CN106582880A - 一种二硫化钼/mil‑101复合光催化材料及其制备方法与应用 - Google Patents
一种二硫化钼/mil‑101复合光催化材料及其制备方法与应用 Download PDFInfo
- Publication number
- CN106582880A CN106582880A CN201611199516.9A CN201611199516A CN106582880A CN 106582880 A CN106582880 A CN 106582880A CN 201611199516 A CN201611199516 A CN 201611199516A CN 106582880 A CN106582880 A CN 106582880A
- Authority
- CN
- China
- Prior art keywords
- mil
- composite photocatalyst
- preparation
- photocatalyst materials
- molybdenum bisuphide
- 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.)
- Granted
Links
- 239000013177 MIL-101 Substances 0.000 title claims abstract description 68
- 239000000463 material Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 37
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 34
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims abstract description 28
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000003115 biocidal effect Effects 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000002351 wastewater Substances 0.000 claims abstract description 15
- 229960003405 ciprofloxacin Drugs 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000006731 degradation reaction Methods 0.000 claims abstract description 12
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000015556 catabolic process Effects 0.000 claims abstract description 10
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 8
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 8
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims description 17
- 239000011733 molybdenum Substances 0.000 claims description 17
- 230000004044 response Effects 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 239000002135 nanosheet Substances 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 238000011010 flushing procedure Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000272186 Falco columbarius Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QEVHRUUCFGRFIF-MDEJGZGSSA-N reserpine Chemical compound O([C@H]1[C@@H]([C@H]([C@H]2C[C@@H]3C4=C(C5=CC=C(OC)C=C5N4)CCN3C[C@H]2C1)C(=O)OC)OC)C(=O)C1=CC(OC)=C(OC)C(OC)=C1 QEVHRUUCFGRFIF-MDEJGZGSSA-N 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 150000003952 β-lactams Chemical class 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
- 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
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
本发明属于光催化材料技术领域，公开了一种二硫化钼/MIL‑101复合光催化材料及其制备方法与在降解处理抗生素废水领域中的应用，特别是在降解含环丙沙星抗生素废水领域中的应用。本发明制备方法包括以下步骤：将硝酸铬、对苯二甲酸和氢氟酸溶于水中，搅拌均匀，加热反应，得到MIL‑101；将钼酸钠和硫代乙酰胺溶于水中，搅拌均匀，再加入步骤(1)制备得到的MIL‑101，搅拌均匀，加热反应，得到MoS2/MIL‑101复合光催化材料。本发明材料结构中含有高度分散的MoS2纳米片及更多裸露的MoS2活性边缘，具有优异的复合光催化性能，可应用于降解处理抗生素废水，特别是实现对含环丙沙星抗生素废水的高效降解处理。
