CN110352983A - 还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料及其制备方法 - Google Patents
还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料及其制备方法 Download PDFInfo
- Publication number
- CN110352983A CN110352983A CN201910640522.0A CN201910640522A CN110352983A CN 110352983 A CN110352983 A CN 110352983A CN 201910640522 A CN201910640522 A CN 201910640522A CN 110352983 A CN110352983 A CN 110352983A
- Authority
- CN
- China
- Prior art keywords
- visible light
- redox graphene
- titanium dioxide
- bismuth
- tungstate
- 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000000463 material Substances 0.000 title claims abstract description 45
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 39
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 38
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 20
- 229940088710 antibiotic agent Drugs 0.000 title claims abstract description 20
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 20
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 150000001621 bismuth Chemical class 0.000 claims description 12
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229960004756 ethanol Drugs 0.000 claims description 7
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- WPZFLQRLSGVIAA-UHFFFAOYSA-N sodium tungstate dihydrate Chemical compound O.O.[Na+].[Na+].[O-][W]([O-])(=O)=O WPZFLQRLSGVIAA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000011941 photocatalyst Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 5
- 230000001580 bacterial effect Effects 0.000 abstract description 3
- 244000005700 microbiome Species 0.000 abstract description 3
- 230000002045 lasting effect Effects 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 9
- 230000001954 sterilising effect Effects 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 241000588724 Escherichia coli Species 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- -1 graphite Alkene Chemical class 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 230000000845 anti-microbial effect Effects 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
- 230000008901 benefit Effects 0.000 description 1
- 229940036359 bismuth oxide Drugs 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- BDJYZEWQEALFKK-UHFFFAOYSA-N bismuth;hydrate Chemical compound O.[Bi] BDJYZEWQEALFKK-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 239000002086 nanomaterial Substances 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
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Plant Pathology (AREA)
- Optics & Photonics (AREA)
