CN113509905A - 表面负载MoS2/ZrO2的煤沥青基复合活性炭球及制备方法 - Google Patents
表面负载MoS2/ZrO2的煤沥青基复合活性炭球及制备方法 Download PDFInfo
- Publication number
- CN113509905A CN113509905A CN202110817070.6A CN202110817070A CN113509905A CN 113509905 A CN113509905 A CN 113509905A CN 202110817070 A CN202110817070 A CN 202110817070A CN 113509905 A CN113509905 A CN 113509905A
- Authority
- CN
- China
- Prior art keywords
- zro
- coal tar
- mos
- activated carbon
- tar pitch
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 39
- 229910052961 molybdenite Inorganic materials 0.000 title claims abstract description 38
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000010426 asphalt Substances 0.000 title claims description 10
- 229910052799 carbon Inorganic materials 0.000 title abstract description 10
- 239000011294 coal tar pitch Substances 0.000 claims abstract description 77
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000011300 coal pitch Substances 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000009395 breeding Methods 0.000 claims description 7
- 230000001488 breeding effect Effects 0.000 claims description 7
- 239000003245 coal Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 239000011280 coal tar Substances 0.000 claims description 5
- 230000005284 excitation Effects 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000011295 pitch Substances 0.000 claims description 5
- 241000143432 Daldinia concentrica Species 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000000944 Soxhlet extraction Methods 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 230000001954 sterilising effect Effects 0.000 abstract description 7
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 7
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 238000011068 loading method Methods 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- 238000005336 cracking Methods 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 241000894006 Bacteria Species 0.000 description 9
- 239000003242 anti bacterial agent Substances 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 244000000010 microbial pathogen Species 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 201000010099 disease Diseases 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000193830 Bacillus <bacterium> Species 0.000 description 2
