CN107774295A - 一种掺杂过渡金属的磁性分子筛催化剂及其制备方法与应用 - Google Patents
一种掺杂过渡金属的磁性分子筛催化剂及其制备方法与应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 47
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002808 molecular sieve Substances 0.000 claims abstract description 48
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- -1 transition metal salt Chemical class 0.000 claims description 10
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
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- 238000006731 degradation reaction Methods 0.000 claims description 7
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- 230000015556 catabolic process Effects 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical group [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
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- DCAYPVUWAIABOU-NJFSPNSNSA-N hexadecane Chemical group CCCCCCCCCCCCCCC[14CH3] DCAYPVUWAIABOU-NJFSPNSNSA-N 0.000 claims 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 14
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- 239000006185 dispersion Substances 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
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- RXGJTUSBYWCRBK-UHFFFAOYSA-M 5-methylphenazinium methyl sulfate Chemical compound COS([O-])(=O)=O.C1=CC=C2[N+](C)=C(C=CC=C3)C3=NC2=C1 RXGJTUSBYWCRBK-UHFFFAOYSA-M 0.000 description 4
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
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- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 241000872198 Serjania polyphylla Species 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
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- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000007800 oxidant agent Substances 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
- 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
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
-
- 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
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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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
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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Abstract
本发明提供一种骨架掺杂过渡金属的磁性分子筛催化剂的制备方法。该催化剂以过渡元素金属为主催化剂,磁性铁物种为磁性源,介孔分子筛类材料为载体,采用水热一锅法合成。制备的催化剂具有介孔分子筛材料的规整孔道结构,提供了较大的吸附活性位;骨架中掺杂的过渡金属提供了高反应活性及稳定性;包裹的磁性铁物种提供了良好的重复利用性。本发明的催化剂具有结晶度高、比表面积大、分散性好、稳定性强及重复利用性好等特点,对Orange II等有机物表现出优异的去除效果,具有良好的经济和社会效益。
Description
技术领域
本发明提出一种掺杂过渡金属的具有磁性的介孔分子筛催化剂在染料降解方面的应用,适用于环境保 护领域的废水处理,在技术上涉及催化剂回收等领域。
背景技术
近年来,有机农药、有机染料以及芳烃类污染物等有机污染物对环境特别是水资源造成严重的污染及 破坏,并且由处理于这类污染物自身毒性高、生物难降解等特点,难以得到有效的处理。目前,常规的废 水处理手段主要有生物法、物理法、化学法等。生物法主要是通过微生物降解对废水中有色物质进行降解 和分离;物理法主要是通过吸附、凝聚、萃取等手段对废水中的相关有机物进行物理分离。这两种方法由 于自身的局限性往往不能达到有机物完全降解的效果。而化学法多是借助于活性催化剂与氧化剂结合,在 反应过程中产生活性极强的自由基,通过自由基与有机物之间作用,快速分解难降解的染料,反应速度快、 活性高,对生物及物理法难降解有机物具有良好的去除效果。
化学法处理有机废水关键是选择活性高、稳定性强、易回收分离的催化剂材料。介孔沸石分子筛由于 其自身的高比表面及规整的孔道结构等特性有利于活性金属的分布并提供较多的吸附位点,被广泛用作催 化剂载体。但介孔分子筛的惰性骨架限制了其在催化反应中的应用,且分子筛多以粉末状存在,在液相反 应过程中不易分离,阻碍分子筛的大范围应用推广。介孔沸石分子筛具有骨架易修饰的特点,通过掺杂法 在分子筛骨架引入活性金属,为分子筛催化剂提供活性位,且骨架掺杂增强了活性金属的稳定性,避免活 性金属在反应及回收过程中的流失,提高催化剂的反应稳定性。而引入磁性物种为分子筛催化剂的回收分 离提供了便利,有效改善分子筛粉末不易分离的缺陷。
因此,本发明旨在提出一种简单易行的制备手段,通过一锅法将过渡金属和磁性铁物种同时引入到介 孔分子筛的骨架及内部,得到骨架掺杂过渡金属的磁性介孔分子筛催化剂。实现了分子筛催化剂在废水处 理过程中具有高活性、易磁分离的特点,且活性金属的高稳定性保证催化剂回收后的重复利用性能,具有 良好的经济效益和实际应用价值。
发明内容
技术问题:
介孔分子筛具有高度有序的孔道结构、孔径分布均匀且尺寸可调、大表面积、活性中心易接近及扩散 阻力小等突出特点,常被用作催化材料。但传统的介孔分子筛由于其自身的惰性性质,存在催化活性低、 难以回收重利用等缺陷。因此,本发明的目的在于提供一种骨架掺杂过渡金属的磁性介孔分子筛催化剂的 制备方法。在催化剂的制备过程中,利用水热合成法一锅合成,合成步骤少、工艺简单;通过加入铁类胶 束,将磁性物种引入介孔分子筛内,为介孔分子筛提供可回收性能;借助原位掺杂在介孔分子筛骨架中一 步引入活性过渡金属,为介孔分子筛提供催化活性。该催化剂同时具有介孔分子筛的多孔特性、磁性物种 的易回收性和过渡金属的反应活性,使得催化剂同时具有优良的催化降解性能和易回收特性,具有明显的 经济和社会效益。
