg·L-1的罗丹明B溶液于烧杯中，加入0.10g的催化剂，在黑暗中搅拌1h，取样，然后以200W的氙灯为光源照射，每隔30min取样1次，取6次样，样品经离心分离，取上层清液，用紫外可见分光光度计在最佳吸收波长(552nm)处测量吸光度，根据公式其中D为降解率，A0为初始溶液吸光度，A为剩余溶液吸光度)。最后计算得到罗丹明B的降解率为60.8％。
实例二
2.0g P123溶于65ml去离子水中室温搅拌3h，加入10ml 2mol·L-1的盐酸溶液于40℃剧烈搅拌1h，分别将0.54g(m(WO3):m(SiO2)＝30％)二水合钨酸钠溶于10ml去离子水后加入上述体系中，搅拌1h后形成澄清溶液，缓慢滴加4.5g正硅酸四乙酯，于40℃搅拌24h。将溶液转移至水热釜中，100℃静置陈化24h，取出，依次用去离子水，乙醇洗涤三次，60℃干燥8h，550℃煅烧6h。准确量取100mL10mg·L-1的罗丹明B溶液于烧杯中，加入0.10g的催化剂，在黑暗中搅拌1h，取样，然后以200W的氙灯为光源照射，每隔30min取样1次，取6次样，样品经离心分离，取上层清液，用紫外可见分光光度计在最佳吸收波长(552nm)处测量吸光度，根据公式其中D为降解率，A0为初始溶液吸光度，A为剩余溶液吸光度)。最后计算得到罗丹明B的降解率为62.2％。
实例三
2.0gP123溶于65ml去离子水中室温搅拌3h，加入10ml 2mol·L-1的盐酸溶液于40℃剧烈搅拌1h，分别将0.72g(m(WO3):m(SiO2)＝40％)二水合钨酸钠溶于10ml去离子水后加入上述体系中，搅拌1h后形成澄清溶液，缓慢滴加4.5g正硅酸四乙酯，于40℃搅拌24h。将溶液转移至水热釜中，100℃静置陈化24h，取出，依次用去离子水，乙醇洗涤三次，60℃干燥8h，550℃煅烧6h。准确量取100mL10mg·L-1的罗丹明B溶液于烧杯中，加入0.10g的催化剂，在黑暗中搅拌1h，取样，然后以200W的氙灯为光源照射，每隔30min取样1次，取6次样，样品经离心分离，取上层清2液，用紫外可见分光光度计在最佳吸收波长(552nm)处测量吸光度，根据公式其中D为降解率，A0为初始溶液吸光度，A为剩余溶液吸光度)。最后计算得到罗丹明B的降解率为73.4％。
实例四
2.0gP123溶于65ml去离子水中室温搅拌3h，加入10ml 2mol·L-1的盐酸溶液于40℃剧烈搅拌1h，分别将0.90g(m(WO3):m(SiO2)＝50％)二水合钨酸钠溶于10ml去离子水后加入上述体系中，搅拌1h后形成澄清溶液，缓慢滴加4.5g正硅酸四乙酯，于40℃搅拌24h。将溶液转移至水热釜中，100℃静置陈化24h，取出，依次用去离子水，乙醇洗涤三次，60℃干燥8h，550℃煅烧6h。准确量取100mL10mg·L-1的罗丹明B溶液于烧杯中，加入0.10g的催化剂，在黑暗中搅拌1h，取样，然后以200W的氙灯为光源照射，每隔30min取样1次，取6次样，样品经离心分离，取上层清液，用紫外可见分光光度计在最佳吸收波长(552nm)处测量吸光度，根据公式其中D为降解率，A0为初始溶液吸光度，A为剩余溶液吸光度)。最后计算得到罗丹明B的降解率为64.8％。
Claims (6)
1.一种一步法制备介孔WO3/SBA-15分子筛的方法，以聚乙二醇—聚丙二醇—聚乙二醇三嵌段聚合物M为模板剂，以选自正硅酸四乙酯、硅溶胶、水玻璃或白炭黑为硅源，以选自偏钨酸铵、仲钨酸铵、钨酸钠或六氯化钨为钨源，在酸性条件下，原料摩尔配比如下:
1SiO2:0.01～0.03M:3～10H+:50～200H2O:0.03～0.25WO3
在晶化温度为20～170℃，压力为凝胶混合物的自生压力下，水热晶化6～120小时获得所需的WO3/SBA-15分子筛。
2.根据权利要求1所述的介孔WO3/SBA-15分子筛的制备方法，其特征在于钨源选自钨酸钠。
3.根据权利要求1所述的介孔WO3/SBA-15分子筛的制备方法，其特征在于硅源选自正硅酸四乙酯。
4.根据权利要求1所述的介孔WO3/SBA-15分子筛的制备方法，其特征在于晶化温度为100℃，晶化时间24小时。
5.根据权利要求1所述的介孔WO3/SBA-15分子筛的制备方法，其特征在于在晶化之前，在20～60℃下先将模板剂M溶于酸性水溶液中，然后加入钨源形成共模板，再加入硅源的溶液。
6.根据权利要求1所述的介孔WO3/SBA-15分子筛的制备方法，其特征在于酸性水溶液的酸选自盐酸。
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| CN1446631A (zh) * | 2003-01-30 | 2003-10-08 | 复旦大学 | 一种用于合成戊二醛的含钨介孔分子筛催化剂及其制造方法 |
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