CN106552620A - 一种选择性降解四环素的分子印迹催化膜的制备方法及用途 - Google Patents
一种选择性降解四环素的分子印迹催化膜的制备方法及用途 Download PDFInfo
- Publication number
- CN106552620A CN106552620A CN201610953221.XA CN201610953221A CN106552620A CN 106552620 A CN106552620 A CN 106552620A CN 201610953221 A CN201610953221 A CN 201610953221A CN 106552620 A CN106552620 A CN 106552620A
- Authority
- CN
- China
- Prior art keywords
- tetracycline
- molecular engram
- solution
- catalytic membrane
- deionized water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004098 Tetracycline Substances 0.000 title claims abstract description 63
- 229960002180 tetracycline Drugs 0.000 title claims abstract description 62
- 229930101283 tetracycline Natural products 0.000 title claims abstract description 62
- 235000019364 tetracycline Nutrition 0.000 title claims abstract description 62
- 150000003522 tetracyclines Chemical class 0.000 title claims abstract description 62
- 239000012528 membrane Substances 0.000 title claims abstract description 45
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 40
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 40
- 230000015556 catabolic process Effects 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005266 casting Methods 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000011521 glass Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 20
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 20
- 229940068984 polyvinyl alcohol Drugs 0.000 claims description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 19
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 10
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 claims description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 5
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229920002301 cellulose acetate Polymers 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 230000000593 degrading effect Effects 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 239000000356 contaminant Substances 0.000 abstract description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 6
