CN111939944B - 一种硒化镉量子点/二硫化钼复合光催化剂的制备与应用 - Google Patents
一种硒化镉量子点/二硫化钼复合光催化剂的制备与应用 Download PDFInfo
- Publication number
- CN111939944B CN111939944B CN202010739733.2A CN202010739733A CN111939944B CN 111939944 B CN111939944 B CN 111939944B CN 202010739733 A CN202010739733 A CN 202010739733A CN 111939944 B CN111939944 B CN 111939944B
- Authority
- CN
- China
- Prior art keywords
- molybdenum disulfide
- composite photocatalyst
- cadmium selenide
- selenide quantum
- quantum dot
- 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.)
- Active
Links
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 86
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000002096 quantum dot Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229940124530 sulfonamide Drugs 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000003456 sulfonamides Chemical class 0.000 claims abstract description 17
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 12
- 229960005404 sulfamethoxazole Drugs 0.000 claims abstract description 11
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229960004306 sulfadiazine Drugs 0.000 claims abstract description 10
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical group NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 235000015393 sodium molybdate Nutrition 0.000 claims description 6
- 239000011684 sodium molybdate Substances 0.000 claims description 6
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 230000006798 recombination Effects 0.000 abstract description 7
- 238000005215 recombination Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 230000003115 biocidal effect Effects 0.000 abstract description 2
- 239000003640 drug residue Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000000707 layer-by-layer assembly Methods 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000011056 performance test Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000003242 anti bacterial agent Substances 0.000 description 6
- 229940088710 antibiotic agent Drugs 0.000 description 6
