CN109289866B - 一种利用阳离子调控形貌的铁锰复合氧化物材料的制备方法及其应用 - Google Patents
一种利用阳离子调控形貌的铁锰复合氧化物材料的制备方法及其应用 Download PDFInfo
- Publication number
- CN109289866B CN109289866B CN201811432077.0A CN201811432077A CN109289866B CN 109289866 B CN109289866 B CN 109289866B CN 201811432077 A CN201811432077 A CN 201811432077A CN 109289866 B CN109289866 B CN 109289866B
- Authority
- CN
- China
- Prior art keywords
- composite oxide
- oxide material
- iron
- manganese composite
- manganese
- 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
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 43
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 150000001768 cations Chemical class 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 8
- 239000000975 dye Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000015556 catabolic process Effects 0.000 claims abstract description 15
- 238000006731 degradation reaction Methods 0.000 claims abstract description 15
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims abstract description 15
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000013032 photocatalytic reaction Methods 0.000 claims abstract description 9
- 150000002696 manganese Chemical class 0.000 claims abstract description 8
- 229910000616 Ferromanganese Inorganic materials 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 230000007935 neutral effect Effects 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005695 Ammonium acetate Substances 0.000 claims abstract description 5
- 229940043376 ammonium acetate Drugs 0.000 claims abstract description 5
- 235000019257 ammonium acetate Nutrition 0.000 claims abstract description 5
- 230000000593 degrading effect Effects 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 230000005389 magnetism Effects 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000004064 recycling Methods 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000001045 blue dye Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002551 Fe-Mn Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 2
- 229940012189 methyl orange Drugs 0.000 claims description 2
- PGSADBUBUOPOJS-UHFFFAOYSA-N neutral red Chemical compound Cl.C1=C(C)C(N)=CC2=NC3=CC(N(C)C)=CC=C3N=C21 PGSADBUBUOPOJS-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 235000004035 Cryptotaenia japonica Nutrition 0.000 claims 1