- 239000013076 target substance Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000003115 biocidal effect Effects 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000012805 post-processing Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 33
- 230000001699 photocatalysis Effects 0.000 description 19
- 238000005516 engineering process Methods 0.000 description 15
- 238000007146 photocatalysis Methods 0.000 description 14
- 238000001179 sorption measurement Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 238000002835 absorbance Methods 0.000 description 6
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 6
- 239000004005 microsphere Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 4
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229960003405 ciprofloxacin Drugs 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 230000002452 interceptive effect Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 229940063650 terramycin Drugs 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 229910004042 HAuCl4 Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- CCBICDLNWJRFPO-UHFFFAOYSA-N 2,6-dichloroindophenol Chemical compound C1=CC(O)=CC=C1N=C1C=C(Cl)C(=O)C(Cl)=C1 CCBICDLNWJRFPO-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000005276 aerator Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- -1 boron Sodium hydride Chemical compound 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940072172 tetracycline antibiotic Drugs 0.000 description 1
Classifications
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
本发明提供了一种选择性降解四环素的分子印迹催化膜的制备方法及用途,制备步骤主要包括:1、制备Ag@Au@TiO2催化剂;2、制备Ag@Au@TiO2催化剂的分散液;3、利用Ag@Au@TiO2催化剂分散液进一步制备铸膜液;4、利用铸膜液在玻璃板上制备共混膜;5、利用共混膜制备选择性降解四环素的分子印迹催化膜。本发明制备的选择性降解四环素的分子印迹催化膜的光催化降解过程可以有效的实现对目标污染物选择性识别、吸附并催化降解的目的,后处理简单方便,提高了对目标物质的有效降解的效率,具有较强的选择性处理抗生素废水的优点。
Description
技术领域
本发明涉及一种利用相转化技术制备贵金属负载半导体的具有光催化作用的分子印迹催化膜的方法,具体为一种选择性降解四环素的分子印迹催化膜的制备方法及用途,属于材料制备及环境污染治理的技术领域。
背景技术
四环素类抗生素对革兰氏阳性和革兰氏阴性引起严重疾病具有很好的抗菌活性,因此广泛用于人类和动物的疾病预防和治疗或者作为家禽饲料添加剂,但是,由于这类化合物在生物活体中的不完全代谢而被排泄至水环境中,残留的抗生素可激发微生物的选择性遗传变异从而导致抗生素耐药病原体的出现,成为一种危害环境及人类健康的潜在风险,国内外学者研究已经证实了在土壤和水环境中存在四环素类抗生素残留,引起了环境生态学的广泛关注,因此,建立和发展有效和经济适用处理手段来选择性移除环境中四环素类抗生素残留是极为迫切的。
