CN106540716A - 一种纳米材料CuS/Ni的制备方法及应用 - Google Patents
一种纳米材料CuS/Ni的制备方法及应用 Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 105
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 55
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Abstract
本发明为一种纳米材料CuS/Ni的制备方法及其应用。该方法包括以下步骤:步骤一、将得到的Ti‑Cu‑Ni非晶合金条带、清洗,干燥;步骤二、将干燥的Ti‑Cu‑Ni非晶合金条带与硫酸一同置于密闭容器中进行反应,反应温度为80‑120℃,反应时间为36‑72h,将反应结束后制得的样品用去离子水冲洗,然后置于40‑70℃下干燥后,得到的粉末即为纳米级团簇结构的硫化铜/镍催化剂。本发明操作简便易行,实施费用低,操作过程易控制,是一种简便经济的合成方法;得到的硫化铜/镍具有较高光催化活性,非常适用于光催化降解染料。
Description
技术领域:
本发明涉及一种纳米级团簇结构的硫化铜/镍的制备方法,该硫化铜/镍应用于光催化领域。
背景技术:
形貌特殊的微纳米材料具有优异的光学、电学、磁学和催化等性能,在微纳米器件上具有巨大的应用前景。硫化铜作为一种宽带隙半导体材料,其带隙宽度约为2.0ev。该硫化铜因其具有一定的催化活性、光致发光等特殊的物理、化学性能,在催化、太阳能电池、超导体、气敏传感器等领域有非常大的应用潜力。目前其合成方法以水热法为主,例如一种硫化铜纳米囊颗粒的制备方法,包括以下步骤:(1)称取L-半胱氨酸和Cu(NO3)2·3H2O,分别溶于双蒸馏水中;(2)将Cu(NO3)2溶液逐滴加入L-半胱氨酸溶液中,于常温下搅拌,得到混合溶液;(3)称取Na2S2O3溶于双蒸馏水中,溶解均匀,得到Na2S2O3溶液;将Na2S2O3溶液逐滴加入混合溶液中,得到深棕色的混合溶液;(4)深棕色的混合溶液在80~100℃反应;(5)反应结束后经离心、清洗、干燥后得到黑色沉淀,即为硫化铜纳米囊颗粒。这种方法制作过程可控性不强,制得的硫化铜颗粒形状不是十分规则。另外,目前还有化学沉积法、声化学法和模板法等,这些合成方法,一般需要较高的反应温度、反应压力、较长的反应时间以及特定的反应装置,这些条件限制了纳米硫化铜在实际生产中的应用,因此寻找操作过程简便易行,反应条件温和,成本费用低的硫化铜纳米材料的制备方法非常重要。
纳米级团簇材料的制备方法有很多种,脱合金法由于其操作过程可控,且容易操作,生产成本低,且制得的纳米级团簇材料具有比表面积大而且形状规则等优势而成为近几年来应用比较广泛的方法之一。脱合金法,是指对电极电位相差较大的多元固溶体合金进行选择性的腐蚀,通过电解液作用将其中较活泼的元素进行选择性溶解,剩下的金属经团聚生长最终形成纳米级团簇结构。脱合金的制备方法具有操作方法可控,且容易操作等优点,并且可以通过改变工艺参数和后续处理来控制纳米结构的大小和形状。这种方法中所用的合金多为非晶态合金,在非晶态合金中元素都以固溶体状态存在而且非晶态合金的性质可以随着合金中元素的改变而改变,因此非晶态合金的脱合金较晶态合金更有优势。
发明内容
本发明的目的为针对当前技术中存在的操作可控性不足,提供了一种操作过程可控,生产费用低、制备过程简单易行的以Ti-Cu-Ni非晶合金条带和浓硫酸为原料,通过化学脱合金法制备具有纳米团簇结构的硫化铜/镍的方法。本发明以非晶合金条带为原料,制备出在纯硫化铜基础上掺杂镍的催化剂,之所以掺杂镍是因为镍可以作为电子捕获剂,结合光生电子用以提高其界面效应,有效地阻止光生电子-空穴对的简单复合,从而提高光生电子和空穴的产率,进而提高催化活性。用非晶合金条带所制得的硫化铜/镍粉末形状规则,比表面积大。本发明是一种简易经济的合成方法。所得纳米级团簇结构的硫化铜/镍具有较好的光催化降解染料性能。
