CN107913667B - 一种磁性石墨烯/四氧化三铁/二氧化锰纳米复合材料及其制备和应用 - Google Patents
一种磁性石墨烯/四氧化三铁/二氧化锰纳米复合材料及其制备和应用 Download PDFInfo
- Publication number
- CN107913667B CN107913667B CN201711008658.7A CN201711008658A CN107913667B CN 107913667 B CN107913667 B CN 107913667B CN 201711008658 A CN201711008658 A CN 201711008658A CN 107913667 B CN107913667 B CN 107913667B
- Authority
- CN
- China
- Prior art keywords
- mno
- temperature
- fecl
- rgo
- water bath
- 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
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 98
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000011259 mixed solution Substances 0.000 claims abstract description 35
- 239000000243 solution Substances 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000008213 purified water Substances 0.000 claims abstract description 16
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims abstract description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 26
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 11
- 239000012286 potassium permanganate Substances 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 13
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 35
- 239000000463 material Substances 0.000 description 29
- 239000000975 dye Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 24
- 230000003197 catalytic effect Effects 0.000 description 18
- 238000003760 magnetic stirring Methods 0.000 description 18
- 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 17
- 229960000907 methylthioninium chloride Drugs 0.000 description 17
- 230000015556 catabolic process Effects 0.000 description 16
- 238000006731 degradation reaction Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000013049 sediment Substances 0.000 description 8
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 7
- 238000001069 Raman spectroscopy Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000005389 magnetism Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 235000013405 beer Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification 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
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000011882 ultra-fine particle 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
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/28002—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 physical properties
- B01J20/28009—Magnetic 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
-
