CN112076752A - 一种mof-74衍生磁性复合催化剂及其制备方法和应用 - Google Patents
一种mof-74衍生磁性复合催化剂及其制备方法和应用 Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 239000013118 MOF-74-type framework Substances 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 40
- 239000011701 zinc Substances 0.000 claims abstract description 33
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 17
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000002791 soaking Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000013110 organic ligand Substances 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 229960002089 ferrous chloride Drugs 0.000 claims description 7
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 7
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- WABMHCVYKWKAAH-UHFFFAOYSA-N dimethyl 2,5-dihydroxybenzene-1,4-dicarboxylate Chemical compound COC(=O)C1=CC(O)=C(C(=O)OC)C=C1O WABMHCVYKWKAAH-UHFFFAOYSA-N 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims 1
- 239000011790 ferrous sulphate Substances 0.000 claims 1
- 235000003891 ferrous sulphate Nutrition 0.000 claims 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims 1
- 239000004246 zinc acetate Substances 0.000 claims 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims 1
- 229960001763 zinc sulfate Drugs 0.000 claims 1
- 229910000368 zinc sulfate Inorganic materials 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 8
- 230000004913 activation Effects 0.000 abstract description 5
- 239000010865 sewage Substances 0.000 abstract description 5
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 abstract description 4
- 230000005389 magnetism Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 abstract 1
- -1 polytetrafluoroethylene Polymers 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 239000003344 environmental pollutant Substances 0.000 description 9
- 231100000719 pollutant Toxicity 0.000 description 9
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 5
- 229910002567 K2S2O8 Inorganic materials 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 229960001680 ibuprofen Drugs 0.000 description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical group O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical group C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 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 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
Classifications