- 206010059866 Drug resistance Diseases 0.000 description 2
- 241001115402 Ebolavirus Species 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 241000607626 Vibrio cholerae Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000009210 therapy by ultrasound 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000204031 Mycoplasma Species 0.000 description 1
- 102000029797 Prion Human genes 0.000 description 1
- 108091000054 Prion Proteins 0.000 description 1
- 241000606701 Rickettsia Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000002458 infectious effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 208000019423 liver disease Diseases 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
- 244000005700 microbiome Species 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 244000045947 parasite Species 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229940118696 vibrio cholerae Drugs 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
-
- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
-
- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3071—Washing or leaching
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
-
- 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
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
-
- 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)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Water Treatment By Sorption (AREA)
Abstract
本发明涉及表面负载MoS2/ZrO2的煤沥青基复合活性炭球及制备方法，所述煤沥青基复合活性炭球的比表在1300m2/g以上，具有丰富的孔道结构且孔道容积大于0.6cm3/g，MoS2与ZrO2形成异质结结构，煤沥青基复合活性炭球表面的MoS2/ZrO2负载层均匀。优点是：本发明通过两次升温可以使煤沥青中官能团缓慢氧化，有效减少了煤沥青球的熔化和开裂；炭球表面的MoS2/ZrO2负载层均匀，该复合活性炭球具有有效的杀菌性能和防脱落性能，可以有效地吸附水中的悬浮物和污染物。
Description
技术领域
本发明属于水处理领域，尤其涉及一种面负载MoS2/ZrO2光催化异质结的煤沥青基复合活性炭球及制备方法。
背景技术
在工业蓬勃发展和国民经济持续增长的同时，水污染问题也日益凸显。据报道，世界范围内有超过9亿人接触不到洁净的水源，每年约有150万的儿童死于饮用污染的水。在众多的水污染物当中，病原微生物污染给生态环境和人类健康安全造成了极大的威胁。据世界卫生组织(WHO)调查结果显示，在发展中国家和偏远农村，由细菌、原生动物、真菌、立克次体、病毒和朊病毒等病原微生物引起的疾病占所有疾病的80％以上。水体中常见的病原微生物有大肠杆菌(Escherichia coli，E.coli)、霍乱弧菌(Vibrio cholerae，V.cholerae)、志贺杆菌(Shiga bacillus，S.bacillus)、支原体、寄生虫、埃博拉病毒(Ebola virus，EBOV)等，这些病原微生物可通过人畜的粪便、生活垃圾、医疗垃圾等途径进入水源，当人们饮用或接触到含有病原微生物的水或食品后，就可能感染胃肠道、呼吸道、传染性肝病等多种疾病，甚者失去生命，从而给人们的健康安全带来了极大的危害。