Description
技术领域
本发明属于光催化材料技术领域，特别涉及一种二硫化钼/MIL-101复合光催化材料及其制备方法与在降解处理抗生素废水领域中的应用，特别是在降解含环丙沙星抗生素废水领域中的应用。
背景技术
环丙沙星是日常生活中使用频率较高的一类抗生素药物，其在环境中存在的半衰期较短，但是大量连续性地向水环境中释放，导致其容易形成“假持久性”污染现象。残留在水环境中的抗生素污染物可通过食物链的富集作用对人体健康造成危害，同时对水体中的生物多样性也会产生重大影响。因此，关于含抗生素废水的去除研究越来越受到人们的关注。目前，国内外的研究主要集中在抗生素的检测以及吸附分离方面，其消除处理则还没有有效的方法。近年来的研究表明，光催化技术可望有效降解抗生素类有机污染物，如对环境中磺胺类、β-内酰胺类等抗生素废水的光催化处理，并取得了一系列的研究进展。
二硫化钼(MoS2)，作为一种新型的二维结构材料，具有与石墨烯类似的结构。它具有优异的电学及光学特性，目前已广泛应用于微电子器件、太阳能电池等领域。MoS2光催化反应的活性位点位于层状结构中裸露的S-Mo-S层的边缘。MoS2导电性较差，且倾向于层层堆叠减少了边缘裸露活性位点的数目，从而降低了其光催化活性。解决这一问题的办法之一就是将MoS2分散在合适的模板材料上，制备具有高硫、多边缘的MoS2材料。
金属有机骨架化合物(MOFs)是由金属离子或金属簇与有机配体通过配位键连接自组装形成的具有周期性网络结构的多维材料，其具有理想的拓扑学分子可设计性。与传统的无机多孔材料相比，MOFs具有巨大的比表面积和超高的孔隙率以及良好的结构可裁性和功能可调性等显著优点。因此，本发明选择具有高比表面积(～3000m2g-1)、较大孔径(～3nm)和良好的化学稳定性的MIL-101框架为载体，将MoS2负载于MIL-101上，这样可以阻止MoS2活性物质的间的堆叠团聚，使MoS2纳米片活性边缘能够更加充分地暴露，从而得到光催化活性优异的MoS2/MIL-101复合光催化材料。
发明内容
为了克服上述现有技术的缺点与不足，本发明的首要目的在于提供一种二硫化钼/MIL-101复合光催化材料的制备方法。本发明方法以MIL-101为载体，通过高温水热法制备得到MoS2/MIL-101复合光催化材料。
本发明另一目的在于提供上述方法制备的二硫化钼/MIL-101复合光催化材料。
本发明再一目的在于提供上述二硫化钼/MIL-101复合光催化材料在降解处理抗生素废水领域中的应用。本发明材料具有优异的复合光催化性能，在降解处理抗生素废水方面具有较好的应用前景，特别是降解含环丙沙星抗生素废水。
本发明的目的通过下述方案实现：
一种二硫化钼/MIL-101复合光催化材料的制备方法，包括以下步骤：
(1)将硝酸铬、对苯二甲酸和氢氟酸溶于水中，搅拌均匀，加热反应，得到MIL-101；
(2)将钼酸钠和硫代乙酰胺溶于水中，搅拌均匀，再加入步骤(1)制备得到的MIL-101，搅拌均匀，加热反应，得到MoS2/MIL-101复合光催化材料。
步骤(1)中所用硝酸铬、对苯二甲酸和氢氟酸的物质的量比优选为1:(1～3):(1～3)，更优选为1:1:1。
所用氢氟酸的质量浓度优选为40～50％，更优选为48％。
所述的加热反应优选在180～230℃反应5～12h，更优选在220℃反应8h。
所述加热反应后优选自然冷却至常温，再将反应产物经水和乙醇冲洗，提纯，过滤，最后将产物于真空干燥箱中150℃干燥一夜，得到MIL-101。
步骤(2)中所用钼酸钠、硫代乙酰胺和MIL-101的质量比为1:(2～5):(0.3～3)。
所述搅拌均匀优选使用磁力搅拌5～8h。
所述的加热反应优选在180～220℃反应8～24h。
所述加热反应后优选自然冷却至常温，再将反应产物经水和乙醇冲洗，提纯，过滤，最后将产物于真空干燥箱中70℃干燥一夜，得到MoS2/MIL-101复合光催化材料。
本发明方法先合成得到载体金属有机骨架材料MIL-101，再通过高温水热法制备得到MoS2/MIL-101复合光催化材料，其优异的复合光催化性能，在降解处理抗生素废水领域具有较好的应用前景，特别是能够有效利用模拟太阳光实现对含环丙沙星抗生素废水的高效降解处理。
本发明制备得到MoS2/MIL-101复合光催化材料中MoS2的质量分数为30～70％。
本发明相对于现有技术，具有如下的优点及有益效果：
(1)本发明采用金属有机骨架材料MIL-101为基体材料，其具有巨大的比表面积和超高的孔隙率，为MoS2的生长提供了大量的位点，从而得到高度分散的MoS2纳米片以及更多裸露的MoS2活性边缘；
(2)本发明采用的金属有机骨架模板材料以及光催化复合材料的制备过程简单，易于操作，对设备要求较低，具有巨大的工业应用价值。
附图说明
图1是MIL-101、MoS2和MoS2/MIL-101复合材料的XRD图。
图2是MIL-101、MoS2和MoS2/MIL-101复合材料的SEM图。
图3是MIL-101、MoS2和MoS2/MIL-101复合材料在模拟太阳光条件下对环丙沙星的光催化降解性能图。
具体实施方式
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。
下列实施例中使用的试剂均可从商业渠道获得。
实施例1
(1)称取1.004g硝酸铬和0.412g对苯二甲酸，量取0.109mL氢氟酸，混合溶于12mL水中，搅拌均匀；
(2)将步骤(1)得到的混合液转移至25mL的不锈钢反应釜中，放入烘箱中于220℃反应8h，然后自然冷却至常温；
(3)将步骤(2)得到的反应产物经水和乙醇冲洗2次，提纯，过滤，最后将产物于真空干燥箱中150℃干燥一夜，得到MIL-101；
(4)分别称取40mg钼酸钠和80mg硫代乙酰胺溶于水中，搅拌均匀；
(5)向步骤(4)得到的混合液中加入40mg的MIL-101粉末，磁力搅拌7h，得到钼酸钠/硫代乙酰胺/MIL-101分散液；