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 238000000103 photoluminescence spectrum Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940044683 chemotherapy drug Drugs 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000002906 medical waste Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000000628 photoluminescence spectroscopy Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000001055 reflectance spectroscopy Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000004054 semiconductor nanocrystal Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000000273 veterinary drug Substances 0.000 description 1
Images
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B01J35/33—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- 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
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
本发明公开了一种硒化镉量子点/二硫化钼复合光催化剂的制备方法，以纳米二硫化钼为基底材料，通过静电自组装将水溶性硒化镉量子点负载于纳米二硫化钼上制备了CdSe QDs@MoS2复合光催化剂，制备过程简单。硒化镉量子点与MoS2复合能够改善光生载流子的迁移和抑制载流子复合，并能显著改善量子点的光催化性能，光电性能测试结果表明该复合光催化剂具有优异的光电特性。将该复合光催化剂用于磺胺、磺胺甲恶唑、磺胺嘧啶三种典型的磺胺类药物的光催化降解，均表现出良好的光催化降解效果，为环境水体中抗生素类药物残留的有效去除提供了一定的方法指导。
Description
技术领域
本发明涉及一种硒化镉量子点/二硫化钼复合光催化剂的制备方法，该复合光催化剂主要用于磺胺类药物的光催化降解，属于复合材料领域和光催化领域。
背景技术
近年来，以抗生素为典型代表的新型有机污染物（PPCPs）以及它们所带来的环境污染问题已经逐渐引起人们的高度关注。近几年随着流行疾病的暴发蔓延，各类抗生素被研发、生产和滥用，导致大量该类物质通过人体排泄、医用垃圾及兽药使用等途径进入水体、甚至水源。尽管抗生素在水环境中的含量大多在ng·L–1~μg·L–1范围内，但即使这种低浓度暴露也会干扰环境中生物的正常代谢及生长、对生物产生毒性效应，造成生物畸变或突变，诱发大量耐药菌株的产生等，对生态环境和健康带来了潜在的风险。磺胺类药物为人工合成的抗菌药，它具有抗菌谱较广、性质稳定、使用简便、生产时不耗用粮食等优点，虽然有大量抗生素问世，但磺胺类药仍是重要的化学治疗药物。光催化技术是以半导体材料作为光催化剂，利用太阳光太阳能为动力能源，光催化材料吸收光子形成相应的电子空穴对，使周围的氧气及水分子激发成极具氧化能力的自由基，实现氧化降解水中存在的有机污染物，甚至完全矿化为二氧化碳和水等无污染物质。为此，研究开发新型半导体光催化剂对处理环境中的抗生素有重要的意义。
二硫化钼（MoS2）是一种具有类石墨烯层状结构的半导体纳米材料，具有优良的光电特性及催化能力。MoS2的边缘结构复杂，具有高不饱和性和高反应活性等特点，多层的MoS2是由几个单层的MoS2通过弱的范德华力结合在一起，其禁带宽度随着片层厚度在1.2~1.9eV范围内变化，这样的带隙宽度能够吸收可见光并且激发出电子空穴对，具有优异的光催化活性。然而纯MoS2作光催化剂时，由于其激子结合能高，光生电子和空穴容易复合，光催化效率不尽如人意。
量子点是由III-V族和II-VI族元素组成的半导体纳米晶体。具有尺寸小、表面积大、独特的电子态同时兼备表面原子不完全配位的性质，从而使其表面活性增加。此外，随着量子点材料粒径的逐渐变小，材料表面粗糙程度逐渐增强，极大地增加了材料与目标分子的接触面积和接触几率。而且量子尺寸效应导致量子点材料的导带和价带能级更加分立，更大程度上降低了光生载流子的复合几率。这些特征都有利于提高量子点材料的光催化活性，使这类材料在半导体光催化领域同样具有光明的应用前景。
发明内容
本发明的目的是提供一种硒化镉量子点/二硫化钼复合光催化剂的制备方法；
本发明另一个目的是提供该硒化镉量子点/二硫化钼复合光催化剂在光催化降解磺胺类药物中的应用。
一、CdSe QDs@MoS2复合光催化剂的制备
本发明CdSe QDs@MoS2复合光催化剂的制备方法，包括以下步骤：