近年来，人类对抗生素的泛滥使用导致细菌的耐药性增强，与临床使用的抗生素相比，新型生物材料具有更强的抗菌活性、更少的耐药性和良好的生物相容性，显示出强大的应用潜力。抗菌材料是具备抑菌或杀菌效能的材料，根据其有效成分(即抗菌剂)的不同，可将其分为三大类，有机抗菌剂、天然抗菌剂和无机抗菌剂。其中，无机抗菌剂因具有广谱抗菌性和安全性而被广泛应用，其主要通过金属离子(如：银、铜、锌离子等)进行抗菌。但金属元素离子抗菌存在着离子扩散造成二次污染的隐患。相比而言，光催化抗菌材料因具有良好的抗菌性、光催化性能、造价成本较低和稳定性等特点，在抗菌和光催化领域受到广泛关注。
活性炭具有比表面积大、吸附能力强等优点被广泛用于水处理吸附剂，其中球形活性炭凭借其球形结构而具有较高的装填密度和流动性，是水处理吸附剂中的佼佼者，但球形活性炭在水处理中仅起到物理吸附作用，对污染物只能起到暂时的消除效果，不能有效的分解水中细菌和污染物。
二氧化锆(ZrO2)具有高熔点、高折射率和低热膨胀系数的性质，常用于耐热耐磨涂层，与其他材料复合后，不易脱落，但ZrO2的禁带宽度约为5.0eV，只能在紫外光激发下同样具有杀菌能力，虽然其光生空穴具有较高的氧化电位，能应对各种结构复杂的微生物，但只对紫外光响应的特性大大限制了其应用。中国专利申请号CN202010415258.3公布了一种光催化异质结在水处理方向上的应用，二硫化钼(MoS2)的能带较窄，约为1.9eV，具有可见光响应高，光吸收能力强的优点。同时，MoS2的导带和价带主要来自Mo的4d轨道，因此，当MoS2被光照产生电子-空穴对时，不会影响Mo-S化学键结合，而且MoS2比离子键合硫化物更耐光腐蚀。此外，MoS2不溶于水，仅溶于王水和热浓硫酸中，处理完污水后容易回收，不产生二次污染。MoS2因具有高的可见光响应和耐光腐蚀性在光催化领域得到了广泛的应用，是与ZrO2复合形成异质结复合材料的不二之选。
发明内容
为克服现有技术的不足，本发明的目的是提供一种表面负载MoS2/ZrO2的煤沥青基复合活性炭球及制备方法，该复合活性炭球可以有效地吸附水中的悬浮物和污染物，并在太阳光激发下杀死水中的细菌，且由于静电吸附作用能够有效避免催化材料在多次使用后脱落的问题。
为实现上述目的，本发明通过以下技术方案实现：
一种表面负载MoS2/ZrO2的煤沥青基复合活性炭球，所述煤沥青基复合活性炭球的比表在1300m2/g以上，具有丰富的孔道结构且孔道容积大于0.6cm3/g，MoS2与ZrO2形成异质结结构，煤沥青基复合活性炭球表面的MoS2/ZrO2负载层均匀。
一种负载MoS2/ZrO2的煤沥青基复合活性炭球的制备方法，包括以下步骤：
1)取煤沥青球1-3倍质量的KOH固体溶于去离子水中，再与煤沥青球混合，真空干燥将溶液蒸发；在氮气气氛下，经过两次升温并保持恒温，再自然冷却后取出样品；样品用盐酸和去离子水冲洗直到中性为止，放入干燥箱中干燥制得煤沥青基球形活性炭；
2)取MoS2与ZrO2，在乙醇溶液中分散，并加入NaOH调节pH值，使pH值大于8，通过水热反应制备出MoS2/ZrO2复合材料；
3)通过静电吸附法将MoS2/ZrO2复合材料负载到煤沥青基球形活性炭表面，并用去离子水洗涤至中性，得到最终产物。
所述的煤沥青球的制备方法，包括以下步骤：
1)用吡啶溶液对煤焦油中温沥青进行索氏抽提，将抽提后的溶液冷却，并抽滤收取滤液；
2)将聚乙烯醇1788型、无水乙醇溶液、去离子水混合放入烧瓶中，在水浴锅中进行磁力搅拌，使聚乙烯醇完全溶解，冷却至室温；
3)将步骤1)得到的滤液和步骤2)得到的聚乙烯醇溶液混合，按所使用煤焦油中温沥青的3wt％～10wt％加入炭黑或煤沥青粉末，对得到的混合溶液超声震荡；
4)将混合溶液在85℃～95℃下进行加热搅拌，再恒温搅拌15～25分钟；
5)搅拌后的溶液冷却至室温，进行抽滤，得到煤沥青球；
6)对煤沥青球进一步处理：将得到的煤沥青球放入管式炉中，在空气气氛下，升温至300℃，在300℃温度下保持3小时，待自然冷却取出；
7)步骤6)得到的样品放入管式炉中，在氮气气氛下，升温至500℃～700℃，在500℃～700℃温度下保持1～3小时，待自然冷却取出得到煤沥青球。
步骤1)中所述的经过两次升温并保持恒温为在管式炉中从室温升温至400℃～450℃，并保持恒温1～2.5小时，再继续升温至700～800℃，并保持恒温1～2.5小时。
步骤2)中所述的水热反应为将乙醇分散液倒入聚四氟乙烯内胆中，并将内胆装入水热反应釜中，将水热反应釜置于鼓风干燥箱中，设置200℃，保持12h～24h。
