CN114985006B - 一种二维层状催化膜材料及制备方法与应用 - Google Patents
一种二维层状催化膜材料及制备方法与应用 Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 title abstract description 23
- 239000000463 material Substances 0.000 title abstract description 12
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 claims abstract description 55
- 229910003321 CoFe Inorganic materials 0.000 claims abstract description 51
- 239000002135 nanosheet Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012266 salt solution Substances 0.000 claims abstract description 16
- 230000015556 catabolic process Effects 0.000 claims abstract description 9
- 150000001868 cobalt Chemical class 0.000 claims abstract description 9
- 238000006731 degradation reaction Methods 0.000 claims abstract description 9
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 8
- 229940088710 antibiotic agent Drugs 0.000 claims abstract description 8
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- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 23
- 239000002064 nanoplatelet Substances 0.000 claims description 15
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000264 sodium ferrocyanide Substances 0.000 claims description 12
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 8
- -1 ferrous cyanide salt Chemical class 0.000 claims description 5
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 238000011085 pressure filtration Methods 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 2
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 2
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical class [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 abstract description 14
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 6
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 229910052723 transition metal Inorganic materials 0.000 description 9
- 239000011943 nanocatalyst Substances 0.000 description 8
- 150000003624 transition metals Chemical class 0.000 description 7
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- 230000005540 biological transmission Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000002077 nanosphere Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000009303 advanced oxidation process reaction Methods 0.000 description 3
- 230000033558 biomineral tissue development Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 description 3