（1）纳米二硫化钼的合成：将钼酸钠和硫脲溶于去离子水中，用盐酸调节pH值至2.5~3.5，于180~190℃下水热反应24~25 h，冷却至室温，离心洗涤，真空干燥，研磨即得黑色粉末状纳米二硫化钼。其中，钼酸钠和硫脲的质量比为1:1~1:1.5；真空干燥是在60 ~70℃下真空干燥12~14h。
（2）前驱体NaHSe的合成：在超纯水中，氮气保护下，硒粉与硼氢化钠以1:5~1:7的质量比，于40~60 ℃的水浴中反应1~1.5 h，得到前驱体NaHSe溶液。
（3）硒化镉量子点的合成：将氯化镉和巯基乙酸溶于去离子水中，用NaOH调节至溶液pH=10~11，在氮气保护下，室温搅拌30 ~40 min；然后迅速加入上述前驱体NaHSe溶液，于90~100℃油浴反应3~4 h；反应结束冷却至室温，用无水乙醇沉淀合成产物，真空干燥得到硒化镉量子点。其中，氯化镉和巯基乙酸的摩尔比为1:1.2~1:1.5；氯化镉与硼氢化钠的摩尔比为1:5~1:10；NaOH的浓度为0.1 mol•L-1。
（4）硒化镉量子点/二硫化钼复合光催化剂的合成：将纳米二硫化钼与硒化镉量子点溶于超纯水中，超声分散，于30~40℃油浴中搅拌24~25 h；反应结束后冷却至室温，真空干燥，得到硒化镉量子点/二硫化钼（CdSe QDs@MoS2）复合光催化剂。其中，纳米二硫化钼与硒化镉量子点的质量比为1:0.5~1:0.6。
二、CdSe QDs@MoS2复合光催化剂的表征
1、形貌表征
图1本发明制备的CdSe QDs@MoS2复合光催化剂的SEM图像。SEM表征结果显示所制备的MoS2为片层结构，且表面粗糙，有部分CdSe纳米颗粒负载于其夹层和表面上。
图2为本发明制备的CdSe QDs@MoS2复合光催化剂的TEM图像。TEM图像可以更加明显的看到复合光催化剂呈片层结构，且MoS2片的边缘和插层中都能够观察到CdSe纳米颗粒的存在。
图3为本发明制备的CdSe QDs@MoS2复合光催化剂的HRTEM图像，从图中可以清晰得观察到MoS2的平面以及边缘层叠部分，同时可以在CdSe QDs@MoS2材料表面观察到黑线状条纹，间距约为0.351nm，对应于立方CdSe（JCPDS 19-0191）的（111）晶面。
2、EDX光谱表征
图4为本发明制备的CdSe QDs@MoS2复合光催化剂的EDX光谱，能够检测到来自MoS2的Mo、S元素以及来自CdSe量子点的Cd、Se元素。
3、X-射线衍射(XRD)表征
图5为本发明制备的CdSe QDs@MoS2复合光催化剂的XRD光谱，如图所示，制备的CdSe QDs@MoS2样品在2θ=9.7°、17.2°、32°和57°有明显的衍射峰，分别对应于MoS2的（002）、（004）、（100）和（110）晶面，且CdSe的衍射峰位（111）、（220）和（110）在复合光催化剂的XRD图中均有显示。
三、CdSe QDs@MoS2复合光催化剂的光电性能
1、紫外-可见漫反射光谱（UV-Vis）
图6为本发明制备的CdSe QDs@MoS2复合光催化剂的紫外-可见漫反射光谱（UV-Vis），如图所示，所有样品均在可见光范围内表现出较强的光吸收特性，与单一的MoS2纳米片相比，复合CdSe量子点后的MoS2纳米片在可见光范围内表现出增强的光吸收特性，且可见光响应也有一定的提升。
2、光致发光光谱（PL）
图7为本发明制备的CdSe QDs@MoS2复合光催化剂的光致发光光谱图（PL）。从图中可以看到，所制备的复合光催化剂在700~800nm范围内均存在明显的发光峰，而经过CdSe量子点复合后的MoS2纳米片呈现出减弱的光致发光特性，这表明适量的CdSe量子点负载有利于抑制光生电子空穴的复合，延长载流子寿命，从而提高MoS2纳米片的光催化活性。
3、电化学阻抗谱（EIS）
图8为本发明制备的CdSe QDs@MoS2复合光催化剂的电化学阻抗谱（EIS）。从图中可以清晰地看到，与单一的MoS2纳米材料相比，所制备的CdSe QDs@MoS2纳米复合光催化剂样品内部有着更小的电阻，电子传输能力更强，这使得更多的电子参与到催化反应中来，进而有助于提高其光催化降解能力。
四、CdSe QDs@MoS2复合光催化剂对磺胺类药物的光催化降解性能
选取三种典型的磺胺类药物：磺胺、磺胺甲恶唑、磺胺嘧啶进行光催化降解实验。具体实施方案为：在50 mL容量瓶中准确配制20 mg/L的磺胺、磺胺甲恶唑、磺胺嘧啶溶液。称取10 mg的CdSe QDs@MoS2复合光催化剂于石英试管中，加入上述配制好的磺胺类药物溶液，超声3 min，使CdSe QDs@MoS2粉末迅速并且均匀地分散在磺胺类药物溶液中。将上述盛有反应液的试管放入到光化学反应仪中，首先对其进行30 min的暗反应，以达到吸附解吸平衡，取样检测其紫外吸光度值。打开光源开关（本反应所用的是长弧氙灯，其发出的光与太阳光光谱接近，波长范围主要在300-8000 nm之间）开始光反应，每隔20 min用吸管吸取2mL左右的反应液于离心管中，离心2 min后取出，将离心液用0.22 μm微孔滤膜过滤后，准确移取1.0 mL滤液，然后用蒸馏水稀释定容至5 mL容量瓶中，检测其紫外吸光度值，根据如下公式计算降解率：