技术方案:
本发明涉及的掺杂过渡金属的磁性介孔分子筛催化剂,以过渡金属元素为主催化剂,以氧化铁物种为 磁性原料,介孔分子筛类材料为催化剂载体。
作为催化剂载体的介孔分子筛为MCM型系列或者SBA型系列的一种或者多种复合物。
作为催化剂中磁性材料的铁类胶束为Fe3O4胶束。
过渡金属元素选自钴、镍、锰、锌或钒中的一种或者几种元素的组合。
一种掺杂过渡金属的磁性介孔分子筛催化剂的制备方法,将模板剂溶于去离子水和浓氨水的混合溶液 中,搅拌使其完全溶解,逐滴加入Fe3O4胶束,搅拌后,将水溶性过渡金属盐加入到上述混合溶液中,搅 拌后,逐滴加入硅源,再搅拌,进行水热反应,水热反应后,洗涤、干燥、煅烧得骨架掺杂过渡金属的磁 性介孔分子筛催化剂。
所述Fe3O4胶束制备过程如下:在氮气氛围下,将三氯化铁和二氯化铁完全溶解于去离子水中,并逐 滴加入到氨水溶液中,形成黑色溶胶,其中可使用超声使三氯化铁和二氯化铁溶解完全,氨水的浓度优选 为1mol/L。
所述过渡金属为选自钴、镍、锰、锌或钒中的一种或者几种元素的组合,优选为钴,所述水溶性过渡 金属盐为过渡金属的卤化盐(优选为氯化物)、醋酸盐等,优选为氯化钴;所述模板剂为十六烷基三甲基 溴化铵,所述硅源为正硅酸四乙酯或正硅酸四甲酯,制备得到的分子筛为MCM型系列或者SBA型系列或 者两者的复合物。
进入水热反应前,确保硅源与过渡金属源水解速度相同。
所述水溶性过渡金属盐为氯化钴;所述水热反应为100-150℃下反应12-72h,优选3-24h,更优选24h; 所述煅烧为在空气氛围中300-600℃,优选400-600℃,更优选400℃,煅烧1-12h,优选3~10h,更优选 4h。
所述模板剂与硅源的质量比为3-15∶25,优选5-10∶25,更优选6∶25;硅源与Fe3O4胶束的质量体积比 为1g∶1-5mL,优选1g∶1-3mL,更优选1g∶2mL;三氯化铁和二氯化铁的质量比为3-10∶2,优选4-6∶2,更优 选5∶2。
掺杂过渡金属的磁性介孔分子筛催化剂用于催化降解有机物,优选Orange II。
掺杂过渡金属的磁性介孔分子筛催化剂的制备方法:
步骤1).Fe3O4胶束的制备:在氮气气氛下,按照一定比例将FeCl3·6H2O和FeCl2·4H2O溶于去离子水 中,超声处理使其完全溶解,将上述溶液逐滴加入到氨水中,形成黑色溶胶;
步骤2).将模板剂溶于水溶液中,逐滴加入步骤1)制得的Fe3O4胶束,加入含有水溶性过渡金属盐的 水溶液与硅源,调节控制pH范围,保证硅源与过渡金属源水解速度相同,最终的混合溶液在100℃-150℃ 水热3-24h;
步骤3).在步骤2)得到的催化剂在60℃-150℃烘干2-24h,然后在400-600℃的空气中煅烧3~10h,得 掺杂过渡金属的磁性介孔分子筛催化剂(以下简称催化剂)。
催化剂催化降解有机物的方法为:将催化剂加入到Orange II溶液中,超声处理,在黑暗环境下机械搅 拌使其达到吸附脱附平衡,加入吩嗪硫酸甲酯(PMS)来激活反应,取样,通过紫外分光光度仪测定溶液 在486nm处的吸光度,测量波长为200-600nm。
本发明与现有技术相比,具有以下优点及突出性效果:
(1)催化剂采用一锅法将过渡金属和磁性物种同时引入介孔分子筛内,制备过程简单、步骤少,节 约能耗。
(2)催化剂以包裹的方式将磁性物种引入分子筛内部,磁性稳定,提供了良好的重复利用性。
(3)催化剂以介孔分子筛为载体,具有规整的孔道结构,形貌均一且在液相中分散性好,具有大容 量和较强的吸附能力。
(4)过渡金属以掺杂的方式引入介孔分子筛骨架,稳定性好,活性高。
(5)针对Orange II等有机物的降解反应,催化剂表现出高活性、高稳定性及重复利用性。
附图说明
图1为掺杂过渡金属的磁性介孔分子筛催化剂的XRD图(催化剂的小角XRD图);
图2为掺杂过渡金属的磁性介孔分子筛催化剂的TEM及EDX图;
图3为掺杂过渡金属的磁性介孔分子筛催化剂的磁性测试图。
具体实施方式
实施例1:
Fe3O4胶束的制备:在氮气氛围下,2g三氯化铁和0.8g二氯化铁溶于10ml去离子水中,超声处理使 其完全溶解,将上述溶液逐滴加入到100ml(1mol/L)氨水溶液中,形成黑色溶胶,搅拌5min。
