CN108246326B - 一种锌/锑双组分负载型纳米碳化硅材料光催化去除甲醛的方法 - Google Patents
一种锌/锑双组分负载型纳米碳化硅材料光催化去除甲醛的方法 Download PDFInfo
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- CN108246326B CN108246326B CN201810000519.8A CN201810000519A CN108246326B CN 108246326 B CN108246326 B CN 108246326B CN 201810000519 A CN201810000519 A CN 201810000519A CN 108246326 B CN108246326 B CN 108246326B
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- silicon carbide
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- antimony
- formaldehyde
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 280
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 100
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 84
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000011701 zinc Substances 0.000 title claims abstract description 71
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 70
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 62
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 16
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- KLDGLPRBBANWAW-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate;trihydrate Chemical compound O.O.O.[K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O KLDGLPRBBANWAW-UHFFFAOYSA-J 0.000 claims description 9
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 claims description 9
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
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- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 3
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- MFYYDVFVCMSTMT-UHFFFAOYSA-J [O-]C(C(C(C([O-])=O)O)O)=O.[O-]C(C(C(C([O-])=O)O)O)=O.OC(C(C(O)=O)O)C(O)=O.O.O.O.O.[K+].[Sb+3] Chemical compound [O-]C(C(C(C([O-])=O)O)O)=O.[O-]C(C(C(C([O-])=O)O)O)=O.OC(C(C(O)=O)O)C(O)=O.O.O.O.O.[K+].[Sb+3] MFYYDVFVCMSTMT-UHFFFAOYSA-J 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- 238000005576 amination reaction Methods 0.000 abstract description 9