降解率=1-Ct/C0=1-At/A0
其中，C0、A0分别代表磺胺类药物的初始浓度和初始的最大吸光度值，Ct、At分别代表磺胺类药物在某一时刻的浓度和最大吸光度值。
图9为CdSe QDs@MoS2复合光催化剂对磺胺、磺胺甲恶唑、磺胺嘧啶降解的光降解曲线图。图中可以看到CdSe QDs@MoS2复合光催化剂在暗反应30min后对磺胺、磺胺甲恶唑、磺胺嘧啶的去除率分别为16%、13%、11%， 光照2 h后对磺胺、磺胺甲恶唑、磺胺嘧啶三种磺胺类药物的去除率分别达到83 %、75 %和70 %，说明CdSe QDs@MoS2光催化剂在光照下对磺胺类药物有良好的降解作用。
综上所述，本发明以纳米二硫化钼为基底材料，通过静电自组装将水溶性硒化镉量子点负载于纳米二硫化钼上制备了CdSe QDs@MoS2复合光催化剂，制备过程简单。硒化镉量子点与MoS2复合能够改善光生载流子的迁移和抑制载流子复合，并能显著改善硒化镉量子点的光催化性能，光电性能测试结果表明该复合光催化剂具有优异的光电特性。将该复合光催化剂用于磺胺、磺胺甲恶唑、磺胺嘧啶三种典型的磺胺类药物的光催化降解，均表现出良好的光催化降解效果，为环境水体中抗生素类药物残留的有效去除提供了一定的方法指导。
附图说明
图1为本发明制备的CdSe QDs@MoS2复合光催化剂的SEM图像。
图2为本发明制备的CdSe QDs@MoS2复合光催化剂的TEM图像。
图3为本发明制备的CdSe QDs@MoS2复合光催化剂的HRTEM图像。
图4为本发明制备的CdSe QDs@MoS2复合光催化剂的EDX光谱。
图5为本发明制备的CdSe QDs@MoS2复合光催化剂的XRD光谱。
图6为本发明制备的CdSe QDs@MoS2复合光催化剂的紫外-可见漫反射光谱（UV-Vis）。
图7为本发明制备的CdSe QDs@MoS2复合光催化剂的光致发光光谱图（PL）。
图8为本发明制备的CdSe QDs@MoS2复合光催化剂的电化学阻抗谱（EIS）。
图9为CdSe QDs@MoS2复合光催化剂对磺胺、磺胺甲恶唑、磺胺嘧啶降解的光降解曲线图。
具体实施方式
下面通过具体实施例对本发明CdSe QDs@MoS2复合光催化剂的制备及性能作进一步说明。
实验试剂：钼酸钠（天津市化学试剂四厂），硫脲（天津市化学试剂一厂），硼氢化钠（>97％），硒粉(>99.99％），均购自上海中秦化学试剂有限公司；氯化镉（>98％，北京化工厂）；巯基乙酸（TGA)（>90％，天津市光复精细化工研究所）；氢氧化钠（>96％，广东光华化学厂有限公司）；实验所用试剂除特别注明外均为分析纯，实验用水均为二次去离子水。
实验仪器：BS 224 S精密电子天平（北京赛多利斯仪器有限公司）；SK2200HP超声仪（上海科导超声仪器有限公司）；PB-10酸度计（德国Sartorius仪器有限公司）；TG18G-II台式通用离心机（湖南凯达科学仪器有限公司)；DZF-6020型真空干燥箱（上海一恒科技有限公司）；ULTRA型场发射扫描电子显微镜（德国卡尔蔡司公司）；Tecnai F30型投射电子显微镜（荷兰FEI公司）；D/max-2400粉末X射线衍射（日本理学公司）；上海辰华电化学工作站（CHI 660D）；UV-757CRT紫外-可见分光光度计（上海精科仪器公司）；光化学反应器（北京纽比特科技有限公司）；循环水冷却机（北京纽比特科技有限公司）。
实施例1
（1）纳米二硫化钼的合成：称取1.2 g的钼酸钠（Na2MoO4•2H2O）和1.6 g的硫脲（CS(NH2)2），加入60 mL去离子水搅拌溶解，在室温下用磁力搅拌器搅拌30 min使其混合均匀，用盐酸调节pH值至3后，将上述溶液转移到100 mL的聚四氟乙烯内衬的反应釜中，于180 ℃下水热反应24 h。待反应液自然冷却至室温，再用蒸馏水和无水乙醇分别离心洗涤三次除去产品中其它可溶性物质，在60 ℃下真空干燥12 h，取出研磨得到黑色粉末状纳米二硫化钼。
（2）前驱体NaHSe的合成：称取0.020 g硒粉和0.120 g硼氢化钠固体于10 mL圆底烧瓶中，通氮气30 min直至烧瓶内环境处于无氧状态后，加入5 mL经氮气处理过的超纯水，于60 ℃的水浴中反应1 h，待硒粉反应完全，得到前驱体NaHSe溶液。
（3）硒化镉量子点的合成：称取0.114 g氯化镉于100 mL三颈烧瓶中，加入50 mL去离子水溶解后加入90μL巯基乙酸（TGA），并用0.1 mol•L-1NaOH调节至溶液pH=10，在氮气保护下室温磁力搅拌30 min；然后迅速加入上述前驱体NaHSe溶液，于90 ℃油浴反应3 h；反应结束冷却至室温，用无水乙醇沉淀合成产物，真空干燥得到硒化镉量子点。
（4）CdSe QDs@MoS2复合光催化剂的制备：称取10 mg上述制备的纳米二硫化钼于三颈烧瓶中，另取5.3 mg硒化镉量子点于30 mL超纯水中，溶解后加入到三颈烧瓶中，超声分散均匀，于35℃油浴加热并磁力搅拌24 h；反应结束冷却至室温，真空干燥得到CdSeQDs@MoS2复合光催化剂。
