CN108295829A - 氢氧化镁/还原氧化石墨烯复合材料的制备和使用方法 - Google Patents
氢氧化镁/还原氧化石墨烯复合材料的制备和使用方法 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 68
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 title claims abstract description 53
- 239000000347 magnesium hydroxide Substances 0.000 title claims abstract description 50
- 229910001862 magnesium hydroxide Inorganic materials 0.000 title claims abstract description 50
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- 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 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
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- 229960000907 methylthioninium chloride Drugs 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 7
- 239000000975 dye Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 159000000003 magnesium salts Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002957 persistent organic pollutant Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- -1 formyl amine Chemical class 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
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- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 241001062009 Indigofera Species 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 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
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
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- 230000015556 catabolic process Effects 0.000 abstract description 9
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
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- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
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- 235000011147 magnesium chloride Nutrition 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
本发明提供了一种具有高效光催化性能的氢氧化镁/还原氧化石墨烯复合材料的制备方法。本发明的另一目的是提供该材料光降解印染污水中有机污染物的高效应用。该复合材料具有极强的光催化降解效果,多次循环下仍有较好的光催化降解能力。另外,由于氢氧化镁密度较大,复合材料易从污水分离,为回收催化剂提供便利。
Description
技术领域
本发明涉及材料技术领域,具体涉及一种氢氧化镁/还原氧化石墨烯复合材料的制备和使用方法。
背景技术
染料广泛应用于纺织、造纸、化妆品、皮革、织物处理等领域,每年都会产生大量的染料污水。而这些染料污水大部分都是有毒且不易降解、或降解产生致癌和有毒物质。目前,染料废水的处理方法主要有:(1)化学处理技术;(2)物理处理技术;(3)生物处理技术;(4)光催化技术。其中,光催化技术是一种环境友好的污染治理技术,在废水废气净化、抗菌环保等领域有着广泛的用途。大量的科技工作者至力于开发、合成新型的光降解催化剂。已被大量文献报道的光降解催化剂包含ZnO/rGO、TiO2/rGO、Fe3O4/rGO等,结果表明采用具有光降解催化功能的无机粒子与石墨烯复合能极大的提高该类材料的光降解能力。