步骤3)中将步骤1)制备的煤沥青基球形活性炭放入浓盐酸溶液中搅拌1h，将步骤2)制备的MoS2/ZrO2复合材料放入十二烷基硫酸钠溶液中搅拌2h，随后直接将两种溶液混合，继续搅拌1h，得到表面负载MoS2/ZrO2的煤沥青基复合活性炭球。
步骤2)中MoS2与ZrO2的质量比为0.1～2。
以太阳光为激发光源，将步骤3)得到的表面负载MoS2/ZrO2的煤沥青基复合活性炭球与锦鲤养殖水混合。
与现有技术相比，本发明的有益效果是：
本发明通过两次升温可以使煤沥青中官能团缓慢氧化，有效减少了煤沥青球的熔化和开裂；KOH的加入使煤沥青球的比表面积进一步扩大，并增加了微孔与介孔的数量，提高了材料的吸附性能；使前驱体溶液分散性良好，炭球表面的MoS2/ZrO2负载层均匀，该复合活性炭球具有有效的杀菌性能和防脱落性能，可以有效地吸附水中的悬浮物和污染物，MoS2的加入使之与ZrO2形成异质结结构，使复合材料能在太阳光激发下具有较高的杀菌效率，杀死水中的细菌，为使用循环水的养殖体系的水处理问题提供了有效解决方案。
附图说明
图1是煤沥青基活性炭球制备流程图。
图2是MoS2/ZrO2复合材料制备流程图。
图3是表面负载MoS2/ZrO2的煤沥青基复合活性炭球的制备流程图。
图4是锦鲤养殖水处理的流程图。
图5是煤沥青基活性炭球的XRD图。
图6是表面负载MoS2/ZrO2的煤沥青基复合活性炭球的XRD图。
图7是活化后的煤沥青基活性炭球的电镜扫描图。
图8是表面负载MoS2/ZrO2的煤沥青基复合活性炭球的电镜扫描图。
图9是表面负载MoS2/ZrO2的煤沥青基复合活性炭球的EDS分析。
图10是煤沥青基复合活性炭球与表面负载MoS2/ZrO2的煤沥青基复合活性炭球孔径分布图。
图11是表面负载MoS2/ZrO2的煤沥青基复合活性炭球的杀菌性能评价效果图。
图11中，(a)是锦鲤养殖原水图；(b)是MoS2与ZrO2质量比为0.5:1的杀菌效果图。
具体实施方式
下面结合说明书附图对本发明进行详细地描述，但是应该指出本发明的实施不限于以下的实施方式。
表面负载MoS2/ZrO2的煤沥青基复合活性炭球的比表在1300m2/g以上，煤沥青基复合活性炭球孔径分布见图10，具有丰富的孔道结构且孔道容积大于0.6cm3/g，MoS2与ZrO2形成异质结结构，煤沥青基复合活性炭球表面的MoS2/ZrO2负载层均匀，见图9。复合材料能在太阳光激发下具有较高的杀菌效率，通过平板涂布法统计水中的细菌数量，发现使用复合材料的溶液中细菌数量明显减少且在多次使用后材料仍表现出优异的杀菌性能。
表面负载ZrO2的煤沥青基复合活性炭球的制备方法，包括以下步骤：
1、煤沥青球的制备：
a.取吡啶溶液对煤焦油中温沥青进行索氏抽提，将抽提后的溶液冷却并抽滤收取滤液。
b.取聚乙烯醇1788型，无水乙醇溶液和去离子水，将其混合放入烧瓶中，在水浴锅中进行磁力搅拌并加热到70-90℃，确保聚乙烯醇完全溶解，最后冷却至室温。
c.将步骤a得到的滤液和步骤b)得到的聚乙烯醇溶液混合，并按混合溶液的3wt％～10wt％加入炭黑或煤沥青粉末，对得到的混合溶液超声震荡。
d.将超声后的混合溶液在85℃下进行热搅拌，温度到达85℃时再恒温搅拌20分钟。
e.搅拌后的溶液冷却至室温，进行抽滤，得到煤沥青球。
f.将得到的煤沥青球放入管式炉中，在空气条件下，从温度25℃升温至300℃，升温时间37～40小时，在300℃温度下恒温3小时，待自然冷却取出样品。
g.在氮气气氛下，从温度25℃升温至700℃，升温时间4小时，在700℃温度下恒温3小时，待自然冷却取出，得到煤沥青球。
2、表面负载MoS2/ZrO2的煤沥青基复合活性炭球的制备：
a.取煤沥青球质量1～3倍的KOH固体，将KOH溶于少量去离子水后与煤沥青球混合，并在60～90℃下真空干燥，接着将干燥好的小球放入管式炉中高温煅烧。在氮气气氛下，煅烧温度从25℃加热到700～800℃，中间在400℃～450℃恒温60～150分钟，随后继续升温3小时，并在700～800℃也恒温60～150分钟。随炉冷却后取出样品，用稀盐酸和去离子水冲洗直到水溶液变回中性为止，放入干燥箱中干燥制得煤沥青基球形活性炭。
b.将MoS2、ZrO2按质量比0.1：1～1：1，分散在乙醇溶液中，搅拌30min使之分散均匀，并在搅拌过程中加入适量NaOH调节pH值至碱性。将分散液倒入水热反应釜中，将水热反应釜置于鼓风干燥箱中，设置加热至200℃，恒温12h～24h。得到MoS2/ZrO2复合材料。
c.将煤沥青基球形活性炭放入浓盐酸溶液中搅拌1h，将MoS2/ZrO2复合材料放入十二烷基硫酸钠SDS溶液中搅拌2h，然后将两种溶液混合，继续搅拌1h，得到得到表面负载MoS2/ZrO2的煤沥青基复合活性炭球。
使用时，以氙灯模拟太阳光作为光源，将一定量的表面负载MoS2/ZrO2的煤沥青基复合活性炭球放入锦鲤养殖水中，搅拌，就可用平板涂布的方法测试MoS2/ZrO2煤沥青基球形活性炭的杀菌性能。
实施例一：
见图1，按照步骤1)及步骤2)的a制备煤沥青基活性炭球：
