CN105709780B - 一种Sn1-0.5xCuxS2纳米花及其制备和应用 - Google Patents
一种Sn1-0.5xCuxS2纳米花及其制备和应用 Download PDFInfo
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Abstract
本发明涉及一种Sn1‑0.5xCuxS2纳米花及其制备和应用;属于特种纳米材料设计制备技术领域。本发明所述纳米花的化学式为Sn1‑0.5xCuxS2,其中x的取值为0.01‑0.25。所述纳米花由Sn1‑ 0.5xCuxS2纳米片通过相互镶嵌或贯穿组成。其直径为1‑5μm、比表面积为63‑83㎡/g。其制备方法为:按设计的组分配取Sn源、Cu源和S源后,将配取的Sn源、Cu源和S源加入溶剂中混合均匀,得到混合溶液,再将混合溶液置于反应釜中,于160‑200℃反应,得到Sn1‑0.5xCuxS2纳米花。本发明所设计Sn1‑0.5xCuxS2纳米花可用于催化分解有机物。本发明组份设计合理,制备工艺简单,所得产品性能优良、稳定,便于大规模的工业化应用。
Description
技术领域
本发明涉及一种Sn1-0.5xCuxS2纳米花及其制备和应用;属于特种纳米材料设计制备技术领域。
背景技术
随着经济的飞速增长,能源短缺和环境污染成为困扰人类的两大问题。不解决能源短缺,人类的发展进步将受到阻碍;不解决环境污染,人类的生存将岌岌可危。因此,世界各国投入了巨大的人力、物力,希望改变这种困境。太阳能是目前所知储量丰富的能源之一,半导体光催化材料可以将太阳能转化为化学能和降解有机或重金属污染物,半导体光催化材料得到了广泛研究。
在光催化降解方面,二氧化钛是被广泛研究的半导体光催化材料之一,归因于其具有许多优良的性质,包括价廉,低毒,高的化学和光学稳定性,但由于其能带隙较宽(锐钛矿: 3.2eV;金红石:3.0eV),只能吸收紫外光,限制了其实际应用。因此,基于应用和经济的目的,需要寻找能够有效利用太阳能可见光催化剂。具有窄带隙的金属硫化物是较好的选择,在硫化物中CdS研究较多,但镉化合物具有致癌风险,限制了其实际应用。SnS2廉价无毒,并且SnS2具有2.1ev左右的禁带宽度,光响应范围大,几乎可以利用全部可见光。
SnS2纳米材料的制备方法有许多,如张亚飞等人(103373742A)水热制备的SnS2纳米材料;张永才(103623845A)等人制备的SnS2/CuS复合催化剂在降解含六价铬离子的废水。但上述方法要么存在制备工艺复杂、要么存在所制备成品的性能不佳等问题。
发明内容
本发明针对现有技术存在的不足之处,首次合成了固溶Sn1-0.5xCuxS2纳米花并同时提供该 Sn1-0.5xCuxS2纳米花的制备方法和应用。
本发明一种Sn1-0.5xCuxS2纳米花,所述纳米花的化学式为Sn1-0.5xCuxS2,其中x的取值为0.001-0.3、优选为0.01-0.25、优选为0.01-0.22。
本发明一种Sn1-0.5xCuxS2纳米花,所述纳米花由Sn1-0.5xCuxS2纳米片通过相互镶嵌和/或贯穿组成。
本发明一种Sn1-0.5xCuxS2纳米花,所述纳米花的直径为1-5μm、优选为1-3μm,比表面积为63-83㎡/g、优选为68-78㎡/g、进一步优选为73.45㎡/g。
本发明一种Sn1-0.5xCuxS2纳米花的制备方法,包括下述步骤:
按设计的组分配取Sn源、Cu源和S源后,将配取的Sn源、Cu源和S源加入溶剂中混合均匀,得到混合溶液,再将混合溶液置于反应釜中,于160-200℃反应,得到Sn1-0.5xCuxS2纳米花;所述Sn源为可溶性锡盐,所述可溶性锡盐中锡的价态为正四价;所述Cu源为可溶性铜盐,所述可溶性铜盐中铜的价态为正二价;S源选自硫代乙酰胺、硫化钠、硫脲中的至少一种、优选为硫代乙酰胺。
