CN110227484A - 一种掺杂型纳米二氧化锰复合材料,制备方法及其应用 - Google Patents
一种掺杂型纳米二氧化锰复合材料,制备方法及其应用 Download PDFInfo
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 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 abstract description 25
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001868 water Inorganic materials 0.000 claims abstract description 13
- 230000015556 catabolic process Effects 0.000 claims abstract description 11
- 238000006731 degradation reaction Methods 0.000 claims abstract description 11
- 239000011572 manganese Substances 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 230000001699 photocatalysis Effects 0.000 claims abstract description 7
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000013049 sediment Substances 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 10
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- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 claims 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims 1
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Abstract
本发明属于一种掺杂型纳米二氧化锰复合材料,公开了一种Ni掺杂的复合纳米光催化材料及其光催化氧化降解亚甲基蓝的应用。采用一步法合成技术,按一定Mn7+:Mn4+的摩尔比及一定Ni:Mn的物质量的比称取高锰酸钾、MnSO4·H2O以及NiCl2·6H2O并用去离子水将其分别配置成溶液,利用氧化还原法,按一定顺序投加所配置的溶液进行反应生成沉淀物,经离心洗涤干燥后得到团簇球状的Ni掺杂纳米二氧化锰催化剂。该催化剂在光催化氧化降解亚甲基蓝中显示出了优越的催化活性。
Description
技术领域:
本发明属于纳米材料制备技术及污水处理领域,具体涉及一种Ni掺杂的纳米光催化剂及其光催化氧化降解亚甲基蓝的应用。
背景技术:
随着生活质量的提升,人们对服饰装扮和制革等染料的需求日趋提高,印染行业成为了当下日渐火爆的行业,但其产生的印染废水如未经有效的处理大量排入水环境,将会对生态环境和人类健康造成严重的危害。在种类繁多的染料中,亚甲基蓝是一种典型的染料,其大量运用于各种物品的染色和着色中,摄入亚甲基蓝会对人体和动物的眼睛造成严重损害,并且还可能引起神经紊乱,恶心呕吐等有害人体健康的不良症状。因此,降解印染废水中的亚甲基蓝使其转变成无害的物质具有重要的意义。
目前,国内外对印染废水的处理方法主要有以物理吸附法、微生物分解法及化学氧化法为主。物理吸附法主要采用活性炭这一类吸附性强的材料,尽管这种处理方法耗能低,短期内效果显著,但是其吸附产物易脱附,易造成二次污染;微生物分解法主要依靠微生物的代谢活动对污染物分解,速度很慢且分解不彻底,甚至存在潜在的污染源;化学氧化法中的光催化氧化是一种清洁有效的处理方法,其处理效果受到催化剂的制约。因此,对于传统光催化剂的改性以及新型光催化剂的研制是十分必要的。
发明内容:
本发明的目的是提供一种新型复合光催化剂的制备方法,并将其应用于光催化氧化降解亚甲基蓝,其制备方法简单,催化降解效率高。
本发明利用氧化还原法,将Ni掺杂于纳米二氧化锰,得到了光催化性能优异的新型复合纳米光催化剂。
为实现上述目的,本发明采用的技术方案为:
一种掺杂型纳米二氧化锰复合材料,该复合材料为Ni掺杂纳米二氧化锰;所述的Ni掺杂纳米二氧化锰的Ni掺杂量为5%,其为团簇的纳米球状多孔结构,孔径大小为3.381nm,比表面积为63.297m2/mg,孔容为0.068cc/g,表面具有细纤维棒状的形貌结构存在,细纤维棒状结构长度为1~3μm,纳米球与纳米球之间通过纤维丝状结构连接或者包覆在一起。
本发明所述的新型复合光催化剂的制备方法包括以下几个步骤:
(1)按Mn7+∶Mn4+反应时的摩尔比2∶3称取一定量的高锰酸钾及MnSO4·H2O,用去离子水将所称量的高锰酸钾、MnSO4·H2O配置成溶液;按照Ni∶Mn的物质的量比为5%称取一定量的NiCl2·6H2O,用去离子水将所称量的NiCl2·6H2O配置成溶液。
(2)将步骤(1)配置的高锰酸钾溶液至于磁力搅拌器上加热搅拌溶解;
(3)在高速搅拌条件下,向步骤(2)所述高锰酸钾溶液中逐滴加入步骤(1)所配置的NiCl2·6H2O溶液至滴加完毕,完成滴加后调大磁力搅拌器的转速;
(4)在剧烈搅拌条件下,向步骤(3)所述反应溶液中逐滴加入步骤(1)所配置的MnSO4·H2O溶液至滴加完毕,完成滴加后,在沸腾的状态下剧烈搅拌2小时至生成沉淀物;
(5)将步骤(4)所述的溶液在室温下自然冷却,冷却后离心得到沉淀物质;
(6)将步骤(5)所述的沉淀物质用去离子水反复洗涤,而后在80℃的条件下恒温干燥12h,即可得到Ni掺杂纳米二氧化锰复合材料。
本发明还提供一种将上述掺杂型纳米二氧化锰复合材料光催化氧化降解亚甲基蓝的应用。具体步骤为:将Ni掺杂纳米二氧化锰复合材料投加至亚甲基蓝溶液中,反应溶液置于紫外光条件下并伴随磁力搅拌,反应3h即可完成对亚甲基蓝的氧化降解。
其中,所述Ni掺杂纳米二氧化锰复合材料投加的质量为10mg~90mg。
优选的,所述Ni掺杂纳米二氧化锰复合材料投加的质量为20mg。
进一步的,所述亚甲基蓝溶液的体积为120ml,浓度为10mg/L。
进一步的,所述反应溶液的PH为3.0~11.0。
进一步的,所述反应溶液的温度为25℃~65℃。
进一步的,所述磁力搅拌转速为300r/min。
相对于现有的技术,本发明所述的Ni掺杂纳米二氧化锰光催化剂的制备及应用具有以下优势:
本发明采用Ni掺杂纳米二氧化锰制成新型复合光催化材料,制备过程简单,催化降解效率高。利用所述光催化剂降解亚甲基蓝,在提高降解效率的同时,有效的缩短了反应时间,减小了PH和反应温度对亚甲基蓝去除率的影响,减少了酸碱试剂的使用,甚至可以省去pH调节环节,降低运行成本。
附图说明:
图1:为实施例1制得的Ni掺杂纳米氧化锰复合材料的电镜扫描图。
图2:为实施例1制得的Ni掺杂纳米氧化锰复合材料的电镜扫描图。
图3:为实施例1制得的Ni掺杂纳米氧化锰复合材料的电镜扫描图。
图4:为实施例1制得的Ni掺杂纳米氧化锰复合材料的电镜扫描图。
具体实施方式:
除有定义外,以下实施例中所用的技术术语具有与本发明所属领域技术人员普遍理解的相同含义。以下实施例中所用的试验试剂,如无特殊说明,均为常规生化试剂,所属实验方法,如无特殊说明,均为常规方法。
下面结合实施例来详细说明本发明及其应用
实施例1
按Mn7+∶Mn4+反应时的摩尔比2∶3称取一定量的高锰酸钾溶及MnSO4·H2O于去离子水中配成溶液,并按照Ni∶Mn的物质的量比为5%称取一定量的NiCl2·6H2O溶于去离子水中配置成溶液。在磁力搅拌器上先将高锰酸钾加热搅拌溶解,然后在高速搅拌下向其中逐滴加入NiCl2·6H2O溶液,滴加完成后将调大磁力搅拌器的转速,在剧烈搅拌并加热的情况下逐滴加入MnSO4·H2O溶液至滴加完毕后,在沸腾的状态下剧烈搅拌小时生成沉淀,室温下自然冷却离心后用去离子水反复洗涤,而后在80℃的条件下恒温干燥12h,得到Ni掺杂纳米二氧化锰。
实施例2
量取一定量10mg/L的亚甲基蓝样品用孔径为0.45μm的微滤膜过滤后,在664.0hm波长下测定其初始吸光度A0=1.670。量取同样的10mg/L亚甲基蓝溶液120ml于250ml石英烧杯中,调整其PH值到9,称取20mg制备的Ni掺杂纳米二氧化锰并将其投加至量取的亚甲基蓝溶液中,在温度为25℃、300r/min磁力搅拌,紫外灯照射条件下,每隔20min取5ml反应溶液,用孔径为0.45μm的微滤膜过滤后,在664.0nm波长下测定其吸光度A,根据公式η=(A0-A)/A0×100%(其中η为去除率)计算出去除率。反应20min后,测得反应溶液的吸光度A=0.220,计算出去除率为86.8%;反应3h后,测得反应溶液的吸光度A=0.013,计算出去除率为99.2%。
实施例3