(6)将步骤(5)得到的分散液转移至25mL不锈钢反应釜中，放入烘箱中于200℃反应24h，然后自然冷却至常温；
(7)将步骤(6)得到的反应产物经水和乙醇冲洗2次，提纯，离心，最后将产物于真空干燥箱中70℃干燥一夜，即得MoS2/MIL-101复合光催化材料。
实施例2
(1)称取2.007g硝酸铬和0.823g对苯二甲酸，量取0.217mL氢氟酸，混合溶于24mL水中，搅拌均匀；
(2)将步骤(1)得到的混合液转移至50mL的不锈钢反应釜中，放入烘箱中于220℃反应8h，然后自然冷却至常温；
(3)将步骤(2)得到的反应产物经水和乙醇冲洗2次，提纯，过滤，最后将产物于真空干燥箱中150℃干燥一夜，得到MIL-101；
(4)分别称取30mg钼酸钠和60mg硫代乙酰胺溶于水中，搅拌均匀；
(5)向步骤(4)得到的混合液中加入20mg的MIL-101粉末，磁力搅拌5h，得到钼酸钠/硫代乙酰胺/MIL-101分散液；
(6)将步骤(5)得到的分散液转移至25mL不锈钢反应釜中，放入烘箱中于180℃反应24h，然后自然冷却至常温；
(7)将步骤(6)得到的反应产物经水和乙醇冲洗2次，提纯，离心，最后将产物于真空干燥箱中70℃干燥一夜，即得MoS2/MIL-101复合光催化材料。
实施例3
(1)称取3.011g硝酸铬和1.235g对苯二甲酸，量取0.326mL氢氟酸，混合溶于36mL水中，搅拌均匀；
(2)将步骤(1)得到的混合液转移至50mL的不锈钢反应釜中，放入烘箱中于220℃反应8h，然后自然冷却至常温；
(3)将步骤(2)得到的反应产物经水和乙醇冲洗2次，提纯，过滤，最后将产物于真空干燥箱中150℃干燥一夜，得到MIL-101；
(4)分别称取67.5mg钼酸钠和135mg硫代乙酰胺溶于水中，搅拌均匀；
(5)向步骤(4)得到的混合液中加入30mg的MIL-101粉末，磁力搅拌8h，得到钼酸钠/硫代乙酰胺/MIL-101分散液；
(6)将步骤(5)得到的分散液转移至25mL不锈钢反应釜中，放入烘箱中于220℃反应24h，然后自然冷却至常温；
(7)将步骤(6)得到的反应产物经水和乙醇冲洗2次，提纯，离心，最后将产物于真空干燥箱中70℃干燥一夜，即得MoS2/MIL-101复合光催化材料。
本发明制得的MoS2/MIL-101复合光催化材料，其表征结果和对环丙沙星的降解性能如下：
(1)XRD表征分析
采用荷兰帕纳科公司生产的Empyrean锐影X射线衍射仪对本发明实施例2制得的MoS2/MIL-101复合光催化材料的晶体结构进行表征，如图1所示，其中操作条件为：铜靶，40KV，40mA，步长0.0131度，扫描速度9.664秒/步。
从图1可以看出，对于MIL-101，衍生峰的强度较高，峰型尖锐，并且特征衍射峰与已有文献报道的峰位一致，证明在本研究中MIL-101合成成功。对于MoS2/MIL-101，在该复合材料的XRD谱图中出现了MoS2的特征衍射峰，且MIL-101的衍生峰也保持不变，说明MIL-101的晶体结构在复合材料中得到保持。
(2)SEM表征分析
采用MERLIN场发射扫描电子显微镜(Carl Zeiss公司，德国)对样品的表面形貌进行表征。结果如图2所示，纯MoS2呈层层堆叠状，团聚现象严重，边缘位点暴露较少；对于MoS2/MIL-101，MoS2的堆叠状况明显得到改善，可以看到MoS2纳米片在MIL-101晶体表面高度分散，并可观察到更多暴露的MoS2活性边缘。
(3)模拟太阳光催化降解环丙沙星的光催化性能测试
采用Agilent 1200高效液相色谱仪测定降解过程中环丙沙星的浓度变化。色谱条件为：色谱柱，Hypersil Gold 4.6×250mm 5μm；流动相，乙腈-0.1％磷酸溶液(20:80)；流速：1.0mL/min；柱温：30度；检测波长，278nm；进样量，10μL。测试结果如图3。
从图3可以看到，环丙沙星在水中基本不发生直接光解；MIL-101载体自身不具有光催化活性；纯MoS2由于自身特性则对环丙沙星显示出一定的光催化降解能力；而对于MoS2/MIL-101复合光催化材料，其对环丙沙星的光催化降解效果显著，几乎完全去除，这可能与MoS2/MIL-101复合光催化材料中MoS2活性边缘暴露数目的增多有密切关系。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (10)
1.一种二硫化钼/MIL-101复合光催化材料的制备方法，其特征在于包括以下步骤：
(1)将硝酸铬、对苯二甲酸和氢氟酸溶于水中，搅拌均匀，加热反应，得到MIL-101；
(2)将钼酸钠和硫代乙酰胺溶于水中，搅拌均匀，再加入步骤(1)制备得到的MIL-101，搅拌均匀，加热反应，得到MoS2/MIL-101复合光催化材料。
2.根据权利要求1所述的二硫化钼/MIL-101复合光催化材料的制备方法，其特征在于：步骤(1)中所用硝酸铬、对苯二甲酸和氢氟酸的物质的量比为1:(1～3):(1～3)。
3.根据权利要求1所述的二硫化钼/MIL-101复合光催化材料的制备方法，其特征在于：步骤(1)中所用硝酸铬、对苯二甲酸和氢氟酸的物质的量比为1:1:1。
4.根据权利要求1所述的二硫化钼/MIL-101复合光催化材料的制备方法，其特征在于：步骤(1)中所用氢氟酸的质量浓度为40～50％；所述的加热反应为在180～230℃反应5～12h。
5.根据权利要求1所述的二硫化钼/MIL-101复合光催化材料的制备方法，其特征在于：步骤(1)中所用氢氟酸的质量浓度为48％；所述的加热反应为在220℃反应8h。
6.根据权利要求1所述的二硫化钼/MIL-101复合光催化材料的制备方法，其特征在于：步骤(2)中所用钼酸钠、硫代乙酰胺和MIL-101的质量比为1:(2～5):(0.3～3)。
7.根据权利要求1所述的二硫化钼/MIL-101复合光催化材料的制备方法，其特征在于：步骤(2)中所述搅拌均匀指使用磁力搅拌5～8h；所述的加热反应为在180～220℃反应8～24h。
8.一种二硫化钼/MIL-101复合光催化材料，其特征在于根据权利要求1～7任一项所述的制备方法得到。