- 102000007641 Trefoil Factors Human genes 0.000 claims 1
- 235000015724 Trifolium pratense Nutrition 0.000 claims 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 abstract description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 abstract description 6
- 239000001632 sodium acetate Substances 0.000 abstract description 6
- 235000017281 sodium acetate Nutrition 0.000 abstract description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 abstract description 4
- 235000011056 potassium acetate Nutrition 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- 150000002505 iron Chemical class 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- -1 iron ions Chemical class 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 description 2
- 229960000282 metronidazole Drugs 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [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 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- AEEAZFQPYUMBPY-UHFFFAOYSA-N [I].[W] Chemical compound [I].[W] AEEAZFQPYUMBPY-UHFFFAOYSA-N 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- ZWXOQTHCXRZUJP-UHFFFAOYSA-N manganese(2+);manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+3].[Mn+3] ZWXOQTHCXRZUJP-UHFFFAOYSA-N 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution 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
- 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
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/33—Electric or 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
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
-
- 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
- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
-
- 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)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种利用阳离子调控形貌的铁锰复合氧化物材料的制备方法及其应用。所述材料的制备方法包括以下步骤:按比例分别称量铁盐和锰盐溶解于乙二醇中形成溶液;向溶液中加入醋酸盐(醋酸锂、醋酸钠、醋酸钾或醋酸铵),溶解后移入水热釜中进行水热反应,温度控制在150~200℃之间,时间6~24h;冷却后过滤洗涤干燥,在300~600℃焙烧2~6h,得到球形或二维树叶状等不同形貌的铁锰复合氧化物材料。本发明的铁锰复合氧化物材料可用于多相芬顿‑光催化反应降解亚甲基蓝等染料,能实现中性条件下高效快速降解染料,30分钟内亚甲基蓝降解率可达近100%,且材料具有磁性可以方便快捷地从反应溶液中分离出来,实现循环使用。
Description
技术领域
本发明涉及材料的自组装合成及其应用于废水处理技术领域,具体涉及一种利用阳离子调控形貌的铁锰复合氧化物材料的制备方法及应用于高级氧化技术处理染料废水。
背景技术