- 229960001180 norfloxacin Drugs 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
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- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
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- 239000011259 mixed solution Substances 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000012984 antibiotic solution Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- UETZVSHORCDDTH-UHFFFAOYSA-N iron(2+);hexacyanide Chemical compound [Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UETZVSHORCDDTH-UHFFFAOYSA-N 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
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- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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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
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- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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Abstract
本发明公开了一种二维层状催化膜材料及制备方法与应用,二维层状催化膜材料是由CoFe PBAs纳米片配成水溶液,通过气体压滤制备得到。CoFe PBAs纳米片是由1‑4mmol/L的亚铁氰根盐溶液以1‑20mL/min的速度滴加到4mmol/L的钴盐溶液共沉淀;收集固体产物,洗涤、干燥后即得到的。本发明基于氰基配位化合物合成方法简单、可控的特点制备二维钴铁氰基配位化合物纳米片,并组装成自支撑的层状膜进行动态水处理应用,实现对水体抗生素有机污染物的高效动态催化降解。
Description
技术领域
本发明涉及催化材料技术领域,具体涉及一种二维层状催化膜材料及制备方法与应用。
背景技术
高级氧化技术(Advanced oxidation processes,AOPs)是一项基于活性自由基作用以实现对有机污染物完全矿化或部分氧化的水处理技术。因其无需对污染物进行二次处理过程,相较其他水处理技术(吸附、离子交换、纳滤等),AOPs更直接、更彻底、应用前景更广阔。而传统的芬顿氧化技术在处理新兴难降解有机废水过程中,羟基自由基利用率低,导致芬顿矿化过程难以进行;而且传统芬顿过程产生大量铁泥,铁泥作为危废处理,成本非常高。针对于此,基于催化剂材料的非均相催化过程可通过催化剂表面有机物浓缩和界面反应实现活性自由基的高效利用,以达到难降解有机污染物的高效矿化降解;而且绝大部分催化剂可回用。其中过渡金属纳米材料是一类性能优越的异相催化剂,能够有效实现水体有机污染物的催化降解。尤其是二维过渡金属纳米材料,高的长径比和超薄二维片层厚度,使其具有高比表面积和高的活性位点暴露,在异相高级氧化中被认为是极具前景的一类催化剂材料。然而纳米催化剂因高比表面积、高活性导致的团聚问题大大限制了其催化活性和传质过程;此外,水处理应用过程中纳米颗粒难以管控,一旦泄露或排放进入环境,其自身便会引起相应的生态和健康风险,产生二次污染,这也是微纳米催化剂所面临的应用难题。
将纳米催化剂与膜分离技术相结合形成的催化膜,不仅克服了微纳米催化剂的应用难题,而且集成了新的理化优势。与其他维度(零维或一维)纳米材料所不同,二维纳米催化剂具有自身可组装成层状膜的优势。因此,二维层状催化膜一方面避免溶液体系中微纳米颗粒的团聚和管控问题;另一方面,催化膜的运行是一个动态过程,反应底物的输入和反应产物的输出在经过膜前后是一个连续和实时更替的过程,有效避免了溶液体系中出现的催化效率逐渐降低的现象,同时也克服了微纳米催化剂在污染物催化中间产物影响下的钝化问题。因此,对于二维过渡金属层状催化膜的组装,关键在于制备流程简单、结构完整、产率高的超薄二维纳米片层,并能够组装成稳定的二维层状膜。
发明内容
针对上述现有技术,本发明的目的是提供一种二维层状催化膜材料及制备方法与应用。本发明基于氰基配位化合物合成方法简单、可控的特点制备二维钴铁氰基配位化合物纳米片,并组装成自支撑的层状膜进行动态水处理应用,实现对水体抗生素有机污染物的高效动态催化降解。
为实现上述目的,本发明采用如下技术方案:
本发明的第一方面,提供一种CoFe PBAs纳米片的制备方法,包括以下步骤:
(1)分别配制1-4mmol/L的亚铁氰根盐溶液和4mmol/L的钴盐溶液,室温下将亚铁氰根盐溶液以1-20mL/min的速度滴加至持续搅拌的钴盐溶液中,随后静置;
(2)静置结束后,抽滤收集固体产物,并用清水洗涤,干燥后即得到CoFe PBAs纳米片。
优选的,步骤(1)中,所述亚铁氰根盐溶液为亚铁氰化钠溶液或亚铁氰化钾溶液;所述钴盐溶液为硫酸钴溶液、氯化钴溶液或硝酸钴溶液;所述亚铁氰根盐溶液与钴盐溶液的体积比为1:5。
优选的,步骤(1)中,所述亚铁氰根盐溶液的浓度为1mmol/L;所述滴加的速度为5mL/min。
优选的,步骤(1)中,所述静置的时间为10~14h。
优选的,步骤(2)中,所述干燥为60℃下真空干燥36h。
本发明的第二方面,提供上述制备方法制备得到的CoFe PBAs纳米片。
本发明的第三方面,提供CoFe PBAs纳米片在制备自支撑二维层状膜或降解抗生素中的应用。
本发明的第四方面,提供一种自支撑CoFe PBAs二维层状膜,由以下方法制备:将CoFe PBAs纳米片配成水溶液,通过气体压滤得到自支撑CoFe PBAs二维层状膜。
优选的,所述水溶液的浓度为0.8mg/mL。
本发明的第五方面,提供自支撑CoFe PBAs二维层状膜在水处理中的应用。
优选的,所述应用为自支撑CoFe PBAs二维层状膜对水体抗生素有机污染物的降解。
本发明的有益效果:
(1)本发明的制备方法简单且产率高,在室温下便可通过共沉积方法直接制备得到二维片层结构,无需其他添加剂或高温高压等条件。
(2)本发明制备的超薄CoFe PBAs二维片层结构完整、径向尺寸可达几个微米(1~5微米),利于成膜。
(3)本发明制备的CoFe PBAs二维片层上Co和Fe过渡金属均匀分布,使得活性位点充分暴露在二维片层表面。
(4)本发明制备的CoFe PBAs纳米片可直接作为基元体组装成自支撑的层状催化膜进行动态水处理应用。
附图说明
图1:不同亚铁氰根盐浓度下制得CoFe PBAs纳米片的电子扫描图;(a)亚铁氰根盐的浓度为1mmol/L;(b)亚铁氰根盐的浓度为2mmol/L;(c)亚铁氰根盐的浓度为4mmol/L;(d)亚铁氰根盐的浓度为6mmol/L;(e)亚铁氰根盐的浓度为8mmol/L;(f)亚铁氰根盐的浓度为12mmol/L;
图2:不同亚铁氰根盐滴加速度下制得CoFe PBAs纳米片的电子扫描图;(a)亚铁氰根盐滴加速度为1mL/min;(b)亚铁氰根盐滴加速度为5mL/min;(c)亚铁氰根盐滴加速度为10mL/min;(d)亚铁氰根盐滴加速度为20mL/min;
图3:CoFe PBAs纳米片的透射电子扫描及过渡金属元素分布图;(a)CoFe PBAs纳米片的透射电子扫描图;(b)单片CoFe PBAs纳米片的透射电子扫描图;(c)扫描透射图;(d)Fe元素分布图;(e)Co元素分布图;
图4:CoFe PBAs纳米片的XPS图;
图5:CoFe PBAs纳米片对抗生素的去除性能比较;
图6:CoFe PBAs纳米片组装得到的自支撑二维层状膜;
图7:二维层状膜的水处理性能比较;(a)去除率;(b)通量。
图8:垂直流向膜池中处理含抗生素污水的过程示意图。
具体实施方式
应该指出,以下详细说明都是例示性的,旨在对本申请提供进一步的说明。除非另有指明,本文使用的所有技术和科学术语具有与本申请所属技术领域的普通技术人员通常理解的相同含义。
正如背景技术部分介绍的,现有技术制备过渡金属二维纳米片通常采用牺牲模板法或表面活性剂引导法,前者制备过程复杂、条件严苛(高温高压等),后者需要添加额外的引导剂。此外,现有技术制得的过渡金属纳米片存在结构缺陷或水稳定性较差,无法组装成完整的层状膜在水处理中进行催化膜运行。
基于此,本发明的目的是提供一种二维层状催化膜材料及制备方法与应用。现有技术制备的钴铁氰基配位化合物均为纳米颗粒或纳米球,纳米球因颗粒间作用面小、结合力弱,无法自组装成稳定的薄膜,而二维纳米片基于其高的长径比可实现片层与片层之间的面对面作用,从而组装成自支撑的二维层状膜。所以本发明基于氰基配位化合物合成方法简单、可控的特点,通过共沉淀制备出二维钴铁氰基配位化合物纳米片,并组装成自支撑的层状膜进行动态水处理应用,实现对水体抗生素有机污染物的高效动态催化降解。在制备纳米片的过程中,只有将特定浓度的二价亚铁氰根离子滴加到二价钴离子中,才能形成纳米片。且亚铁氰根盐和钴盐都需要在特定的浓度和滴加速度下才能形成均一且径向尺寸较大的纳米片。
为了使得本领域技术人员能够更加清楚地了解本申请的技术方案,以下将结合具体的实施例详细说明本申请的技术方案。
本发明实施例中所用的试验材料均为本领域常规的试验材料,均可通过商业渠道购买得到。
实施例1
(1)分别配制1mmol/L的亚铁氰化钠溶液100mL和4mmol/L的硫酸钴溶液500mL。在室温(25℃)条件下,通过蠕动泵控速的方法将亚铁氰化钠溶液以5mL/min的速度滴入持续搅拌的硫酸钴溶液中,随后静置12小时。
(2)12小时后,通过真空泵抽滤收集固体产物,并用去离子水清洗3次。将清洗好的固体产物在60度下真空干燥36小时后即可得到CoFe PBAs纳米片材料。
(3)将40mg二维CoFe PBAs纳米片配成50mL水溶液,通过气体压滤装置在1bar
压力下组装制备自支撑的二维层状膜(见图6)。
CoFe PBAs纳米片材料的透射电子扫描及过渡金属元素分布图和XPS图分别见图3和4,CoFe PBAs二维片层上Co和Fe过渡金属均匀分布,使得活性位点充分暴露的二维片层表面。
