CN108714435A - 一种具有降解性能的碳纳米管电催化膜及其制备方法 - Google Patents
一种具有降解性能的碳纳米管电催化膜及其制备方法 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 121
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 230000015556 catabolic process Effects 0.000 title claims abstract description 27
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 27
- 239000012528 membrane Substances 0.000 claims abstract description 49
- 210000002469 basement membrane Anatomy 0.000 claims abstract description 32
- 210000004379 membrane Anatomy 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 22
- 238000001179 sorption measurement Methods 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 14
- 239000008236 heating water Substances 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 150000001768 cations Chemical class 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 7
- 239000002105 nanoparticle Substances 0.000 claims abstract description 4
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
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- 239000000243 solution Substances 0.000 claims description 12
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- 239000002253 acid Substances 0.000 claims description 9
- 239000002238 carbon nanotube film Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000002091 cationic group Chemical group 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- -1 EtOH-DI water Chemical compound 0.000 claims description 6
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical group OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 230000005518 electrochemistry Effects 0.000 claims description 3
- 229940074391 gallic acid Drugs 0.000 claims description 3
- 235000004515 gallic acid Nutrition 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- WBJXZTQXFVDYIZ-UHFFFAOYSA-N [Sb].[N+](=O)(O)[O-] Chemical compound [Sb].[N+](=O)(O)[O-] WBJXZTQXFVDYIZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
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- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