目前,光催化技术已广泛应用于研究水环境中四环素类抗生素的残留。人们对半导体及复合半导体进行改性来处理环境污染取得很好的效果,但是不具有选择性,难以在多种污染物共存的复杂水体中把目标物去除。为提高光催化技术的选择性,利用分子印迹技术与光电催化技术结合,可在多污染物共存的体系中,优先选择去除目标污染物。虽然此项技术在选择性催化降解污染物已经取得很大的发展,但是仍存在他的局限性,光催化剂通常是粉末状的,后续的分离回收再利用繁琐,同传统粒子型分子印迹聚合物(MIPs)相比,四环素分子印迹催化膜(MIM)具有无需研磨等繁琐的制备过程,扩散阻力小,易于应用等独特的优点;同时比一般生物材料更稳定,抗恶劣环境能力更强,在传感器领域和生物活性材料领域具有很大的应用前景;将MIM应用于分离催化领域,由于其具有连续操作、易于放大、能耗低、能量利用率高等优点,可在医药、食品、化工和农业等行业的分离、分析与降解过程中实现“绿色化学”生产。因此,采用分子印迹膜与光催化技术相结合制备的分子印迹催化膜技术实现污染物的选择性降解,是对传统方法降解污染物的改革创新,具有重要的研究与实际生产意义。
分子印迹膜技术是一种将具有选择性识别特性的分子印迹技术与具备分离能力的膜技术相结合,它是是指包含或由分子印迹聚合物组成的一类膜,通过聚合物对模板分子的记忆识别性能达到分子识别的目的,其分子空间识别能力强,可实现高选择性分离;基本思路是在聚合介质中加入印迹分子,成膜后将印迹分子除去,印迹聚合层网状结构中就留下了与印迹分子尺寸大小相匹配的空穴,生成的印迹膜与印迹分子之间存在相互作用,将其用于分离印迹分子与其它物质构成的混合物时,印迹膜能识别出印迹分子,从而有效地将目标物从混合物中分离。在光催化过程中,其对目标物质具有特定的识别性能,进而达到优先降解目标物质的目的。
将分子印迹膜技术与光催化技术相结合,制备得到具有选择性降解目标物的分子印迹催化膜,MIM在特异性识别四环素的同时,也可以优先对其催化降解,降解后再次实现吸附降解的循环体系,进而达到协同及促进选择性光催化降解目标污染物的目的。因此在选择性移除环境中四环素类抗生素残留方面具有广阔的应用前景。
发明内容
本发明利用相转化技术为制备手段,制备出一种对目标污染物四环素具有特定选择性的分子印迹催化膜复合光催化剂。其优点在于在体系中构建一个循环过程,实现了对目标物质先吸附再催化降解,然后再吸附降解的循环过程,进而有效的利用光源达到有效降解环境中四环素抗生素废水的目的。
本发明采用的技术方案是:
一种选择性降解四环素的分子印迹催化膜的制备方法,按以下步骤进行:
步骤1、将聚乙烯醇(PVA)溶于去离子水中,得到聚乙烯醇溶液;
步骤2、将氯金酸(HAuCl4·4H2O)溶于去离子水中,得到氯金酸溶液,将硝酸银(AgNO3)溶于氯金酸溶液中,得到混合液A,将混合液A与步骤1中所得到的聚乙烯醇溶液混合,得到混合液B;
步骤3、将硼氢化钠(NaBH4)于冰水浴中溶于去离子水中,得到硼氢化钠溶液,将硼氢化钠溶液滴加到步骤2中所得到的混合液B中,得到混合液C;
步骤4、将二氧化钛(TiO2)分散于混合液C中,得到混合液D,磁力搅拌,随后用去离子水和无水乙醇洗涤,离心分离后干燥,得到Ag@Au@TiO2催化剂;
步骤5、取Ag@Au@TiO2催化剂加入二甲亚砜(DMSO)中,超声分散得到Ag@Au@TiO2催化剂分散液;
步骤6、向步骤5得到的Ag@Au@TiO2催化剂分散液中加入醋酸纤维素(CA)、壳聚糖(CHI)和四环素,40±5℃下搅拌混匀,机械搅拌均匀,得到铸膜液;
步骤7、步骤6得到的铸膜液,于40±5℃下保温静置,脱去搅拌产生的气泡,然后取一洁净的玻璃板,将铸膜液平铺于玻璃板上,用玻璃棒刮出一定厚度,放置一段时间后,缓慢将其浸入去离子水中,浸泡一段时间后取出,得到共混膜;
步骤8、将步骤7得到的共混膜从玻璃板上剥下,室温储存于去离子水中;
步骤9、将步骤8储存于去离子水中的共混膜采用体积比为9:1的甲醇/醋酸混合液为提取液,以脱除四环素,再用甲醇洗涤,得到选择性降解四环素的分子印迹催化膜(MIM),储存于甲醇中,备用。
步骤1中,制备聚乙烯醇溶液时,所使用的聚乙烯醇与去离子水的质量比为1:99。
步骤2中,制备氯金酸溶液时,所使用的氯金酸与去离子水的质量比为1:10;制备混合液A时,所使用的硝酸银与氯金酸溶液的用量比为0.157g:0.418mL;制备混合液B时,所使用的混合液A与聚乙烯醇溶液的体积比为0.418:4。
步骤3中,所述硼氢化钠溶液的浓度为0.1mol·L-1;制备混合液C时,所使用的硼氢化钠溶液与混合液B中聚乙烯醇溶液的体积比为1:2。
步骤4中,制备混合液D时,所使用的二氧化钛与混合液C中聚乙烯醇溶液的用量比为1g:4mL;所述磁力搅拌的时间为1~2h;所述用去离子水和无水乙醇洗涤为用去离子水和无水乙醇分别洗涤3次;所述干燥的温度为120℃~180℃,干燥时间为24h~48h。