本发明一种Sn1-0.5xCuxS2纳米花的制备方法,所述溶剂选自乙醇。
本发明一种Sn1-0.5xCuxS2纳米花的制备方法,所述可溶性铜盐选自氯化铜、硝酸铜、硫酸铜中的至少一种,优选为氯化铜。
本发明一种Sn1-0.5xCuxS2纳米花的制备方法,所述可溶性锡盐选自结晶四氯化锡和无水四氯化锡中的一种,优选为结晶四氯化锡。
本发明一种Sn1-0.5xCuxS2纳米花的制备方法,所述混合溶液中,四价锡的浓度为0.017-0.333mol/L、优选为0.033-0.167mol/L、进一步优选为0.033-0.100mol/L。
本发明一种Sn1-0.5xCuxS2纳米花的制备方法,所述混合溶液中,二价铜的浓度为0.0033-0.167mol/L、优选为0.0005-0.001mol/L。
本发明一种Sn1-0.5xCuxS2纳米花的制备方法,所述混合溶液中,硫源的浓度为0.033-0.667 mol/L、优选为0.067-0.333mol/L、进一步优选为0.067-0.200mol/L。
本发明一种Sn1-0.5xCuxS2纳米花的制备方法,将混合溶液置于反应釜中,于160-180℃反应10-14小时、优选为12小时后,随炉冷却至室温,得到含有Sn1-0.5xCuxS2纳米花的混合液,混合液经离心洗涤、干燥,得到Sn1-0.5xCuxS2纳米花。
本发明一种Sn1-0.5xCuxS2纳米花的应用,所述应用包括用于催化分解有机物。
本发明一种Sn1-0.5xCuxS2纳米花的应用,还可以作用吸附剂。
本发明一种Sn1-0.5xCuxS2纳米花的应用,所述催化分解为光催化分解。
本发明一种Sn1-0.5xCuxS2纳米花的应用,所述有机物优选为有机染料。所述有机染料选自罗丹明B、直接蓝、亚甲基蓝中的至少一种,进一步优选为罗丹明B。
本发明一种Sn1-0.5xCuxS2纳米花的应用,以可见光为光源,以Sn1-0.5xCuxS2纳米花纳米花为催化剂,以罗丹明B溶液为光催化分解对象,按质量比,催化剂:罗丹明B=100:9,配取催化剂和罗丹明B溶液后,经120min的光催化分解后,罗丹明B溶液中罗丹明B的剩余量小于等于10%;所述Sn1-0.5xCuxS2纳米花中,x的取值为0.18-0.22、优选为0.2。
原理
本发明所设计的Sn1-0.5xCuxS2纳米花,巧妙的利用了CuS和SnS属性,通过二者的合理搭配,取得了意想不到的光催化分解有机物的效果。本发明所设计的Sn1-0.5xCuxS2纳米花能以可见光为官员,对有机物进行快速的吸附-分解,在30min内即可完成代理处理物质70%以上的吸附- 分解。其原因可能在于:Sn1-0.5xCuxS2纳米花为层状结构,比表面积大利于电子的传输,比表面积大空穴电子对能在表面缺陷出快速分离,载流子迁移率高,光催化性能好。
优势
Sn1-0.5xCuxS2纳米花具有很大的比表面积,特殊的表面效应,使得材料有着很高的表面活性和表面能,在制备高性能吸附剂方面具有巨大的潜力。
本发明采用一锅煮的方式,在S源含量不变时,控制Sn和Cu的比例合成吸附于催化性能高的Sn1-0.5xCuxS2纳米花。反应操作简单,反应条件易于控制,原料均为无毒性原料,具有良好的工业化推广前景。
附图说明
图1为实施例1所制Sn1-0.5xCuxS2的SEM图。
图2为实施例2所制备的Sn1-0.5xCuxS2的SEM图。
图3为实施例3所制备的Sn1-0.5xCuxS2的SEM图。
图4为对比例1所制备SnS2、实施例1所制备Sn1-0.5xCuxS2、实施例2所制备Sn1- 0.5xCuxS2以及实施例3所制备Sn1-0.5xCuxS2纳米花的XRD图。
图5为对比例1所制备SnS2、对比例2所制备CuS、实施例1所制备Sn1-0.5xCuxS2实施例2所制备Sn1-0.5xCuxS2以及实施例2所制备Sn1-0.5xCuxS2纳米花的光降解曲线。