Fe3O4(磁铁矿,magnetite),面心立方密堆积,反尖晶石型结构,由于其稳定、低毒、生物兼容性等特点而广泛地应用于生物医药与技术和催化领域,限制其应用的主要原因是Fe3O4材料具有超顺磁性和较高的表面能极易使粒子之间相互聚集。Mn3O4(黑锰矿),在催化、电化学、传感、吸附和磁性等方面显示了特殊的理化性质。将这两种应用广泛的材料复合在一起,可以改善单一材料的性质,且铁锰元素之间可以构成氧化还原反应Mn3++Fe2+→Mn2++Fe3+,提高复合材料的氧化还原性,进而改善其磁性、电容性质及催化活性。所以,这类铁锰复合氧化物材料的自组装合成具有非常重要的意义。
水是人类生存和发展的重要资源,随着我国经济的高速发展,水资源短缺和污染严重制约了经济的可持续发展,因此发展水处理技术具有特别重要的意义。传统的水处理技术,如混凝絮凝法、膜过滤法、吸附法和离子交换法等,难以实现有机物的高效去除,而高级氧化技术则能够实现难降解有机物的去除。多相芬顿-光催化反应在众多高级氧化水处理技术中,因具有处理效果好,成本较低以及操作简便,易于扩大等优点而得到广泛应用和研究。
铁锰复合氧化物能被可见光激发,提高太阳能的利用率,同时也具有多相芬顿反应效应。大量研究成果表明,铁锰复合氧化物材料在一定时间内可以较好地实现多相芬顿-可见光催化降解有机污染物,但大多需要调节反应溶液的pH值。酸性环境会使催化剂中的铁离子溶解,造成催化剂组分流失而失活,且铁离子溶解在废水中也容易造成二次污染。因此,制备能够在中性条件下高效降解有机污染物的铁锰复合氧化物材料具有非常重要的意义。
发明内容
本发明所要解决的技术问题在于,克服现有技术中存在的问题,提供一种利用阳离子调控形貌的铁锰复合氧化物材料的制备方法及其应用,该材料能够解决现有的催化剂需在低pH值下工作造成水体污染的问题。
为了解决上述问题本发明的技术方案是这样的:
一种利用阳离子调控形貌的铁锰复合氧化物材料的制备方法,包括如下步骤:
S1:按照摩尔比1:20~20:1的比例分别称量铁盐和锰盐,加入乙二醇中溶解,形成盐浓度为0.05~0.5mol/L的混合溶液;
S2:向上述S1混合溶液中加入醋酸盐,浓度为1~40g/L;
S3:将反应液置于水热合成反应釜中,于烘箱中加热反应,温度控制在150~200℃之间,时间控制在6~24h;
S4:经S3步骤后的溶液自然冷却至室温后,将上层清液倒掉,固体取出低速离心,反复用去离子水及无水乙醇洗涤五次,再在恒温干燥箱中60~120℃干燥6~12h,得到固体粉末;
S5:将上述S4得到的固体粉末在马弗炉中进行焙烧,焙烧温度为300~600℃,时间为2~6h,得到具有球形或二维树叶状等不同形貌的铁锰复合氧化物材料。
S1中所用的铁盐和锰盐均为氯化物,铁锰摩尔比为10:7,金属盐浓度为0.18mol/L。
S2中,所加醋酸盐可以是醋酸锂、醋酸钠、醋酸钾、醋酸铵中任一种,且浓度为20g/L。
S3中,反应温度为180℃,反应时间为12h。
S4中,干燥温度为80℃,时间为8h。
S5中,焙烧温度为400℃,时间为2h。
一种利用阳离子调控形貌的铁锰复合氧化物材料的应用,用于中性条件下多相芬顿-光催化反应降解各种染料。
所述铁锰复合氧化物材料作为多相芬顿-光催化反应降解各种染料溶液的过程如下:取100mL浓度为5~50mg/L的染料溶液,向其中加入0.1~1g/L铁锰复合氧化物材料和0~5mL的过氧化氢,暗室吸附30min后,在可见光源下照射1h,反应结束后,固液体分离,取上清液用紫外可见分光光度计测定染料浓度,根据反应前后染料浓度变化计算降解率。
所述染料为亚甲基蓝染料、中性红或甲基橙的一种或几种组合。
30分钟亚甲基蓝染料降解率100%。
所述可见光源为碘钨灯。
铁锰复合氧化物材料具有磁性,可从反应溶液中分离出来,实现循环使用。
有益效果,本发明所述的铁锰复合氧化物材料能够解决现有的催化剂需在低pH值下工作造成水体污染的问题,可在中性条件下多相芬顿-光催化反应降解各种染料。30分钟亚甲基蓝染料降解率100%。
附图说明
下面结合附图和具体实施方式来详细说明本发明;
图1为不同醋酸盐得到的铁锰复合氧化物的SEM电镜对比图片;
图2为铁锰复合氧化物的XRD图片。
具体实施方式
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解,下面结合具体图示,进一步阐述本发明。
实施例1:球形铁锰复合氧化物材料的制备,将1.35g FeCl3·6H2O、0.693gMnCl2·4H2O和1g醋酸锂(醋酸钠或醋酸钾)溶于50mL乙二醇中,室温下磁力搅拌半小时溶解后,移入100mL带聚四氟乙烯内衬的水热反应釜中,放入烘箱中180℃加热12h,待加热完成后,自然冷却至室温,过滤并用去离子水和无水乙醇洗涤,然后将所得固体于80℃干燥6h,在马弗炉中400℃焙烧2h,得到球形铁锰复合氧化物材料。
实施例2:二维树叶状铁锰复合氧化物材料的制备,将1.35g FeCl3·6H2O、0.693gMnCl2·4H2O和1g醋酸铵、溶于50mL乙二醇中,室温下磁力搅拌半小时溶解后,移入100mL带聚四氟乙烯内衬的水热反应釜中,放入烘箱中180℃加热12h,待加热完成后,自然冷却至室温,过滤并用去离子水和无水乙醇洗涤,然后将所得固体于80℃干燥6h,在马弗炉中400℃焙烧2h,得到二维树叶状铁锰复合氧化物材料。
图1为加不同醋酸盐得到的铁锰复合氧化物的SEM电镜图片对比,图中可以看出,加醋酸锂、醋酸钠和醋酸钾得到的是球形颗粒,颗粒比较均匀,粒径大致80nm。加醋酸铵得到的是树叶状二维结构的形貌,长1.8μm。