- Thermal Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Inorganic Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Plasma & Fusion (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料及其制备方法,所述方法包括通过水热合成方法将二氧化钛与钨酸铋进行掺杂,同时通过还原氧化石墨烯负载。本发明工艺简单、安全性高、无二次污染、成本低,所得复合可见光触媒抗菌材料能够在可见光条件下高效杀灭细菌微生物,杀菌性能持久稳定,无毒无害。
Description
技术领域
本发明属于可见光催化材料制备和环境应用领域,特别涉及一种还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料及其制备方法。
背景技术
随着工业的快速发展和人类活动的频繁,环境污染日益严重,为对人体健康具有风险的微生物繁殖和变异创造了有利条件,特别是致病性微生物,如细菌、病毒、真菌和寄生虫等,若不能高效地将水中致病微生物杀灭,将会给生物体造成巨大危害。
目前,我国城市污水处理厂消毒工艺主要为化学消毒和紫外消毒,其中以氯消毒为代表的传统化学消毒技术已被证实会产生三氯甲烷等致癌、致畸、致突变副产物,而紫外消毒技术虽然具有光谱杀菌能力,无二次污染,但其持续杀菌能力较弱,且紫外灯套管需定期清洗,运行成本较高。由此可见,研发具有安全性高、无二次污染、持续杀菌能力强等特点的抗菌技术已成为当前水污染控制领域的研究热点。
光催化被认为是一种非常具有应用潜力的灭菌技术,新型光催化材料的研发一直以来是环境材料领域的热点课题。二氧化钛作为传统半导体光催化材料,在紫外光激发下可有效抑制细菌微生物生长,破坏细胞膜或DNA分子链,但其本省带隙过宽,仅在紫外光条件具有响应,从而限制了其光催化效果。近年来,通过掺杂其它半导体材料被认为是一种能够显著提高其光催化效能的有效方法。钨酸铋/二氧化钛复合光催化剂可在可见光激发下有效降解环境有机污染物,尽管其可见光吸收性能良好,但其产生的光生电子和光生空穴易发生复合,导致其实际电子效率较低。还原氧化石墨烯是石墨烯的一种衍生物,具有二维层状结构、比表面积大、含氧官能团丰富、力学热学电学性能优越,是一种理想的纳米材料复合载体。
发明内容
本发明要解决的技术问题是如何获得工艺简单,成本低廉,且具有持续强杀菌能力的复合可见光触媒抗菌材料。
为了解决上述技术问题,本发明的技术方案是提供一种还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料的制备方法,其特征在于,包括以下步骤:
步骤1:将二水合钨酸钠溶于去离子水,超声分散,得到钨酸钠溶液;将铋盐溶于无水乙醇,超声分散,得到铋盐悬浊液;然后将所得的钨酸钠溶液和铋盐悬浊液混合,得到混合液;
步骤2:将钛酸四丁酯滴入步骤1制备所得的混合液中,然后加入一元弱酸反应,然后使用碱液调节pH值,磁力搅拌均匀,进行水热反应,过滤、洗涤、干燥、煅烧、研磨,可得钨酸铋/二氧化钛粉末;
步骤3:将步骤2制备所得的钨酸铋/二氧化钛粉末和还原氧化石墨烯于无水乙醇中超声分散,磁力搅拌均匀,然后进行水热反应,过滤、洗涤、干燥、研磨,可得还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料。
优选地,所述步骤1中,铋盐为柠檬酸铋、五水合硝酸铋或氯化铋中的一种。
优选地,所述步骤1中,铋盐与钨酸钠质量比为(2.0~3.0):1,无水乙醇与去离子水体积比为(1.0~2.0):1。
优选地,所述步骤1中,钨酸钠浓度为0.025~0.055g/mL,铋盐和无水乙醇质量比为(0.06~0.22):1。
优选地,所述步骤2中,钛酸四丁酯和步骤1所得的混合液的体积比为(0.02~0.08):1。
优选地,所述步骤2中,一元弱酸可为甲酸或乙酸,浓度为0.1~0.5mol/L,一元弱酸与钛酸四丁酯体积比为1:(8.0~40.0)。
优选地,所述步骤2中,所使用碱液为氢氧化钠或氢氧化钾溶液,浓度为1.0~2.0mol/L,最后调节pH值至2.0~5.0。
优选地,所述步骤2中,水热反应温度为160~180℃,反应时间为6~8h。
优选地,所述步骤2中,煅烧是在通有氮气的马弗炉中进行,温度为450~550℃,反应时间为2~4h。
优选地,所述步骤3中,钨酸铋/二氧化钛粉末和还原氧化石墨烯质量比为(100~150):1,还原氧化石墨烯与无水乙醇的质量体积比为0.25~0.5g/L。
优选地,所述步骤3中,水热反应温度为180~200℃,反应时间为6~8h。
优选地,所述步骤2和3中,洗涤包括去离子水和乙醇洗涤;干燥采用真空干燥箱,时间为20~30h,温度为45~65℃。
本发明还提供了上述方法制备的还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料。
相比现有技术,本发明具有如下有益效果:
(1)本发明工艺简单、安全性高、无二次污染、成本低,通过水热合成方法将二氧化钛与钨酸铋进行掺杂,同时通过还原氧化石墨烯负载,显著增大其比表面积,有效抑制晶粒团聚和晶相转变,避免颗粒之间相互遮挡,增加光辐射离子数目,从而显著提高可见光吸收利用率。
(2)本发明还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料能够充分利用可见光,在可见光条件下可高效杀灭细菌微生物,杀菌性能持久稳定,无毒无害,克服了当前消毒工艺产生副产物,或仅能在紫外光条件下有效的缺陷。
附图说明
图1为复合可见光触媒抗菌材料的制备流程示意图;
图2为复合可见光触媒抗菌材料的电子扫描电镜图;
图3为实施例1中在可见光条件下的抗菌实验验证结果。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
本发明实施例中所使用的试剂除氧化石墨烯外均购自国药集团化学试剂有限公司,氧化石墨烯购自苏州思彬纳米科技有限公司。