取块状煤沥青进行粉碎，过筛，60-100目，用吡啶作为煤沥青的抽提溶剂对煤沥青进行抽提处理，抽滤后和聚乙烯醇溶液混合并进行超声处理。最后进行热搅拌，混合液体冷却后进行抽滤，抽滤后得到的固体煤沥青小球，接着进行不熔化、炭化和KOH活化处理得到煤沥青基活性炭球。见图7，经过500℃炭化后，得到粒径均匀，并且粒径在100-300μm范围。见图8，煤沥青球经质量分数为50％KOH浸泡后，在氮气保护下、温度在700℃～800℃下进行活化，得到煤沥青基活性炭球。
见图2，分别取0.05g、0.01g、0.1g的MoS2，分别和0.1gZrO2分散在30ml无水乙醇溶液中，搅拌过程中加NaOH调节pH均至9，随后倒入水热反应釜中，将水热反应釜置于鼓风干燥箱中，设置加热至200℃，恒温12h后得到MoS2/ZrO2复合材料。
见图3，取0.1g煤沥青基活性炭球置于烧杯，加入质量分数为36％的浓盐酸15ml搅拌1h。取0.1g MoS2/ZrO2复合材料置于另一烧杯，加入0.01mol/l的十二烷基硫酸钠(SDS)溶液30ml，搅拌2h。将上述两种溶液混合，继续搅拌1h得到在表面负载MoS2/ZrO2的煤沥青基复合活性炭球。见图5、图6，通过与标准卡(图6的b曲线，c曲线)的比对证明MoS2与ZrO2均被成功地包覆在球形活性炭表面。见图8，球形活性炭表面光滑，表面无明显团聚，负载层均匀，且球形度完整。见图9，从图上可以看出Zr,O,Mo,S四种元素密集且均匀地分布在煤沥青基复合球形活性炭表面，证明MoS2和ZrO2已经均匀地通过静电吸附作用均匀地包覆到沥青基复合球形活性炭表面。
见图4，取两只40ml的烧杯(酒精消毒)分别加入20ml的锦鲤养殖水，取表面负载MoS2/ZrO2的煤沥青基复合活性炭球0.1g放入其中一只烧杯中，两只烧杯用保鲜膜封口，在氙灯模拟的太阳光照射下磁力搅拌1小时，用原样水作空白对照，用平板涂布法对烧杯中锦鲤养殖水的细菌进行计数，每组做3个平行样。由图11可以看出表面负载MoS2/ZrO2的煤沥青基复合活性炭球在紫外光下对水中的细菌显示了明显的杀菌能力。通过静电吸附在球形活性炭包覆的负载层将在多次回收的实际水产养殖水净化过程中起着重要作用。
本发明提供了新型的光催化杀菌材料表面负载MoS2/ZrO2的煤沥青基复合活性炭球的制备方法，通过静电吸附将MoS2/ZrO2与煤沥青活性炭球的复合，将活性炭的吸附性能与光催化性能有效地结合起来，并大大增加其机械性能。将该型复合球形活性炭用于养殖用水处理，不仅能克服如TiO2等材料不耐磨容易脱落等缺点，还因为其在可见光范围内的吸收特性，大大减少了能源消耗。
Claims (8)
1.一种表面负载MoS2/ZrO2的煤沥青基复合活性炭球，其特征在于，所述煤沥青基复合活性炭球的比表在1300m2/g以上，具有丰富的孔道结构且孔道容积大于0.6cm3/g，MoS2与ZrO2形成异质结结构，煤沥青基复合活性炭球表面的MoS2/ZrO2负载层均匀。
2.根据权利要求1所述的表面负载MoS2/ZrO2的煤沥青基复合活性炭球的制备方法，其特征在于，包括以下步骤：
1)取煤沥青球1-3倍质量的KOH固体溶于去离子水中，再与煤沥青球混合，真空干燥将溶液蒸发；在氮气气氛下，经过两次升温并保持恒温，再自然冷却后取出样品；样品用盐酸和去离子水冲洗直到中性为止，放入干燥箱中干燥制得煤沥青基球形活性炭；
2)取MoS2与ZrO2，在乙醇溶液中分散，并加入NaOH调节pH值，使pH值大于8，通过水热反应制备出MoS2/ZrO2复合材料；
3)通过静电吸附法将MoS2/ZrO2复合材料负载到煤沥青基球形活性炭表面，并用去离子水洗涤至中性，得到最终产物。
3.根据权利要求2或3所述的表面负载MoS2/ZrO2的煤沥青基复合活性炭球的制备方法，其特征在于，所述的煤沥青球的制备方法，包括以下步骤：
1)用吡啶溶液对煤焦油中温沥青进行索氏抽提，将抽提后的溶液冷却，并抽滤收取滤液；
2)将聚乙烯醇1788型、无水乙醇溶液、去离子水混合放入烧瓶中，在水浴锅中进行磁力搅拌，使聚乙烯醇完全溶解，冷却至室温；
3)将步骤1)得到的滤液和步骤2)得到的聚乙烯醇溶液混合，按所使用煤焦油中温沥青的3wt％～10wt％加入炭黑或煤沥青粉末，对得到的混合溶液超声震荡；
4)将混合溶液在85℃～95℃下进行加热搅拌，再恒温搅拌15～25分钟；
5)搅拌后的溶液冷却至室温，进行抽滤，得到煤沥青球；
6)对煤沥青球进一步处理：将得到的煤沥青球放入管式炉中，在空气气氛下，升温至300℃，在300℃温度下保持3小时，待自然冷却取出；
7)步骤6)得到的样品放入管式炉中，在氮气气氛下，升温至500℃～700℃，在500℃～700℃温度下保持1～3小时，待自然冷却取出得到煤沥青球。
4.根据权利要求2所述的表面负载MoS2/ZrO2的煤沥青基复合活性炭球的制备方法，其特征在于，步骤1)中所述的经过两次升温并保持恒温为在管式炉中从室温升温至400℃～450℃，并保持恒温1～2.5小时，再继续升温至700～800℃，并保持恒温1～2.5小时。
5.据权利要求2所述的表面负载MoS2/ZrO2的煤沥青基复合活性炭球的制备方法，其特征在于，步骤2)中所述的水热反应为将乙醇分散液倒入聚四氟乙烯内胆中，并将内胆装入水热反应釜中，将水热反应釜置于鼓风干燥箱中，设置200℃，保持12h～24h。