步骤5中,所使用的Ag@Au@TiO2催化剂与二甲亚砜的质量比为0.1~0.4:16.74~17.04;所述超声分散的时间为1~2h。
步骤6中,所述铸膜液中:所述醋酸纤维素的质量分数为铸膜液的13%,壳聚糖的质量分数为铸膜液的1.0%,四环素的质量分数为铸膜液的0.3%;所述机械搅拌的时间为3~4h。
步骤7中,所述的保温静置时间为24~48h,膜的厚度为2.0mm;所述的放置的时间为30s,在去离子水中浸泡的时间为30min。
上述的技术方案中所述的Ag@Au@TiO2,其作用为催化剂,降解四环素。
上述的技术方案中所述的二甲亚砜,其作用为溶剂,溶解醋酸纤维素和四环素,以制备铸膜液。
上述的技术方案中所述的醋酸纤维素,其作用为基质。
上述的技术方案中所述的壳聚糖,其作用为功能聚合物。
上述的技术方案中所述的去离子水,其作用为非溶剂。
上述的技术方案中所述的甲醇醋酸混合提取液,其作用为阻断模板分子和功能聚合物间的氢键作用,从而洗脱模板分子。
利用本发明采用分子印迹膜技术制备出的对四环素具有选择性的分子印迹催化膜,对模板分子四环素具有较高的选择性降解效果。
对应的非印迹共混膜(NIM)的制备方法与上述相同,但不加模板分子四环素。
光催化活性评价:在DW-01型光化学反应仪(购自扬州大学教学仪器厂)中进行,可见光灯照射,将70mL一定浓度的四环素模拟废水加入反应器中并测定其初始值,然后加入一定量的印迹膜及非印迹膜光催化剂,磁力搅拌并开启曝气装置通入空气保持催化剂处于悬浮或飘浮状态,可以提供光催化过程中的氧气,光照过程中每间隔30min取样分析,离心分离后取上层清液在紫外-可见分光光度计λmax=358nm处测定吸光度,并通过公式:DC=[(A0-Ai)/A0]×100%算出降解率,其中A0为达到吸附平衡时四环素溶液的吸光度,Ai为定时取样测定的四环素溶液的吸光度。
本发明的技术优点:选择性降解四环素的分子印迹催化膜的光催化降解过程可以有效的实现对目标污染物选择性识别、吸附并催化降解的目的,后处理简单方便,提高了对目标物质的有效降解的效率,具有较强的选择性处理抗生素废水的优点。
具体实施方式
下面结合具体实施实例对本发明做进一步说明。
本发明以铸膜液总质量为20g为例。
实施例1:
(1)Ag@Au@TiO2催化剂的制备
首先,将1g聚乙烯醇(PVA)溶解到99mL去离子水中,将1g氯金酸(HAuCl4·4H2O)溶于10mL去离子水中,取0.157g硝酸银(AgNO3)溶于0.418mL氯金酸溶液中,然后将上述混合液缓慢滴加到4mL质量分数为1%的PVA水溶液中,取2mL浓度为0.1mol·L-1NaBH4水溶液滴加到上述溶液中,最后取1g的二氧化钛(TiO2)分散于上述溶液中,磁力搅拌1~2h,随后用去离子水和无水乙醇分别洗3次,离心分离后在120℃~180℃下干燥24h~48h,最终得到Ag@Au@TiO2催化剂;
(2)分子印迹催化膜的制备
首先,取0.1g Ag@Au@TiO2催化剂加入17.04g二甲亚砜(DMSO)中,超声分散1~2h得到Ag@Au@TiO2分散液,然后加入0.06g模板分子(四环素)、2.6g膜基质(醋酸纤维素)和0.2g功能聚合物(壳聚糖),在40±5℃条件下机械搅拌3~4h至溶解均匀得到铸膜液,于40±5℃下保温静置24h~48h,脱去搅拌产生的气泡,然后取一洁净的玻璃板,将铸膜液平铺于玻璃板上,用玻璃棒刮出2.0mm厚度的膜,30s后缓慢将其浸入去离子水中,浸泡30min后取出,即得分子印迹催化膜储存于去离子水中。非印迹膜的制备方法与上述相同,但不加模板分子四环素。最后采用体积比为9:1的甲醇/醋酸混合溶液为提取液,以脱除模板分子四环素,再用水洗涤数次至中性,将制得的分子印迹催化膜储存于水中,作为对比,以同样的方法和步骤合成了空白非印迹催化膜,除了在聚合过程中不加模板分子四环素。
(3)分子印迹催化膜的光催化活性实验
取10g步骤(2)中制备的样品在光化学反应仪中进行光催化降解试验,加入70mL,20mg·L-1的四环素溶液中,磁力搅拌暗吸附1h,打开循环水源,光源,进行光催化降解实验,每30min吸取4-6ml反应器中的光催化降解液,用于紫外-可见分光光度计测其在358nm处的吸光度,并通过公式:DC%=[(A0-Ai)/A0]×100%算出降解率,其中A0为达到吸附平衡时四环素溶液的吸光度,Ai为定时取样测定的四环素溶液的吸光度。降解率表示(2)中制备的催化剂的光催化活性。
实施例2:
(1)通过改变Ag@Au@TiO2光催化剂的用量(0.2g,0.3g,0.4g)来考查催化剂投加量对光催化降解的影响,在改变Ag@Au@TiO2光催化剂的用量的同时,改变二甲亚砜的用量,保证Ag@Au@TiO2光催化剂、二甲亚砜的总质量分数为85.7%,结果表明在催化剂用量为0.4g时,其对四环素的降解效率最高,可以达到95%以上。所以实验中所选择的催化剂用量为0.4g。
