CN110368990B - 一种Cu系多金属氧酸盐-功能化氧化石墨烯纳米材料的制备方法及其应用 - Google Patents
一种Cu系多金属氧酸盐-功能化氧化石墨烯纳米材料的制备方法及其应用 Download PDFInfo
- Publication number
- CN110368990B CN110368990B CN201910651417.7A CN201910651417A CN110368990B CN 110368990 B CN110368990 B CN 110368990B CN 201910651417 A CN201910651417 A CN 201910651417A CN 110368990 B CN110368990 B CN 110368990B
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- series
- polyoxometallate
- functionalized graphene
- anderson
- 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
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000009835 boiling Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010992 reflux Methods 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 229940043267 rhodamine b Drugs 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical group [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000011964 heteropoly acid Substances 0.000 abstract 1
- 238000001782 photodegradation Methods 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 17
- 239000002131 composite material Substances 0.000 description 16
- 238000006731 degradation reaction Methods 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 7
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- -1 hydroxyl radicals Chemical class 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910019614 (NH4)6 Mo7 O24.4H2 O Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J37/34—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- 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)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Toxicology (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Plasma & Fusion (AREA)
- Optics & Photonics (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种Cu系多金属氧酸盐‑功能化氧化石墨烯纳米材料的制备方法,包括以下步骤:S1:向沸腾的(NH4)6Mo7O24﹒4H2O水溶液中滴加CuSO4的水溶液并实时搅拌过滤,析出Cu系Anderson型多酸晶体;S2:将氧化石墨烯在乙醇中超声分散,之后向其中加入乙二胺,加热反应,得到功能化的氧化石墨烯;S3:利用Cu系Anderson型多酸晶体配制Cu系Anderson型多酸水溶液,将功能化的氧化石墨烯浸泡于Cu系Anderson型多酸水溶液中,之后加热回流12~14h,获得Cu系多金属氧酸盐‑功能化氧化石墨烯纳米材料成品。与现有技术相比,本发明制备方法简单,原料易得,与传统杂多酸光降解反应需要紫外灯相比,制备得到的催化材料可在太阳光条件下用于水体中有机污染物去除,催化反应活性高,可循环使用。
Description
技术领域
本发明涉及化学催化新材料领域,尤其是涉及一种Cu系多金属氧酸盐-功能化氧化石墨烯纳米材料的制备方法及其应用。