9.权利要求8所述的二硫化钼/MIL-101复合光催化材料在降解处理抗生素废水领域中的应用。
10.权利要求8所述的二硫化钼/MIL-101复合光催化材料在降解处理含环丙沙星抗生素废水领域中的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611199516.9A CN106582880B (zh) | 2016-12-22 | 2016-12-22 | 一种二硫化钼/mil-101复合光催化材料及其制备方法与应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611199516.9A CN106582880B (zh) | 2016-12-22 | 2016-12-22 | 一种二硫化钼/mil-101复合光催化材料及其制备方法与应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106582880A true CN106582880A (zh) | 2017-04-26 |
| CN106582880B CN106582880B (zh) | 2019-12-03 |
Family
ID=58600860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611199516.9A Active CN106582880B (zh) | 2016-12-22 | 2016-12-22 | 一种二硫化钼/mil-101复合光催化材料及其制备方法与应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106582880B (zh) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108295870A (zh) * | 2018-01-30 | 2018-07-20 | 上海大学 | 硫化物-石墨烯复合材料光电催化剂的制备方法 |
| CN108607512A (zh) * | 2018-04-04 | 2018-10-02 | 大连理工大学 | 钼基硫化物改性mof材料的方法 |
| CN108786855A (zh) * | 2017-05-04 | 2018-11-13 | 中国计量大学 | 一种介孔二硫化钼可见光催化剂材料的制备方法及其在降解抗生素废水领域中的应用 |
| CN108786856A (zh) * | 2018-05-29 | 2018-11-13 | 江苏大学 | 一种MoS2/Co3O4异质结光催化剂的制备方法及其应用 |
| CN109021244A (zh) * | 2018-06-12 | 2018-12-18 | 昆明理工大学 | 一种MOFs材料的制备方法及应用 |
| CN109603810A (zh) * | 2018-12-28 | 2019-04-12 | 湖南大学 | 二硫化钼纳米片/多孔石墨化生物炭复合材料及其制备方法和应用 |
| CN110038598A (zh) * | 2019-03-27 | 2019-07-23 | 平顶山学院 | 一种铁酸锌/二硫化钼复合光催化材料的制造方法及其应用 |
| CN110270381A (zh) * | 2019-07-02 | 2019-09-24 | 哈尔滨理工大学 | 一种二硫化钼/TpPa-1复合材料的制备及光解水制氢 |
| CN110424022A (zh) * | 2019-06-26 | 2019-11-08 | 武汉科技大学 | 纳米棒α-氧化铁复合MIL-101异质结光阳极及其制备方法 |
| CN110523438A (zh) * | 2019-09-02 | 2019-12-03 | 中国科学技术大学 | 一种改性的铁基金属有机骨架材料、其制备方法及应用 |
| CN110918126A (zh) * | 2019-12-23 | 2020-03-27 | 西北师范大学 | 一种花状二硫化钼结合UiO-66光催化剂的制备方法 |
| CN110918125A (zh) * | 2019-12-23 | 2020-03-27 | 西北师范大学 | UiO-66负载硫化锡纳米颗粒光催化剂的制备方法 |
| CN111167521A (zh) * | 2020-01-18 | 2020-05-19 | 河南师范大学 | 催化材料及其制备方法、光催化剂、电催化剂 |
| CN111659468A (zh) * | 2020-06-17 | 2020-09-15 | 南京师范大学 | 一种MoS2/缺陷型MIL-100(Fe)的复合催化剂、制备方法及应用 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060182681A1 (en) * | 2004-12-28 | 2006-08-17 | Fortum Oyj | Catalytic materials and method for the preparation thereof |
| CN104307537A (zh) * | 2014-09-22 | 2015-01-28 | 江苏大学 | 一种MoS2/Ag2S纳米复合光催化材料的制备方法 |
-
2016
- 2016-12-22 CN CN201611199516.9A patent/CN106582880B/zh active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060182681A1 (en) * | 2004-12-28 | 2006-08-17 | Fortum Oyj | Catalytic materials and method for the preparation thereof |
| CN104307537A (zh) * | 2014-09-22 | 2015-01-28 | 江苏大学 | 一种MoS2/Ag2S纳米复合光催化材料的制备方法 |