图2为树叶状二维结构铁锰复合氧化物的XRD图谱,从图可以看出,该氧化物为立方相Fe3O4,未发现有锰氧化物相,说明锰离子很好地进入到Fe3O4立方晶格中。
实施例3:铁锰复合氧化物的多相芬顿-光催化反应性能
反应体系中含20mg加不同醋酸盐制备的铁锰复合氧化物催化剂、浓度为20mg/L的亚甲基蓝溶液100mL和H2O2 0.5mL,暗室吸附30min后可见光照射开始反应。在前30min的暗室吸附过程中,各催化剂对亚甲基蓝的吸附作用较弱。光照反应开始后,各催化剂对亚甲基蓝的降解作用较快,40min后几乎所有的催化剂都能够实现完全降解亚甲基蓝。
实施例4:H2O2量的影响
反应体系中含20mg加醋酸钠制备的铁锰复合氧化物催化剂、浓度为20mg/L亚甲基蓝水溶液100mL、和一定量的H2O2(H2O2量分别为1mL、0.5mL、80μL、50μL和20μL),经暗室30min吸脱附平衡后,在可见光下照射30min。H2O2的量有一最佳值,即在80μL时降解速率最快,亚甲基蓝的降解率达到100%,H2O2过多或过少降解率都降低。
实施例5:染料种类的影响
反应体系中含20mg加醋酸钠制备的铁锰复合氧化物球形催化剂、100mL的不同染料溶液(亚甲基蓝、甲硝唑、罗丹明B、结晶紫,其浓度均为20mg/L)及80μL H2O2。经暗室吸脱附平衡30min后,在可见光照射下开始反应。在40min内,结晶紫、罗丹明B和亚甲基蓝可以实现近100%降解,甲硝唑的降解率可以达到90%。
本发明所述的铁锰复合氧化物材料能够解决现有的催化剂需在低pH值下工作造成水体污染的问题,可在中性条件下多相芬顿-光催化反应降解各种染料。30分钟亚甲基蓝染料降解率100%。
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明专利要求保护的范围由所附的权利要求书及其等同物界定。
Claims (10)
1.一种利用阳离子调控形貌的铁锰复合氧化物材料的制备方法,其特征是,包括如下步骤:
S1:按照摩尔比1:20 ~ 20:1的比例分别称量铁盐和锰盐,加入乙二醇中溶解,形成盐浓度为0.05 ~ 0.5 mol/L的混合溶液;所述铁盐和锰盐均为氯化物;
S2:向上述S1混合溶液中加入醋酸盐,浓度为1 ~ 40 g/L;所述醋酸盐是醋酸铵;
S3:将反应液置于水热合成反应釜中,于烘箱中加热反应,温度控制在150 ~ 200℃之间,时间控制在6 ~ 24 h;
S4:经S3步骤后的溶液自然冷却至室温后,将上层清液倒掉,固体取出低速离心,反复用去离子水及无水乙醇洗涤五次,再在恒温干燥箱中60 ~ 120℃干燥6 ~12 h,得到固体粉末;
S5:将上述S4得到的固体粉末在马弗炉中进行焙烧,焙烧温度为300 ~ 600℃,时间为2~ 6 h,得到具有二维树叶状形貌的铁锰复合氧化物材料。
2.根据权利要求1所述的一种利用阳离子调控形貌的铁锰复合氧化物材料的制备方法,其特征是,S1中铁锰摩尔比为10:7,金属盐浓度为0.18 mol/L。
3.根据权利要求1所述的一种利用阳离子调控形貌的铁锰复合氧化物材料的制备方法,其特征是,S2中,所加醋酸盐的浓度为20 g/L。
4.根据权利要求1所述的一种利用阳离子调控形貌的铁锰复合氧化物材料的制备方法,其特征是,S3中,反应温度为180℃,反应时间为12 h。
5.根据权利要求1所述的一种利用阳离子调控形貌的铁锰复合氧化物材料的制备方法,其特征是,S4中,干燥温度为80℃,时间为8 h。
6.根据权利要求1所述的一种利用阳离子调控形貌的铁锰复合氧化物材料的制备方法,其特征是,S5中,焙烧温度为400℃,时间为2 h。
7.权利要求1-6中任一项所述的制备方法得到的一种利用阳离子调控形貌的铁锰复合氧化物材料的应用,其特征是,用于中性条件下多相芬顿-光催化反应降解各种染料。
8.根据权利要求7所述的一种利用阳离子调控形貌的铁锰复合氧化物材料的应用,其特征是,所述铁锰复合氧化物材料作为多相芬顿-光催化反应降解各种染料溶液的过程如下:取100 mL浓度为5~50 mg/L的染料溶液,向其中加入0.1~1 g/L铁锰复合氧化物材料和0~5 mL的过氧化氢,暗室吸附30 min后,在可见光源下照射1 h,反应结束后,固液体分离,取上清液用紫外可见分光光度计测定染料浓度,根据反应前后染料浓度变化计算降解率。
9.根据权利要求7所述的一种利用阳离子调控形貌的铁锰复合氧化物材料的应用,其特征是,所述染料为亚甲基蓝染料、中性红或甲基橙的一种或几种组合。
10.根据权利要求7所述的一种利用阳离子调控形貌的铁锰复合氧化物材料的应用,其特征是,铁锰复合氧化物材料具有磁性,可从反应溶液中分离出来,实现循环使用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811432077.0A CN109289866B (zh) | 2018-11-28 | 2018-11-28 | 一种利用阳离子调控形貌的铁锰复合氧化物材料的制备方法及其应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811432077.0A CN109289866B (zh) | 2018-11-28 | 2018-11-28 | 一种利用阳离子调控形貌的铁锰复合氧化物材料的制备方法及其应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109289866A CN109289866A (zh) | 2019-02-01 |