(2)用0.4g光催化剂所制备的分子印迹催化膜在可见光下催化降解不同浓度(10,20,30,40,50mg·L-1)的四环素溶液,考查在不同浓度时分子印迹光催化膜对四环素的降解动力学,通过计算并且拟合动力学方程可知,分子印迹光催化剂降解四环素的过程符合准一级动力学模型,当四环素起始浓度为20mg·L-1时,分子印迹光催化膜对四环素的平均降解速率为0.046min-1。
实施例3:
分别用例1中的(2)中制备的光催化膜降解相同浓度的四环素和干扰物质(环丙沙星)的混合溶液,通过计算对不同物质的降解效率进而计算其对不同物质的选择性系数。
其中C0,Ce分别为四环素起始和降解后的浓度(mg·L-1);D为分配系数,DCIP,DM分别为四环素和干扰物质的分配系数;α是选择性系数,αi,αn分别为印迹和空白聚合物光催化剂的选择性系数,αr是相对选择性系数。
实验结果表明,分子印迹光催化膜对四环素的降解效率明显高于其他对比的物质,选择性系数也都大于其他干扰物质,分子印迹光催化膜对四环素和环丙沙星的相对选择性系数分别为4.37和1.26。说明用此方法合成的分子印迹催化膜对四环素具有较好的选择性,从而实现了对目标物质四环素选择性催化降解的目的。
实施例4:
(1)首先用实施例1中的(2)中制备的光催化剂单独吸附不同浓度的四环素、环丙沙星,土霉素的溶液。根据公式计算印迹催化膜对不同物种的吸附容量。Q=(C0-Ce)*V/m,其中Q是吸附剂的吸附容量(mg·g-1),C0,Ce分别为四环素吸附前和吸附平衡后的浓度(mg·L-1),V是四环素溶液的体积(L),m是吸附剂的质量(g)。实验结果显示,分子印迹光催化膜对模板分子四环素的吸附容量普遍大于对其他物质的吸附容量,而非印迹催化膜对这几种物质的吸附容量相差不大。
(2)分别用实施例1中的(2)中制备的光催化膜吸附相同浓度的四环素、环丙沙星和土霉素的混合溶液,经过相同的吸附时间,离心分离悬浮溶液,测定上清液的浓度,根据公式计算催化剂对不同物种的吸附容量,然后计算其对不同物质的吸附选择性。结果表明分子印迹光催化膜对四环素的吸附容量明显高于其对环丙沙星和土霉素的吸附容量,而非印迹催化膜对三者的吸附容量差别不大,说明在印迹过程中提高了印迹膜对四环素的吸附容量。
Claims (9)
1.一种选择性降解四环素的分子印迹催化膜的制备方法,其特征在于,按以下步骤进行:
步骤1、将聚乙烯醇溶于去离子水中,得到聚乙烯醇溶液;
步骤2、将氯金酸溶于去离子水中,得到氯金酸溶液,将硝酸银溶于氯金酸溶液中,得到混合液A,将混合液A与步骤1中所得到的聚乙烯醇溶液混合,得到混合液B;
步骤3、将硼氢化钠于冰水浴中溶于去离子水中,得到硼氢化钠溶液,将硼氢化钠溶液滴加到步骤2中所得到的混合液B中,得到混合液C;
步骤4、将二氧化钛分散于混合液C中,得到混合液D,磁力搅拌,随后用去离子水和无水乙醇洗涤,离心分离后干燥,得到Ag@Au@TiO2催化剂;
步骤5、取Ag@Au@TiO2催化剂加入二甲亚砜中,超声分散得到Ag@Au@TiO2催化剂分散液;
步骤6、向步骤5得到的Ag@Au@TiO2催化剂分散液中加入醋酸纤维素,壳聚糖和四环素,40±5℃下搅拌混匀,机械搅拌均匀,得到铸膜液;
步骤7、步骤6得到的铸膜液,于40±5℃下保温静置,脱去搅拌产生的气泡,然后取一洁净的玻璃板,将铸膜液平铺于玻璃板上,用玻璃棒刮出一定厚度,放置一段时间后,缓慢将其浸入去离子水中,浸泡一段时间后取出,得到共混膜;
步骤8、将步骤7得到的共混膜从玻璃板上剥下,室温储存于去离子水中;
步骤9、将步骤8储存于去离子水中的共混膜采用体积比为9:1的甲醇/醋酸混合液为提取液,以脱除四环素,再用甲醇洗涤,得到选择性降解四环素的分子印迹催化膜,储存于甲醇中,备用。
2.根据权利要求1所述的一种选择性降解四环素的分子印迹催化膜的制备方法,其特征在于,步骤1中,制备聚乙烯醇溶液时,所使用的聚乙烯醇与去离子水的质量比为1:99。
3.根据权利要求1所述的一种选择性降解四环素的分子印迹催化膜的制备方法,其特征在于,步骤2中,制备氯金酸溶液时,所使用的氯金酸与去离子水的质量比为1:10;制备混合液A时,所使用的硝酸银与氯金酸溶液的用量比为0.157g:0.418mL;制备混合液B时,所使用的混合液A与聚乙烯醇溶液的体积比为0.418:4。
4.根据权利要求1所述的一种选择性降解四环素的分子印迹催化膜的制备方法,其特征在于,步骤3中,所述硼氢化钠溶液的浓度为0.1mol·L-1;制备混合液C时,所使用的硼氢化钠溶液与混合液B中聚乙烯醇溶液的体积比为1:2。
5.根据权利要求1所述的一种选择性降解四环素的分子印迹催化膜的制备方法,其特征在于,步骤4中,制备混合液D时,所使用的二氧化钛与混合液C中聚乙烯醇溶液的用量比为1g:4mL;所述磁力搅拌的时间为1~2h;所述用去离子水和无水乙醇洗涤为用去离子水和无水乙醇分别洗涤3次;所述干燥的温度为120℃~180℃,干燥时间为24h~48h。