- 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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F2101/308—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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Thermal Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明公开了一种磁性石墨烯/四氧化三铁/二氧化锰纳米复合材料及其制备方法和应用,制备如下:(1)恒温水浴中将氧化石墨烯、聚乙二醇分散在纯净水中,超声形成均匀的悬浮液:(2)滴加FeCl3和FeCl2,无氧环境下持续反应4~6小时,然后加入氨水调pH至10.5~11.5,升高水浴温度至70~80℃,继续反应2~3小时,得混合液;(3)向所得混合液中加入MnSO4溶液,然后加入KMnO4和KOH,反应2~4小时,然后进行后处理即得。本发明以石墨烯片层为载体,依次在石墨烯片层上原位沉淀生长Fe3O4和MnO2纳米粒子,阻止石墨烯的团聚;同时利用氧化石墨烯的片层结构作为Fe3O4和MnO2纳米粒子固定载体,以阻止Fe3O4和MnO2纳米粒子的团聚。本发明提供的纳米复合材料方法具有绿色环保、快速简便的特点。
Description
技术领域
本发明属于纳米材料及环境科学技术领域,尤其涉及一种具有吸附和催化降解功能的磁性rGO/Fe3O4/MnO2纳米复合材料及其应用。
背景技术
染料广泛应用于纺织、皮革、造纸、印刷和化妆品等行业,据统计我国染料的年产量约75万吨,居世界首位。染料在生产和使用过程中约有10~15%要释放到环境中,因染料污染导致的水体安全问题已引起广泛关注。通常染料分子具有复杂的芳香结构很稳定,在水环境中很难自然降解。目前,染料废水的处理方法主要有吸附法、膜分离法,和催化氧化降解等。吸附法是废水深度处理的重要技术,在众多的吸附剂中,活性炭已广泛应用染料废水处理中。但活性炭存在吸附量不大、活化温度高、孔分布过宽、机械性能差、不易再生和表面不容易修饰等缺点。碳纳米材料,因其具有高的比表面积和良好的化学稳定性,在废水中污染物的吸附中显示了巨大的潜力和诱人的应用前景。
石墨烯是一种新型二维纳米材料,比表面积大,理论计算达2630m2/g,具有超强的吸附能力。Ramesha等(Ramesha G K,Vijaya Kumara A,Muralidhara H B,Sampath S,Graphene and Graphene Oxide as Effective Adsorbents Toward Anionic andCationic Dyes,Journal of Colloid and Interface Science,2011,361,270-277)研究发现,石墨烯与有机染料之间可以产生非常强的络合反应,从而对有机染料有很强的吸附能力。但是由于石墨烯的纳米片层结构,在水体中较难分离、回收,易泄露到环境中引起健康和环境问题。此外,由于石墨烯片层之间存在范德华作用,在水体中易团聚,导致有效表面积减少,从而降低吸附能力。因此开发具有亲水性、易回收的石墨烯或石墨烯复合材料,是基于石墨烯的新型吸附功能材料的研究开发方向。
Wang等(Zhao Guixia,Jiang,Lang He,Yu dong,Li Jiaxing,Dong Huanli,WangXiangke,Hu Wenping,Sulfonated Graphene for Persistent Aromatic PollutantManagement,Advanced Materials,2011,23(34),3959-3963)对石墨烯表面进行磺酸基亲水功能化处理,不但可以提高石墨烯的分散性,而且可以提高石墨烯的吸附能力。研究结果显示,这种功能化石墨烯对萘和萘酚的吸附能力达到了每克2.4mmol,是目前吸附能力较高的材料。
磁性吸附材料既具有良好的吸附能力,又可通过外加磁场从水体分离,已经成为近年来环境净化的新一代材料。
催化氧化降解也是去除有机污染物有效方法之一。相比于吸附法,催化氧化法利用催化剂降解水体中的有机污染物,从而达到环境治理的目的。MnO2具有较高的氧化电位,能够氧化很多有机化合物,作为氧化剂被广泛应用于水处理中。但MnO2的视密度较小,在水中易形成超细颗粒,使用后难以实现固液分离。
发明内容
本发明提供一种磁性rGO/Fe3O4/MnO2纳米复合材料及其制备方法和应用,复合材料具有很好的吸附和催化降解功能。
一种磁性石墨烯/四氧化三铁/二氧化锰纳米复合材料的制备方法,包括如下步骤:
(1)20~40℃恒温水浴中将氧化石墨烯、聚乙二醇分散在纯净水中,超声形成均匀的悬浮液:
(2)将所述悬浮液继续在20~40℃恒温水浴中持续搅拌、并除氧后滴加FeCl3和FeCl2的混合溶液,无氧环境下持续反应4~6小时,然后加入氨水调pH至10.5~11.5,加快搅拌速度、升高水浴温度至70~80℃,继续反应2~3小时,得含有rGO/Fe3O4的混合液;
(3)保持搅拌速度和水浴温度不变,向所得混合液中加入MnSO4溶液,然后再快速加入KMnO4和KOH的混合溶液,反应2~4小时,得到包含有rGO/Fe3O4/MnO2的混合液;
(4)将含有rGO/Fe3O4/MnO2的混合液反复过滤、洗涤后于140~160℃真空干燥箱内热处理20~25小时即得。
本发明以石墨烯片层为载体,依次在石墨烯片层上原位沉淀生长Fe3O4和MnO2纳米粒子,利用原位生长的Fe3O4和MnO2纳米粒子阻止石墨烯的团聚;同时利用氧化石墨烯的片层结构作为Fe3O4和MnO2纳米粒子固定载体,以阻止Fe3O4和MnO2纳米粒子的团聚。