纳米氢氧化镁作为价格低廉的无机纳米材料广泛作为阻燃剂、吸附剂、脱酸剂、光降解剂、绿色水处理剂等助剂使用,亦被称为“绿色安全水处理剂”。纳米氢氧化镁具有比表面积大、活性高及很强的吸附能力,能吸附工业废液中的重金属离子,还可一并处理工业废水中常见的有机物和络合物。同时,纳米氢氧化镁作为吸附剂还具有无毒、无害、无腐蚀、绿色环保等优点,可有效避免二次危害和污染。
本发明采用原位的方法将高吸附性的氢氧化镁与高效光催化剂还原氧化石墨烯复合,制备得到氢氧化镁/还原氧化石墨烯复合材料。该复合材料同时利用氢氧化镁密度大的特点,利于复合材料与染料污水的快速分离,有效减少分离时间。本发明的制备方法简单,成本低廉,并且通过该方法所制得的复合材料具有高校光催化性能及能实现多次循环利用。
发明内容
本发明的目的是提供一种具有高效光催化性能的氢氧化镁/还原氧化石墨烯复合材料的制备方法。本发明的另一目的是提供该材料光降解印染污水中有机污染物的高效应用。该复合材料具有极强的光催化降解效果,多次循环下仍有较好的光催化降解能力。另外,由于氢氧化镁密度较大,复合材料易从污水分离,为回收催化剂提供便利。
本发明是通过如下技术方案实现的:
一种氢氧化镁/还原氧化石墨烯复合材料的制备方法,包括以下步骤:
步骤一),制备氧化石墨烯悬浮液:取1-3质量份的天然石墨、50ml~150ml质量分数为98%的浓硫酸、7-21质量份的高锰酸钾分批加入反应器中,保持反应温度为0℃,强烈搅拌反应2h,再升温至50℃,反应10-12h;将反应物冷却至室温后倾入到30%质量分数的H2O2水溶液中,所述H2O2水溶液以冰水冷却;用30%稀盐酸洗涤反应产物,再分别用乙醇和去离子水洗涤、离心反应产物数次后得到氧化石墨烯;直接将氧化石墨烯分散于水中得到氧化石墨烯的悬浮液,所述氧化石墨烯的浓度范围控制在0.006~0.009g/mL;
步骤二)制备氢氧化镁/还原氧化石墨烯复合材料
将氧化石墨烯悬浮液倒入熔融的内酰胺中,在70℃下进行超声分散,超声分散时间为30min~60min;加入镁盐,磁力搅拌分散30~120min;在140~180℃下减压蒸馏除水,除水完成后冷却至100℃;缓慢加入碱性物质,在100℃下反应1.5~3h,使氧化石墨烯被还原为还原氧化石墨烯;反应结束后在70℃下离心分离内酰胺,所得的沉淀用去离子水洗涤、干燥后即得到氢氧化镁/还原氧化石墨烯复合材料;所述氢氧化镁/还原氧化石墨烯复合材料中氢氧化镁与还原氧化石墨烯的重量比为(10~100):100。
进一步的改进,所述步骤一)中氧化石墨烯的浓度范围控制为0.007g/mL。
进一步的改进,所述步骤二)中除水完成后缓慢加入碱性物质,在100℃下反应2.5h。
进一步的改进,所述镁盐为氯化镁、硝酸镁、醋酸镁、硫酸镁中的一种或几种的混合物。
进一步的改进,所述内酰胺为丁内酰胺、己内酰胺、辛内酰胺、十二内酰胺中的一种或几种的混合物。
进一步的改进,所述碱性物质为氢氧化锂、氢氧化钠、氢氧化钾中的一种或几种混合。
进一步的改进,所述氢氧化镁/还原氧化石墨烯复合材料中氢氧化镁与还原氧化石墨烯的重量比为30:100。
进一步的改进,镁离子与氢氧根的摩尔比为1:2。
一种使用氢氧化镁/还原氧化石墨烯复合材料去除印染污水中有机污染物的方法,使用氢氧化镁/还原氧化石墨烯复合材料吸附有机污染物,再使用紫外线照射氢氧化镁/还原氧化石墨烯复合材料,通过光催化反应降解有机污染物;再将氢氧化镁/还原氧化石墨烯复合材料洗涤干净,重复使用于吸附、降解有机污染物。
进一步的改进,所述有机污染物为亚甲基蓝、甲基橙、直接蓝86、反应型偶氮染料等中的任一种或多种。
与现有技术相比,本发明具有以下优点:
本发明的复合材料中氢氧化镁堆积成花朵状,直径约为40μm,氢氧化镁片厚度约为60-80nm(如图2)。在污水处理方面这种3D花朵状结构非常有利于与污水的充分接触和吸附,增加吸附效果,从而快速吸附降解。同时利用氢氧化镁密度大的特点,利于复合材料与染料污水的快速分离,有效减少分离时间。本发明的复合材料具有高效光催化性能能够,利用光催化反应可以快速降解有机污染物。而且可以进行多次循环利用,并可实现快速回收。
附图说明
图1为制备的氧化石墨烯的TEM图;
图2为氢氧化镁/还原氧化石墨烯复合材料的FESEM图;
图3为氢氧化镁/还原氧化石墨烯复合材料光降解亚甲基蓝曲线。
具体实施方式
实施例1
实施例1
高效光催化剂氢氧化镁/还原氧化石墨烯复合材料的制备
步骤一),制备氧化石墨烯悬浮液:取1-3质量份的天然石墨、50ml~150ml质量分数为98%的浓硫酸、7-21质量份的高锰酸钾分批加入反应器中,保持反应温度为0℃,强烈搅拌反应2h,再升温至50℃,反应10-12h;将反应物冷却至室温后倾入到30%质量分数的H2O2水溶液中,所述H2O2水溶液以冰水冷却;用30%稀盐酸洗涤反应产物,再分别用乙醇和去离子水洗涤、离心反应产物数次后得到氧化石墨烯;直接将氧化石墨烯分散于水中得到氧化石墨烯的悬浮液,所述氧化石墨烯的浓度为0.007g/mL;