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- B01J35/33—
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
-
- 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
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
本发明属于污水处理领域,特别涉及一种MOF‑74衍生磁性复合催化剂及其制备方法和应用,所述MOF‑74衍生磁性复合催化剂的制备方法为:步骤1:将含锌的金属盐、有机配体加入到溶剂中并搅拌均匀,经水热反应制得基于MOF‑74结构的晶体材料;步骤2,将步骤1制得的基于MOF‑74结构的晶体材料置于亚铁盐溶液中浸泡后制得复合晶体;步骤3,在惰性气体(如氮气)环境下,将步骤2制得的复合晶体煅烧制得MOF‑74衍生磁性复合催化剂;本发明制得的MOF‑74衍生磁性复合催化剂对过一硫酸盐和过二硫酸盐有很好的活化效果,从而高效快速去除水体中各种有机污染物,同时,MOF‑74衍生磁性复合催化剂具有良好的磁性,可通过磁铁进行回收再利用。
Description
技术领域
本发明属于污水处理领域,特别涉及一种MOF-74衍生磁性复合催化剂及其制备方法和在快速去除水中有机污染物中应用。
背景技术
近些年,国民经济的快速发展导致每年的工业废水排放量大幅增加,这些污水中含有大量有机污染物。同时,生活用水中的有机污染物从种类到含量上也显著提高。有机污染物对环境危害极大,特别是水中的有机污染会通过各种途径进入到人体,严重损害人类的身体健康。
传统污水处理方法难以有效去除有机污染物,特别是在污染物浓度较大的条件下,传统污水处理方法在速度、效率和深度上劣势明显。而高级氧化法成为近年来处理有机污染物的有效方法。其中,基于活化过硫酸盐而生成硫酸根自由基(SO4-·)处理水体有机污染物的高级氧化技术在近些年备受青睐,其拥有氧化选择性强,pH适用范围广,半衰期(30-40us)长,降解速度快,降解完全等优点。
过渡金属活化过硫酸盐产生SO4-·具有常温活化、重复使用等优势。然而催化材料的回收成为阻碍其广泛应用的挑战。
发明内容
本发明解决现有技术中存在的上述技术问题,提供一种MOF-74衍生磁性复合催化剂及其制备方法和在快速去除水中有机污染物中应用。
为解决上述问题,本发明的技术方案如下:
一种MOF-74衍生磁性复合催化剂的制备方法,包括以下步骤:
步骤1:将含锌的金属盐、有机配体加入到溶剂中并搅拌均匀,经水热反应制得基于MOF-74结构的晶体材料;
步骤2,将步骤1制得的基于MOF-74结构的晶体材料置于亚铁盐溶液中浸泡后制得复合晶体;
步骤3,在惰性气体(如氮气)环境下,将步骤2制得的复合晶体煅烧制得MOF-74衍生磁性复合催化剂。
优选地,所述步骤1中,含锌的金属盐为六水硝酸锌(Zn(NO3)2.6H2O)、二水醋酸锌(Zn(COOCH3)2.2H2O)、氯化锌(ZnCl2)、七水硫酸锌(ZnSO4.7H2O)中任意一种。
优选地,所述步骤1中,有机配体为2,5-二羟基对苯二甲酸二甲酯(DHTA,CAS:610-92-4)。
优选地,所述步骤1中,将含锌的金属盐、有机配体加入到溶剂中并搅拌均匀制得的溶液中,含锌的金属盐的摩尔浓度为10mM~50mM;有机配体的摩尔浓度为10mM~50mM。
优选地,所述步骤1中,溶剂为去离子水(H2O)、二甲基甲酰胺(DMF)、乙醇中的一种或几种。
优选地,所述步骤1中,水热反应的反应温度为80-170℃,反应时间为8-72小时。
优选地,所述步骤2中,亚铁盐为七水硫酸亚铁(FeSO4.7H2O),四水氯化亚铁(FeCl2.4H2O)中任意一种。
优选地,所述步骤2中,亚铁盐溶液的浓度为1g/L-50g/L,浸泡时间为1-24h。
优选地,所述步骤3中,煅烧温度为900-1400℃,煅烧时间为2-6h。
上述MOF-74衍生磁性复合催化剂对过硫酸盐(过二硫酸钾(K2S2O8)、过一硫酸氢钾(Oxone))有很好的活化效果,该MOF-74衍生磁性复合催化剂-过硫酸盐体系,可以快速去除水体中各种有机污染物,达到污水净化的目的。
相对于现有技术,本发明的优点如下,
金属有机骨架(MOF)是一类具有周期性网络结构的晶态多孔材料,利用金属锌在900℃左右蒸发的特点,可将含锌MOF煅烧为多孔碳材料。同时,MOF-74结构中的苯酚基团具有良好的氧化性,可将亚铁盐氧化为氧化铁,使材料具有磁性可回收的性质。因此,将含锌的MOF-74晶体亚铁盐相结合,并高温煅烧,可得到吸附和催化能力均很强的磁性催化剂,用于活化过硫酸盐,高效快速去除水中有机污染物;该复合催化剂具有良好的磁性,可通过磁铁进行回收再利用;可应用于高效去除污水中各类有机污染物。
具体实施方式
实施例1:
将Zn(COOCH3)2.2H2O(219.5mg,1.0mmol)与DHTA(1000.0mg,5.0mmol)加入到100mLDMF/H2O/乙醇(体积比9/1/1)的溶剂中,搅拌均匀后放入聚四氟反应釜,放入烘箱内,80℃反应72h后取出,用乙醇清洗三次后过滤得到MOF-74(Zn)晶体。将100mg MOF-74(Zn)晶体置于100mL浓度为20g/L的四水氯化亚铁(FeCl2.4H2O)溶液中浸泡12h;在将浸泡后的复合晶体清洗若干次后,放入管式炉中,在氮气环境下,在1200℃下煅烧4h以去除锌元素,最终得到磁性复合催化剂。1mM该磁性催化剂与2mM的Oxone结合,可以在10分钟内将浓度为2mM的罗丹明B完全去除,同样污染物降解实验条件重复使用5次,污染物去除效率不降低。
实施例2:
将Zn(NO3)2.6H2O(297.5mg,1.0mmol)与DHTA(200.0mg,1.0mmol)加入到100mLDMF/H2O(体积比9/1)的溶剂中,搅拌均匀后放入聚四氟反应釜,放入烘箱内,170℃反应8h后取出,用乙醇清洗三次后过滤得到MOF-74(Zn)晶体。将100mg MOF-74(Zn)晶体置于100mL浓度为1g/L的七水硫酸亚铁(FeSO4.7H2O)溶液中浸泡24h;在将浸泡后的复合晶体清洗若干次后,放入管式炉中,在氮气环境下,在900℃下煅烧6h以去除锌元素,最终得到磁性复合催化剂。2mM该磁性催化剂与0.5mM的K2S2O8结合,可以在10分钟内将浓度为1mM的双酚A完全去除,同样污染物降解实验条件重复使用5次,污染物去除效率不降低。
实施例3:
将ZnCl2(136.3mg,1.0mmol)与DHTA(600.0mg,3.0mmol)加入到100mL DMF的溶剂中,搅拌均匀后放入聚四氟反应釜,放入烘箱内,140℃反应48h后取出,用乙醇清洗三次后过滤得到MOF-74(Zn)晶体。将100mg MOF-74(Zn)晶体置于100mL浓度为50g/L的四水氯化亚铁(FeCl2.4H2O)溶液中浸泡1h;在将浸泡后的复合晶体清洗若干次后,放入管式炉中,在氮气环境下,在1400℃下煅烧2h以去除锌元素,最终得到磁性复合催化剂。1mM该磁性催化剂与5mM的Oxone结合,可以在10分钟内将浓度为1mM的4-氯酚完全去除,同样污染物降解实验条件重复使用5次,污染物去除效率不降低。
实施例4:
将ZnSO4.7H2O(1437.8mg,5.0mmol)与DHTA(1000.0mg,5.0mmol)加入到100mL DMF的溶剂中,搅拌均匀后放入聚四氟反应釜,放入烘箱内,160℃反应36h后取出,用乙醇清洗三次后过滤得到MOF-74(Zn)晶体。将100mg MOF-74(Zn)晶体置于100mL浓度为10g/L的四水氯化亚铁(FeCl2.4H2O)溶液中浸泡36h;在将浸泡后的复合晶体清洗若干次后,放入管式炉中,在氮气环境下,在1000℃下煅烧4h以去除锌元素,最终得到磁性复合催化剂。1mM该磁性催化剂与2mM的K2S2O8结合,可以在10分钟内将浓度为1mM的布洛芬完全去除,同样污染物降解实验条件重复使用5次,污染物去除效率不降低。
对比例1:
将ZnSO4.7H2O(287.56mg,1.0mmol)与DHTA(800.0mg,4.0mmol)加入到100mL DMF的溶剂中,搅拌均匀后放入聚四氟反应釜,放入烘箱内,160℃反应36h后取出,用乙醇清洗三次后过滤得到MOF-74(Zn)晶体。将100mg MOF-74(Zn)晶体置于100mL浓度为10g/L的四水氯化亚铁(FeCl2.4H2O)溶液中浸泡36h;在将浸泡后的复合晶体清洗若干次后,放入管式炉中,在氮气环境下,在700℃下煅烧4h,最终得到的复合催化剂,体系中的锌元素无法去除,单位质量催化效率较低。1mM该催化剂与2mM的K2S2O8结合,去除浓度为1mM的布洛芬需要30分钟。
对比例2:
将ZnCl2(136.3mg,1.0mmol)与DHTA(600.0mg,3.0mmol)加入到100mL DMF的溶剂中,搅拌均匀后放入聚四氟反应釜,放入烘箱内,140℃反应48h后取出,用乙醇清洗三次后过滤得到MOF-74(Zn)晶体。将100mg MOF-74(Zn)晶体置于100mL浓度为50g/L的四水氯化亚铁(FeCl2.4H2O)溶液中浸泡1h;在将浸泡后的复合晶体清洗若干次后,放入管式炉中,在氮气环境下,在1600℃下煅烧2h后,体系中铁元素含量少于1%,几乎没有磁性,降解试验后难以回收。
需要说明的是上述实施例仅仅是本发明的较佳实施例,并没有用来限定本发明的保护范围,在上述基础上做出的等同替换或者替代均属于本发明的保护范围。
Claims (10)
1.一种MOF-74衍生磁性复合催化剂的制备方法,其特征在于,包括以下步骤:
步骤1:将含锌的金属盐、有机配体加入到溶剂中并搅拌均匀,经水热反应制得基于MOF-74结构的晶体材料;
步骤2,将步骤1制得的基于MOF-74结构的晶体材料置于亚铁盐溶液中浸泡后制得复合晶体;
步骤3,在惰性气体环境下,将步骤2制得的复合晶体煅烧制得MOF-74衍生磁性复合催化剂。
2.如权利要求1所述的制备方法,其特征在于,所述步骤1中,含锌的金属盐为硝酸锌、醋酸锌、氯化锌、硫酸锌中任意一种,有机配体为2,5-二羟基对苯二甲酸二甲酯。
3.如权利要求1所述的制备方法,其特征在于,所述步骤1中,将含锌的金属盐、有机配体加入到溶剂中并搅拌均匀制得的溶液中,含锌的金属盐的摩尔浓度为10mM~50mM;有机配体的摩尔浓度为10mM~50mM。
4.如权利要求1所述的制备方法,其特征在于,所述步骤1中,溶剂为去离子水、二甲基甲酰胺、乙醇中的一种或几种。
5.如权利要求1所述的制备方法,其特征在于,所述步骤1中,水热反应的反应温度为80-170℃,反应时间为8-72小时。
6.如权利要求1所述的制备方法,其特征在于,所述步骤2中,亚铁盐为硫酸亚铁或氯化亚铁。
7.如权利要求1所述的制备方法,其特征在于,所述步骤2中,亚铁盐溶液的浓度为1g/L-50g/L,浸泡时间为1-24h。
8.如权利要求1所述的制备方法,其特征在于,所述步骤3中,煅烧温度为900-1400℃,煅烧时间为2-6h。
9.如权利要求1-8任一项所述的制备方法制得的MOF-74衍生磁性复合催化剂。
10.如权利要求1-8任一项所述的制备方法制得的MOF-74衍生磁性复合催化剂在去除水中有机污染物中的应用。
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