本发明以GO为载体,首先选用FeCl3和FeCl2为前驱体,PEG为还原剂和纳米粒子分散稳定剂,采用沉淀法制备rGO/Fe3O4纳米复合物,再以MnSO4和KMnO4为前驱体,通过沉淀法制备rGO/Fe3O4/MnO2纳米复合材料。本发明制备的rGO/Fe3O4/MnO2纳米复合材料用于染料废水的吸附和光催化降解去除,表现出较好的去除性能,且可利用外加磁场从水体中分离、回收。
本发明的新颖之处表现为制备的rGO/Fe3O4/MnO2纳米复合材料,通过GO、Fe3O4与MnO2的纳米复合及协同作用,纳米复合材料不仅具有了优良的染料吸附能力,而且具有良好的光催化降解性能,同时还具有一定的磁性,可利用外加磁场从水体中分离、回收。本发明提供的rGO/Fe3O4/MnO2纳米复合材料方法具有绿色环保、快速简便的特点。
优选地,步骤(1)中投加的GO质量与纯净水体积比为1/1.5~1/2.0mg/mL,GO中氧含量为4.5~6.5%,GO可通过市售获得,也可利用Hummers等方法(D.C.Marcano,D.V.Kosynkin,J.M.Berlin,et al.Improved synthesis of graphene oxid[J].ACSNano,2010,4:4806-4814)进行制备;投加的PEG与GO质量比为5~10,PEG优选PEG-400、PEG-600、PEG-800。
步骤(1)中氧化石墨烯质量与纯净水体积的比进一步优选为1mg:1.7~1.8mL。
优选地,步骤(2)中FeCl2与GO质量比为1/1~1.5/1;FeCl3与FeCl2摩尔比为2/1。
优选地,步骤(3)中MnSO4与FeCl2和FeCl3总质量比为0.6/1~0.75/1;KMnO4与MnSO4质量比为1/1.1~1/1.2;KOH与MnSO4和KMnO4总质量比为0.9/1~1/1。
优选地,步骤(1)中超声时间为45~60min,进一步优选为1小时。
优选地,步骤(2)中20~40℃恒温水浴中搅拌速度为1400~1600rpm;70~80℃恒温水浴中搅拌速度为2800~3200rpm。
优选地,步骤(2)中所用氨水为25mg/mL的氨水溶液。
优选地,步骤(1)中恒温水浴温度为30℃;步骤(2)中升温前为30℃,升温后为75℃。
进一步优选地,步骤(2)中30℃恒温水浴中搅拌速度为1500rpm;75℃恒温水浴中搅拌速度为3000rpm。
进一步优选地,步骤(2)为:
步骤(1)所得悬浮液在1500rpm磁力搅拌下、30℃的恒温水浴中,通N2除氧1小时,然后缓慢滴加FeCl3和FeCl2的混合溶液,FeCl2与GO质量比为1/1~1.5/1;投加的FeCl3与FeCl2摩尔比为2/1,继续搅拌并通N2除氧5小时,紧接着快速加入氨浓度为25mg/mL的氨水溶液调节pH至11左右,再将磁力搅拌调至3000rpm,水浴温度升至75℃,反应3小时,得到包含有rGO/Fe3O4的混合液。
进一步优选地,步骤(3)为:
3000rpm磁力搅拌下、75℃的恒温水浴中向步骤(2)所得混合液中加入MnSO4溶液,然后再快速加入KMnO4和KOH的混合溶液,反应3小时,得到包含有rGO/Fe3O4/MnO2的混合液,MnSO4与FeCl2和FeCl3总质量比为0.6/1~0.75/1,投加的KMnO4与MnSO4质量比为1/1.1~1/1.2;,投加的KOH与MnSO4和KMnO4总质量比为0.9/1~1/1。
进一步优选地,步骤(4)为:
用抽滤瓶对步骤(3)获得的混合液进行过滤,并用纯净水对过滤沉积物进行多次洗涤;最后将过滤﹑洗涤后所得产物放置于150℃真空烘箱中热处理24小时,得到rGO/Fe3O4/MnO2纳米复合材料。
与现有技术相比,本发明具有如下优点:
本发明采用两步沉淀法制备rGO/Fe3O4/MnO2纳米复合材料,在复合物的制备过程中,Fe3O4和MnO2纳米粒子在石墨烯片层间原位沉淀生长,利用氧化石墨烯的二维平面结构固载和分散Fe3O4和MnO2纳米粒子,同时阻止氧化石墨烯片层的团聚。所制备的rGO/Fe3O4/MnO2纳米复合材料,通过GO、Fe3O4与MnO2的纳米复合及相互协同作用,显示出优良的染料吸附能力和光催化降解性能,同时还可以外加磁场从水体中分离、回收。
附图说明
图1是本发明实施例1、对比例1、对比例2、对比例3、对比例4所制备的纳米复合材料的透射电镜(TEM)照片。(A:实施例1;B:对比例1;C:对比例2;D:对比例3;E:对比例4)
图2是本发明实施例1、对比例1、对比例2、对比例4所制备的纳米复合材料的拉曼光谱(Raman)图。(实施例1:rGO/Fe3O4/MnO2(Ⅰ);对比例2:rGO/MnO2;对比例1:rGO/Fe3O4;对比例4:rGO)
图3是本发明实施例1、对比例1所制备的纳米复合材料的磁滞回线。(实施例1:Fe3O4/MnO2/rGO(Ⅰ);对比例1:rGO/Fe3O4)
具体实施方式
下面介绍的为本发明较为优选的实施例,但并不用于对本发明的限定。
以下通过具体实施例来进一步说明利用本发明如何制备rGO/Fe3O4/MnO2纳米复合材料,及其染料吸附能力和光催化降解性能。
1.rGO/Fe3O4/MnO2纳米复合材料的染料吸附性能评价:
实验选取亚甲基蓝(MB)为目标物进行rGO/Fe3O4/MnO2纳米复合材料的吸附性能评价,取8mg的MB和80mL的纯净水加到250mL锥形瓶中配制MB溶液,然后将50mg超声分散好的rGO/Fe3O4/MnO2加入到上述混合液中,放入30℃恒温水浴磁力搅拌。每隔5min用一次性注射器吸取2mL的溶液,用0.45μm滤膜过滤,用分光光度计测定过滤液的吸光度(λ=664nm),通过朗伯比尔定律计算出过滤液中MB的浓度,并由下式计算MB的吸附去除率。
吸附去除率=(c0-ct)/c0
式中,c0:MB的初始浓度;ct:吸附t分钟后MB的浓度。
2.rGO/Fe3O4/MnO2纳米复合材料的染料催化降解性能评价:
实验选取亚甲基蓝(MB)为目标物进行rGO/Fe3O4/MnO2纳米复合材料的催化降解评价,取8mg的MB和80ml的纯净水加到250mL锥形瓶中配制MB溶液,用0.1mg/L的HCl溶液调节pH至5.0,再加入50mg超声分散好的rGO/Fe3O4/MnO2,放入30℃恒温水浴中磁力搅拌30min至吸附平衡,量取2mL、30%H2O2加入到上述混合液中反应60min。每隔5min用一次性注射器吸取2mL的反应溶液,用0.45μm滤膜过滤,用分光光度计测定过滤液的吸光度(λ=664nm),通过朗伯比尔定律计算出过滤液中MB的浓度,并由下式计算MB的催化降解去除率。
催化降解去除率=(C0-Ct)/C0
式中,C0:MB的初始浓度;Ct:反应t分钟后MB的浓度。
实施例1
分别称取200mg的GO(含氧功能基团为5.2wt%)和1000mg的PEG-600溶于350ml去离子水中,30℃下超声1小时形成均匀的悬浮液。1500rpm磁力搅拌下并通N2除氧1小时,30℃下将浓度分别为100mg/mL(0.789mmol/mL)、256mg/mL(1.578mmol/mL)的FeCl2和FeCl3的混合溶液2mL缓慢滴加到上述悬浮液中,继续搅拌并通N2除氧5小时,紧接着快速加入氨浓度为25mg/mL的氨水调节pH至11,然后将磁力搅拌速率调至3000rpm,恒温水浴温度升至75℃下反应3小时。3000rpm磁力搅拌作用下,75℃的恒温水浴中向上述混合液中加入浓度为120mg/mL的MnSO4溶液4mL,再快速加入浓度分别为60mg/mL、120mg/mL的KMnO4和KOH的混合溶液7mL,反应3小时。用抽滤瓶对上述获得的混合物进行过滤,并用去纯净水对过滤沉积物进行多次洗涤;最后将过滤﹑洗涤后所得产物放置于50℃真空烘箱中干燥24小时,得到rGO/Fe3O4/MnO2纳米复合材料。
本实施例所制备的rGO/Fe3O4/MnO2纳米复合材料的透射电镜(TEM)照片如图1中A所示;所制备的rGO/Fe3O4/MnO2纳米复合材料的拉曼光谱(Raman)图参见图2。
本实施例所制备的rGO/Fe3O4/MnO2纳米复合材料的染料吸附和催化降解性能见表1。
实施例2
分别称取200mg的GO(含氧功能基团为5.2wt%)和1200mg的PEG-600溶于350ml去离子水中,30℃下超声1小时形成均匀的悬浮液。1500rpm磁力搅拌下并通N2除氧1小时,30℃下将浓度分别为100mg/mL(0.789mmol/mL)、256mg/mL(1.578mmol/mL)的FeCl2和FeCl3的混合溶液2.5mL缓慢滴加到上述悬浮液中,继续搅拌并通N2除氧5小时,紧接着快速加入氨浓度为25mg/mL的氨水调节pH至11,然后将磁力搅拌速率调至3000rpm,恒温水浴温度升至75℃下反应3小时。3000rpm磁力搅拌作用下,75℃的恒温水浴中向上述混合液中加入浓度为120mg/mL的MnSO4溶液4.5mL,再快速加入浓度分别为60mg/mL、120mg/mL的KMnO4和KOH的混合溶液8mL,反应3小时。用抽滤瓶对上述获得的混合物进行过滤,并用去纯净水对过滤沉积物进行多次洗涤;最后将过滤﹑洗涤后所得产物放置于50℃真空烘箱中干燥24小时,得到rGO/Fe3O4/MnO2纳米复合材料。
本实施例所制备的rGO/Fe3O4/MnO2纳米复合材料的染料吸附和催化降解性能见表1。
实施例3
分别称取200mg的GO(含氧功能基团为5.2wt%)和1400mg的PEG-600溶于350ml去离子水中,30℃下超声1小时形成均匀的悬浮液。1500rpm磁力搅拌下并通N2除氧1小时,30℃下将浓度分别为100mg/mL(0.789mmol/mL)、256mg/mL(1.578mmol/mL)的FeCl2和FeCl3的混合溶液3mL缓慢滴加到上述悬浮液中,继续搅拌并通N2除氧5小时,紧接着快速加入氨浓度为25mg/mL的氨水调节pH至11,然后将磁力搅拌速率调至3000rpm,恒温水浴温度升至75℃下反应3小时。3000rpm磁力搅拌作用下,75℃的恒温水浴中向上述混合液中加入浓度为120mg/mL的MnSO4溶液6mL,再快速加入浓度为分别为60mg/mL、120mg/mL的KMnO4和KOH的混合溶液11mL,反应3小时。用抽滤瓶对上述获得的混合物进行过滤,并用去纯净水对过滤沉积物进行多次洗涤;最后将过滤﹑洗涤后所得产物放置于50℃真空烘箱中干燥24小时,得到rGO/Fe3O4/MnO2纳米复合材料。
本实施例所制备的rGO/Fe3O4/MnO2纳米复合材料的染料吸附和催化降解性能见表1。
对比例1
分别称取200mg的GO(含氧功能基团为5.2wt%)和1000mg的PEG-600溶于350ml去离子水中,30℃下超声1小时形成均匀的悬浮液。1500rpm磁力搅拌下并通N2除氧1小时,30℃下将浓度分别为100mg/mL(0.789mmol/mL)、256mg/mL(1.578mmol/mL)的FeCl2和FeCl3的混合溶液2mL缓慢滴加到上述悬浮液中,继续搅拌并通N2除氧5小时,紧接着快速加入氨浓度为25mg/mL的氨水调节pH至11,然后将磁力搅拌速率调至3000rpm,恒温水浴温度升至75℃下反应3小时。用抽滤瓶对上述获得的混合物进行过滤,并用去纯净水对过滤沉积物进行多次洗涤;最后将过滤﹑洗涤后所得产物放置于50℃真空烘箱中干燥24小时,得到rGO/Fe3O4纳米复合材料。
本实施例所制备的rGO/Fe3O4纳米复合材料的透射电镜(TEM)照片如图1中B所示;所制备的rGO/Fe3O4纳米复合材料的拉曼光谱(Raman)图参见图2。
本实施例所制备的rGO/Fe3O4纳米复合材料的染料吸附和催化降解性能见表1。
对比例2
分别称取200mg的GO(含氧功能基团为5.2wt%)和1200mg的PEG-600溶于350ml去离子水中,30℃下超声1小时形成均匀的悬浮液。3000rpm磁力搅拌作用下,75℃的恒温水浴中向上述悬浮液中加入浓度为120mg/mL的MnSO4溶液4.5mL,再快速加入浓度分别为60mg/mL、120mg/mL的KMnO4和KOH的混合溶液8mL,反应3小时。用抽滤瓶对上述获得的混合液进行过滤,并用去纯净水对过滤沉积物进行多次洗涤;最后将过滤﹑洗涤后所得产物放置于50℃真空烘箱中干燥24小时,得到rGO/MnO2纳米复合材料。