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 8
- 239000005011 phenolic resin Substances 0.000 abstract description 8
- 229920001568 phenolic resin Polymers 0.000 abstract description 8
- 239000007789 gas Substances 0.000 abstract description 7
- 229960001763 zinc sulfate Drugs 0.000 abstract description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 abstract 2
- ZPPDVMVFQVSVKZ-UHFFFAOYSA-J [O-]C(C(C(C([O-])=O)O)O)=O.[O-]C(C(C(C([O-])=O)O)O)=O.OC(C(C(O)=O)O)C(O)=O.O.[K+].[Sb+3] Chemical compound [O-]C(C(C(C([O-])=O)O)O)=O.[O-]C(C(C(C([O-])=O)O)O)=O.OC(C(C(O)=O)O)C(O)=O.O.[K+].[Sb+3] ZPPDVMVFQVSVKZ-UHFFFAOYSA-J 0.000 abstract 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
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- 125000003277 amino group Chemical group 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 238000010521 absorption reaction Methods 0.000 description 4
- AUJJPYKPIQVRDH-UHFFFAOYSA-N antimony potassium Chemical compound [K].[Sb] AUJJPYKPIQVRDH-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 208000013469 light sensitivity Diseases 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- -1 aldehyde compound Chemical class 0.000 description 2
- CZJCMXPZSYNVLP-UHFFFAOYSA-N antimony zinc Chemical class [Zn].[Sb] CZJCMXPZSYNVLP-UHFFFAOYSA-N 0.000 description 2
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 2
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- 206010067125 Liver injury Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 229910003107 Zn2SnO4 Inorganic materials 0.000 description 1
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- CUHVTYCUTYWQOR-UHFFFAOYSA-N formaldehyde Chemical compound O=C.O=C CUHVTYCUTYWQOR-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 231100000753 hepatic injury Toxicity 0.000 description 1