背景技术
有机染料废水对饮用水和生态环境造成危害,已经对人们的正常生活和生活环境构成威胁。目前,染料的种类是多种多样的,大致可以分为三类:阳离子染料,阴离子染料和非离子染料。而处理染料废水的传统方法包括吸附和光催化,吸附方法操作简单,但是会发生脱附过程,对已处理的污水造成二次污染;而光催化降解效率高、可以完全降解各种有机染料,但是对反应环境的pH值和溶液中无机离子等其他条件要求比较苛刻。尽管这些方法有一定的效果,但成本高昂,反应不完全,需要后处理,对环境造成二次污染。另外,随着中国化学工业的发展,有机染料的种类越来越多种化,导致使用传统处理染料废水的方法变得越来越乏力。
多金属氧酸盐是一类离子金属氧簇类化合物。多金属氧酸盐(POM)也称多金属氧簇,具有优异的氧化还原性能,可修饰性强,其多样的结构可广泛应用于许多环保型氧化反应中。
目前有机污染物的主要降解方法为自由基降解法和光催化法,自由基降解法需要使用大量用于产生自由基的原材料,成本较高;光催化法通常需要紫外的辅助照射才能完成降解,难以实现工业化的推广,因此亟需设计一种可通过太阳光就可实现有机物降解的催化材料。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种Cu系多金属氧酸盐-功能化氧化石墨烯纳米材料的制备方法及其应用。
本发明的目的可以通过以下技术方案来实现:
一种Cu系多金属氧酸盐-功能化氧化石墨烯纳米材料的制备方法,包括以下步骤:
S1:配制(NH4)6Mo7O24﹒4H2O水溶液并加热至沸腾,向沸腾的(NH4)6Mo7O24﹒4H2O水溶液中滴加CuSO4的水溶液并实时搅拌,最终使得两者的混合溶液中CuSO4与(NH4)6Mo7O24﹒4H2O的摩尔比为1:4~1:6,趁热过滤,将滤液冷却至室温,析出Cu系Anderson型多酸晶体,将晶体收集;
S2:将氧化石墨烯在乙醇中超声分散,之后向其中加入乙二胺,加热反应,反应结束后降温冷却,真空干燥去除溶剂,得到功能化的氧化石墨烯;
S3:利用Cu系Anderson型多酸晶体配制Cu系Anderson型多酸水溶液,将功能化的氧化石墨烯浸泡于Cu系Anderson型多酸水溶液中,超声分散,之后加热回流12~14h,之后过滤并真空干燥,获得Cu系多金属氧酸盐-功能化氧化石墨烯纳米材料成品。
进一步地,所述的氧化石墨烯由改进的Hummers法制备获得。
进一步地,步骤S2中氧化石墨烯和乙醇的质量体积比为1:5~15:1mg/mL。
进一步地,步骤S2中的超声分散时间为0.5~3h。
进一步地,步骤S2中氧化石墨烯和乙二胺的质量体积比为1:1~15:1g/mL。
进一步地,步骤S3中使得(NH4)6Mo7O24﹒4H2O和氧化石墨烯的比例为1:20~1:400mmol/mg。
进一步地,步骤S3中Cu系Anderson型多酸水溶液中(NH4)6Mo7O24﹒4H2O的浓度为0.1~3g/L。
本发明中Cu系多金属氧酸盐-功能化氧化石墨烯纳米材料在催化剂中具有应用。
本发明中杂多酸-氧化石墨烯复合催化材料在处理水体中有机污染物方面的应用。
进一步地,有机污染物为罗丹明B。
与现有技术相比,本发明具有以下优点:
1)本发明使用胺对氧化石墨烯进行改性,形成三维的网状结构,该三维的网状结构具有优异的吸附能力,使得催化反应中吸附解离过程迅速,同时将Anderson型的多酸均匀的负载在网状的氧化石墨烯上,负载于Cu系多金属氧酸盐在降解过程中产生羟基自由基,进攻含有苯环结构的染料分子,得到苯氧自由基,苯氧自由基开环,染料分子降解成其他有机小分子,对芳香类化合物有优异的降解效果。可以在可见光区实现降解,30min的太阳光光照射可实现污染物的完全降解,在可将光范围内实现污染物的快速降解。
2)本发明中制备的Cu系多金属氧酸盐-功能化氧化石墨烯纳米材料兼具吸附和降解有机物的功能,在无光条件下可实现有机污染物的有效吸附,在富集有机污染物后,实现可循环的多酸-氧化石墨烯复合材料的功能,以此应用于吸附、回收、光催化分解再生的往复循环。
3)本发明中制备的Cu系多金属氧酸盐-氧化石墨烯复合催化材料还可直接用于吸附与光催化反应的同时进行,相比于普通的光催化反应器可实现更快的吸附效率与反应速率,显著提升了决速步骤的反应速率,使得整体的反应速率提升。
附图说明
图1是本发明实施例1制备的复合催化材料的扫描电镜图。
图2是本发明实施例1的复合催化材料降解有机污染物的紫外可见吸收光谱图。
图3是本发明实施例2的复合催化材料降解有机污染物的紫外可见吸收光谱图。反应条件:20mg/L罗丹明b,25℃,取样时间依次为5min,10min,15min,20min,30min。
图4是本发明实施例3的复合催化材料降解有机污染物的紫外可见吸收光谱图。反应条件:20mg/L罗丹明b,25℃,取样时间依次为5min,10min,15min,20min,30min。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。