本实施例所制备的rGO/MnO2纳米复合材料的透射电镜(TEM)照片如图1中C所示;所制备的rGO/MnO2纳米复合材料的拉曼光谱(Raman)图参见图2。
本实施例所制备的rGO/MnO2纳米复合材料的染料吸附和催化降解性能见表1。
对比例3
称取1400mg的PEG-600溶于350ml去离子水中,30℃下超声1小时形成均匀的溶液。1500rpm磁力搅拌下并通N2除氧1小时,30℃下将浓度分别为100mg/mL(0.789mmol/mL)、256mg/mL(1.578mmol/mL)的FeCl2和FeCl3的混合溶液3mL缓慢滴加到上述溶液中,继续搅拌并通N2除氧5小时,紧接着快速加入氨浓度为25mg/mL的氨水调节pH至11,然后将磁力搅拌速率调至3000rpm,恒温水浴温度升至75℃下反应3小时。3000rpm磁力搅拌作用下,75℃的恒温水浴中向上述混合液中加入浓度为120mg/mL的MnSO4溶液6mL,再快速加入浓度为分别为60mg/mL、120mg/mL的KMnO4和KOH的混合溶液11mL,反应3小时。用抽滤瓶对上述获得的混合物进行过滤,并用去纯净水对过滤沉积物进行多次洗涤;最后将过滤﹑洗涤后所得产物放置于50℃真空烘箱中干燥24小时,得到Fe3O4/MnO2纳米复合材料。
本实施例所制备的Fe3O4/MnO2纳米复合材料的透射电镜(TEM)照片如图1中D所示。
本实施例所制备的Fe3O4/MnO2纳米复合材料的染料吸附和催化降解性能见表1。
对比例4
分别称取200mg的GO(含氧功能基团为5.2wt%)和1000mg的PEG-600溶于350ml去离子水中,30℃下超声1小时形成均匀的悬浮液。用抽滤瓶对上述获得的悬浮液进行过滤,并用去纯净水对过滤沉积物进行多次洗涤;最后将过滤﹑洗涤后所得产物放置于50℃真空烘箱中干燥24小时,得到rGO纳米材料。
本实施例所制备的rGO纳米材料的透射电镜(TEM)照片如图1中E所示。
图1是rGO/Fe3O4、rGO/MnO2、rGO/Fe3O4/MnO2与rGO的TEM照片。从图1中E可以看出rGO呈现完全剥离的,半透明的片状纱状结构。从图1中D、C、B、A可以看出Fe3O4/MnO2、Fe3O4、MnO2均呈球状纳米粒子形貌,且Fe3O4、MnO2、Fe3O4/MnO2纳米粒子都较为均匀的分布在rGO片层上。
通过图2可以看到,rGO与rGO/Fe3O4、rGO/MnO2、rGO/Fe3O4/MnO2的拉曼光谱都在1350cm-1和1580cm-1处出现缺陷,其中1350cm-1处的缺陷峰(D峰),它反映的是rGO片层中碳原子的晶格缺陷即sp3缺陷或者无定形碳,1580cm-1处的缺陷峰(G峰),它对应的则是rGO片层中C原子sp2杂化的面内伸缩振动。从样品的拉曼光谱图及其ID/IG值可以清楚得到,加入Fe3O4、MnO2、Fe3O4/MnO2之后rGO的ID/IG值有所提高,这是由于在rGO片层上形成粒径较小纳米粒子后,使得sp2杂化碳原子平均区域减小,导致ID/IG值升高。
图3是实施例1、对比例1所制备的纳米复合材料的磁滞回线,表明本方法所制备的rGO/Fe3O4/MnO2、rGO/Fe3O4均具有较强的磁性,可通过外加磁场从水体分离回收。
本实施例所制备的rGO纳米材料的染料吸附和催化降解性能见表1。
表1是本发明实施例所制备的rGO/Fe3O4/MnO2纳米复合材料及对比例1、对比例2、对比例3、对比例4所制备的纳米复合材料的染料吸附和催化降解性能。
表1
表1中分别列出了实施例1-3制备的rGO/Fe3O4/MnO2纳米复合材料、对比例1-4分别制备的rGO/Fe3O4纳米复合材料、rGO/MnO2纳米复合材料、Fe3O4/MnO2纳米复合材料、GO的MB吸附去除率和催化降解去除率。与rGO/Fe3O4纳米复合材料、rGO/MnO2纳米复合材料、Fe3O4/MnO2纳米复合材料、GO相比,rGO/Fe3O4/MnO2纳米复合材料不仅具有了优良的染料吸附能力,而且具有良好的光催化降解性能,同时还具有一定的磁性,可利用外加磁场从水体中分离、回收。
Claims (7)
1.一种磁性石墨烯/四氧化三铁/二氧化锰纳米复合材料的制备方法,其特征在于,包括如下步骤:
(1)20~40℃恒温水浴中将氧化石墨烯、聚乙二醇分散在纯净水中,超声形成均匀的悬浮液;
(2)将所述悬浮液继续在20~40℃恒温水浴中持续搅拌、并除氧后滴加FeCl3和FeCl2的混合溶液,无氧环境下持续反应4~6小时,然后加入氨水调pH至10.5~11.5,加快搅拌速度、升高水浴温度至70~80℃,继续反应2~3小时,得含有rGO/Fe3O4的混合液;FeCl2与氧化石墨烯的质量比为1/1~1.5/1;
(3)保持搅拌速度和水浴温度不变,向所得混合液中加入MnSO4溶液,然后再快速加入KMnO4和KOH的混合溶液,反应2~4小时,得到包含有rGO/Fe3O4/MnO2的混合液;MnSO4与FeCl2和FeCl3总质量比为0.6/1~0.75/1;KMnO4与MnSO4质量比为1/1.1~1/1.2;KOH与MnSO4和KMnO4总质量比为0.9/1~1/1;
(4)将含有rGO/Fe3O4/MnO2的混合液反复过滤、洗涤后于140~160℃真空干燥箱内热处理20~25小时即得。
2.根据权利要求1所述制备方法,其特征在于,步骤(1)中氧化石墨烯质量与纯净水体积的比为1mg:1.5~2.0mL,氧化石墨烯中氧含量为4.5~6.5%,聚乙二醇与氧化石墨烯的质量比为5~10。
3.根据权利要求1所述制备方法,其特征在于,步骤(2)中FeCl3与FeCl2摩尔比为2/1。
4.根据权利要求1所述制备方法,其特征在于,步骤(1)中超声时间为45~60min。