本发明的技术方案为:
一种纳米材料CuS/Ni的制备方法,包括以下步骤:
步骤一、按照以下原子百分比制备Ti-Cu-Ni非晶合金条带:Ti的含量为50%,Cu的含量为39%-50%,Ni的含量为5-11%;将得到的厚度为10μm-30μm、宽度为5-10mm的Ti-Cu-Ni非晶合金条带裁剪成长度为2cm-3cm的条带;该条带在无水乙醇中超声8~12min后,用去离子水进行清洗,然后置于空气中,合金条带干燥后备用;
步骤二、将干燥的Ti-Cu-Ni非晶合金条带与硫酸一同置于密闭容器中进行反应,反应温度为80-120℃,反应时间为36-72h,将反应结束后制得的样品用去离子水冲洗,然后置于40-70℃下干燥后,得到的粉末即为纳米级团簇结构的硫化铜/镍催化剂。
所述的硫酸的浓度优选为10-15M。
所述的步骤二中的物料配优选为每0.1-0.3克Ti-Cu-Ni非晶合金条带加入到25-35ml硫酸中。
所述的一种CuS/Ni的应用,应用于可见光下降解有机染料,特别是亚甲基蓝。
本发明的有益效果是:纳米尺寸的硫化铜制备方法有很多种,脱合金法由于其操作可控性强,简单易行,制得的纳米级团簇材料具有比表面积大而且形状规则,成本低等优势而成为近几年来应用比较广泛的方法之一。脱合金法,是指对电极电位相差较大的多元固溶体合金进行选择性的腐蚀,通过电解液作用将其中较活泼的元素进行选择性溶解,剩下的金属经团聚生长最终形成纳米级团簇结构。在此基础上,通过理论研究与多次尝试后发现加入镍元素后,增加了催化剂捕获电子的能力,可以提高催化剂的界面效应,提高光生电子和空穴的产率,从而提高催化能力。脱合金的制备方法具有操作过程可控、方法简单易行、费用低等优点,并且可以通过改变工艺参数和后续处理来控制纳米结构的大小和形状。这种方法中所用的合金多为非晶态合金,在非晶态合金中元素都以固溶体状态存在而且非晶态合金的性质可以随着合金中元素的改变而改变,因此非晶态合金的脱合金较晶态合金更有优势。
相对于目前的技术,本发明的优点:(1)该硫化铜/镍粉体制备方法操作简便易行,实施费用低,操作过程易控制,是一种简便经济的合成方法;(2)从制备得到的硫化铜/镍的微观形貌照片可以看出纳米级团簇结构形状规则,大小均匀;(3)通过硫化铜/镍对亚甲基蓝的降解曲线可以得出该纳米级团簇结构的硫化铜/镍具有较高光催化活性,非常适用于光催化降解染料。
附图说明
图1为实施例1-3中得到的硫化铜/镍的微观形貌照片,其中,图1(a)为实施例1制得的硫化铜/镍的微观形貌照片;图1(b)为实施例2制得的硫化铜/镍的微观形貌照片;图1(c)为实施例3制得的硫化铜/镍的微观形貌照片。
图2为实施例1-3中得到的硫化铜/镍的XRD图。
图3为实施例1-3中得到的硫化铜/镍对亚甲基蓝的降解图。
具体实施方式
下面通过具体实施案例对本发明做具体的说明。下面所提供的具体实施案例是为了更加系统的了解本发明,而不是限制本发明。
实施例1:
对Ti-Cu-Ni非晶态合金条带进行化学脱合金法,制备纳米级团簇结构的硫化铜/镍催化剂。其制备步骤如下:
步骤一、按照以下原子百分比含量制备Ti-Cu-Ni非晶合金条带:Ti的含量为50%,Cu的含量为45%,Ni的含量为5%,利用单辊甩带法制备出非晶合金条带。
步骤二、将步骤一得到的厚度为20μm、宽度为6mm Ti50Cu45Ni5非晶合金条带裁剪成长度为2cm的条带;该条带在无水乙醇中超声10min后,用去离子水清洗,然后置于空气中,合金条带干燥后备用;
步骤三、将步骤二制备得到的Ti50Cu45Ni5非晶合金条带称取0.2g与27.5ml的摩尔浓度为15M的硫酸水溶液一同置于密闭容器中,并放于90℃干燥箱保温48h,反应结束后得到的样品用去离子水冲洗,在60℃的干燥箱中干燥,干燥后得到的粉末即为纳米级团簇结构的硫化铜/镍粉体。