Non-Patent Citations (3)
| Title |
|---|
| JIAO HE，ET AL: "Significantly enhanced photocatalytic hydrogen evolution under visible light over CdS embedded on metal-organic frameworks", 《CHEMCOMM》 * |
| XUEJUN LU，ET AL: "Controllable synthesis of graphitic C3N4/ultrathin MoS2 nanosheet hybrid nanostructures with enhanced photocatalytic performance", 《DALTON TRANSACTIONS》 * |
| 朱洪法: "《催化剂载体制备及应用技术（第二版）》", 31 October 2014, 石油工业出版社 * |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786855A (zh) * | 2017-05-04 | 2018-11-13 | 中国计量大学 | 一种介孔二硫化钼可见光催化剂材料的制备方法及其在降解抗生素废水领域中的应用 |
| CN108295870B (zh) * | 2018-01-30 | 2020-10-30 | 上海大学 | 硫化物-石墨烯复合材料光电催化剂的制备方法 |
| CN108295870A (zh) * | 2018-01-30 | 2018-07-20 | 上海大学 | 硫化物-石墨烯复合材料光电催化剂的制备方法 |
| CN108607512A (zh) * | 2018-04-04 | 2018-10-02 | 大连理工大学 | 钼基硫化物改性mof材料的方法 |
| CN108607512B (zh) * | 2018-04-04 | 2021-03-30 | 大连理工大学 | 钼基硫化物改性mof材料的方法 |
| CN108786856A (zh) * | 2018-05-29 | 2018-11-13 | 江苏大学 | 一种MoS2/Co3O4异质结光催化剂的制备方法及其应用 |
| CN109021244A (zh) * | 2018-06-12 | 2018-12-18 | 昆明理工大学 | 一种MOFs材料的制备方法及应用 |
| CN109021244B (zh) * | 2018-06-12 | 2021-01-05 | 昆明理工大学 | 一种MOFs材料的制备方法及应用 |
| CN109603810A (zh) * | 2018-12-28 | 2019-04-12 | 湖南大学 | 二硫化钼纳米片/多孔石墨化生物炭复合材料及其制备方法和应用 |
| CN109603810B (zh) * | 2018-12-28 | 2020-08-07 | 湖南大学 | 二硫化钼纳米片/多孔石墨化生物炭复合材料及其制备方法和应用 |
| CN110038598A (zh) * | 2019-03-27 | 2019-07-23 | 平顶山学院 | 一种铁酸锌/二硫化钼复合光催化材料的制造方法及其应用 |
| CN110424022A (zh) * | 2019-06-26 | 2019-11-08 | 武汉科技大学 | 纳米棒α-氧化铁复合MIL-101异质结光阳极及其制备方法 |
| CN110270381A (zh) * | 2019-07-02 | 2019-09-24 | 哈尔滨理工大学 | 一种二硫化钼/TpPa-1复合材料的制备及光解水制氢 |
| CN110523438A (zh) * | 2019-09-02 | 2019-12-03 | 中国科学技术大学 | 一种改性的铁基金属有机骨架材料、其制备方法及应用 |
| CN110918126A (zh) * | 2019-12-23 | 2020-03-27 | 西北师范大学 | 一种花状二硫化钼结合UiO-66光催化剂的制备方法 |
| CN110918125A (zh) * | 2019-12-23 | 2020-03-27 | 西北师范大学 | UiO-66负载硫化锡纳米颗粒光催化剂的制备方法 |
| CN110918126B (zh) * | 2019-12-23 | 2022-06-14 | 西北师范大学 | 一种花状二硫化钼结合UiO-66光催化剂的制备方法 |
| CN111167521A (zh) * | 2020-01-18 | 2020-05-19 | 河南师范大学 | 催化材料及其制备方法、光催化剂、电催化剂 |
| CN111167521B (zh) * | 2020-01-18 | 2023-02-17 | 河南师范大学 | 催化材料及其制备方法、光催化剂、电催化剂 |
| CN111659468A (zh) * | 2020-06-17 | 2020-09-15 | 南京师范大学 | 一种MoS2/缺陷型MIL-100(Fe)的复合催化剂、制备方法及应用 |
| CN111659468B (zh) * | 2020-06-17 | 2023-06-20 | 南京师范大学 | 一种MoS2/缺陷型MIL-101(Fe)的复合催化剂、制备方法及应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106582880B (zh) | 2019-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106582880A (zh) | 一种二硫化钼/mil‑101复合光催化材料及其制备方法与应用 | |
| Jiang et al. | Modified 2D-2D ZnIn2S4/BiOCl van der Waals heterojunctions with CQDs: Accelerated charge transfer and enhanced photocatalytic activity under vis-and NIR-light | |