CN109289866B true CN109289866B (zh) | 2021-11-09 |
Family
ID=65143156
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811432077.0A Active CN109289866B (zh) | 2018-11-28 | 2018-11-28 | 一种利用阳离子调控形貌的铁锰复合氧化物材料的制备方法及其应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109289866B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115487684B (zh) * | 2022-09-27 | 2024-04-05 | 浙江理工大学 | 一种高效清洗陶瓷膜的方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011086567A1 (en) * | 2010-01-12 | 2011-07-21 | Council Of Scientific & Industrial Research | Magnetic dye-adsorbent catalyst |
CN102285691A (zh) * | 2011-03-17 | 2011-12-21 | 青岛大学 | 一种磁性铁氧体纳米颗粒的制备方法 |
CN103482706A (zh) * | 2013-10-15 | 2014-01-01 | 大连交通大学 | 一种空心球形纳米铁酸锰,其制备方法及其应用 |
CN104607227A (zh) * | 2015-01-23 | 2015-05-13 | 哈尔滨工业大学 | 一种α-Fe2O3介孔纳米片/氮掺杂石墨烯复合材料的制备方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9272275B2 (en) * | 2009-10-28 | 2016-03-01 | University Of Vermont And State Agricultural College | Method and system for the selective oxidative decarboxylation of fatty acids |
CN102531068B (zh) * | 2010-12-31 | 2015-02-25 | 湖南工业大学 | 一种大量合成单分散四氧化三铁纳米晶的方法 |
KR102373455B1 (ko) * | 2015-09-24 | 2022-03-11 | 삼성전자주식회사 | 멕신(MXene) 나노시트 및 그 제조방법 |
CN106335929B (zh) * | 2016-08-15 | 2018-05-25 | 中南大学 | 一种微纳米结构的四氧化三锰的制备方法 |
CN108565132B (zh) * | 2018-05-15 | 2019-09-27 | 中国科学院深圳先进技术研究院 | 一种具有金属氧化物纳米结构的纤维材料及其制备方法 |
-
2018
- 2018-11-28 CN CN201811432077.0A patent/CN109289866B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011086567A1 (en) * | 2010-01-12 | 2011-07-21 | Council Of Scientific & Industrial Research | Magnetic dye-adsorbent catalyst |
CN102285691A (zh) * | 2011-03-17 | 2011-12-21 | 青岛大学 | 一种磁性铁氧体纳米颗粒的制备方法 |
CN103482706A (zh) * | 2013-10-15 | 2014-01-01 | 大连交通大学 | 一种空心球形纳米铁酸锰,其制备方法及其应用 |
CN104607227A (zh) * | 2015-01-23 | 2015-05-13 | 哈尔滨工业大学 | 一种α-Fe2O3介孔纳米片/氮掺杂石墨烯复合材料的制备方法 |
Non-Patent Citations (2)
Title |
---|
MnFe2O4的合成及其非均相 Fenton 法降解工业废水的性能;陆清华,李沅瑾,宋凤丹,陈昊,齐随涛;《化工进展》;20180805;第37卷(第8期);第3021页摘要,第3022页左栏,第1-5行,右栏,1.4多相Fenton降解测试, * |
α-Fe2O3 nanosheet-assembled hierchical hollow mesoporous microspheres: Microwave-assisted solvothermal synthesis and application in photocatalysis;Tuan-Wei Sun et al;《Journal of Colloid and Interface Science》;20151022;第463卷;第108页左栏2.1preparetion of α- Fe2O3 HHMSs,第113页左栏第9-12行,Fig.6a,b,参见第114页左栏第2-8行 * |