（5）CdSe QDs@MoS2复合光催化剂对磺胺类药物的光催化降解性能：CdSe QDs@MoS2复合光催化剂在暗反应30min后对磺胺、磺胺甲恶唑、磺胺嘧啶的去除率分别为16%、13%、11%， 光照2 h后对磺胺、磺胺甲恶唑、磺胺嘧啶三种磺胺类药物的去除率分别达到83 %、75%和70 %。
Claims (7)
1.一种硒化镉量子点/二硫化钼复合光催化剂的制备方法，包括以下步骤：
（1）纳米二硫化钼的合成：将钼酸钠和硫脲溶于去离子水中，用盐酸调节pH值至2.5~3.5，于180~190℃下水热反应24~25 h，冷却至室温，离心洗涤，真空干燥，研磨即得黑色粉末状纳米二硫化钼；钼酸钠和硫脲的质量比为1:1~1:1.5；
（2）前驱体NaHSe的合成：在超纯水中，氮气保护下，硒粉与硼氢化钠以1:5~1:7的质量比，于40~60 ℃的水浴中反应1~1.5 h，得到前驱体NaHSe溶液；
（3）硒化镉量子点的合成：将氯化镉和巯基乙酸溶于去离子水中，用NaOH调节至溶液pH=10~11，在氮气保护下，室温搅拌30 ~40 min；然后迅速加入上述前驱体NaHSe溶液，于90~100℃油浴反应3~4 h；反应结束冷却至室温，用无水乙醇沉淀合成产物，真空干燥得到硒化镉量子点；
（4）硒化镉量子点/二硫化钼复合光催化剂的合成：将纳米二硫化钼与硒化镉量子点溶于超纯水中，超声分散，于30~40℃油浴中搅拌24~25 h；反应结束后冷却至室温，真空干燥，得到硒化镉量子点/二硫化钼复合光催化剂；纳米二硫化钼与硒化镉量子点的质量比为1:0.5~1:0.6。
2.如权利要求1所述一种硒化镉量子点/二硫化钼复合光催化剂的制备方法，其特征在于：步骤（1）中，真空干燥是在60 ~70℃下真空干燥12~14h。
3.如权利要求1所述一种硒化镉量子点/二硫化钼复合光催化剂的制备方法，其特征在于：步骤（3）中，氯化镉和巯基乙酸的摩尔比为1:1.2~1:1.5。
4.如权利要求1所述一种硒化镉量子点/二硫化钼复合光催化剂的制备方法，其特征在于：步骤（3）中，氯化镉与硼氢化钠的摩尔比为1:5~1:10。
5.如权利要求1所述一种硒化镉量子点/二硫化钼复合光催化剂的制备方法，其特征在于：步骤（3）中，NaOH的浓度为0.1 mol•L-1。
6.如权利要求1所述方法制备的硒化镉量子点/二硫化钼复合光催化剂在磺胺类药物的光催化降解中的应用。
7.如权利要求1所述方法制备的硒化镉量子点/二硫化钼复合光催化剂在磺胺类药物的光催化降解中的应用，其特征在于：磺胺类药物为磺胺、磺胺甲恶唑、磺胺嘧啶。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010739733.2A CN111939944B (zh) | 2020-07-28 | 2020-07-28 | 一种硒化镉量子点/二硫化钼复合光催化剂的制备与应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010739733.2A CN111939944B (zh) | 2020-07-28 | 2020-07-28 | 一种硒化镉量子点/二硫化钼复合光催化剂的制备与应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111939944A CN111939944A (zh) | 2020-11-17 |
| CN111939944B true CN111939944B (zh) | 2022-09-06 |
Family
ID=73338570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010739733.2A Active CN111939944B (zh) | 2020-07-28 | 2020-07-28 | 一种硒化镉量子点/二硫化钼复合光催化剂的制备与应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111939944B (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114632528B (zh) * | 2022-03-30 | 2023-07-25 | 青岛科技大学 | 一种硒化镉/钼酸钙光催化剂及其制备方法与应用 |
| CN115532286B (zh) * | 2022-11-24 | 2023-04-07 | 河北地质大学 | 一种MoS2量子点/Bi2WO6异质结型复合催化剂制备方法及其应用 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437548A (zh) * | 2013-09-12 | 2015-03-25 | 华东师范大学 | 一种可见光光催化薄膜及制备方法以及具有他的照明灯具 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005068181A1 (en) * | 2004-01-16 | 2005-07-28 | Domo Oudenaarde Nv | Photocatalytic particles in floor laminates |