图1中的(a)示出了利用S-4800型场发射电子扫描显微镜获得的实施例1制备得到的硫化铜/镍的微观形貌照片,图2中示出了利用Rigaku D/max-Ra型X射线衍射仪获得的实施例1制备得到的硫化铜/镍的XRD图。
将本发明制备得到的纳米级团簇结构的硫化铜/镍应用在光催化降解染料中,步骤是:
(1)按照1:3的配比配置亚甲基蓝染料和去离子水得到亚甲基蓝溶液;
(2)取6ml亚甲基蓝溶液,加入实施例1制得的CuS/Ni粉末10mg,电磁搅拌暗反应5min;加入2ml的双氧水,搅拌20-30s取该溶液作为0时刻的溶度;
(3)依次取每2min光反应后的溶液,取至10min截止,在紫外可见分光光度计中进行检测亚甲基蓝的光降解程度。
图3中示出了利用UV-6100紫外可见分光光度计获得的实施例1制备得到的硫化铜/镍对亚甲基蓝的降解曲线。
实施例2:
对Ti-Cu-Ni非晶态合金条带进行化学脱合金法,制备纳米级团簇结构的硫化铜/镍催化剂。其制备步骤如下:
步骤一、按照以下原子百分比含量制备Ti-Cu-Ni非晶合金条带:Ti的含量为50%,Cu的含量为42%,Ni的含量为8%,利用单辊甩带法制备出非晶合金条带。
步骤二、将步骤一得到的厚度为20μm、宽度为6mm的Ti50Cu42Ni8非晶合金条带裁剪成长度为2cm的条带;该条带在无水乙醇中超声10min后,用去离子水清洗,然后置于空气中,合金条带干燥后备用;
步骤三、将步骤二制备得到的Ti50Cu42Ni8非晶合金条带称取0.2g与27.5ml的摩尔浓度为15M的硫酸水溶液一同置于密闭容器中,并放于90℃干燥箱保温48h,反应结束后得到的样品用去离子水冲洗,在60℃的干燥箱中干燥,干燥后得到的粉末即为纳米级团簇硫化铜/镍粉体。
图1中的(b)示出了利用S-4800型场发射电子扫描显微镜获得的实施例2制备得到的硫化铜/镍的微观形貌照片,图2中示出了利用Rigaku D/max-Ra型X射线衍射仪获得的实施例2制备得到的硫化铜/镍的XRD图。
将本发明制备得到的纳米级团簇结构的硫化铜/镍应用在光催化降解染料中,步骤是:
(1)按照1:3的配比配置亚甲基蓝染料和去离子水得到亚甲基蓝溶液;
(2)取6ml亚甲基蓝溶液,加入实施例2制得的CuS/Ni粉末10mg,电磁搅拌暗反应5min;加入2ml的双氧水,搅拌20-30s取该溶液作为0时刻的溶度;
(3)依次取每2min光反应后的溶液,取至10min截止,在紫外可见分光光度计中进行检测亚甲基蓝的光降解程度。
图3中示出了利用UV-6100紫外可见分光光度计获得的实施例2制备得到的硫化铜/镍对亚甲基蓝的降解曲线。
实施例3:
对Ti-Cu-Ni非晶态合金条带进行化学脱合金法,制备纳米级团簇结构的硫化铜/镍催化剂。其制备步骤如下:
步骤一、按照以下原子百分比含量制备Ti-Cu-Ni非晶合金条带:Ti的含量为50%,Cu的含量为39%,Ni的含量为11%,利用单辊甩带法制备出非晶合金条带。
步骤二、将步骤一得到的厚度为20μm、宽度为6mm的Ti50Cu39Ni11非晶合金条带裁剪成长度为2cm的条带;该条带在无水乙醇中超声10min后,用去离子水清洗,然后置于空气中,合金条带干燥后备用;
步骤三、将步骤二制备得到的Ti50Cu39Ni11非晶合金条带称取0.2g与27.5ml的摩尔浓度为15M的硫酸水溶液一同置于密闭容器中,并放于90℃干燥箱保温48h,反应结束后得到的样品用去离子水冲洗,在60℃的干燥箱中干燥,干燥后得到的粉末即为纳米级团簇结构的硫化铜/镍粉体。
图1中的(c)示出了利用S-4800型场发射电子扫描显微镜获得的实施例3制备得到的硫化铜/镍的微观形貌照片,图2中示出了利用Rigaku D/max-Ra型X射线衍射仪获得的实施例3制备得到的硫化铜/镍的XRD图。
将本发明制备得到的纳米级团簇结构的硫化铜/镍应用在光催化降解染料中,步骤是:
(1)按照1:3的配比配置亚甲基蓝染料和去离子水得到亚甲基蓝溶液;
(2)取6ml亚甲基蓝溶液,加入实施例3制得的CuS/Ni粉末10mg,电磁搅拌暗反应5min;加入2ml的双氧水,搅拌20-30s取该溶液作为0时刻的溶度;