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- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 238000000527 sonication Methods 0.000 claims description 2
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- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 230000005685 electric field effect Effects 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 4
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 14
- 238000012545 processing Methods 0.000 description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 11
- 238000012986 modification Methods 0.000 description 10
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- 229910052718 tin Inorganic materials 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
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- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- KSVSZLXDULFGDQ-UHFFFAOYSA-M sodium;4-aminobenzenesulfonate Chemical compound [Na+].NC1=CC=C(S([O-])(=O)=O)C=C1 KSVSZLXDULFGDQ-UHFFFAOYSA-M 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
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- 241000894006 Bacteria Species 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 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 description 1
- 239000005864 Sulphur Substances 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 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 1
- 229940012189 methyl orange Drugs 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
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- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
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- 210000001519 tissue Anatomy 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
- 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
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/46115—Electrolytic cell with membranes or diaphragms
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种具有降解性能的碳纳米管电催化膜及其制备方法。本发明催化膜以有机滤膜为基础骨架材料,将碳纳米管粉末通过真空抽滤固定到有机滤膜上,然后再把具有电催化活性的金属纳米颗粒负载到膜上,即通过电化学吸附方法、按照一定比例引入具有电催化活性的金属阳离子,在一定温度梯度内通过水浴加热实现金属氧化物纳米颗粒修饰并负载在碳纳米管基膜上。本发明方法:首先对碳纳米管粉末进行预处理以去除杂质,然后,将一定质量的碳纳米管粉末均匀地抽滤到作为骨架材料的有机滤膜上,接下来将碳纳米管基膜作为阴极,放置于按一定比例配制的含有特定金属阳离子的电解质溶液中,在外加直流电场作用下完成电化学吸附;最后进行水浴加热。本发明易于实现大规模生产,适用范围广。
Description
技术领域
本发明属于功能分离材料制备及水处理技术领域,具体涉及一种具有高通量和高污染物降解效率的碳纳米管(CNTs)电催化膜材料制备及其修饰方法。
背景技术
水资源危机是当前社会面临的最大挑战之一。人类在使用水资源过程中存在的严重浪费以及污染,使得人类可以获取的清洁水源总量正在持续减少。据***估计,全球大约7.8亿人无法获得安全清洁的饮用水。近年来,大量的工业废水和生活污水进入水体环境,对人类、水生生物、水生态环境的安全造成了严重威胁。尤其是水体环境中存在的一些具有高毒性的难以降解有机污染物,随着时间延长,在食物链中富集,对人类及其他生物具有长期慢性的毒性,甚至有致癌、致畸作用,严重影响人体健康。
近年来,电催化膜技术受到广泛关注,并有望成为一种非常重要的水处理方法。电催化膜技术是将电化学催化氧化技术和传统的膜分离技术集成而产生的一种新型水处理技术,在电场作用下,电催化膜产生羟基自由基·OH、O2-等具有强氧化性的基团,通过氧化作用降解水中的有机污染物和微生物,同时还通过膜分离作用截留污染物。相对于单一使用膜分离技术通过物理分离作用实现水的处理,这种电催化膜集成技术能更有效的将污染物降解,更符合环境保护要求。但由于受到膜材料、负载催化剂及制备工艺等技术限制,电催化膜技术常出现的降解电流效率低、能耗高的问题,极大限制了其大规模的工业化应用。
目前,国内电催化膜材料主要有煤基碳、石墨烯、Ti4O7和金属钛等,通过在膜上负载催化剂可以提高膜的电化学性能。现有的电催化膜制备方法主要有溶胶凝胶法、水热法和化学气相沉积法等,工艺较为复杂,而且使用这些方法制备的电催化膜难以应用于连续式处理装置。有研究证明,在相同条件下,连续式处理装置的动力学参数和污染物降解效果是间歇式处理装置的10倍以上。能够应用于连续式处理装置的电催化膜需要同时满足三个方面的要求:1)形成无粘合剂掺杂的导电网络;2)形成机械稳定的三维多孔结构;3)用于修饰电催化膜表面的纳米催化剂的电催化活性高、毒性小。溶胶凝胶法和水热方法可以有效将纳米催化剂负载到膜表面,但是在制备过程中需要添加一定量的导电物质或粘合剂,以降低电化学阻抗并增加结构稳定性。化学气相沉积法虽然可以制备结构稳定无粘合剂的膜,但是基膜材料多为金属基,无法形成多孔的网络结构,不能应用于连续式处理装置。
为此,近年来研究人员逐渐将电催化膜的研究重点放在可用于连续式处理装置的新型膜材料和具有高催化活性的纳米催化剂的研究上。碳纳米管(CNTs)不仅是有效的均相电极材料,而且是一种性能优异的高比表面积催化剂载体。有研究人员使用有机物、无机物、微生物等对CNTs进行表面修饰,发现负载物质可以显著影响碳纳米管的物理和化学特性,使用二氧化锡(SnO2)修饰的SnO2-CNT可以有效实现苯甲酸的矿化。美国哈佛大学ChadD.Vecitis课题组采用负载SnO2纳米颗粒的碳纳米管膜作为阳极,多孔钛板为阴极,组成电化学膜过滤***,用来处理水中有机污染物以及细菌、病毒等,通过碳纳米管的吸附性能以及电化学氧化的作用,该膜过滤***对亚甲基蓝、甲基橙、苯酚、大肠杆菌以及MS2病毒均有良好的去除效果。SnO2作为典型的宽隙带半导体,具有高达1.7V的析氧电势(OEP),是一种常见的无机修饰材料。因此,通过掺杂一些无毒性的金属离子(如Bi3+、Sb3+等)可以形成与碳纳米管紧密结合的金属氧化物纳米催化剂,能够促使电子优先通过空穴迁移,提高碳纳米管的电催化性能,具有潜在的市场价值。
中国专利ZL 201110299121.7介绍了一种碳纳米管的表面修饰方法,首先通过浓硝酸和二氯亚砜实现碳纳米管的酰氯化,然后将碳纳米管与对氨基苯磺酸钠超声通过分散和搅拌进行反应,制备出对氨基苯磺酸钠修饰的多壁碳纳米管。该方法制备的对氨基苯磺酸钠修饰碳纳米管对金属粒子具有一定的吸附性能,但是对于大分子有机污染物吸附效果不佳,可处理的污染物种类较为单一,且该材料呈粉末状,电化学应用能力差,回收较为困难,容易造成二次污染。
中国专利ZL201410353923.5介绍了一种碳纳米管的表面修饰方法,将碳纳米管加入到没食子酸水溶液中分散、静置并抽滤烘干,得到表面经过修饰的碳纳米管粉末。该方法制备的碳纳米管不是碳纳米管膜,而且表面没有负载催化剂,电催化性能差。