| WO2011106864A1 (en) * | 2010-03-02 | 2011-09-09 | Trojan Technologies | Photocatalyst composition of matter |
| CN103506139A (zh) * | 2013-03-14 | 2014-01-15 | 江苏大学 | 水热合成CdSe 量子点光催化剂的制备方法及其应用 |
| CN104338547B (zh) * | 2013-07-29 | 2016-08-31 | 中国科学院理化技术研究所 | 基于量子点/棒和二硫化钼纳米片的光催化剂、制备方法、光催化体系及其重整生物质制氢的方法 |
| CN103599799B (zh) * | 2013-10-29 | 2016-01-20 | 江苏大学 | CdSe@CdS核壳结构量子点光催化剂的制备方法及其应用 |
| CN105289505B (zh) * | 2015-11-07 | 2017-09-29 | 长春工业大学 | 一种硒化镉量子点和锆基配位聚合物复合材料及制法 |
| CN108620135A (zh) * | 2018-05-17 | 2018-10-09 | 西北师范大学 | 一种二硫化钼复合材料的制备方法 |
| CN109126829B (zh) * | 2018-09-18 | 2021-12-14 | 合肥学院 | 一种三维异质结构CdS-MoS2复合粉体的制备方法 |
-
2020
- 2020-07-28 CN CN202010739733.2A patent/CN111939944B/zh active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437548A (zh) * | 2013-09-12 | 2015-03-25 | 华东师范大学 | 一种可见光光催化薄膜及制备方法以及具有他的照明灯具 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111939944A (zh) | 2020-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shi et al. | Onion-ring-like g-C3N4 modified with Bi3TaO7 quantum dots: A novel 0D/3D S-scheme heterojunction for enhanced photocatalytic hydrogen production under visible light irradiation | |
| Hong et al. | Promoting visible-light-induced photocatalytic degradation of tetracycline by an efficient and stable beta-Bi2O3@ g-C3N4 core/shell nanocomposite | |
| Tang et al. | Enhanced photocatalytic degradation of tetracycline antibiotics by reduced graphene oxide–CdS/ZnS heterostructure photocatalysts | |
| Li et al. | Visible-light-driven CQDs@ MIL-125 (Ti) nanocomposite photocatalyst with enhanced photocatalytic activity for the degradation of tetracycline | |
| Guo et al. | Oxygen-defective ZnO porous nanosheets modified by carbon dots to improve their visible-light photocatalytic activity and gain mechanistic insight | |
| Wu et al. | Surfactants-assisted preparation of BiVO4 with novel morphologies via microwave method and CdS decoration for enhanced photocatalytic properties | |
| Vattikuti et al. | Physicochemcial characteristic of CdS-anchored porous WS2 hybrid in the photocatalytic degradation of crystal violet under UV and visible light irradiation | |