5.根据权利要求1所述制备方法,其特征在于,步骤(2)中20~40℃恒温水浴中搅拌速度为1400~1600rpm;70~80℃恒温水浴中搅拌速度为2800~3200rpm。
6.根据权利要求1所述制备方法,其特征在于,步骤(2)中所用氨水为25mg/mL的氨水溶液。
7.根据权利要求1所述制备方法,其特征在于,步骤(1)中恒温水浴温度为30℃;步骤(2)中升温前为30℃、升温后为75℃。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711008658.7A CN107913667B (zh) | 2017-10-25 | 2017-10-25 | 一种磁性石墨烯/四氧化三铁/二氧化锰纳米复合材料及其制备和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711008658.7A CN107913667B (zh) | 2017-10-25 | 2017-10-25 | 一种磁性石墨烯/四氧化三铁/二氧化锰纳米复合材料及其制备和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107913667A CN107913667A (zh) | 2018-04-17 |
CN107913667B true CN107913667B (zh) | 2020-10-13 |
Family
ID=61895708
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201711008658.7A Active CN107913667B (zh) | 2017-10-25 | 2017-10-25 | 一种磁性石墨烯/四氧化三铁/二氧化锰纳米复合材料及其制备和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107913667B (zh) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109821532A (zh) * | 2019-02-27 | 2019-05-31 | 知合环境(北京)有限责任公司 | 一种磁性氧化石墨烯改性臭氧氧化催化剂及其制备方法 |
CN110368900B (zh) * | 2019-08-20 | 2022-06-07 | 厦门理工学院 | 一种竹炭改性材料及其制备方法和用途 |
CN110694639B (zh) * | 2019-10-16 | 2022-07-29 | 天津大学 | 一种多界面磁性异质结的制备方法 |
CN111389373B (zh) * | 2020-03-19 | 2022-11-08 | 北京林业大学 | 一种负载双金属的木质素磁性吸附材料的制备方法 |
CN111686679A (zh) * | 2020-06-01 | 2020-09-22 | 山西大学 | 一种二氧化锰气凝胶材料的制备方法和应用 |
CN111592744A (zh) * | 2020-06-29 | 2020-08-28 | 江西伟普科技有限公司 | 一种金属负载碳/聚合物基电磁屏蔽材料及其制备方法 |
CN111548618A (zh) * | 2020-06-29 | 2020-08-18 | 江西伟普科技有限公司 | 一种金属负载碳/聚合物基电磁屏蔽材料及其制备方法 |
CN113426418A (zh) * | 2021-06-16 | 2021-09-24 | 山东银鹰股份有限公司 | 一种纳米纤维素/纳米双过渡金属氧化物三元复合材料及其制备方法和应用 |
CN113398949A (zh) * | 2021-08-16 | 2021-09-17 | 广西大学 | 一种磁性还原氧化石墨烯/钨酸银复合光催化剂及其制备方法与应用 |
CN114534741B (zh) * | 2022-01-21 | 2023-10-20 | 厦门理工学院 | 凹凸棒石/二氧化锰/四氧化三铁纳米复合材料及其制备方法和应用 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101306864A (zh) * | 2008-06-25 | 2008-11-19 | 浙江工业大学 | 一种水体中环境***类污染物的降解方法 |
CN102120619A (zh) * | 2011-01-11 | 2011-07-13 | 河北师范大学 | 一种脑珊瑚状水钠锰矿型二氧化锰的制备方法 |
CN103285874A (zh) * | 2013-06-13 | 2013-09-11 | 江苏中核华纬工程设计研究有限公司 | 一种具有过氧化物酶性质的无机纳米复合催化剂及其催化分解tmb的应用 |
CN103693639A (zh) * | 2013-12-13 | 2014-04-02 | 天津工业大学 | 铁/锰氧化物掺杂石墨烯复合材料的制备方法 |
CN104888706A (zh) * | 2015-06-08 | 2015-09-09 | 河海大学 | 一种可磁性分离复合吸附剂、其制备方法及其应用 |
CN105289493A (zh) * | 2015-11-17 | 2016-02-03 | 辽宁大学 | 一种用于As(Ⅲ)吸附的铁锰改性的秸秆活性炭吸附剂及其应用 |
CN106115796A (zh) * | 2016-06-29 | 2016-11-16 | 广西桂柳化工有限责任公司 | 一种含磁性铁的石墨烯‑二氧化锰纳米材料的制备方法 |
CN106140090A (zh) * | 2016-08-31 | 2016-11-23 | 南京尚易环保科技有限公司 | 一种用于去除室内甲醛的MnO2‑ACF材料及其制备方法 |