具体实施方式
对比例1
室温下,在洁净、干燥的50mL的聚四氟乙烯内衬中加入2.5mmol结晶四氯化锡(SnCl4·5H2O)、5mmol硫代乙酰胺(CH3CSNH2)和30mL乙醇,放入搅拌子搅拌至溶液澄清,取出搅拌子,将内衬放入反应釜中在恒温烘箱中180℃保温12h,停止加热后,在烘箱中冷却至室温,离心分离,用去离子水和乙醇各洗三次后,在恒温干燥箱中烘干,得到产品SnS2,用于后续的分析和表征。
对比例2
室温下,在洁净、干燥的50mL的聚四氟乙烯内衬中加入2.5mmol二水合氯化铜(Cu2Cl4·2H2O)、2.5mmol硫代乙酰胺(CH3CSNH2)和30mL乙醇,放入搅拌子搅拌至溶液澄清,取出搅拌子,将内衬放入反应釜中在恒温烘箱中180℃保温12h,停止加热后,在烘箱中冷却至室温,离心分离,用去离子水和乙醇各洗三次后,在恒温干燥箱中烘干,得到产品CuS,用于后续的分析。
实施例1
室温下,在洁净、干燥的50mL的聚四氟乙烯内衬中加入2.488mmol结晶四氯化锡(SnCl4·5H2O)、0.0249mmol二水氯化铜(CuCl2·2H2O)、5mmol硫代乙酰胺(CH3CSNH2) 和30mL乙醇,搅拌至溶液澄清,取出搅拌子,将内衬放入反应釜中,在恒温烘箱中180℃保温12h,停止加热后,在烘箱中冷却至室温,离心分离,用去离子水和乙醇各洗三次后,在 60℃恒温干燥箱中烘干,得到产品标记为Sn1-0.5xCuxS2-1,(x=0.01)用于后续的分析。产品纳米花的直径为3μm左右,比表面积为68㎡/g。
实施例2
室温下,在洁净、干燥的50mL的聚四氟乙烯内衬中加入2.2mmol结晶四氯化锡(SnCl4·5H2O)、0.56mmol二水氯化铜(CuCl2·2H2O)、5mmol硫代乙酰胺(CH3CSNH2) 和30mL乙醇,搅拌至溶液澄清,取出搅拌子,将内衬放入反应釜中,在恒温烘箱中180℃保温12h,停止加热后,在烘箱中冷却至室温,离心分离,用去离子水和乙醇各洗三次后,在 60℃恒温干燥箱中烘干,得到产品标记为Sn1-0.5xCuxS2-2,(x=0.25)用于后续的分析和表征。产品纳米花的直径为5μm左右,比表面积为70㎡/g。
实施例3
室温下,在洁净、干燥的50mL的聚四氟乙烯内衬中加入2.25mmol结晶四氯化锡(SnCl4·5H2O)、0.5mmol二水氯化铜(CuCl2·2H2O)、5mmol硫代乙酰胺(CH3CSNH2)和 30mL乙醇,放入搅拌子搅拌至溶液澄清,取出搅拌子,将内衬放入反应釜中在恒温烘箱中 180℃保温12h,停止加热后,在烘箱中冷却至室温,离心分离,用去离子水和乙醇各洗三次后,在恒温干燥箱中烘干,得到产品Sn1-0.5xCuxS2-3,(x=0.2)用于后续的分析和表征。产品纳米花的直径为3μm左右,比表面积为73.45㎡/g。
将样品Sn1-0.5xCuxS2-1、Sn1-0.5xCuxS2-2和Sn1-0.5xCuxS2-3分别采用扫描电子显微镜(SEM) 表征所制得的样品的形貌,尺寸大小等,结果如图1~3所示。
所制备的SnS2、Sn1-0.5xCuxS2-1、Sn1-0.5xCuxS2-2和Sn1-0.5xCuxS2-3分别采用X射线衍射仪 (XRD)进行表征其物相合结晶度,如图4所示。
Sn1-0.5xCuxS2纳米花在光催化降解有机燃料的应用,特别是在吸附和可见光降解有机燃料 RhB的应用。
吸附测试方法 分别取SnS2、CuS、Sn1-0.5xCuxS2-1、Sn1-0.5xCuxS2-2和Sn1-0.5xCuxS2-3样品5mg,加到带有搅拌子的试管中,加入7.5mL的去离子水,超声使得样品均匀分散于水中,然后加入40mg/L的RhB母液于试管中配成15mL的20mg/L的RhB溶液,试管置于黑暗中,用磁力搅拌器一直搅拌,使之保持均匀分散在溶液中。30min后达到吸附-解吸附平衡,取5mL试样,离心(13000r,5min)后,取上清液置于比色皿中。通过测量吸收图谱,算出吸附量,结果如图5所示。