步骤二),取20ml浓度为0.00835g/ml的自制氧化石墨烯(如图1)分散于熔融的100g己内酰胺中,70℃下超声分散30min,然后,加入3.045g的六水合氯化镁,磁力搅拌分散60min。混合物于150℃下减压蒸馏除水,完成后冷却至100℃,逐步加入1.2g氢氧化钠,在此温度下反应2.5h。反应过程中,氧化石墨烯被同步还原为还原氧化石墨烯(rGO)。反应结束后冷却至70℃离心分离己内酰胺,沉淀用去离子水洗涤10次,干燥得黑色氢氧化镁/还原氧化石墨烯复合材料。通过场发射扫描电镜可以看出,复合材料中氢氧化镁堆积成花朵状,直径约为40μm,氢氧化镁片厚度约为60-80nm(如图2)。在污水处理方面这种3D花朵状结构非常有利于与污水的充分接触和吸附,增加吸附效果,从而快速吸附降解。
实施例2
氢氧化镁/还原氧化石墨烯复合材料对于亚甲基蓝的光降解实验
首先,配置2.0*10-5M的亚甲基蓝水溶液,取20mg复合材料加入50mL亚甲基蓝溶液,黑暗环境下磁力搅拌30min以完全吸附。在365nm的紫外光照射5min,亚甲基蓝完全降解,溶液变为无色。并经过紫外可见吸收光谱测试,结果显示亚甲基蓝完全降解。其次,为检测复合材料的可循环利用能力,将悬浮液离心分离后得到的黑色固体,浸泡于10mL无水乙醇中磁力搅拌2h,离心洗涤后烘干,重复上述光催化步骤。结果显示(如图3),第二次循环过程仍可在5min内降解完全,第三次循环过程仍可在80min内降解完全,远高于同类催化剂,归因于其花朵状的三维结构。
以上实施例仅用于说明本发明,但不用来限制本发明的范围,凡是依据本发明的技术实质对以下实例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
Claims (10)
1.一种氢氧化镁/还原氧化石墨烯复合材料的制备方法,其特征在于,包括以下步骤:
步骤一),制备氧化石墨烯悬浮液:取1-3质量份的天然石墨、50ml~150ml质量分数为98%的浓硫酸、7-21质量份的高锰酸钾分批加入反应器中,保持反应温度为0℃,强烈搅拌反应2h,再升温至50℃,反应10-12h;将反应物冷却至室温后倾入到30%质量分数的H2O2水溶液中,所述H2O2水溶液以冰水冷却;用30%稀盐酸洗涤反应产物,再分别用乙醇和去离子水洗涤、离心反应产物数次后得到氧化石墨烯;直接将氧化石墨烯分散于水中得到氧化石墨烯的悬浮液,所述氧化石墨烯的浓度范围控制在0.006~0.009g/mL;
步骤二)制备氢氧化镁/还原氧化石墨烯复合材料
将氧化石墨烯悬浮液倒入熔融的内酰胺中,在70℃下进行超声分散,超声分散时间为30min~60min;加入镁盐,磁力搅拌分散30~120min;在140~180℃下减压蒸馏除水,除水完成后冷却至100℃;缓慢加入碱性物质,在100℃下反应1.5~3h,使氧化石墨烯被还原为还原氧化石墨烯;反应结束后在70℃下离心分离内酰胺,所得的沉淀用去离子水洗涤、干燥后即得到氢氧化镁/还原氧化石墨烯复合材料;所述氢氧化镁/还原氧化石墨烯复合材料中氢氧化镁与还原氧化石墨烯的重量比为(10~100):100。
2.根据权利要求1所述的一种氢氧化镁/还原氧化石墨烯复合材料的制备方法,其特征在于,所述步骤一)中氧化石墨烯的浓度范围控制为0.007g/mL。
3.根据权利要求1所述的一种氢氧化镁/还原氧化石墨烯复合材料的制备方法,其特征在于,所述步骤二)中除水完成后缓慢加入碱性物质,在100℃下反应2.5h。
4.根据权利要求1所述的一种氢氧化镁/还原氧化石墨烯复合材料的制备方法,其特征在于,所述镁盐为氯化镁、硝酸镁、醋酸镁、硫酸镁中的一种或几种的混合物。
5.根据权利要求1所述的一种氢氧化镁/还原氧化石墨烯复合材料的制备方法,其特征在于,所述内酰胺为丁内酰胺、己内酰胺、辛内酰胺、十二内酰胺中的一种或几种的混合物。
6.根据权利要求1所述的一种氢氧化镁/还原氧化石墨烯复合材料的制备方法,其特征在于,所述碱性物质为氢氧化锂、氢氧化钠、氢氧化钾中的一种或几种混合。
7.根据权利要求1所述的一种氢氧化镁/还原氧化石墨烯复合材料的制备方法,其特征在于,所述氢氧化镁/还原氧化石墨烯复合材料中氢氧化镁与还原氧化石墨烯的重量比为30:100。
8.根据权利要求1所述的一种氢氧化镁/还原氧化石墨烯复合材料的制备方法,其特征在于,镁离子与氢氧根的摩尔比为1:2。
9.一种使用氢氧化镁/还原氧化石墨烯复合材料去除印染污水中有机污染物的方法,其特征在于,使用氢氧化镁/还原氧化石墨烯复合材料吸附有机污染物,再使用紫外线照射氢氧化镁/还原氧化石墨烯复合材料,通过光催化反应降解有机污染物;再将氢氧化镁/还原氧化石墨烯复合材料洗涤干净,重复使用于吸附、降解有机污染物。
10.如权利要求9所述的一种使用氢氧化镁/还原氧化石墨烯复合材料去除印染污水中有机污染物的方法,其特征在于,所述有机污染物为亚甲基蓝、甲基橙、直接蓝86、反应型偶氮染料等中的任一种或多种。
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