中国专利ZL 201510717154.7介绍了一种碳纳米管超滤膜的制备方法,通过真空冷冻干燥实现了碳纳米管官能化,使用静电纺丝技术将官能化碳纳米管配合溶剂、表面活性剂及致孔剂成功制备出超滤膜。虽然该方法能制备出碳纳米管膜,但制备过程中引入了添加剂,工艺复杂,膜成份容易产生毒性,导电性差,不能作为电催化技术应用于水处理。
中国专利ZL 201110456881.4介绍了一种导电炭膜的制备方法,按一定质量百分比混合的含碳物质、粘结剂、造孔剂和导电剂等物质通过混合研磨、混合捏合、加压成型、炭化等过程制备出导电炭膜。该导电炭膜抗腐蚀性能较好,但是膜表面结构致密,膜通量较低。膜制备过程中掺入了粘结剂、造孔剂和导电剂等物质,使得膜本身带有一定的杂质,会造成潜在的二次污染,而且催化剂并不能集中在起主要催化作用的膜表面,电催化性能较差。
中国专利ZL 200810012222.X介绍了一种卷式炭膜的制备方法,通过配置前驱体聚合物溶液、刮膜、浸渍、刷涂等步骤,实现了卷式炭膜的制备。该膜作为传统的分离膜可用于气体或液体混合物的分离,但是膜本身形态结构使其只能应用于间歇式处理装置,卷曲的结构导致其无法应用于连续式处理装置,污染物降解动力学较低,降解效果不明显。
目前,尚没有通过真空抽滤并负载纳米催化制备碳纳米管电催化膜的相关制备技术。
发明内容
针对现有电催化膜制备技术存在的不足,本发明的目的在于提供一种制备工艺简单、易于操作、电化学性能高、膜通量大的电催化膜及其制备方法。
本发明一种具有降解性能的碳纳米管电催化膜,以有机滤膜为基础骨架材料,将碳纳米管粉末通过真空抽滤固定到有机滤膜上,然后再把具有电催化活性的金属纳米颗粒负载到膜上,即通过电化学吸附方法、按照0.1~0.5摩尔比引入具有电催化活性的金属阳离子,在60~90℃温度梯度内通过水浴加热实现金属氧化物纳米颗粒修饰并负载在碳纳米管基膜上。
本发明一种有降解性能的碳纳米管电催化膜的制备方法,首先对碳纳米管粉末进行预处理以去除杂质,提高对电解质溶液中的金属阳离子的吸附性能;然后,通过真空抽滤,将一定质量的碳纳米管粉末均匀地抽滤到作为骨架材料的有机滤膜上,制备出碳纳米管基膜,接下来将碳纳米管基膜作为阴极,放置于按一定比例配制的含有特定金属阳离子的电解质溶液中,使用惰性金属材料极板作为阳极,在外加直流电场作用下,完成碳纳米管基膜对电解质溶液中的阳离子的电化学吸附;最后,将经过电化学吸附的碳纳米管基膜,在一定温度范围内进行水浴加热,以沉淀膜表面的金属氧化物,最终制备出碳纳米管电催化膜。
本发明有降解性能的碳纳米管电催化膜的制备方法具体如下:
1)碳纳米管粉末的煅烧预处理,为去除碳纳米管粉末内的非晶和非碳杂质,将一定质量的碳纳米管在管式炉中进行煅烧处理,按照预定升温速率升高至目标温度,到达目标温度后保持一定时间。
预处理使用的碳纳米管质量为15-40mg。煅烧升温速率为5-10℃/min,目标温度范围为300-600℃,煅烧时间为1-4h。
2)碳纳米管粉末的酸洗预处理,为去除碳纳米管粉末在制备过程中残留的金属元素,如铁、镍元素等,增强碳纳米管对金属阳离子的吸附性能,经过上述步骤1)预处理的碳纳米管粉末酸溶液中进行酸洗,加热,超声搅拌。
使用的酸溶液为没食子酸、浓盐酸、浓硝酸等,容积为0.5-1.0L,加热温度为70-80℃,搅拌时间为12-24h。碳纳米管管束表面的缺陷位点可以与强酸产生的羧基及羟基等带负电官能团相结合,实现碳纳米管的表面修饰,这不仅可以改善碳纳米管粉末的分散性能,同时还能更有效地吸附电解质溶液中的金属阳离子。
3)经过上述步骤2)预处理的碳纳米管粉末分散至有机溶液中,在室温下进行超声处理,以实现碳纳米管粉末的充分分散。将经过分散的碳纳米管溶液均匀地抽滤到作为骨架材料的有机滤膜上,制备出碳纳米管基膜。抽滤完成后依次使用乙醇、乙醇-去离子水、去离子水洗涤干净,放在烘箱中烘干。
分散使用的有机溶液为乙醇、四氯化碳、二甲基亚砜等。超声处理时间为1-5h。用作骨架的有机滤膜为聚四氟乙烯膜、聚酰胺膜、混和纤维素酯膜、聚偏氟乙烯膜等。滤膜的孔径分布范围为0.2-5.0μm。洗涤用乙醇和水溶液体积为250-500ml。烘干温度为60-100℃。
4)经过上述步骤3)烘干后制备的碳纳米管基膜,浸入按照一定比例配制的含有特定金属阳离子盐和锡盐的混合电解质溶液中。使用惰性金属极板作阳极,碳纳米管基膜作阴极,外接直流电源,在一定电压范围内进行电化学吸附。电化学吸附结束后,使用乙醇和去离子水将碳纳米管基膜洗涤干净。
惰性金属极板为钛板、钽板、铂板等,面积为3×3cm2-5×5cm2。特定金属阳离子盐为硝酸铋、氯化铋、硫酸铋、氯化锑、硝酸锑等,锡盐为氯化亚锡、草酸亚锡、结晶四氯化锡等。混合电解质溶液中特定金属阳离子盐和锡盐的摩尔比为0.1-0.5,特定阳离子盐水溶液的摩尔浓度为0.05-0.1M,电解质溶液的体积为200-500ml,外加直流电压的范围是1-3V,电化学吸附的时间为1-3h。