量取一定量10mg/L的亚甲基蓝样品用孔径为0.45μm的微滤膜过滤后,在664.0nm波长下测定其初始吸光度A0=1.670。量取同样的10mg/L亚甲基蓝溶液120ml于250ml石英烧杯中,调整其PH值到9,称取30mg制备的Ni掺杂纳米二氧化锰并将其投加至量取的亚甲基蓝溶液中,在温度为25℃、300r/min磁力搅拌,紫外灯照射条件下,每隔20min取5ml反应溶液,用孔径为0.45μm的微滤膜过滤后,在664.0nm波长下测定其吸光度A,根据公式η=(A0-A)/A0×100%(其中η为去除率)计算出去除率。反应20min后,测得反应溶液的吸光度A=0.15,计算出去除率为91.0%;反应3h后,测得反应溶液的吸光度A=0.009,计算出去除率为99.5%。
实施例4
量取一定量10mg/L的亚甲基蓝样品用孔径为0.45μm的微滤膜过滤后,在664.0nm波长下测定其初始吸光度A0=1.855。量取同样的10mg/L亚甲基蓝溶液120ml于250ml石英烧杯中,调整其PH值到7,称取20mg制备的Ni掺杂纳米二氧化锰并将其投加至量取的亚甲基蓝溶液中,在温度为25℃、300r/min磁力搅拌,紫外灯照射条件下,每隔20min取5ml反应溶液,用孔径为0.45μm的微滤膜过滤后,在664.0nm波长下测定其吸光度A,根据公式η=(A0-A)/A0×100%(其中η为去除率)计算出去除率。反应20min后,测得反应溶液的吸光度A=0.103,计算出去除率为94.5%;反应3h后,测得反应溶液的吸光度A=0.008,计算出去除率为99.6%。
实施例5
量取一定量10mg/L的亚甲基蓝样品用孔径为0.45μm的微滤膜过滤后,在664.0nm波长下测定其初始吸光度A0=1.800。量取同样的10mg/L亚甲基蓝溶液120ml于250ml石英烧杯中,调整其PH值到7,称取20mg制备的Ni掺杂纳米二氧化锰并将其投加至量取的亚甲基蓝溶液中,在温度为35℃、300r/min磁力搅拌,紫外灯照射条件下,每隔20min取5ml反应溶液,用孔径为0.45μm的微滤膜过滤后,在664.0nm波长下测定其吸光度A,根据公式η=(A0-A)/A0×100%(其中η为去除率)计算出去除率。反应20min后,测得反应溶液的吸光度A=0.449,计算出去除率为76.0%;反应3h后,测得反应溶液的吸光度A=0.105,计算出去除率为94.2%。
从实施例1-5中可以看出,本发明采用Ni掺杂纳米二氧化锰制成新型复合光催化材料的制备过程简单,且催化降解效率高。同时可以看出,不同条件下利用所述光催化剂降解处理亚甲基蓝,在反应20min后的去除率均能达到75%以上,反应3h后的去除率均能超过90%,有效的缩短了反应的时间,减小了PH和反应温度对亚甲基蓝去除率的影响,减少酸碱试剂的使用,甚至可以省去pH调节环节,降低运行成本。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (5)
1.一种掺杂型纳米二氧化锰复合材料,其特征在于,该复合材料为Ni掺杂纳米二氧化锰;所述的Ni掺杂二氧化锰复合材料为团簇的纳米球状多孔结构,表面具有细纤维棒状的形貌结构存在,纳米球与纳米球之间通过过纤维丝状结构连接或者包覆在一起。
2.权利要求1所述的Ni掺杂纳米二氧化锰复合材料,其特征在于,Ni掺杂量为5%。
3.权利要求1-2任一项所述Ni掺杂纳米二氧化锰复合材料的制备方法,其特征在于,包括以下步骤:
(1)按Mn7+∶Mn4+反应时的摩尔比2∶3称取一定量的高锰酸钾及MnSO4·H2O,用去离子水将所称量的高锰酸钾、MnSO4·H2O配置成溶液;按照Ni∶Mn的物质的量比为5%称取一定量的NiCl2·6H2O,并用去离子水将所称量的NiCl2·6H2O配置成溶液;
(2)将步骤(1)配置的高锰酸钾溶液置于磁力搅拌器上加热搅拌溶解;
(3)高速搅拌条件下,向步骤(2)所述高锰酸钾溶液中逐滴加入步骤(1)所配置的NiCl2·6H2O溶液至滴加完毕;
(4)向步骤(3)所述反应溶液中逐滴加入步骤(1)所配置的MnSO4·H2O溶液至滴加完毕,在沸腾的状态下剧烈搅拌2小时至生成沉淀物;
(5)将步骤(4)所述的反应溶液在室温下自然冷却,冷却后离心得到沉淀物质;
(6)将步骤(5)所述的沉淀物质用去离子水反复洗涤,而后在80℃的条件下恒温干燥12h,即可得到Ni掺杂纳米二氧化锰复合材料。
4.权利要求1-3任一项所述Ni掺杂纳米二氧化锰复合材料在光催化氧化降解亚甲基蓝的应用。
5.权利要求4中所述应用,其特征在于,具体步骤如下:将10mg~90mg的Ni掺杂纳米二氧化锰复合材料投加至120ml 10mg/L的亚甲基蓝溶液中,反应溶液置于紫外光照射下并伴随300r/min磁力搅拌,反应PH为3.0~11.0,反应温度为25℃~65℃,反应3h即可完成对亚甲基蓝的氧化降解。
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