催化剂的合成步骤:将2.4g十六烷基三甲基溴化铵溶于120ml去离子水和10.5ml浓氨水的混合溶液 中,搅拌30min使其完全溶解,逐滴加入20ml Fe3O4胶束,搅拌1min后,将0.3g的氯化钴加入到上述混 合溶液中,搅拌30min后,逐滴加入10g正硅酸四乙酯,再搅拌2h,最终的混合样品在120℃下水热24h。 水热后的样品,用去离子水和乙醇分别洗涤3次,在60℃下干燥。最后在空气氛围中400℃煅烧4h。
催化剂的催化性能测定:将20mg催化剂加入到100ml 70mg/L的Orange II溶液中,超声处理5min, 在黑暗环境下机械搅拌(200rpm)60min使其达到吸附脱附平衡,通过加入1.2mol/L的吩嗪硫酸甲酯(PMS) 来激活反应,取样,通过紫外分光光度仪测定溶液在486nm处的吸光度,测量波长为200-600nm,反应50min 后,Orange II去除率为100%,磁分离30s后完全分层。
实施例2:
氧化铁胶束制备过程同实施例1,选取1.2g三氯化铁和0.8g二氯化铁,制备形成黑色溶胶。
使用氯化镍替代实施例1中氯化钴,其他制备过程与实施例1相同,选取1.2g十六烷基三甲基硅烷, 逐滴加入30ml Fe3O4胶束,加入10g正硅酸四乙酯,最终的混合样品在150℃下水热48h。水热后的样品, 用去离子水和乙醇分别洗涤3次,在60℃下干燥。最后在空气氛围中500℃煅烧6h。催化剂的催化性能测 定步骤同实施例1,反应60min后,Orange II去除率为100%,磁分离35s后完全分层。
实施例3:
氧化铁胶束制备过程同实施例1,选取3g三氯化铁和0.8g二氯化铁,制备形成黑色溶胶。
使用氯化锰替代实施例1中氯化钴,其他制备过程与实施例1相同,选取3.6g十六烷基三甲基硅烷, 逐滴加入10ml Fe3O4胶束,加入10g正硅酸四乙酯,最终的混合样品在100℃下水热72h。水热后的样品, 用去离子水和乙醇分别洗涤3次,在60℃下干燥。最后在空气氛围中600℃煅烧8h。催化剂的催化性能测 定步骤同实施例1,反应55min后,Orange II去除率为100%,磁分离32s后完全分层。
Claims (10)
1.一种掺杂过渡金属的磁性介孔分子筛催化剂,以过渡金属元素为主催化剂,以Fe3O4为磁性原料,介孔分子筛类材料为催化剂载体。
2.如权利要求1所述的一种掺杂过渡金属的磁性介孔分子筛催化剂,其中过渡金属元素选自钴、镍、锰、锌或钒中的一种或者多种的组合,所述催化剂载体为MCM型系列或者SBA型系列或者两者的复合物。
3.一种掺杂过渡金属的磁性介孔分子筛催化剂的制备方法,其特征在于,将模板剂溶于去离子水和浓氨水的混合溶液中,搅拌使其完全溶解,逐滴加入Fe3O4胶束,搅拌后,将水溶性过渡金属盐加入到上述混合溶液中,搅拌后,逐滴加入硅源,再搅拌,进行水热反应,水热反应后,洗涤、干燥、煅烧得骨架掺杂过渡金属的磁性介孔分子筛催化剂。
4.根据权利要求3所述的一种掺杂过渡金属的磁性介孔分子筛催化剂的制备方法,所述Fe3O4胶束制备过程如下:在氮气氛围下,将三氯化铁和二氯化铁完全溶解于去离子水中,并逐滴加入到氨水溶液中,形成黑色溶胶。
5.根据权利要求3所述的一种掺杂过渡金属的磁性介孔分子筛催化剂的制备方法,所述过渡金属为选自钴、镍、锰、锌或钒中的一种或者几种元素的组合;所述模板剂为十六烷基三甲基溴化铵,所述硅源为正硅酸四乙酯或正硅酸四甲酯,制备得到的分子筛为MCM型系列或者SBA型系列或者两者的复合物。
6.根据权利要求3-5任一项所述的一种掺杂过渡金属的磁性介孔分子筛催化剂的制备方法,其特征在于:进入水热反应前,确保硅源与过渡金属源水解速度相同。
7.根据权利要求3所述的一种掺杂过渡金属的磁性介孔分子筛催化剂的制备方法,所述水溶性过渡金属盐为氯化钴;所述水热反应为100-150℃下反应12-72h;所述煅烧为在空气氛围中300-600℃下煅烧1-12h。
8.根据权利要求4所述的一种掺杂过渡金属的磁性介孔分子筛催化剂的制备方法,所述模板剂与硅源的质量比为5-15∶25,硅源与Fe3O4胶束的质量体积比为1g∶1-5mL,三氯化铁和二氯化铁的质量比为3-10∶2。
9.权利要求3-8任一项所制备得到的掺杂过渡金属的磁性介孔分子筛催化剂。
10.权利要求1-2、9任一项的掺杂过渡金属的磁性介孔分子筛催化剂用于催化降解有机物,优选Orange II。
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