5)经过上述步骤4)制备的碳纳米管膜放入恒温水浴锅中,在一定温度范围内进行水浴加热,以沉淀电化学吸附在碳纳米管膜上的金属阳离子。水浴加热结束后,将碳纳米管膜放入烘箱中烘干,最终制备碳纳米管电催化膜。
水浴加热温度范围为60-90℃,水浴加热时间为1-2h,烘箱烘干温度为80-100℃,烘干时间为1-3h。
本发明具有下述有益效果:
本发明制备的碳纳米管电催化膜制备工艺简单,电化学性能优异,污染物降解效率高效,成本较低,易于实现大规模生产,适用范围广,具有很大的市场应用价值。
附图说明:
图1为实施例1所得产物的XPS谱图;
图2为实施例1所得产物的EIS谱图;
图3a为实施例1所得产物的SEM照片之一;
图3b为实施例1所得产物的SEM照片之二;
图4为实施例1所得产物的EDS照片;
图5为实施例1所得产物的苯酚降解效率图。
具体实施方式
下面结合实施例进一步叙述本发明,具体实施例不限制本发明的权利要求。
实施例1
取原始碳纳米管粉末20mg,在温度为400℃下煅烧,煅烧时间为1h。用浓盐酸搅拌处理24h,通过真空抽滤制备出碳纳米管基膜,然后在直流电场作用下把碳纳米管基膜浸没在200ml溶解有5.00g SnCl2和0.535g Bi(NO3)3·5H2O的电解质溶液中进行电化学吸附,外加直流电压为2V,吸附时间为2h。电化学吸附结束后,样品置于温度为90℃的恒温水浴锅中进行水浴加热,以沉淀表面金属氧化物,加热时间为1.5h,并用去离子水洗涤,将所得样品在烘箱中烘干,烘干温度为80℃,即可制备出碳纳米管电催化膜。
采用电化学工作站测量碳纳米管电催化膜的EIS值,采用苯酚(水溶液浓度为100mg/L)作为目标污染物,在水通量为0.5mL/min等一定实验条件下测量碳纳米管电催化膜对苯酚的降解效果。检测结果显示,碳纳米管电催化膜的EIS为7.6Ω,苯酚降解率为95%。
图1为实施例1所得产物的XPS谱图,可以确认碳纳米管电催化膜的表面化学状态和元素组成情况,电催化膜含有C、O、Sn、Bi元素,说明本发明方法可以成功使碳纳米管基膜表面负载Bi-SnO2催化剂。
图2为实施例1所得产物的EIS谱图,阻抗谱图由低频区的直线段和高频区的半圆弧构成。低频区的直线表明该时刻内电荷转移主要受电极中电子的扩散控制,而高频区的半圆弧表明溶液与电极之间的电荷的传递,因此谱图中半圆弧的直径代表了电子传递阻抗的大小。EIS谱图显示,碳纳米管基膜的电子传递阻抗EIS为12.1Ω,而碳纳米管电催化膜的电子传递阻抗EIS为7.6Ω,明显小于碳纳米管基膜,说明碳纳米管基膜经过Bi-SnO2纳米催化剂的修饰,其电子传递阻抗明显降低,电子转移速率加快,导电性提高。
图3为实施例1所得产物的SEM照片,其中a为碳纳米管基膜的SEM图,b为碳纳米管电催化膜的SEM图。从图3a可以看出,碳纳米管基膜具有丰富的多孔结构,且碳纳米管颗粒在三维空间尺度上取向随机,形成一个多孔的网络结构,膜的比表面积大,可充分发挥膜的分离性能,而且碳纳米管管壁整洁光滑,无催化剂颗粒附着。从图3b可以看出,碳纳米管的平均长度和网络结构经Bi-SnO2修饰前后没有明显改变,管束表面均匀负载了Bi-SnO2纳米催化颗粒,原本光滑的管状结构变得粗糙,大大增加了膜的比表面积,表明使用本发明方法可以成功制备出碳纳米管电催化膜。
图4为实施例1所得产物的EDS照片,经Bi-SnO2修饰的碳纳米管电催化膜中除含有C元素和O元素外,还含有Sn和Bi元素,Sn和Bi的质量百分数分别为10.72%和3.84%(具体组分见表1),说明Bi-SnO2已成功地负载到碳纳米管表面上。
表1
图5为实施例1所得产物的苯酚降解效果图,未经Bi-SnO2修饰的碳纳米管基膜对苯酚最大降解率为40%,而经Bi-SnO2修饰的碳纳米管电催化膜的苯酚降解率可达95%,说明经过纳米催化剂负载修饰的碳纳米管电催化膜的电催化降解性能有了极大的提高,可以有效降解水中的苯酚等有机污染物。
实施例2
取原始碳纳米管粉末15mg,在温度为500℃下煅烧,煅烧时间为2h。用浓盐酸搅拌处理36h,通过真空抽滤制备出碳纳米管基膜,然后在直流电场作用下把碳纳米管基膜浸没在300ml溶解有3.00g SnO2和0.15g SbCl3的电解质溶液中进行电化学吸附,外加电压1.5V,学吸附时间为2h。电化学吸附结束后,样品置于70℃恒温水浴锅中进行水浴加热,以沉淀表面金属氧化物,加热时间为1h,后用去离子水洗涤,将所得样品在烘箱中烘干,烘干温度为90℃,即可制备出碳纳米管电催化膜。
采用电化学工作站测量碳纳米管电催化膜的EIS值,采用苯酚(水溶液浓度为100mg/L)作为目标污染物,在水通量为3.0mL/min等一定实验条件下测量碳纳米管电催化膜对苯酚的降解效果。检测结果显示,碳纳米管电催化膜的EIS为10.2Ω,苯酚降解率为83%。
实施例3