- 229940076153 heptahydrate zinc sulfate Drugs 0.000 description 1
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Abstract
本发明属于生态环保材料技术领域,具体涉及一种锌/锑双组分负载型纳米碳化硅材料光催化去除甲醛的方法。本发明以硫酸锌为锌前体,以酒石酸氧锑钾为锑前体,通过水热法负载于氨基化改性的纳米碳化硅颗粒上形成一种高比表面积的催化材料,可用于催化降解室内甲醛气体、车内甲醛气体、甲醛废水及其酚醛树脂废水。
Description
技术领域
本发明属于生态环保材料技术领域,具体涉及一种锌/锑双组分负载型纳米碳化硅材料光催化去除甲醛的方法。
背景技术
甲醛(formaldehyde)属于高挥发性有机化合物(volatileorganic chemicals,Vocs),在常温下是无色有刺激性气味的气体,极易溶于水,是一种化学性质比较活泼的小分子醛类化合物,一旦人员暴露量超过允许量,即对眼、呼吸道粘膜产生强烈刺激、高浓度接触可引起肝脏损伤和免疫损伤等毒性作用。甲醛是一种具有较高毒性的破坏生物细胞蛋白质的原生质毒物,能与蛋白质的氨基结合,使蛋白质变性凝固。近年来在工人间进行的流行病学调查认为甲醛暴露与白血病,特别是骨髓白血病有密切联系。
因此,人们越来越关注室内甲醛的去除,市场上也随之出现了多样化的除醛产品,其中甲醛去除剂的使用最为广泛。市场中销量较高、使用广泛的甲醛去除剂主要分为光触媒甲醛去除剂和生物酶甲醛去除剂两种。生物酶甲醛去除剂虽然绿色无污染,但是其活性成分多为蛋白多肽稳定性差,限制了其应用的范围。光触媒甲醛去除剂多以光催化材料为主要成分,其通过吸收一定光源的能量,产生带负电荷的活性电子和对应带正电荷的空穴,活性电子与催化剂表面吸附的氧气发生还原反应生成.O2 -自由基,空穴能与催化剂表面吸附的水分子或者羟基发生氧化反应生成·OH自由基,生成的两种自由基具有很高的化学活性,能与甲醛反应生成二氧化碳和水,从而达到去除甲醛的目的,并且不产生二次污染。
用于除甲醛的光催化剂多为半导体材料,如TiO2、BiO3(Effect of peptizingconditions on nanometer properties and photocatalytic activity of TiO2hydrosols prepared by H2TiO3[J] Journal of Hazardous Materials,2008,155(1):90);还有利用纳米氧化镁对甲醛进行吸收的,纳米氧化镁颗粒具有很高的反应活性,羰基和表面的氧化镁单元形成牢固的四元环,使得甲醛中羰基的活性降低(Theoretical Studyof the Adsorption of Formaldehyde on Magnesium Oxide Nanosurfaces:SizeEffects and the Role of Low-Coordinated and Defect Sites[J]J. Phys. Chem. B 2004, 108, 18140-18148)。这些光电催化中尤其以TiO2催化活性最高、稳定性最好,但其光电转化效率低(仅在紫外光区范围内具有较好的催化效果,可见光下效果差)而且催化剂容易失活,所以限制了TiO2的催化应用。由于非TiO2催化的体系具有优异的光催化效率,引起了广大研究者的兴趣,如Zn2SnO4体系(Transformation processandphotocatalyticactivitiesofhydrothermallysynthesizedZn2SnO4 nanocrystals, J. Phys. Chem. C 112(2008) 4159–4167),但其制备的材料比表面积往往比较低,而且制备工艺较为繁琐。
寻找新的吸附材料与非TiO2催化材料结合用来制备新的去除甲醛的材料是现阶段的研发热点,同样有着诱人的市场应用前景。
发明内容
本发明的目的是提供一种新型高比表面积的锌/锑双组分负载型纳米碳化硅材料,本发明以硫酸锌为锌前体,以酒石酸氧锑钾为锑前体,通过水热法负载于氨基化改性的纳米碳化硅颗粒上形成一种高比表面积的催化材料,可用于催化降解室内甲醛、车内甲醛、甲醛废水及其酚醛树脂废水。
根据本发明的一个方面,本发明提供了一种高比表面积的锌/锑双组分负载型纳米碳化硅材料的制备方法,包括以下步骤:
1)将七水硫酸锌、酒石酸氧锑钾三水合物置于水溶液中,然后加入十六烷基三甲基溴化铵搅拌10-30min得第一混合液;按摩尔比计算,七水硫酸锌:酒石酸氧锑钾三水合物:十六烷基三甲基溴化铵的摩尔比为2-3:1:0.3-0.4;
2)向第一混合液中加入纳米碳化硅颗粒,升温至60-80℃搅拌分散均匀后缓慢滴加氢氧化钾水溶液,调节pH至10-11析出固体颗粒沉积到纳米碳化硅颗粒表面和孔径内,然后保温搅拌24h得黑色混合液;所述纳米碳化硅颗粒重量为酒石酸氧锑钾三水合物重量的100-150倍;
3)将黑色混合液置于水热反应釜中于200-260℃的外温下水热反应48h,降温至室温、沉淀物过滤、水洗、乙醇洗涤、干燥得高比表面积的锌/锑双组分负载型纳米碳化硅材料;所述干燥为氮气氛围下于150-160℃下煅烧2-3h。
优选的,步骤2)所述加入纳米碳化硅颗粒为氨基化纳米碳化硅颗粒,所述氨基化纳米碳化硅颗粒由以下改性方法制备而得:
1)将10.0g纳米碳化硅颗粒置于100ml甲苯溶液中,然后加入0.3g乙烯基三(β-甲氧乙氧基)硅烷在氮气氛围下回流反应2-5h;
2)降温至室温,过滤、丙酮洗涤、干燥后得硅烷化表面改性的纳米碳化硅颗粒;试验中为了克服纳米碳化硅颗粒易聚集的问题,发明首先将纳米碳化硅颗粒进行硅烷化处理,硅烷化处理后下步进行硝基化,使硝基在纳米碳化硅表面分布更加均匀;
3)将硅烷化表面改性的纳米碳化硅颗粒置于10ml浓硝酸和浓硫酸的混合溶液中浸渍超声24h,然后过滤,水洗、干燥得硝基化纳米碳化硅;所述浓硝酸和浓硫酸的混合液中浓硫酸与浓硝酸的重量比为1:1;
4)将硝基化纳米碳化硅置于2mol/L盐酸的乙醇溶液中,加入1.2g锌粉回流反应2-3h后过滤、水洗、干燥得氨基化纳米碳化硅颗粒;
本发明对载体纳米碳化硅进行硅烷化-硝基化-氨基化处理后使纳米碳化硅表面和孔径内负载了部分氨基,单纯纳米碳化硅颗粒对甲醛的吸附效果很弱,仅存在部分的物理吸附作用;硅烷化和氨基化处理后的纳米碳化硅由于表面负载了硅氧基和氨基,加大了与甲醛的吸附作用,而且氨基和甲醛可存在部分的化学吸附作用,可将低浓度的甲醛聚集进行吸附和聚集,从而使制备出的锌/锑双组分负载型纳米碳化硅材料克服了仅能够降解低浓度的甲醛,无法降解高浓度的甲醛的问题,而且大大缩短了甲醛降解时间;另外,首先进行硅烷化处理解决了后期氨基化过程中碳化硅颗粒容易聚集导致硝基在碳化硅表面分布不均,最终硝基还原后催化剂吸附效果差的的缺点;而且在一定程度上增加了载体对锌/锑组分的结合力,使活性组分不宜流失,从而保证了催化剂的稳定性。
本发明以酒石酸氧锑钾三水合物为锑前体,将锑元素引入到锌负载到碳化硅载体上形成锌/锑双组分负载的纳米碳化硅催化材料,比单纯碳化硅负载锌相比大大提高了材料的光感性能,从紫外吸收区域延伸到了400nm以外的可见光区,使其对光的感应在紫外和可见光区均具有较好的吸收,并且对甲醛有较强的催化活性,解决了仅能够利用紫外光进行催化降解甲醛的缺点。
根据本发明的另一个方面,本发明提供了一种高比表面积的锌/锑双组分负载型纳米碳化硅材料的用途,在紫外-可见光下,用于催化降解甲醛废水:具体催化降解甲醛废水方案如下:
1)配制1L含600mg/L甲醛的水溶液,将pH调节至碱性,然后加入高比表面积的锌/锑双组分负载型纳米碳化硅材料0.5-10.0g搅拌均匀得待处理甲醛废水溶液;
2)将待处理甲醛废水溶液升温至一定温度,置于30W的紫外灯下照射2-3h后检测水中甲醛浓度。
优选的,步骤1)中所述碱性的pH为10.2-10.8;在催化降解过程中将甲醛水溶液调节至碱性有利于催化剂载体表面的氨基裸露,可以迅速与水中的甲醛结合并吸附,起到富集到催化剂表面的作用,当处于酸性时催化剂表面的氨基会被质子化,试验证明其催化效率在10.2-10.8之间甲醛降解率最高。
优选的,步骤2)中所述一定温度是指40-60℃,温度过低分子运动速度过慢,催化效率也低,温度过高会产生不必要的能耗。
本发明制备的高比表面积的锌/锑双组分负载型纳米碳化硅材料还可以在紫外可见光下用于净化室内甲醛气体、车内甲醛气体和酚醛树脂废水等污染。
本发明所述的浓硝酸为市售硝酸质量分数约为68%的硝酸溶液;浓硫酸为市售质量分数大于或等于70%的硫酸溶液;本发明技术方案中所使用的硫酸锌、酒石酸氧锑钾可为无水物或者其对应的水合物,例如硫酸锌可以采用无水硫酸锌、一水硫酸锌或七水硫酸锌;酒石酸氧锑钾可为酒石酸氧锑钾三水合物。
与现有技术相比,本发明具有如下优点:
1)首先本发明采取传统的水热法制备了新型锌/锑双组分负载型纳米碳化硅材料;
2)本发明首次采用锑组分杂化到锌负载的纳米碳化硅颗粒表面,使制备出的锌/锑双组分负载型纳米碳化硅材料光感度增强,其紫外可见吸收范围拓展到了400nm以上,即在自然光的作用下也能够降解甲醛;
3)本发明对载体碳化硅进行了表面改性,依次通过硅烷化-硝基化-氨基化等步骤的改性,使得氨基化改性的载体碳化硅对甲醛的吸附作用更强,可将低浓度的甲醛聚集进行吸附和聚集,从而使制备出的锌/锑双组分负载型纳米碳化硅材料克服了仅能够降解低浓度的甲醛,无法降解高浓度的甲醛的问题,而且大大缩短了甲醛降解时间;而且在一定程度上增加了载体对锌/锑组分的结合力,使活性组分不宜流失,从而保证了催化剂的稳定性;
4)本发明制备的锌/锑双组分负载型纳米碳化硅材料可用于催化降解甲醛废水、室内甲醛气体、车内甲醛气体和酚醛树脂废水等污染。
5)本发明制备的锌/锑双组分负载型纳米碳化硅材料稳定性好,在催化甲醛废水过程中可循环套用,降低了环保处理成本。
附图说明
图1为Cat-SiC-N/锌材料和Cat-SiC-N/锌/锑材料的紫外吸光图(200nm-600nm);
图2为Cat-SiC/锌/锑与Cat-SiC-N/锌/锑体系对甲醛的催化降解率随时间变化曲线;
图3为Cat-SiC-N/锌/锑催化剂降解室内甲醛的循环套用图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明了,下面结合具体实施方式,对本发明进一步详细说明。应该理解,这些描述只是示例性的,而并非要限制本发明的范围。
纳米碳化硅来自于北京德科岛金科技有限公司,型号为DK-SiC-001,平均粒径为40nm,比表面积为39.8m2/g;酒石酸氧锑钾三水合物来自于西格玛奥德里奇(上海)贸易有限公司。
实施例1
制备氨基化纳米碳化硅颗粒:
1)将10.0g纳米碳化硅颗粒(型号为DK-SiC-001,未经任何前处理)置于100ml甲苯溶液中,然后加入0.3g乙烯基三(β-甲氧乙氧基)硅烷在氮气氛围下回流反应2-5h;
2)降温至室温,过滤、30ml丙酮洗涤、60℃下减压干燥后得硅烷化表面改性的纳米碳化硅颗粒;
3)将步骤2)所得全部硅烷化表面改性的纳米碳化硅颗粒置于10ml浓硝酸和浓硫酸的混合溶液中(浓硝酸与浓硫酸等重量)浸渍超声24h,然后过滤,水洗至滤液成中性后于60℃下减压干燥得硝基化纳米碳化硅;
4)将硝基化纳米碳化硅置于2mol/L盐酸的乙醇溶液中,加入1.2g锌粉回流反应2-3h后过滤、水洗、于氮气氛围下在90℃下干燥24h得氨基化纳米碳化硅颗粒,简写为SiC-N。
实施例2
制备高比表面积的锌/锑双组分负载型纳米碳化硅材料,包括以下步骤:
1)将七水硫酸锌(2.88g,10mmol)、酒石酸氧锑钾三水合物置于水溶液中,然后加入十六烷基三甲基溴化铵搅拌10-30min得第一混合液(按摩尔比计算,七水硫酸锌:酒石酸氧锑钾三水合物:十六烷基三甲基溴化铵的摩尔比为3:1:0.4);
2)向第一混合液中加入氨基化纳米碳化硅颗粒(SiC-N),升温至60-80℃搅拌分散均匀后缓慢滴加氢氧化钾水溶液,调节pH至10-11析出固体颗粒沉积到纳米碳化硅颗粒表面和孔径内,然后保温搅拌24h得黑色混合液;氨基化纳米碳化硅颗粒(SiC-N)加入的重量为步骤1)中酒石酸氧锑钾三水合物重量的120倍;
3)将黑色混合液置于水热反应釜中于200-260℃的外温下水热反应48h,降温至室温、沉淀物过滤、水洗、乙醇洗涤、氮气氛围下于150-160℃下煅烧2-3h得高比表面积的锌/锑双组分负载型纳米碳化硅材料,简写为Cat-SiC-N/锌/锑。
与实施例2中制备方法相比,采用单因素变量法,采用相同重量的DK-SiC-001型纳米碳化硅颗粒代替氨基化纳米碳化硅颗粒(SiC-N)来制备锌/锑双组分负载型纳米碳化硅材料,所得产品定义为Cat-SiC /锌/锑。
与实施例2中制备方法相比,采用单因素变量法,不添加酒石酸氧锑钾三水合物,其余与实施例2制备方法完全一致;得到的产品定义为Cat-SiC-N/锌。
一、理化性质检测:
对原料纳米碳化硅颗粒(DK-SiC-001)、改性的氨基化纳米碳化硅颗粒(SiC-N)、锌/锑双组分负载型纳米碳化硅材料(Cat-SiC-N/锌/锑)和未经氨基化改性制备的材料(Cat-SiC/锌/锑)进行理化性质的检测:美国Quanta Chrome公司生产的CHEMBET-3000型吸附仪上测定其比表面积和孔结构参数;采用容量法于77.4K下以高纯氮为吸附介质,在相对压力为10-6~1的宽度范围内测定吸附等温线;采用元素分析仪测量锌/锑双组分负载型纳米碳化硅材料中氮/碳的摩尔比值,结果如表1所示:
表1纳米碳化硅颗粒及其改性材料的理化性质
样品 | 比表面积(m<sup>2</sup>/g) | 孔体积(ml/g) | N/C(mol%) |
DK-SiC-001 | 49.8 | 0.69 | 0 |
SiC-N | 68.2 | 0.48 | 4.2 |
Cat-SiC/锌/锑 | 45.8 | 0.51 | 0 |
Cat-SiC-N/锌/锑 | 52.1 | 0.49 | 4.1 |
理化检测结果表明,通过对纳米碳化硅颗粒进行氨基化表面改性负载了部分氨基,其中N/C(mol%)达到了4.2%,比表面积也得到了较大提高,但孔体积有所减小;增大的比表面积有利于下一步锌/锑的杂化负载。
二、紫外可见吸光度检测:
对Cat-SiC-N/锌和Cat-SiC-N/锌/锑进行紫外全波长扫描,结果如图1所示;结果表明引入锑元素制备出的Cat-SiC-N/锌/锑催化剂相对于Cat-SiC-N/锌催化剂在紫外区(200-400nm)吸光度要强,而且延伸到了可见光区(400nm以上),说明Cat-SiC-N/锌/锑催化剂在紫外区的光感性增强,而且可吸收部分可见光区的自然光。
实施例3
甲醛废水降解试验:将市售37.0-40.0wt%的甲醛水溶液用水稀释配制不同浓度(10000mg/L,600mg/L,20mg/L)的甲醛水溶液,采用600mg/L的甲醛测试催化剂性能检测:
1)配制1L含600mg/L甲醛的水溶液,将pH用氢氧化钠调节至9-10,然后加入纳米碳化硅颗粒(DK-SiC-001)、氨基化纳米碳化硅颗粒(SiC-N)、非氨基化改性锌锑双杂化纳米碳化硅材料(Cat-SiC/锌/锑)、锌杂化的纳米碳化硅材料(Cat-SiC-N/锌)或锌锑双杂化的纳米碳化硅材料(Cat-SiC-N/锌/锑)各1g搅拌均匀得待处理甲醛废水溶液;
2)将待处理甲醛废水溶液升温至45℃,置于30W的紫外灯下照射(飞利浦紫外线光源灯管,型号为TUV30W),每隔20min检测一次甲醛浓度,3h后检测最终水中甲醛浓度,并计算甲醛降解率(依据中华人民共和国国家环境保护标准HJ601-2011水质-甲醛的测定-乙酰丙酮分光光度法),计算降解率,结果如表2所示:
表2不同材料对甲醛的光催化降解率
DK-SiC-001 | SiC-N | Cat-SiC-N/锌 | Cat-SiC/锌/锑 | Cat-SiC-N/锌/锑 | |
降解率/% | 3.2 | 15.8 | 76.8 | 79.7 | 95.6 |
试验结果表明,仅纳米碳化硅颗粒载体本身基本无甲醛的降解作用,当对其进行氨基化改性后具有了一定的甲醛“降解”作用(此处可能是由于催化剂表面的氨基与甲醛的羰基起作用,并非真正的光催化降解);未经氨基改性制备的纳米碳化硅颗粒负载锌锑后完全具备了光催化降解甲醛的作用,降解率达到了79.7%;进行氨基化改性的纳米碳化硅颗粒负载锌后降解率为76.8%;锌/锑双组分负载型纳米碳化硅材料催化效果最好,达到了95.6%。
对Cat-SiC/锌/锑与Cat-SiC-N/锌/锑体系对甲醛的催化降解率随时间作图,如图2所示,图2中结果可以看出,Cat-SiC-N/锌/锑体系不仅甲醛最终降解率高,而且降解速率快基本上80min就达到了降解平衡。
以Cat-SiC-N/锌/锑为催化剂,对紫外光光催化降解甲醛废水进行了优化,得出pH为10.2-10.8的碱性条件下甲醛降解率最高,仅用0.5g催化剂在45℃即可达到98.6%的降解率。
在pH=10.5±0.1、45℃的条件下,以0.5gCat-SiC-N/锌/锑为催化剂,验证本发明Cat-SiC-N/锌/锑催化剂对1L不同甲醛浓度水溶液的降解效果,结果如表3所示:
表3不同甲醛浓度的降解率
甲醛浓度 | 10000mg/L | 20mg/L | 2mg/L |
降解率/% | 98.6 | 97.2 | 97.8 |
试验结果表明无论是在高浓度甲醛水溶液还是低浓度甲醛水溶液,采用本发明催化体系均能够起到良好的降解效率,解决了低浓度甲醛废水不宜降解的问题,可能是由于本发明催化剂中氨基对甲醛起到了吸附和富集的作用。
实施例4