6.根据权利要求1所述的一种选择性降解四环素的分子印迹催化膜的制备方法,其特征在于,步骤5中,所使用的Ag@Au@TiO2催化剂与二甲亚砜的质量比为0.1~0.4:16.74~17.04;所述超声分散的时间为1~2h。
7.根据权利要求1所述的一种选择性降解四环素的分子印迹催化膜的制备方法,其特征在于,步骤6中,所述铸膜液中:所述醋酸纤维素的质量分数为铸膜液的13%,壳聚糖的质量分数为铸膜液的1.0%,四环素的质量分数为铸膜液的0.3%;所述机械搅拌的时间为3~4h。
8.根据权利要求1所述的一种选择性降解四环素的分子印迹催化膜的制备方法,其特征在于,步骤7中,所述的保温静置时间为24~48h,膜的厚度为2.0mm;所述的放置的时间为30s,在去离子水中浸泡的时间为30min。
9.权利要求1~8任意一项所述的方法制备的选择性降解四环素的分子印迹催化膜的用途,其特征在于,所述的选择性降解四环素的分子印迹催化膜用于降解四环素。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610953221.XA CN106552620A (zh) | 2016-10-27 | 2016-10-27 | 一种选择性降解四环素的分子印迹催化膜的制备方法及用途 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610953221.XA CN106552620A (zh) | 2016-10-27 | 2016-10-27 | 一种选择性降解四环素的分子印迹催化膜的制备方法及用途 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN106552620A true CN106552620A (zh) | 2017-04-05 |
Family
ID=58443896
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610953221.XA Pending CN106552620A (zh) | 2016-10-27 | 2016-10-27 | 一种选择性降解四环素的分子印迹催化膜的制备方法及用途 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106552620A (zh) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107162097A (zh) * | 2017-05-10 | 2017-09-15 | 同济大学 | 共存体系中低浓度17β‑雌二醇的选择性光电催化去除方法 |
CN107324488A (zh) * | 2017-07-27 | 2017-11-07 | 东北师范大学 | 一种基于共代谢手段光催化‑生物直接耦合体系处理抗生素废水的方法 |
CN110523398A (zh) * | 2019-09-11 | 2019-12-03 | 山东大学 | 一种碳纳米片层负载TiO2分子印迹材料及其制备方法和应用 |
CN111504966A (zh) * | 2020-04-24 | 2020-08-07 | 济南大学 | 一种检测并降解氨苄青霉素的生物传感器及其制备方法与应用 |
CN112371094A (zh) * | 2020-10-29 | 2021-02-19 | 江苏大学 | 一种多巴胺增效自清洁型分子印迹膜的制备方法及其应用 |
CN113563406A (zh) * | 2021-07-19 | 2021-10-29 | 西安海斯夫生物科技有限公司 | 植物甾醇异硬脂酸酯及其制备方法 |
CN114018998A (zh) * | 2021-11-09 | 2022-02-08 | 东莞理工学院 | 一种检测盐酸四环素的TiO2基分子印迹型光电化学传感器及其制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103447095A (zh) * | 2013-09-13 | 2013-12-18 | 天津工业大学 | 一种光催化降解有机物的分子印迹复合膜及其制备方法 |
CN104193615A (zh) * | 2014-05-16 | 2014-12-10 | 江苏大学 | 一种1,2-丙二醇催化氧化的方法 |
CN104759263A (zh) * | 2015-03-25 | 2015-07-08 | 江苏大学 | 一种多壁碳纳米管掺杂水杨酸共混印迹膜的制备方法 |
-
2016
- 2016-10-27 CN CN201610953221.XA patent/CN106552620A/zh active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103447095A (zh) * | 2013-09-13 | 2013-12-18 | 天津工业大学 | 一种光催化降解有机物的分子印迹复合膜及其制备方法 |