实施例1
如图1所示,本实施例提供了一种还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料的制备方法,具体步骤如下:
步骤1:将0.825g二水合钨酸钠溶于30mL去离子水中,超声30min,形成钨酸钠透明溶液;将2.4254g五水合硝酸铋溶于30mL无水乙醇中,超声30min,形成硝酸铋悬浊液;将上述制备所得的钨酸钠透明溶液和硝酸铋悬浊液混合,磁力搅拌30min,转速为500r/min,得到混合液;
步骤2:将4mL钛酸四丁酯滴入步骤1得到的混合液中,然后加入0.2mL浓度为0.05mol/L冰醋酸反应30min,然后使用浓度为1.0mol/L的氢氧化钠溶液调节pH值至2.0,磁力搅拌60min,在180℃下水热反应6h,真空过滤,依次采用去离子水和乙醇洗涤,置于60℃真空干燥箱中干燥24h,然后置于450℃马弗炉中煅烧2h,煅烧产物采用玛瑙研钵研磨,然后过400目筛网,得到钨酸铋/二氧化钛粉末;
步骤3:取2.000g上述钨酸铋/二氧化钛粉末与0.015g还原氧化石墨烯于50mL无水乙醇中超声30min,再磁力搅拌60min,转速为500r/min,水热反应6h,真空过滤,依次采用去离子水和乙醇洗涤,置于60℃真空干燥箱中干燥24h,然后使用玛瑙研钵磨细过400目筛网,可得还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料。
实施例2
如图1所示,本实施例提供了一种还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料的制备方法,具体步骤如下:
步骤1:将1.650g二水合钨酸钠溶于40mL去离子水中,超声30min,形成钨酸钠透明溶液;将3.160g氯化铋溶于40mL无水乙醇中,超声30min,形成氯化铋悬浊液;将上述制备所得的钨酸钠透明溶液和氯化铋悬浊液混合,磁力搅拌30min,转速为300r/min,得到混合液;
步骤2:将6mL钛酸四丁酯滴入步骤1得到的混合液中,然后加入0.6mL浓度为0.125mol/L冰醋酸反应30min,然后使用浓度为1.5mol/L的氢氧化钠溶液调节pH值至3.0,磁力搅拌60min,在160℃下水热反应8h,真空过滤,依次采用去离子水和乙醇洗涤,置于55℃真空干燥箱中干燥24h,然后置于500℃马弗炉中煅烧3h,煅烧产物采用玛瑙研钵研磨,然后过400目筛网,得到钨酸铋/二氧化钛粉末;
步骤3:取1.00g上述钨酸铋/二氧化钛粉末与0.01g还原氧化石墨烯于40mL无水乙醇中超声60min,再磁力搅拌30min,转速为300r/min,水热反应6h,真空过滤,依次采用去离子水和乙醇洗涤,置于65℃真空干燥箱中干燥24h,然后使用玛瑙研钵磨细过400目筛网,可得还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料。
图2为实施例1~2的复合可见光触媒抗菌材料的电子扫描电镜图,如图2所示,本发明制备得到的钨酸铋/二氧化钛颗粒,均匀负载在还原氧化石墨烯表面,且上述材料能在室温下稳定存在,容易保存。
利用平板涂布法测试实施例1~2中所得的还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料在可见光条件下对大肠杆菌的杀菌效果。
首先将所得的还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料加入大肠杆菌溶液中,在可见光条件下反应60min,每隔固定时间取样涂布,放入培养箱在37℃下培养24h,然后观察其菌落数量,计算大肠杆菌杀菌率,结果如表1所示。
如图3所示,实验结果表明,本发明实施例1制备所得的可见光响应还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料对大肠杆菌杀菌效果好,稳定性高,速率快,在60min内杀菌率维持在98.5%以上。
表1复合可见光触媒抗菌材料在可见光条件下反应60min后抗菌效果
Claims (10)
1.一种还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料的制备方法,其特征在于,包括以下步骤:
步骤1:将二水合钨酸钠溶于去离子水,超声分散,得到钨酸钠溶液;将铋盐溶于无水乙醇,超声分散,得到铋盐悬浊液;然后将所得的钨酸钠溶液和铋盐悬浊液混合,得到混合液;
步骤2:将钛酸四丁酯滴入步骤1制备所得的混合液中,然后加入一元弱酸反应,然后使用碱液调节pH值,磁力搅拌均匀,进行水热反应,过滤、洗涤、干燥、煅烧、研磨,可得钨酸铋/二氧化钛粉末;
步骤3:将步骤2制备所得的钨酸铋/二氧化钛粉末和还原氧化石墨烯于无水乙醇中超声分散,磁力搅拌均匀,然后进行水热反应,过滤、洗涤、干燥、研磨,可得还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料。
2.如权利要求1所述的还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料的制备方法,其特征在于,所述步骤1中,铋盐为柠檬酸铋、五水合硝酸铋或氯化铋中的一种。
3.如权利要求1所述的还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料的制备方法,其特征在于,所述步骤1中,铋盐与钨酸钠质量比为(2.0~3.0):1,无水乙醇与去离子水体积比为(1.0~2.0):1;钨酸钠浓度为0.025~0.055g/mL,铋盐和无水乙醇质量比为(0.06~0.22):1。
4.如权利要求1所述的还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料的制备方法,其特征在于,所述步骤2中,钛酸四丁酯和步骤1所得的混合液的体积比为(0.02~0.08):1。