CN106531472A (zh) * | 2016-11-29 | 2017-03-22 | 桂林理工大学 | 一种聚吡咯/石墨烯/锰氧化物复合材料的制备方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9149833B2 (en) * | 2013-06-19 | 2015-10-06 | Indian Institute Of Technology Madras | Metal nanoparticle decorated carbon nanotubes and methods of preparation and use |
-
2017
- 2017-10-25 CN CN201711008658.7A patent/CN107913667B/zh active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101306864A (zh) * | 2008-06-25 | 2008-11-19 | 浙江工业大学 | 一种水体中环境***类污染物的降解方法 |
CN102120619A (zh) * | 2011-01-11 | 2011-07-13 | 河北师范大学 | 一种脑珊瑚状水钠锰矿型二氧化锰的制备方法 |
CN103285874A (zh) * | 2013-06-13 | 2013-09-11 | 江苏中核华纬工程设计研究有限公司 | 一种具有过氧化物酶性质的无机纳米复合催化剂及其催化分解tmb的应用 |
CN103693639A (zh) * | 2013-12-13 | 2014-04-02 | 天津工业大学 | 铁/锰氧化物掺杂石墨烯复合材料的制备方法 |
CN104888706A (zh) * | 2015-06-08 | 2015-09-09 | 河海大学 | 一种可磁性分离复合吸附剂、其制备方法及其应用 |
CN105289493A (zh) * | 2015-11-17 | 2016-02-03 | 辽宁大学 | 一种用于As(Ⅲ)吸附的铁锰改性的秸秆活性炭吸附剂及其应用 |
CN106115796A (zh) * | 2016-06-29 | 2016-11-16 | 广西桂柳化工有限责任公司 | 一种含磁性铁的石墨烯‑二氧化锰纳米材料的制备方法 |
CN106140090A (zh) * | 2016-08-31 | 2016-11-23 | 南京尚易环保科技有限公司 | 一种用于去除室内甲醛的MnO2‑ACF材料及其制备方法 |
CN106531472A (zh) * | 2016-11-29 | 2017-03-22 | 桂林理工大学 | 一种聚吡咯/石墨烯/锰氧化物复合材料的制备方法 |
Non-Patent Citations (1)
Title |
---|
"Adsorption of As (III) and As (V) from water using magnetite Fe3O4-reduced graphite oxide-MnO2 nanocomposites";Xubiao Luo et al.;《Chemical Engineering Journal》;20120430;第187卷;第46-47页 * |
Also Published As
Publication number | Publication date |
---|---|
CN107913667A (zh) | 2018-04-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107913667B (zh) | 一种磁性石墨烯/四氧化三铁/二氧化锰纳米复合材料及其制备和应用 | |
Zhang et al. | Ultrathin gC 3 N 4 nanosheets coupled with amorphous Cu-doped FeOOH nanoclusters as 2D/0D heterogeneous catalysts for water remediation | |
US10745294B2 (en) | Graphene oxide/magnesium oxide nanocomposites as superior sorbents for methylene blue removal from aqueous solutions | |
Pan et al. | Research progress of graphene-based nanomaterials for the environmental remediation | |
Ren et al. | One-step solvothermal synthesis of Fe3O4@ Carbon composites and their application in removing of Cr (VI) and Congo red | |
Fan et al. | Hybridization of graphene sheets and carbon-coated Fe 3 O 4 nanoparticles as a synergistic adsorbent of organic dyes | |
Hu et al. | A highly efficient catalyst: In situ growth of Au nanoparticles on graphene oxide–Fe3O4 nanocomposite support | |
Gemeay et al. | Graphene oxide/polyaniline/manganese oxide ternary nanocomposites, facile synthesis, characterization, and application for indigo carmine removal | |