实施例1
1)将1mmol(NH4)6Mo7O24﹒4H2O于100ml水溶液加热至沸腾,向其中逐滴加入2mmolCuSO4,混合液在蒸气浴上蒸发,趁热过滤热溶液,冷却至室温,让其自然析出晶体。
2)功能化石墨烯纳米材料的制备
将100mg氧化石墨烯(GO)加入到100ml乙醇中,超声0.5h分散,转移至锥形瓶中加入0.1ml乙二胺,水热反应至90℃,反应12h,然后在60℃下真空干燥去除溶剂。
3)Cu系多金属氧酸盐-氧化石墨烯复合催化材料的制备
将步骤2)制备的功能化的氧化石墨烯浸泡在制备的0.1mg/L的Cu系Anderson型多金属氧酸盐水溶液中,先超声0.5h,在90℃的条件下,加热回流,然后过滤,再真空干燥。
4)降解染料污水测试
将步骤3)得到的10mg杂多酸-氧化石墨烯复合催化材料加入至200ml,浓度为20mg/l,25℃的罗丹明B溶液染料废水中反应30min,光源为室外太阳光。通过紫外-可见光吸收光谱分析降解后亚甲基蓝溶液浓度。(参见图2,对应反应条件:20mg/L罗丹明b,25℃,取样时间依次为5min,10min,15min,20min,30min,依次对应谱图中又上至下的五条曲线。)反应结束后,过滤后真空干燥得到可重复利用的杂多酸-氧化石墨烯复合催化材料。
实施例2
1)将1mmol(NH4)6Mo7O24﹒4H2O于100ml水溶液加热至沸腾,向其中逐滴加入4mmolCuSO4,混合液在蒸气浴上蒸发,趁热过滤热溶液,冷却至室温,让其自然析出晶体。
2)功能化石墨烯纳米材料的制备
将150mg GO加入到100ml乙醇中,超声0.5h分散,转移至锥形瓶中加入0.15ml乙二胺,水热反应至90℃,反应12h,然后真空干燥去除溶剂。
3)Cu系多金属氧酸盐-氧化石墨烯复合催化材料的制备
将步骤2)制备的功能化的氧化石墨烯浸泡在制备的0.1mg/L的Cu系Anderson型水溶液中,先超声0.5h,在90℃的条件下,加热回流,然后过滤,再真空干燥。
4)降解染料污水
将步骤3)得到的10mg杂多酸-氧化石墨烯复合催化材料加入至200ml,浓度为20mg/l,25℃的亚甲基蓝溶液染料废水中反应30min,光源为室外太阳光。(参见图3,对应反应条件:20mg/L罗丹明b,25℃,取样时间依次为5min,10min,15min,20min,30min,依次对应谱图中又上至下的五条曲线。)通过紫外-可见光吸收光谱分析降解后亚甲基蓝溶液浓度。反应结束后,过滤后真空干燥得到可重复利用的杂多酸-氧化石墨烯复合催化材料。
实施例3
1)将1mmol(NH4)6Mo7O24﹒4H2O于100ml水溶液加热至沸腾,向其中逐滴加入6mmolCuSO4,混合液在蒸气浴上蒸发,趁热过滤热溶液,冷却至室温,让其自然析出晶体。
2)功能化石墨烯纳米材料的制备
将150mg的GO加入到100ml乙醇中,超声0.5h分散,转移至锥形瓶中加入0.15ml乙二胺,水热反应至90℃,反应12h,然后真空干燥去除溶剂。
3)Cu系多金属氧酸盐-氧化石墨烯复合催化材料的制备
将步骤2)制备的功能化的氧化石墨烯浸泡在2)制备的0.1mg/L的Cu系Anderson型水溶液中,先超声0.5h,在90℃的条件下,加热回流,然后过滤,再真空干燥。
4)降解染料污水
将步骤3)得到的10mg杂多酸-氧化石墨烯复合催化材料加入至200ml,浓度为20mg/l,25℃的亚甲基蓝溶液染料废水中反应30min,光源为室外太阳光。(参见图4,对应反应条件:20mg/L罗丹明b,25℃,取样时间依次为5min,10min,15min,20min,30min,依次对应谱图中又上至下的五条曲线。)通过紫外-可见光吸收光谱分析降解后亚甲基蓝溶液浓度。反应结束后,过滤后真空干燥得到可重复利用的杂多酸-氧化石墨烯复合催化。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (5)
1.一种Cu系多金属氧酸盐-功能化氧化石墨烯纳米材料的制备方法,其特征在于,包括以下步骤:
S1:配制(NH4)6Mo7O24﹒4H2O水溶液并加热至沸腾,向沸腾的(NH4)6Mo7O24﹒4H2O水溶液中滴加CuSO4的水溶液并实时搅拌,最终使得两者的混合溶液中CuSO4与(NH4)6Mo7O24﹒4H2O的摩尔比为1:4~1:6,趁热过滤,将滤液冷却至室温,析出Cu系Anderson型多酸晶体,将晶体收集;
S2:将氧化石墨烯在乙醇中超声分散,之后向其中加入乙二胺,加热反应,反应结束后降温冷却,真空干燥去除溶剂,得到功能化的氧化石墨烯;
S3:利用Cu系Anderson型多酸晶体配制Cu系Anderson型多酸水溶液,将功能化的氧化石墨烯浸泡于Cu系Anderson型多酸水溶液中,超声分散,之后加热回流12~14h,之后过滤并真空干燥,获得Cu系多金属氧酸盐-功能化氧化石墨烯纳米材料成品;
步骤S2中氧化石墨烯和乙醇的质量体积比为1:5~15:1mg/mL;
步骤S2中的超声分散时间为0.5~3h;