CN104193615A (zh) * | 2014-05-16 | 2014-12-10 | 江苏大学 | 一种1,2-丙二醇催化氧化的方法 |
CN104759263A (zh) * | 2015-03-25 | 2015-07-08 | 江苏大学 | 一种多壁碳纳米管掺杂水杨酸共混印迹膜的制备方法 |
Non-Patent Citations (3)
Title |
---|
JULIA KENNEDY ET AL.: ""Photocatalytic hydrogen production by reforming of methanol using Au/TiO2,Ag/TiO2 and Au-Ag/TiO2 catalysts"", 《CATALYSIS,STRUCTURE&REACTIVITY》 * |
王红涛等: ""分子印迹膜修饰 TiO2纳米管及其光催化降解盐酸四环素"", 《科学通报》 * |
祁鲁梁等: "《水处理工艺与运行管理实用手册》", 31 May 2002 * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107162097A (zh) * | 2017-05-10 | 2017-09-15 | 同济大学 | 共存体系中低浓度17β‑雌二醇的选择性光电催化去除方法 |
CN107324488A (zh) * | 2017-07-27 | 2017-11-07 | 东北师范大学 | 一种基于共代谢手段光催化‑生物直接耦合体系处理抗生素废水的方法 |
CN107324488B (zh) * | 2017-07-27 | 2019-10-08 | 东北师范大学 | 一种基于共代谢手段光催化-生物直接耦合体系处理抗生素废水的方法 |
CN110523398A (zh) * | 2019-09-11 | 2019-12-03 | 山东大学 | 一种碳纳米片层负载TiO2分子印迹材料及其制备方法和应用 |
CN110523398B (zh) * | 2019-09-11 | 2021-08-06 | 山东大学 | 一种碳纳米片层负载TiO2分子印迹材料及其制备方法和应用 |
CN111504966A (zh) * | 2020-04-24 | 2020-08-07 | 济南大学 | 一种检测并降解氨苄青霉素的生物传感器及其制备方法与应用 |
CN112371094A (zh) * | 2020-10-29 | 2021-02-19 | 江苏大学 | 一种多巴胺增效自清洁型分子印迹膜的制备方法及其应用 |
CN112371094B (zh) * | 2020-10-29 | 2023-05-05 | 江苏大学 | 一种多巴胺增效自清洁型分子印迹膜的制备方法及其应用 |
CN113563406A (zh) * | 2021-07-19 | 2021-10-29 | 西安海斯夫生物科技有限公司 | 植物甾醇异硬脂酸酯及其制备方法 |
CN114018998A (zh) * | 2021-11-09 | 2022-02-08 | 东莞理工学院 | 一种检测盐酸四环素的TiO2基分子印迹型光电化学传感器及其制备方法 |
WO2023082383A1 (zh) * | 2021-11-09 | 2023-05-19 | 东莞理工学院 | 一种检测盐酸四环素的 TiO2 基分子印迹型光电化学传感器及其制备方法 |
CN114018998B (zh) * | 2021-11-09 | 2023-10-27 | 东莞理工学院 | 一种检测盐酸四环素的TiO2基分子印迹型光电化学传感器及其制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106552620A (zh) | 一种选择性降解四环素的分子印迹催化膜的制备方法及用途 | |
CN106955726B (zh) | 一种选择性降解环丙沙星的分子印迹催化膜及制备方法 | |
Dassanayake et al. | Recent advances in biopolymer-based dye removal technologies | |
CN106076419B (zh) | 一种负载型金属有机框架复合材料,制备方法及其应用 | |
CN107715861B (zh) | 竹茎生物碳量子点修饰Bi4Ti3O12复合光催化剂的制备及其应用 | |
Emam et al. | Separation of anthocyanin from roselle extract by cationic nano-rode ZIF-8 constructed using removable template | |