(3)依次取每2min光反应后的溶液,取至10min截止,在紫外可见分光光度计中进行检测亚甲基蓝的光降解程度。
图3中示出了利用UV-6100紫外可见分光光度计获得的实施例3制备得到的硫化铜/镍对亚甲基蓝的降解曲线。
通过上述各实施例和图1至图3可以得到本发明制备得到的纳米级团簇结构的硫化铜/镍。其中的纳米团簇结构形状规则,大小均匀;在SEM图中,可看出由于成分中所含Ni含量不同,CuS/Ni的形貌也不相同,(a)、(c)为较均匀的纳米颗粒,纳米颗粒直径大概在300nm左右,部分颗粒团簇在一起,颗粒与颗粒间也不致密,存在一定的孔隙。(b)为片状结构堆叠而成,片状结构的长度尺寸为300-500nm,厚度为10-50nm。此外,纳米片堆叠的并不致密,片层之间存在大量孔隙,孔隙直径为50-150nm,由于这些孔隙的存在,使得此种CuS/Ni具有较大的比表面积,并能够提供较多的催化活性位点,从而有着较高的光催化活性。
图2是脱合金法合成的纳米CuS/Ni的XRD图谱,从图中可以发现实施例1,2,3都检测到了CuS的(100),(101),(102),(103),(006),(110),(108)和(116)晶面,与标准卡片一致,说明脱合金法能得到CuS晶体,但是由于浓硫酸浸泡后得到的粉末中Ni的含量很少,XRD中并没有检测到它的特征峰。
综合上面的实施例,由图3可得知实施例1,2,3在10min的光催化降解亚甲基蓝的实验中光催化效果相差不大,相差不到1%。实施例1,原始非晶条带中Ni含量为5%,前6min反应速度基本不变,反应较快,6-10min降解趋于平缓,10min后降解率达到98.9%。实施例2,原始非晶条带中Ni含量为8%,光催化降解亚甲基蓝速度最慢,10min后降解量达到98.4%。实施例3,原始非晶条带中Ni含量为11%,光催化降解速度最快,在6min时降解率就达到了96%,10min时达到98%。综合来看,实施例3的效果最好。所以,改变Ti-Cu-Ni原子比,减少Cu原子在条带中的原子百分比含量;增加Ni原子在条带中的原子百分比含量到一定程度,有助于提高CuS/Ni粉末的光降解亚甲基蓝的性能。
通过以上介绍结合附图对本发明进行了描述,但上述的具体实施案例仅仅是示意性的不能够依据实施案例限制本发明。本领域的相关技术人员依据本发明或不脱离本发明宗旨的情况下,还可以进行多种多样的变化,这些变形都在本发明的保护之内。
本发明未尽事宜为公知技术。
Claims (5)
1.一种纳米材料CuS/Ni的制备方法,其特征为该方法包括以下步骤:
步骤一、按照以下原子百分比制备Ti-Cu-Ni非晶合金条带:Ti的含量为50%,Cu的含量为39%-50%,Ni的含量为5-11%;将得到的厚度为10μm-30μm、宽度为5-10mm的Ti-Cu-Ni非晶合金条带裁剪成长度为2cm-3cm的条带;该条带在无水乙醇中超声8~12min后,用去离子水进行清洗,然后置于空气中,合金条带干燥后备用;
步骤二、将干燥的Ti-Cu-Ni非晶合金条带与硫酸一同置于密闭容器中进行反应,反应温度为80-120℃,反应时间为36-72h,将反应结束后制得的样品用去离子水冲洗,然后置于40-70℃下干燥后,得到的粉末即为纳米级团簇结构的硫化铜/镍。
2.如权利要求1所述的纳米材料CuS/Ni的制备方法,其特征为所述的硫酸的浓度优选为10-15M。
3.如权利要求1所述的纳米材料CuS/Ni的制备方法,其特征为所述的步骤二中的物料配优选为每0.1-0.3克Ti-Cu-Ni非晶合金条带加入到25-35ml硫酸中。
4.如权利要求1所述的纳米材料CuS/Ni的应用方法,其特征为应用于可见光下有机染料的降解。
5.如权利要求4所述的纳米材料CuS/Ni的应用方法,其特征为优选为应用于可见光下降解亚甲基蓝。
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