5.如权利要求1所述的还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料的制备方法,其特征在于,所述步骤2中,一元弱酸可为甲酸或乙酸,浓度为0.1~0.5mol/L,一元弱酸与钛酸四丁酯体积比为1:(8.0~40.0)。
6.如权利要求1所述的还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料的制备方法,其特征在于,所述步骤2中,所使用碱液为氢氧化钠或氢氧化钾溶液,浓度为1.0~2.0mol/L,最后调节pH值至2.0~5.0;水热反应温度为160~180℃,反应时间为6~8h;煅烧是在通有氮气的马弗炉中进行,温度为450~550℃,反应时间为2~4h。
7.如权利要求1所述的还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料的制备方法,其特征在于,所述步骤3中,,钨酸铋/二氧化钛粉末和还原氧化石墨烯质量比为(100~150):1,还原氧化石墨烯与无水乙醇的质量体积比为0.25~0.5g/L。
8.如权利要求1所述的还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料的制备方法,其特征在于,所述步骤3中,水热反应温度为180~200℃,反应时间为6~8h。
9.如权利要求1所述的还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料的制备方法,其特征在于,所述步骤2和3中,洗涤包括去离子水和乙醇洗涤;干燥采用真空干燥箱,时间为20~30h,温度为45~65℃。
10.权利要求1~9任一项所述方法制备的还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910640522.0A CN110352983A (zh) | 2019-07-16 | 2019-07-16 | 还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910640522.0A CN110352983A (zh) | 2019-07-16 | 2019-07-16 | 还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料及其制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN110352983A true CN110352983A (zh) | 2019-10-22 |
Family
ID=68219581
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910640522.0A Pending CN110352983A (zh) | 2019-07-16 | 2019-07-16 | 还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110352983A (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111282591A (zh) * | 2020-03-20 | 2020-06-16 | 桂林电子科技大学 | 土壤修复用三硫化二锑/AgI/Ag/BON光催化剂的制备方法 |
CN112275272A (zh) * | 2020-09-08 | 2021-01-29 | 广州户户通科技发展有限公司 | 一种还原氧化石墨烯二氧化钛复合材料的制备方法及应用 |
CN115025769A (zh) * | 2022-06-17 | 2022-09-09 | 暨南大学 | 一种光生电子-热电子增强型等离子体光催化剂及其制备方法和应用 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104923205A (zh) * | 2015-05-25 | 2015-09-23 | 嘉兴学院 | 二氧化钛抗菌除甲醛复合材料及其制备方法和用途 |
CN106311220A (zh) * | 2016-09-29 | 2017-01-11 | 吉林师范大学 | 一种Bi2MoO6/TiO2/RGO复合光催化剂及其制备方法 |
-
2019
- 2019-07-16 CN CN201910640522.0A patent/CN110352983A/zh active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104923205A (zh) * | 2015-05-25 | 2015-09-23 | 嘉兴学院 | 二氧化钛抗菌除甲醛复合材料及其制备方法和用途 |
CN106311220A (zh) * | 2016-09-29 | 2017-01-11 | 吉林师范大学 | 一种Bi2MoO6/TiO2/RGO复合光催化剂及其制备方法 |
Non-Patent Citations (2)
Title |
---|
AGNIESZKA WANAG ET AL.: "Antibacterial properties of TiO2 modified with reduced graphene oxide", 《ECOTOXICOLOGY AND ENVIRONMENTAL SAFETY》 * |
YANAN JIA ET AL.: "Fabrication of TiO2−Bi2WO6 Binanosheet for Enhanced Solar Photocatalytic Disinfection of E. coli: Insights on the Mechanism", 《 APPL. MATER. INTERFACES》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111282591A (zh) * | 2020-03-20 | 2020-06-16 | 桂林电子科技大学 | 土壤修复用三硫化二锑/AgI/Ag/BON光催化剂的制备方法 |