Yi et al. | Photocatalytic Cr (VI) reduction over MIL-88A (Fe) on polyurethane sponge: From batch to continuous-flow operation | |
CN107159110A (zh) | 一种柚子皮基多级孔碳材料的制备方法及其用途 | |
CN105728041B (zh) | 一种选择性专一识别的PPy@ZnFe2O4磁性印迹复合光催化剂的制备方法 | |
CN106955718A (zh) | 一种ZnS/Bi2O3异质结分子印迹光催化膜及制备方法和用途 | |
CN105566400B (zh) | 非均相钴金属-有机骨架及制备与在废水处理领域中的应用 | |
Wei et al. | Removal of organic contaminants from wastewater with GO/MOFs composites | |
CN107486247A (zh) | 一种光催化‑生物复合催化剂及其制备与应用 | |
Bahmani et al. | BiFeO3–BiOI impregnation to UiO-66 (Zr/Ti) as a promising candidate visible-light-driven photocatalyst for boosting urea photodecomposition in a continuous flow-loop thin-film slurry flat-plate photoreactor | |
Kang et al. | Molecularly imprinted polymer based on metal-organic frameworks: synthesis and application on determination of dibutyl phthalate | |
Hassan et al. | Photocatalytic degradation of industrial dye using hybrid filler impregnated poly-sulfone membrane and optimizing the catalytic performance using Box-Behnken design | |
Radoor et al. | Low-cost and eco-friendly PVA/carrageenan membrane to efficiently remove cationic dyes from water: Isotherms, kinetics, thermodynamics, and regeneration study | |
CN101584988B (zh) | 一种双组分复合型金属催化剂及其应用 | |
Hidayat et al. | Mechanism adsorption–reduction into the incorporation of microbial fuel cell–metal organic framework and overview of hydrodynamics effects for enhanced reduction of Cr (VI) | |
CN109046456B (zh) | 负载型锰-金属有机框架复合材料的制备方法及其应用 | |
Kondaveeti et al. | Efficiency of air-dried and freeze-dried alginate/xanthan beads in batch, recirculating and column adsorption processes | |
Alanazi et al. | Citric acid-cross linked with magnetic metal-organic framework composite sponge for superior adsorption of indigo carmine blue dye from aqueous solutions: Characterization and adsorption optimization via Box–Behnken design | |
CN106542606A (zh) | 一种在可见光下降解罗丹明b的方法 | |
CN103586088B (zh) | 一种选择性降解对苯二酚复合光催化剂的制备方法 | |
CN109772376A (zh) | 一种三元复合光催化剂及制备方法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170405 |
|
RJ01 | Rejection of invention patent application after publication |