Also Published As
Publication number | Publication date |
---|---|
CN109289866A (zh) | 2019-02-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103301809B (zh) | 磁性载铁有序介孔碳及其制备方法和应用 | |
Chen et al. | Porous magnetic manganese oxide nanostructures: Synthesis and their application in water treatment | |
CN108311117B (zh) | 一种用于重金属废水处理的磁性生物炭材料及其制备方法 | |
Zhao et al. | Recent advances in metal organic frame photocatalysts for environment and energy applications | |
CN107913662B (zh) | 一种磁性铁/镧复合除砷吸附材料及其制备方法 | |
CN111359580A (zh) | 一种多孔结构的碳铁复合材料的制备方法及应用 | |
CN110354887B (zh) | 一种用于光催化降解抗生素的可磁分离的催化剂及其制备方法和应用 | |
CN103272553B (zh) | 一种用于除去水体中砷的磁性纳米氧化铁吸附剂的制备方法 | |
CN108393073A (zh) | 一种通用磁性吸附剂的制备方法与应用 | |
CN112521617B (zh) | 一种可用于吸附抗生素的多酸基金属有机框架材料及其制备方法和用途 | |
CN104190422A (zh) | 一种异相光芬顿催化剂及其用途 | |
CN106881111A (zh) | 氧化亚铜和银共同负载的钒酸铋复合光催化剂及其制备方法和应用 | |
Cai et al. | In-situ growth of amorphous MnO2 on C-decorated Fe-based geopolymer sphere with rich structure defects for efficient solar light-induced photo-thermal-Fenton reaction | |
Palanisamy et al. | Construction of magnetically recoverable novel Z-scheme La (OH) 3/α-MnO2/MnFe2O4 photocatalyst for organic dye degradation under UV–visible light illumination | |
WO2018129773A1 (zh) | 一种高锝酸根吸附剂及其合成方法与在处理放射性废水中的应用 | |
CN104941585A (zh) | 一种富含羧基并可磁性回收的重金属吸附剂的制备方法 | |
CN109289866B (zh) | 一种利用阳离子调控形貌的铁锰复合氧化物材料的制备方法及其应用 | |
Mukherjee et al. | A comprehensive study on the uptake of dyes, Cu (II) and radioactive 137Cs (I) by sonochemically synthesized strontium/yttrium tungstate and molybdate nanoparticles | |
CN104891513B (zh) | 一种磁性膨润土的制备方法 | |
CN107876006A (zh) | 一种碳纳米纤维‑水滑石复合材料吸附剂的制备方法及其应用 | |
CN108714426A (zh) | 一种纳米立方体钙钛矿型催化剂及其制备方法和应用 | |
CN109046373B (zh) | 可磁分离的非均相类Fenton催化剂CeO2/MZFS的制备方法及应用 | |
CN113908802A (zh) | 一种用于有机阴离子染料吸附的铜基复合物 | |
Wu et al. | ZIF-67 derived magnetic Bi12O17Cl2/Y-TCPP/Co-NC double Z-scheme heterojunction enhanced photocatalytic performance for antibiotic degradation | |
Zhang et al. | Activation of ozone by CoFe-LDO-BC heterogeneous catalyst for efficient mineralization of methylene blue: The role of oxygen vacancies and acidic sites |
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 |