CN112275272A (zh) * | 2020-09-08 | 2021-01-29 | 广州户户通科技发展有限公司 | 一种还原氧化石墨烯二氧化钛复合材料的制备方法及应用 |
CN115025769A (zh) * | 2022-06-17 | 2022-09-09 | 暨南大学 | 一种光生电子-热电子增强型等离子体光催化剂及其制备方法和应用 |
CN115025769B (zh) * | 2022-06-17 | 2024-03-22 | 暨南大学 | 一种光生电子-热电子增强型等离子体光催化剂及其制备方法和应用 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Dhull et al. | An overview on InVO4-based photocatalysts: Electronic properties, synthesis, enhancement strategies, and photocatalytic applications | |
Wang et al. | Hollow spherical WO3/TiO2 heterojunction for enhancing photocatalytic performance in visible-light | |
CN110352983A (zh) | 还原氧化石墨烯负载钨酸铋/二氧化钛复合可见光触媒抗菌材料及其制备方法 | |
Yan et al. | Recent advances in graphite carbon nitride-based nanocomposites: structure, antibacterial properties and synergies | |
Gao et al. | A review on mechanism, applications and influencing factors of carbon quantum dots based photocatalysis | |
CN109603882B (zh) | 利用改性碳量子点负载中空管状氮化碳光催化剂处理有机污染物和光催化杀菌的方法 | |
CN104998665A (zh) | 一种钒酸铋-溴氧化铋异质结光催化剂,制备方法及其应用 | |
CN105289674A (zh) | 一种AgVO3/Ag3PO4异质结复合光催化剂及其制备方法和应用 | |
Zuo et al. | Construction of visible light driven silver sulfide/graphitic carbon nitride pn heterojunction for improving photocatalytic disinfection | |
CN105728010A (zh) | 一种抗菌钼酸银石墨相氮化碳复合可见光催化剂的制备方法 | |
Li et al. | Construction of a novel double S-scheme structure WO3/g-C3N4/BiOI: Enhanced photocatalytic performance for antibacterial activity | |
CN110373891A (zh) | 负载钨酸铋/二氧化钛/还原氧化石墨烯可见光响应复合抗菌织物及其制备方法 | |
CN105289579A (zh) | 一种纳米片状铈掺杂钼酸铋催化剂及其制备方法和应用 | |
CN105435847A (zh) | 一种Bi2WO6/BiOI@季铵盐无机/有机复合光催化杀菌剂及其制备方法 | |
CN113244393B (zh) | 一种二氧化钛纳米管/二硫化钼纳米花复合物及其制备方法和应用 | |
CN107890877A (zh) | 一种Bi3O4Cl/CdS复合材料及制备方法和用途 | |
Li et al. | Fabrication of carbon quantum dots/1D MoO3-x hybrid junction with enhanced LED light efficiency in photocatalytic inactivation of E. ácoli and S. áaureus | |
CN105268438A (zh) | 一种等离子体复合光催化剂及其制备方法和应用 | |
CN112774664A (zh) | 一种具有光热协同作用纳米TiO2@MnO2复合材料及其制备方法和应用 | |
CN103120944A (zh) | 一种磷酸银立方体/p25双功能复合材料及其制备方法 | |
CN103638960B (zh) | 一种聚合物光催化剂及其制备方法和应用 | |
CN111744503A (zh) | 一种Z型异质结MoS2/Bi2WO6复合光催化剂及其制备方法和应用 | |
CN105457663A (zh) | 一种Bi2WO6/Ag3PO4复合光催化杀菌剂及其制备方法 | |
Chen et al. | A study on the photocatalytic sterilization performance and mechanism of Fe-SnO 2/gC 3 N 4 heterojunction materials | |
Mohamed et al. | Improved photocatalytic oxidation of ciprofloxacin by NiS-coupled WO3 nanorods synthesized by solvothermal method under visible light |
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 |