步骤S2中氧化石墨烯和乙二胺的质量体积比为1:1~15:1 g/ml;
步骤S1中加入的(NH4)6Mo7O24﹒4H2O和S3中使用的氧化石墨烯的比例为1:20~1:400mmol/mg。
2.根据权利要求1所述的一种Cu系多金属氧酸盐-功能化氧化石墨烯纳米材料的制备方法,其特征在于,所述的氧化石墨烯由改进的Hummers法制备获得。
3.一种根据权利要求1~2中任意一项所述的制备方法获得的Cu系多金属氧酸盐-功能化氧化石墨烯纳米材料在处理水体中有机污染物催化剂中的应用。
4.一种根据权利要求1~2中任意一项所述的Cu系多金属氧酸盐-功能化氧化石墨烯纳米材料的制备方法得到的材料成品在处理水体中有机污染物方面的应用。
5.根据权利要求4所述的应用,其特征在于,有机污染物为罗丹明B。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910651417.7A CN110368990B (zh) | 2019-07-16 | 2019-07-16 | 一种Cu系多金属氧酸盐-功能化氧化石墨烯纳米材料的制备方法及其应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910651417.7A CN110368990B (zh) | 2019-07-16 | 2019-07-16 | 一种Cu系多金属氧酸盐-功能化氧化石墨烯纳米材料的制备方法及其应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110368990A CN110368990A (zh) | 2019-10-25 |
CN110368990B true CN110368990B (zh) | 2022-08-23 |
Family
ID=68254001
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910651417.7A Active CN110368990B (zh) | 2019-07-16 | 2019-07-16 | 一种Cu系多金属氧酸盐-功能化氧化石墨烯纳米材料的制备方法及其应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110368990B (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111468100B (zh) * | 2020-04-18 | 2023-05-30 | 河南大学 | 一种原位生长的多酸铌/石墨烯光催化剂的制备方法及其在降解四环素中的应用 |
CN111499589B (zh) * | 2020-04-21 | 2021-12-03 | 太原工业学院 | 一种过渡金属取代的砷钼酸盐化合物及其制备方法和应用 |
CN112023984A (zh) * | 2020-09-18 | 2020-12-04 | 上海应用技术大学 | 一种铬基无机催化材料及其在含苯废液中的应用 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108906123A (zh) * | 2018-07-03 | 2018-11-30 | 上海应用技术大学 | 一种杂多酸-氧化石墨烯复合催化材料、制备方法及其应用 |
-
2019
- 2019-07-16 CN CN201910651417.7A patent/CN110368990B/zh active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108906123A (zh) * | 2018-07-03 | 2018-11-30 | 上海应用技术大学 | 一种杂多酸-氧化石墨烯复合催化材料、制备方法及其应用 |
Also Published As
Publication number | Publication date |
---|---|
CN110368990A (zh) | 2019-10-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Dolbecq et al. | Polyoxometalate-based materials for efficient solar and visible light harvesting: application to the photocatalytic degradation of azo dyes | |
CN110368990B (zh) | 一种Cu系多金属氧酸盐-功能化氧化石墨烯纳米材料的制备方法及其应用 | |
CN108855011B (zh) | 具有吸附-可见光催化降解协同作用的复合材料及其用途 | |