Wang et al. | Magnetic mesoporous carbon nanospheres from renewable plant phenol for efficient hexavalent chromium removal | |
Talukdar et al. | Recent progress in research on multifunctional graphitic carbon nitride: An emerging wonder material beyond catalyst | |
Zhou et al. | Preparation of Fe 3 O 4-embedded graphene oxide for removal of methylene blue | |
Zuo et al. | Preparation of polyaniline–polypyrrole binary composite nanotube using halloysite as hard-template and its characterization | |
Guo et al. | Molecularly imprinted polymer-based photocatalyst for highly selective degradation of methylene blue | |
Du et al. | SiO2/Ga2O3 nanocomposite for highly efficient selective removal of cationic organic pollutant via synergistic electrostatic adsorption and photocatalysis | |
Zhang et al. | Photocatalytic Poly (vinylidene fluoride) membrane of Ag3PO4/GO/APTES for water treatment | |
Song et al. | Fast and highly-efficient removal of methylene blue from aqueous solution by poly (styrenesulfonic acid-co-maleic acid)-sodium-modified magnetic colloidal nanocrystal clusters | |
Rabeie et al. | Graphene quantum dot incorporation in the zeolitic imidazolate framework with sodalite (SOD) topology: Synthesis and improving the adsorption ability in liquid phase | |
Chen et al. | Synthesis of a novel graphene-based gold nanocomposite using PVEIM-b-PNIPAM as a stabilizer and its thermosensitivity for the catalytic reduction of 4-nitrophenol | |
Shan et al. | Surface modification of graphene oxide by goethite with enhanced tylosin photocatalytic activity under visible light irradiation | |
CN107913668B (zh) | 一种具有吸附和催化降解功能的纳米复合材料及其制备方法和应用 | |
Sun et al. | Thiourea-modified Fe3O4/graphene oxide nanocomposite as an efficient adsorbent for recycling Coomassie brilliant blue from aqueous solutions | |
Liu et al. | Understanding the high adsorption-reduction performance of triethanolamine modified graphene oxide for silver ions | |
Yu et al. | Highly dispersible and charge-tunable magnetic Fe 3 O 4 nanoparticles: facile fabrication and reversible binding to GO for efficient removal of dye pollutants | |
Tao et al. | Ultrasound-assisted bottom-up synthesis of Ni-graphene hybrid composites and their excellent rhodamine B removal properties | |
Ruiyi et al. | Histidine-functionalized carbon-based dot-Zinc (II) nanoparticles as a novel stabilizer for Pickering emulsion synthesis of polystyrene microspheres |
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 |