采用本发明实施例2制备的Cat-SiC-N/锌/锑催化剂对室内甲醛进行降解试验:在25℃下,相对湿度为70%的封闭室内(室内甲醛初始浓度为1mg/m3),每立方米加入平均分散Cat-SiC-N/锌/锑催化剂5.0g,采用飞利浦55W紫外节能灯照射84h后,检测甲醛浓度为0.07mg/m3(采用乐控牌手持式甲醛测试仪检测),降解率高达93%,而且最终甲醛浓度小于0.08 mg/m3,符合《民用建筑室内环境污染控制规范》;对使用过的催化剂进行套用,结果如图3所示,循环使用4次催化性能基本无差异。
若是不采用紫外节能灯,仅在自然光下进行试验,10天后甲醛浓度为0.46mg/m3,虽然远高于0.08 mg/m3,但表明自然光下可进行部分甲醛的降解,可替代部分无法使用紫外光照射的场景。
实施例5
取酚醛保温材料厂家预处理后的酚醛树脂废水,水质情况如下,pH=8.3,CODcr=12830,甲醛含量13108mg/L,苯酚含量为9450mg/L,采用本发明实施例2制备的Cat-SiC-N/锌/锑催化剂进行光催化降解处理:1L酚醛树脂废水,加入1gCat-SiC-N/锌/锑催化剂,调节酚醛树脂废水值10.5,控温至50℃搅拌,在35W的紫外灯下照射24h后,检测水质,结果如表4所示:
表4酚醛树脂废水处理结果
CODcr(mg/L) | 甲醛含量mg/L | 苯酚含量mg/L | |
处理前 | 12830 | 13108 | 9450 |
处理后 | 4582 | 686 | 1473 |
试验结果表明,该体系对酚醛树脂中的甲醛也具有良好的降解效果,甲醛降解率达到了95%的去除率,而且对苯酚具有一定的降解作用,降解率达到了84.5%。
尽管已经详细描述了本发明的实施方式,但是应该理解的是,在不偏离本发明的精神和范围的情况下,可以对本发明的实施方式做出各种改变、替换和变更。
Claims (6)
1.一种高比表面积的锌/锑双组分负载型纳米碳化硅材料的制备方法,包括以下步骤:
1)将七水硫酸锌、酒石酸氧锑钾三水合物置于水溶液中,然后加入十六烷基三甲基溴化铵搅拌10-30min得第一混合液;
2)向第一混合液中加入纳米碳化硅颗粒,升温至60-80℃搅拌分散均匀后缓慢滴加氢氧化钾水溶液,调节pH至10-11析出固体颗粒沉积到纳米碳化硅颗粒表面和孔径内,然后保温搅拌24h得黑色混合液;
3)将黑色混合液置于水热反应釜中于200-260℃的外温下水热反应48h,降温至室温、沉淀物过滤、水洗、乙醇洗涤、干燥得高比表面积的锌/锑双组分负载型纳米碳化硅材料;
制备的所述高比表面积的锌/锑双组分负载型纳米碳化硅材料在紫外-可见光下,用于催化降解甲醛废水;
所述加入纳米碳化硅颗粒为氨基化纳米碳化硅颗粒,所述氨基化纳米碳化硅颗粒由以下制备方法制备:
1)将10.0g纳米碳化硅颗粒置于100ml甲苯溶液中,然后加入0.3g乙烯基三(β-甲氧乙氧基)硅烷在氮气氛围下回流反应2-5h;
2)降温至室温,过滤、丙酮洗涤、干燥后得硅烷化表面改性的纳米碳化硅颗粒;
3)将硅烷化表面改性的纳米碳化硅颗粒置于10ml浓硝酸和浓硫酸的混合溶液中浸渍超声24h,然后过滤,水洗、干燥得硝基化纳米碳化硅;所述浓硝酸和浓硫酸的混合液中浓硫酸与浓硝酸的重量比为1:1;
4)将硝基化纳米碳化硅置于2mol/L盐酸的乙醇溶液中,加入1.2g锌粉回流反应2-3h后过滤、水洗、干燥得氨基化纳米碳化硅颗粒;
步骤1)中按摩尔比计算,七水硫酸锌:酒石酸氧锑钾三水合物:十六烷基三甲基溴化铵的摩尔比为2-3:1:0.3-0.4。
2.根据权利要求1所述的制备方法,其特征在于:步骤2)所述纳米碳化硅颗粒重量为酒石酸氧锑钾三水合物重量的100-150倍。
3.根据权利要求1所述的制备方法,其特征在于:步骤3)干燥得高比表面积的锌/锑双组分负载型纳米碳化硅材料,所述干燥为氮气氛围下于150-160℃下煅烧2-3h。
4.根据权利要求1所述的制备方法,其特征在于:所述在紫外-可见光下,用于催化降解甲醛废水的具体步骤为:
1)配制1L含600mg/L甲醛的水溶液,将pH调节至碱性,然后加入高比表面积的锌/锑双组分负载型纳米碳化硅材料0.5-10.0g搅拌均匀得待处理甲醛废水溶液;
2)将待处理甲醛废水溶液升温至一定温度,置于30W的紫外灯下照射2-3h后检测水中甲醛浓度。
5.根据权利要求4所述的制备方法,其特征在于:所述碱性的pH为10.2-10.8。
6.根据权利要求4所述的制备方法,其特征在于:所述一定温度是指40-60℃。
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