| Wang et al. | MOF-derived N-doped ZnO carbon skeleton@ hierarchical Bi2MoO6 S-scheme heterojunction for photodegradation of SMX: Mechanism, pathways and DFT calculation | |
| Chen et al. | In situ construction of biocompatible Z-scheme α-Bi2O3/CuBi2O4 heterojunction for NO removal under visible light | |
| Zhou et al. | Novel dual-effective Z-scheme heterojunction with g-C3N4, Ti3C2 MXene and black phosphorus for improving visible light-induced degradation of ciprofloxacin | |
| Gao et al. | Strongly coupled g‐C3N4 nanosheets‐Co3O4 quantum dots as 2D/0D heterostructure composite for peroxymonosulfate activation | |
| Zhou et al. | Ti3C2 MXene-induced interface electron separation in g-C3N4/Ti3C2 MXene/MoSe2 Z-scheme heterojunction for enhancing visible light-irradiated enoxacin degradation | |
| Lv et al. | MOF-derived CoFe2O4/Fe2O3 embedded in g-C3N4 as high-efficient Z-scheme photocatalysts for enhanced degradation of emerging organic pollutants in the presence of persulfate | |
| Zhang et al. | Theoretical guidance for the construction of electron-rich reaction microcenters on C–O–Fe bridges for enhanced Fenton-like degradation of tetracycline hydrochloride | |
| Yuan et al. | Fabrication of a dual S-scheme Bi7O9I3/g-C3N4/Bi3O4Cl heterojunction with enhanced visible-light-driven performance for phenol degradation | |
| He et al. | Photocatalytic degradation of tetracycline by metal-organic frameworks modified with Bi2WO6 nanosheet under direct sunlight | |
| Ruan et al. | A visible-light-driven Z-scheme CdS/Bi12GeO20 heterostructure with enhanced photocatalytic degradation of various organics and the reduction of aqueous Cr (VI) | |
| Zhang et al. | Carbon nitride nanotubes anchored with high-density CuNx sites for efficient degradation of antibiotic contaminants under photo-Fenton process: Performance and mechanism | |
| Bao et al. | Cooperation of oxygen vacancy and FeIII/FeII sites in H2-reduced Fe-MIL-101 for enhanced Fenton-like degradation of organic pollutants | |
| Mumtaz et al. | Nanoengineered metal-organic framework for adsorptive and photocatalytic mitigation of pharmaceuticals and pesticide from wastewater | |
| Zhou et al. | Adsorption and photocatalysis removal of fulvic acid by TiO 2–graphene composites | |
| Gao et al. | Photocatalytic producing dihydroxybenzenes from phenol enabled by gathering oxygen vacancies in ultrathin porous ZnO nanosheets | |
| Zhao et al. | Dual II heterojunctions metallic phase MoS2/ZnS/ZnO ternary composite with superior photocatalytic performance for removing contaminants | |