光降解测试方法:将达到吸附-解吸附平衡后的溶液,用300W氙灯(λ>420nm)作为可见光照射光源。每隔15min取5mL溶液,离心(13000r,5min)后,取3mL上清液置于比色皿中。通过测量紫外吸收的图谱,算出光降解降解量。
样品SnS2、CuS、Sn1-0.5xCuxS2-1、Sn1-0.5xCuxS2-2和Sn1-0.5xCuxS2-3分别在300W氙灯下做吸附和光降解实验,如图5所示。在暗场吸附30min时,达到吸附-解吸附平衡,两样品的吸附量达到75%左右,开灯后120min Sn1-0.5xCuxS2-3吸附和降解达到90%。此外可以看出量样品的吸附量差不多,但是降解量不同,说明Sn1-0.5xCuxS2-3光催化活性优于Sn1-0.5xCuxS2-2和Sn1-0.5xCuxS2-1,对比样SnS2几乎没有降解。
Claims (10)
1.一种Sn1-0.5xCuxS2纳米花,其特征在于:所述纳米花的化学式为Sn1-0.5xCuxS2,其中x的取值为0.001-0.3;所述纳米花的应用包括用于催化分解有机物;所述催化分解为光催化分解。
2.根据权利要求1所述的一种Sn1-0.5xCuxS2纳米花,其特征在于:
所述纳米花由Sn1-0.5xCuxS2纳米片通过相互镶嵌和/或贯穿组成。
3.根据权利要求2所述的一种Sn1-0.5xCuxS2纳米花,其特征在于:所述纳米花的直径为1-5μm,比表面积为63-83㎡/g。
4.一种制备如权利要求1-3任意一项所述Sn1-0.5xCuxS2纳米花的方法,其特征在于包括下述步骤:
按设计的组分配取Sn源、Cu源和S源后,将配取的Sn源、Cu源和S源加入溶剂中混合均匀,得到混合溶液,再将混合溶液置于反应釜中,于160-200℃反应,得到Sn1-0.5xCuxS2纳米花;所述Sn源为可溶性锡盐,所述可溶性锡盐中锡的价态为正四价;所述Cu源为可溶性铜盐,所述可溶性铜盐中铜的价态为正二价;S源选自硫代乙酰胺、硫化钠、硫脲中的至少一种。
5.根据权利要求4所述的一种Sn1-0.5xCuxS2纳米花的制备方法,其特征在于:所述溶剂选自乙醇。
6.根据权利要求4所述的一种Sn1-0.5xCuxS2纳米花的制备方法,其特征在于:
所述可溶性铜盐选自氯化铜、硝酸铜、硫酸铜中的至少一种;
所述可溶性锡盐选自结晶四氯化锡和无水四氯化锡中的一种。
7.根据权利要求4所述的一种Sn1-0.5xCuxS2纳米花的制备方法,其特征在于:所述混合溶液中,
四价锡的浓度为0.017-0.0.333mol/L;
二价铜的浓度为0.0033-0.167mol/L;
硫源的浓度为0.033-0.667mol/L。
8.一种如权利要求1-3任意一项所述Sn1-0.5xCuxS2纳米花的应用,其特征在于:所述应用包括用于催化分解有机物。
9.根据权利要求8所述的一种Sn1-0.5xCuxS2纳米花的应用,其特征在于:所述催化分解为光催化分解;所述有机物为有机染料,所述有机染料选自罗丹明B、直接蓝、亚甲基蓝中的至少一种。
10.根据权利要求8所述的一种Sn1-0.5xCuxS2纳米花的应用,其特征在于:以可见光为光源,以Sn1-0.5xCuxS2纳米花为催化剂,以罗丹明B溶液为光催化分解对象,按质量比,催化剂:罗丹明B=100:9,配取催化剂和罗丹明B溶液后,经120min的光催化分解后,罗丹明B溶液中罗丹明B的剩余量小于等于10%;所述Sn1-0.5xCuxS2纳米花中,x的取值为0.18-0.22。
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