Binaeian et al. | Preparation of titanium dioxide nanoparticles supported on hexagonal mesoporous silicate (HMS) modified by oak gall tannin and its photocatalytic performance in degradation of azo dye | |
CN103934034A (zh) | 负载型铁基金属有机骨架异相Fenton催化剂的制备方法及其应用 | |
Hameed et al. | Photocatalytic degradation of Acid Red 1 dye using ZnO catalyst in the presence and absence of silver | |
CN106238083A (zh) | 一种石墨相氮化碳/二氧化钛复合材料催化剂的制备方法 | |
CN105776494B (zh) | 一种苯酚废水的处理方法 | |
CN101066795A (zh) | 一种利用Fe0/TiO2光催化还原水中硝酸氮的方法 | |
CN110756163A (zh) | 一种纳米CoFe2O4/碳纤维毡复合材料及其制备方法和应用 | |
Wu et al. | Preparation of photo-Fenton heterogeneous catalyst (Fe-TS-1 zeolite) and its application in typical azo dye decoloration | |
CN111617805A (zh) | 光Fenton催化剂、其制备方法、其应用及水处理剂 | |
MacDonald et al. | Photo-Fenton abatement of aqueous organics using metal-organic frameworks: An advancement from benchmark zeolite | |
Huang et al. | Synthesis of recyclable 3D LC/h-ZIF-8 by Zn (Ⅱ) containing wastewater for photocatalytic degradation of mixed-dye under UV-Vis irradiation | |
CN115196739A (zh) | 一种提高染料废水中亚甲基蓝催化降解率的方法 | |
Shen et al. | Carbon dot–doped titanium dioxide sheets for the efficient photocatalytic performance of refractory pollutants | |
Jiang et al. | Cornstalk biochar-TiO2 composites as alternative photocatalyst for degrading methyl orange | |
CN105268479B (zh) | 基于铁与邻菲罗啉的高效光催化剂的制备方法 | |
Kang et al. | Insight into the existent state of nitrogen-doped carbon dots in titanate nanotubes and their roles played toward simultaneous removal of coexisted Cu2+ and norfloxacin in water | |
Yang et al. | Well-designed MOF-derived hollow octahedral structure TiO2 coupled with ultra-thin porous g-C3N4 to enhance the degradation of real liquor brewing wastewater | |
CN105013448A (zh) | 一种二氧化钛/壳聚糖层层自组装复合薄膜材料的制备及应用 | |
CN111889126A (zh) | 一种具有可见光响应的类芬顿材料的制备方法及应用 | |
Binaeian et al. | Surface modification of mesoporous silicate by tannin for immobilization of TiO2 nanoparticles: Study of photocatalytic performance | |
CN117205931A (zh) | 铜掺杂的铁酸镧催化剂及其制备方法和在硝基苯类污染物中的应用 | |
AU2021105539A4 (en) | Preparation Method, Product and Application of Graphene Photocatalyst |
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 |