6.据权利要求2所述的表面负载MoS2/ZrO2的煤沥青基复合活性炭球的制备方法，其特征在于，步骤3)中将步骤1)制备的煤沥青基球形活性炭放入浓盐酸溶液中搅拌1h，将步骤2)制备的MoS2/ZrO2复合材料放入十二烷基硫酸钠溶液中搅拌2h，随后直接将两种溶液混合，继续搅拌1h，得到表面负载MoS2/ZrO2的煤沥青基复合活性炭球。
7.据权利要求2所述的表面负载MoS2/ZrO2的煤沥青基复合活性炭球的制备方法，其特征在于，步骤2)中MoS2与ZrO2的质量比为0.1～2。
8.据权利要求2所述的表面负载MoS2/ZrO2的煤沥青基复合活性炭球的制备方法，其特征在于，以太阳光为激发光源，将步骤3)得到的表面负载MoS2/ZrO2的煤沥青基复合活性炭球与锦鲤养殖水混合。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110817070.6A CN113509905A (zh) | 2021-07-20 | 2021-07-20 | 表面负载MoS2/ZrO2的煤沥青基复合活性炭球及制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110817070.6A CN113509905A (zh) | 2021-07-20 | 2021-07-20 | 表面负载MoS2/ZrO2的煤沥青基复合活性炭球及制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113509905A true CN113509905A (zh) | 2021-10-19 |
Family
ID=78068062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110817070.6A Pending CN113509905A (zh) | 2021-07-20 | 2021-07-20 | 表面负载MoS2/ZrO2的煤沥青基复合活性炭球及制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113509905A (zh) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114471477A (zh) * | 2022-01-06 | 2022-05-13 | 南华大学 | 一种三维多孔壳聚糖/煤基活性炭复合海绵及其制备方法和海水提铀应用 |
| CN116282574A (zh) * | 2023-03-17 | 2023-06-23 | 湖南科美洁环保科技有限公司 | 一种垃圾渗滤液的高效处理方法 |
| CN117142810A (zh) * | 2023-09-12 | 2023-12-01 | 浙江威克赛新材料科技有限公司 | 一种高强度透水型沥青混凝土及制备方法 |
| CN117142810B (zh) * | 2023-09-12 | 2024-05-17 | 浙江威克赛新材料科技有限公司 | 一种高强度透水型沥青混凝土及制备方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120165184A1 (en) * | 2009-06-22 | 2012-06-28 | Nanyang Technological University | Doped catalytic carbonaceous composite materials and uses thereof |
| CN112791699A (zh) * | 2021-01-20 | 2021-05-14 | 辽宁科技大学 | 一种ZrO2/煤沥青基复合活性炭球的制备方法 |
-
2021
- 2021-07-20 CN CN202110817070.6A patent/CN113509905A/zh active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120165184A1 (en) * | 2009-06-22 | 2012-06-28 | Nanyang Technological University | Doped catalytic carbonaceous composite materials and uses thereof |
| CN112791699A (zh) * | 2021-01-20 | 2021-05-14 | 辽宁科技大学 | 一种ZrO2/煤沥青基复合活性炭球的制备方法 |
Non-Patent Citations (3)
| Title |
|---|
| SURYA VEERENDRA PRABHAKAR VATTIKUTI ET AL.: "ZrO2/MoS2 Heterojunction Photocatalysts for Efficient Photocatalytic Degradation of Methyl Orange" * |