| Chen et al. | A high-performance composite CDs@ Cu-HQCA/TiO2 flower photocatalyst: Synergy of complex-sensitization, TiO2-morphology control and carbon dot-surface modification | |
| Chen et al. | Peroxymonosulfate activation by β-cyclodextrin modified amorphous manganese oxides for a high-efficiency bisphenol A degradation | |
| Chen et al. | Z-scheme structure SnS 2–Au–CdS with excellent photocatalytic performance for simultaneous removal of Cr (VI) and methyl orange | |
| Yin et al. | Synergistically enhanced photocatalytic degradation of tetracycline hydrochloride by Z-scheme heterojunction MT-BiVO4 microsphere/P-doped g-C3N4 nanosheet composite | |
| Xie et al. | Nitrogen-doped Fe-MOFs derived carbon as PMS activator for efficient degradation of tetracycline | |
| Gu et al. | Efficient photocatalytic removal of phthalates easily implemented over a bi-functional {001} TiO2 surface | |
| Zhang et al. | Defect engineering in 0D/2D TiO2/g-C3N4 heterojunction for boosting photocatalytic degradation of tetracycline in a tetracycline/Cu2+ combined system |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230109 Address after: Room 236, Building 15, No. 1, Xuefu Road, Songshan Lake Park, Dongguan City, Guangdong Province, 523830 Patentee after: Dongguan Hua Gong Cooperative Innovation Technology Development Co.,Ltd. Patentee after: Cheng Jianhua Address before: 523808 room 168, productivity building, Songshan Lake high tech Industrial Development Zone, Dongguan, Guangdong Patentee before: SOUTH CHINA INSTITUTE OF COLLABORATIVE INNOVATION |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230827 Address after: Room 546, Building 15, No.1 Xuefu Road, Songshan Lake Park, Dongguan City, Guangdong Province, 523830 Patentee after: Huagong Tongchuang (Dongguan) Environmental Protection Technology Co.,Ltd. Address before: Room 236, Building 15, No. 1, Xuefu Road, Songshan Lake Park, Dongguan City, Guangdong Province, 523830 Patentee before: Dongguan Hua Gong Cooperative Innovation Technology Development Co.,Ltd. Patentee before: Cheng Jianhua |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240425 Address after: Room 236, Building 15, No.1 Xuefu Road, Songshanhu Park, Dongguan City, Guangdong Province, 510630 Patentee after: Dongguan Hua Gong Cooperative Innovation Technology Development Co.,Ltd. Country or region after: China Address before: Room 546, Building 15, No.1 Xuefu Road, Songshan Lake Park, Dongguan City, Guangdong Province, 523830 Patentee before: Huagong Tongchuang (Dongguan) Environmental Protection Technology Co.,Ltd. Country or region before: China |