| Li et al. | Controlled preparation of MoS2/PbBiO2I hybrid microspheres with enhanced visible-light photocatalytic behaviour | |
| Smrithi et al. | Carbon dots decorated cadmium sulphide heterojunction-nanospheres for the enhanced visible light driven photocatalytic dye degradation and hydrogen generation | |
| CN111939944B (zh) | 一种硒化镉量子点/二硫化钼复合光催化剂的制备与应用 | |
| Jiang et al. | Preparation of magnetically separable and recyclable carbon dots/NiCo 2 O 4 composites with enhanced photocatalytic activity for the degradation of tetracycline under visible light | |
| Meng et al. | Preparation and high visible-light-induced photocatalytic activity of CdSe and CdSe-C60 nanoparticles | |
| CN113649052B (zh) | 一种石墨相氮化碳基光催化复合材料及其制备和应用 | |
| Wu et al. | Polyoxometalate-based yolk@ shell dual Z-scheme superstructure tandem heterojunction nanoreactors: encapsulation and confinement effects | |
| CN110560092A (zh) | 一种MoS2/BiVO4异质结复合光催化剂的制备方法及其应用 | |
| Sehrawat et al. | Optimal synthesis of MoS2/Cu2O nanocomposite to enhance photocatalytic performance towards indigo carmine dye degradation | |
| CN108187687B (zh) | 一种光芬顿催化剂的制备方法 | |
| Altin | CuO-TiO2/graphene ternary nanocomposite for highly efficient visible-light-driven photocatalytic degradation of bisphenol A | |
| Huang et al. | Design and synthesis of Z-scheme LaFeO3/MoS2/graphene heterojunction with enhanced photocatalytic performance | |
| Wang et al. | Different Morphology MoS 2 Over the gC 3 N 4 as a Boosted Photo-Catalyst for Pollutant Removal Under Visible-Light | |
| Zhou et al. | Construction of AgI/Bi2MoO6/AgBi (MoO4) 2 multi-heterostructure composite nanosheets for visible-light photocatalysis | |
| Li et al. | Synthesis of recyclable magnetic mesoporous RH-FSBA photoelectrocatalyst with double cavity structure | |
| Li et al. | Synthesizing ZnWO4 with enhanced performance in photoelectrocatalytic inactivating marine microorganisms | |
| Zhou et al. | Assembly of direct Z-scheme ZnIn2S4/BiVO4 composite for enhanced photodegradation of tetracycline hydrochloride | |
| CN104826639B (zh) | 磷酸银/还原石墨烯/二氧化钛纳米复合材料及制备方法 |
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 |