| V.R. PATEL ET AL.: "Optoelectronic properties of 2D heterojunction ZrO2– MoS2 material using first-principles calculations" * |
| ZIANG XU ET AL.: "Fabrication and Sterilization Characteristics of Visible Light Photocatalyst of CuO/ZrO2/CB/Coal-Tar-Pitch-SAC" * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114471477A (zh) * | 2022-01-06 | 2022-05-13 | 南华大学 | 一种三维多孔壳聚糖/煤基活性炭复合海绵及其制备方法和海水提铀应用 |
| CN116282574A (zh) * | 2023-03-17 | 2023-06-23 | 湖南科美洁环保科技有限公司 | 一种垃圾渗滤液的高效处理方法 |
| CN116282574B (zh) * | 2023-03-17 | 2024-04-26 | 湖南科美洁环保科技有限公司 | 一种垃圾渗滤液的高效处理方法 |
| CN117142810A (zh) * | 2023-09-12 | 2023-12-01 | 浙江威克赛新材料科技有限公司 | 一种高强度透水型沥青混凝土及制备方法 |
| CN117142810B (zh) * | 2023-09-12 | 2024-05-17 | 浙江威克赛新材料科技有限公司 | 一种高强度透水型沥青混凝土及制备方法 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Raut et al. | Synthesis and characterization of chitosan-TiO2: Cu nanocomposite and their enhanced antimicrobial activity with visible light | |
| US10046980B2 (en) | Bismuth-titanium oxide nanowire material used for photocatalysis, and preparation method | |
| Saud et al. | Preparation and photocatalytic activity of fly ash incorporated TiO2 nanofibers for effective removal of organic pollutants | |
| CN113509905A (zh) | 表面负载MoS2/ZrO2的煤沥青基复合活性炭球及制备方法 | |
| Ji et al. | ZnO/Ag nanoparticles incorporated multifunctional parallel side by side nanofibers for air filtration with enhanced removing organic contaminants and antibacterial properties | |
| CN112791699A (zh) | 一种ZrO2/煤沥青基复合活性炭球的制备方法 | |
| Wang et al. | Ag@ AgCl nanoparticles in-situ deposited cellulose acetate/silk fibroin composite film for photocatalytic and antibacterial applications | |
| Wang et al. | Hollow porous core–shell ZnFe2O4/AgCl nanocubes coated with EDTA and Ag nanoparticles for enhanced photocatalytic performances of visible–light–driven | |
| Suresh et al. | Recent progress in green and biopolymer based photocatalysts for the abatement of aquatic pollutants | |
| Zhang et al. | Graphitic carbon nitride loaded with bismuth nanoparticles displays antibacterial photocatalytic activity | |