实施例2
与实施例1的区别在于:亚铁氰化钠的浓度为2mmol/L。
实施例3
与实施例1的区别在于:亚铁氰化钠的浓度为4mmol/L。
实施例4
与实施例1的区别在于:亚铁氰化钠溶液的滴加速度为1mL/min。
实施例5
与实施例1的区别在于:亚铁氰化钠溶液的滴加速度为10mL/min。
实施例6
与实施例1的区别在于:亚铁氰化钠溶液的滴加速度为20mL/min。
对比例1
与实施例1的区别在于:亚铁氰化钠的浓度为6mmol/L,得到的是CoFe PBAs片层与颗粒的混合物,无法得到纯相CoFe PBAs纳米片(见图1),所以无法制备CoFe PBAs二维层状膜。
对比例2
与实施例1的区别在于:亚铁氰化钠的浓度为8mmol/L,得到的是CoFe PBAs无规则颗粒,无法得到CoFe PBAs纳米片(见图1),所以无法制备CoFe PBAs二维层状膜。
对比例3
与实施例1的区别在于:亚铁氰化钠的浓度为12mmol/L,得到的是CoFe PBAs颗粒,无法得到CoFe PBAs纳米片(见图1),所以无法制备CoFe PBAs二维层状膜。
对比例4
按照申请号201710300143.8磁性纳米催化剂CoFe-PBAs@rGO催化Oxone降解有机燃料废水的方法中实施例2的方法制备CoFe-PBAs纳米球:
(1)在常温常压下,将40mL含2mmoL K3[Fe(CN)6]的水溶液滴加到40mL含3mmoLCoCl2·H2O和1.2gPVP的水溶液中,搅拌24h后离心收集沉淀,用无水乙醇和去离子水各洗涤3次,然后在烘箱中于60℃烘干,得到普鲁士蓝类配合物Co3[Fe(CN)6]2,呈小球形,粒径为20nm左右,并且颗粒堆积在一起。
(2)将40mg CoFe PBAs纳米球配成50mL水溶液,通过气体压滤装置无法制备自支撑的二维层状膜。
由图1不同前驱体浓度下制得CoFe PBAs纳米片的电子扫描图可以看出,前驱体Fe(CN)6 4-的浓度在(1~4)mmol/L时才能形成CoFe PBAs纳米片,超过4mmol/L则无法形成二维的片层;低于1mmol/L则金属离子利用率与产率太低。
Co2+与Fe(CN)6 4-的比例决定最后的二维层状催化膜性能,以Co2+(4mmol/L)浓度不变为例,Fe(CN)6 4-浓度从1mmol/L增加到4mmol/L,催化膜性能(通量和去除率)依次降低,因此4mmol/L的Co2+与1mmol/L的Fe(CN)6 4-为最佳配比,在此配比下制备的纳米片结构完整、径向尺寸可达几个微米(1~5微米),利于成膜。
由图2不同前驱体滴加速度下制得CoFe PBAs纳米片的电子扫描图可以看出,Fe(CN)6 4-溶液滴加到Co2+溶液中的速度从1mL/min增加到20mL/min,在5mL/min下制得的二维片层最均一且径向尺寸较大;而低速(1mL/min)和高速(10,20mL/min)条件下制得的产物均匀性较差,且径向尺寸相对较小。
应用例1
(1)分别将40mg实施例1~3制备的CoFe PBA纳米片加入到400mL、10mg/L的诺氟沙星抗生素溶液中,并在25℃下磁力搅拌30min。
(2)在上述混合溶液中添加20mg过硫酸氢钾作为氧化剂,实施例1制备的CoFe PBA纳米片可在10min内实现抗生素污染物接近100%的去除。
应用例2
(1)将实施例1~3制备好的CoFe PBA二维层状膜装载在连续运行的垂直流向膜池中(见图8)。空白对照为不添加CoFe PBA二维层状膜下的运行结果。
(2)通过蠕动泵将含有5mg/L浓度诺氟沙星和50mg/L浓度过硫酸氢钾的混合溶液以0.3bar压力输送进入膜池。
(3)经过CoFe PBA二维层状膜的连续动态催化便可实现对诺氟沙星的瞬时催化去除(见图7a)。
说明本发明制备的CoFe PBA二维层状膜可广泛用于工业和生活污水中抗生素的去除。
以上所述仅为本申请的优选实施例而已,并不用于限制本申请,对于本领域的技术人员来说,本申请可以有各种更改和变化。凡在本申请的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本申请的保护范围之内。
Claims (5)
1. 一种CoFe PBAs纳米片的制备方法,其特征在于,包括以下步骤:
(1)将浓度为1mmol/L的亚铁氰根盐溶液在室温下,以5mL/min的速度滴加至持续搅拌的4 mmol/L的钴盐溶液中,随后静置;所述亚铁氰根盐溶液为亚铁氰化钠溶液或亚铁氰化钾溶液;所述钴盐溶液为硫酸钴溶液、氯化钴溶液或硝酸钴溶液;所述亚铁氰根盐溶液与钴盐溶液的体积比为1:5;所述静置的时间为10~14h;
(2)静置结束后,收集固体产物,洗涤、干燥后即得到CoFe PBAs纳米片;所述洗涤为用清水洗涤3次,所述干燥为60℃下真空干燥36h。
2.权利要求1所述的制备方法制备得到的CoFe PBAs纳米片,所述CoFe PBAs纳米片的尺寸为1~5微米。
3.权利要求2所述的CoFe PBAs纳米片在制备自支撑二维层状膜或降解抗生素中的应用。
4.一种自支撑CoFe PBAs二维层状膜,其特征在于,由以下方法制备:将权利要求2所述的CoFe PBAs纳米片配成水溶液,通过气体压滤得到自支撑CoFe PBAs二维层状膜;所述水溶液的浓度为0.8mg/mL。
5.权利要求4所述的自支撑CoFe PBAs二维层状膜在水处理中的应用。
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