取原始碳纳米管10mg,在温度为500℃下煅烧,煅烧时间为3h。用浓盐酸搅拌处理12h,通过真空抽滤制备出碳纳米管基膜,然后在直流电场作用下把碳纳米管基膜浸没在500ml溶解有1.00g SnCl2和0.107g Bi(NO3)3·5H2O的电解质溶液中进行电化学吸附,外加电压1V,吸附时间为1h。电化学吸附结束后,样品置于恒温水浴锅中,在60℃温度下进行水浴加热,以沉淀表面金属氧化物,加热时间为2h,后用去离子水洗涤,将所得样品在烘箱中烘干,烘干温度为90℃,即可制备出碳纳米管电催化膜。
采用电化学工作站测量碳纳米管电催化膜的EIS值,采用苯酚(水溶液浓度为100mg/L)作为目标污染物,在水通量为5.0mL/min等一定实验条件下测量碳纳米管电催化膜对苯酚的降解效果。检测结果显示,碳纳米管电催化膜的EIS为13.2Ω,苯酚降解率为73%。
实施例4
取原始碳纳米管40mg,在温度为400℃下煅烧,煅烧时间为4h。用浓盐酸搅拌处理24h,通过真空抽滤制备出碳纳米管基膜,然后在直流电场作用下把碳纳米管基膜浸没在400ml溶解有5.00g SnO2和0.25g SbCl3的电解质溶液中进行电化学吸附,外加电压为3V,吸附时间为1h。电化学吸附结束后,样品置于恒温水浴锅中,在90℃温度下进行水浴加热,以沉淀表面金属氧化物,加热时间为1h,后用去离子水洗涤,将所得样品在烘箱中烘干,烘干温度为100℃,即可制备出碳纳米管电催化膜。
采用电化学工作站测量碳纳米管电催化膜的EIS值,采用苯酚(水溶液浓度为100mg/L)作为目标污染物,在水通量为1.5mL/min等一定实验条件下测量碳纳米管电催化膜对苯酚的降解效果。检测结果显示,碳纳米管电催化膜的EIS为8.6Ω,苯酚降解率为89%。
Claims (6)
1.一种具有降解性能的碳纳米管电催化膜,其特征是,以有机滤膜为基础骨架材料,将碳纳米管粉末通过真空抽滤固定到有机滤膜上,然后再把具有电催化活性的金属纳米颗粒负载到膜上,即通过电化学吸附方法、按照0.1~0.5摩尔比引入具有电催化活性的金属阳离子,在60~90℃温度范围内通过水浴加热实现金属氧化物纳米颗粒修饰并负载在碳纳米管基膜上。
2.一种如权利要求1所述的具有降解性能的碳纳米管电催化膜的制备方法,其特征是,按照下述步骤进行:
1)碳纳米管粉末的煅烧预处理:
预处理使用的碳纳米管质量为15~40mg;煅烧升温速率为5~10℃/min,升温至目标温度,范围为300~600℃,煅烧时间为1~4h;
2)碳纳米管粉末的酸洗预处理:
将经过上述步骤1)预处理的碳纳米管粉末酸溶液中进行酸洗,加热,超声搅拌,加热温度为70~80℃,搅拌时间为12~24h;
3)将经过上述步骤2)预处理的碳纳米管粉末分散至有机溶液中,在室温下进行超声处理,超声处理时间为1~5h;将经过分散的碳纳米管溶液均匀地抽滤到作为骨架材料的有机滤膜上,制备出碳纳米管基膜;抽滤完成后依次使用乙醇、乙醇-去离子水、去离子水洗涤干净,放在烘箱中烘干,烘干温度为60~100℃;
4)经过上述步骤3)烘干后制备的碳纳米管基膜,浸入按照一定比例配制的含有特定金属阳离子盐和锡盐的混合电解质溶液中,使用惰性金属极板作阳极,碳纳米管基膜作阴极,外接直流电源,在一定电压范围内进行电化学吸附,电化学吸附结束后,使用乙醇和去离子水将碳纳米管基膜洗涤干净;
所述特定金属阳离子盐为硝酸铋、氯化铋、硫酸铋、氯化锑或硝酸锑,锡盐为氯化亚锡、草酸亚锡或结晶四氯化锡;混合电解质溶液中特定金属阳离子盐和锡盐的摩尔比为0.1~0.5,特定阳离子盐水溶液的摩尔浓度为0.05~0.1M,外加直流电压的范围是1~3V,电化学吸附的时间为1~3h;
5)经过上述步骤4)制备的碳纳米管膜放入恒温水浴锅中,在60~90℃温度范围内进行水浴加热,水浴加热时间为1~2h,以沉淀电化学吸附在碳纳米管膜上的金属阳离子,水浴加热结束后,将碳纳米管膜放入烘箱中烘干,烘箱烘干温度为80~100℃,烘干时间为1~3h,最终制备碳纳米管电催化膜。
3.根据权利要求2所述的具有降解性能的碳纳米管电催化膜的制备方法,其特征是,所述步骤2)中使用的酸溶液为没食子酸、浓盐酸或浓硝酸,容积为0.5~1.0L。
4.根据权利要求2所述的具有降解性能的碳纳米管电催化膜的制备方法,其特征是,所述步骤3)中分散使用的有机溶液为乙醇、四氯化碳或二甲基亚砜。
5.根据权利要求2所述的具有降解性能的碳纳米管电催化膜的制备方法,其特征是,所述步骤3)中用作骨架的有机滤膜为聚四氟乙烯膜、聚酰胺膜、混和纤维素酯膜或聚偏氟乙烯膜,有机滤膜的孔径分布范围为0.2~5.0μm。
6.根据权利要求2所述的具有降解性能的碳纳米管电催化膜的制备方法,其特征是,所述步骤4)中惰性金属极板为钛板、钽板或铂板,惰性金属极板面积为3×3cm2~5×5cm2。
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