| Zhang et al. | Visible-light responsive PVDF/carbon sphere@ TiO2 membrane for dye scavenging and bacteria inactivation | |
| Hariram et al. | Phytochemical process for the functionalization of materials with metal nanoparticles: Current trends and future perspectives | |
| Guo et al. | Singlet oxygen mediated efficient photocatalytic degradation of rhodamine B and disinfection by ZnO@ PDA/Ag-Ag2O nanocomposite under LED light | |
| Shinde et al. | Template free synthesis of mesoporous carbon from fire cracker waste and designing of ZnO-Mesoporous carbon photocatalyst for dye (MO) degradation | |
| Chen et al. | Hydrophilic ZnO/C nanocomposites with superior adsorption, photocatalytic, and photo-enhanced antibacterial properties for synergistic water purification | |
| Almasi et al. | Photocatalytic activity and water purification performance of in situ and ex situ synthesized bacterial cellulose‐CuO nanohybrids | |
| CN108927172A (zh) | 一种负载金纳米粒子的磁性生物质碳材料的制备及其应用 | |
| CN110813099B (zh) | 一种CdS/MIL-101(Cr)光催化剂改性的PVDF超滤膜及其制备方法与应用 | |
| CN109621932A (zh) | 白炭黑-二氧化钛复合光催化抗菌剂的制备方法 | |
| CN115368911A (zh) | 一种氟喹诺酮类抗生素污染土壤修复方法 | |
| Sharma et al. | Carbon quantum dots embedded trimetallic oxide: Characterization and photocatalytic degradation of Ofloxacin | |
| CN108714428B (zh) | 一种纳米线光催化剂及其制备方法与应用 | |
| Chaisorn et al. | Adsorption-photocatalytic degradation abilities of γ-irradiated chitosan-ZnO-AgNP composite for organic dye removal and antibacterial activity | |
| KR102508388B1 (ko) | 다공성 탄화 목재를 포함하는 다기능성 일체형 친환경 필터 | |
| CN112657555B (zh) | 一种单分散Fe-O簇掺杂的Ni基金属有机骨架复合光催化剂及其制备方法与应用 |
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 | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220407 Address after: 114213 Ying Luo Zhen Qian Ying Cun, Haicheng City, Anshan City, Liaoning Province Applicant after: HAICHENG SHENHE TECH. CO.,LTD. Address before: 114051, No. 185, Qianshan Road, hi tech Zone, Liaoning, Anshan Applicant before: University of Science and Technology Liaoning |
|
| TA01 | Transfer of patent application right | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211019 |
|
| RJ01 | Rejection of invention patent application after publication |