CN108273521A - 一种由纳米片构成的硫化铜锌花状微米球超结构可见光催化剂的制备方法 - Google Patents
一种由纳米片构成的硫化铜锌花状微米球超结构可见光催化剂的制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- FENQZYRPJMQVRW-UHFFFAOYSA-N [Cu]S[Zn] Chemical compound [Cu]S[Zn] FENQZYRPJMQVRW-UHFFFAOYSA-N 0.000 title claims abstract description 14
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
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Abstract
本发明提供了一种由纳米片构成的硫化铜锌花状微米球超结构可见光催化剂的制备方法。该方法是先将锌盐与铜盐分别加入到邻羟基二醇中,搅拌溶解后,加入硫脲,继续搅拌至硫脲完全溶解,再加入聚乙烯吡咯烷酮(PVP),在120~160℃搅拌回流1~3小时;然后,自然冷却到室温,离心分离;将所得沉淀洗涤、干燥后,得由纳米片构成的花状微米球超结构可见光催化剂ZnxCu1‑xS(0.05≤x≤0.3)。本发明制备的产品比表面积大,抗光腐蚀能力强,可见光光催化活性高,能充分利用太阳光对环境污染物进行光催化降解。该方法具有生产工艺简单、生产过程安全、反应参数容易控制和易于实现大规模工业化生产的优点。
Description
技术领域
本发明属于光催化技术领域,具体涉及一种采用回流法制备由纳米片构成的ZnxCu1-xS(0.05≤x≤0.3)(硫化铜锌)花状微米球超结构可见光催化剂的方法。
背景技术
随着社会经济的发展,环境污染问题越来越严重,环境污染的治理与控制是人类21世纪面临和亟待解决的重大课题。半导体多相光催化由于在去除各种环境难降解污染物方面表现出强氧化性、污染物矿化完全、可直接利用太阳光等优点而备受人们的青睐。目前,在多相光催化反应所应用的半导体催化剂中,对太阳光敏感且具有光催化特性的半导体的能带间隙一般为1.9~3.1eV,带隙太宽则只能吸收太阳光中的紫外光,而太阳光中紫外光能只占到太阳光总能量的3%~4%,因而太阳能的利用率低,如TiO2(3.2eV)、ZnO(3.4eV)、ZnS(3.6eV)等光催化剂;相反,若带隙太窄则对污染物的氧化降解能力较弱,如Bi2S3(1.2~1.7eV)、Sb2S3(1.5~2.2eV)、CuS(1.8~2.0eV)、CuO(1.7eV)等。此外,ZnS、CuS、CdS等金属硫化物半导体光催化剂在光催化过程中不稳定,容易产生光腐蚀,也限制了其实际应用,但若将其制备成多元金属硫化物则能提高其稳定性,使之不容易产生光腐蚀。由于Zn2+与Cu2+具有相近的离子半径(Zn2+与Cu2+的离子半径分别为和),若在CuS中掺入Zn2+,Zn2+即能取代六方相CuS晶体中的Cu2+而形成取代固溶体ZnxCu1-xS(硫化铜锌),这样不但能提高ZnxCu1-xS的稳定性,而且能提高其能带间隙,使其对污染物的氧化降解能力更强。
众所周知,纳米材料的性质取决于其形貌和尺寸,然而如何调控它的形貌和尺寸仍然是科学工作者所面临的难题。因此,对纳米材料形貌和尺寸的可控制备成为材料科学研究的热点和前沿。近年来,纳米材料特别是由一维、二维纳米材料构筑成的具有特殊形貌的纳米结构由于具有优异的光学、电学、催化等性能以及在纳米器件上的潜在应用,引起了科技工作者的广泛关注。本发明用回流法来制备由ZnxCu1-xS纳米片构筑成的花状微米球超结构,由于纳米片具有非常高的比表面积,能够吸收更多的光子并激发产生电子-空穴对,同时,纳米尺寸的薄片可以抑制光生电子与空穴的复合,因而提高了ZnxCu1-xS的可见光光催化活性。
本发明以硫脲(Tu)、可溶性的锌盐及铜盐为原料,邻羟基二醇为溶剂,聚乙烯吡咯烷酮(PVP)为表面活性剂,用回流法制备了由纳米片构成的ZnxCu1-xS(0.05≤x≤0.3)花状微米球超结构可见光催化剂。众所周知,晶体的形成过程包括成核和生长两个阶段,晶体的形貌主要受晶体的生长习性以及外界条件的影响,而晶体的生长习性又与晶体的结构及晶体不同晶面的表面能有关。硫化铜是一种六角相具有各向异性结构的半导体材料,在不同晶面具有不同的表面能,其容易沿一定方向择优生长而形成片状形貌。在本发明中,Cu2+与硫脲在邻羟基二醇中先形成配合物[但硫脲与Zn2+的配位能力很弱,Cu(Tu)2 2+与Zn(Tu)2 2+的稳定常数分别为2.51×1015和59],配合物在回流、加热的条件下分解而生成六角相的CuS晶核(ZnS的溶度积常数比CuS的溶度积常数大,此时不会形成ZnS的晶核),由于的半径与的半径相近,在晶体生长过程中,Zn2+便会进入CuS的晶格内部部分取代Cu2+而形成六角相的取代固溶体ZnxCu1-xS,并择优生长为纳米片。且由于纳米片比表面积大,比表面自由能高,不稳定,因此,ZnxCu1-xS纳米片便会聚集在一起自组装为微米球超结构以降低其表面自由能而达到稳定状态。另外,加入的表面活性剂PVP能选择性地吸附在晶体的某些界面控制该晶面的生长速率并阻止晶体的团聚,也有利于形成具有良好形貌的由纳米片构成的微米球超结构。本发明制备的由纳米片构成的ZnxCu1-xS(0.05≤x≤0.3)花状微米球超结构可见光催化剂,不但由于Zn2+的掺杂提高了其能带间隙(其对光的吸收仍然在可见光范围内)、增加了其对污染物的氧化降解能力,而且其比表面积大,纳米尺寸的薄片还可以抑制光生电子与空穴的复合,因而其可见光光催化活性高。实验结果表明,产品不但对可见光具有强的吸收,有高的可见光光催化活性,能充分利用太阳光及室内自然光对环境污染物进行光催化降解,而且其抗光腐蚀能力强、稳定性高。
发明内容
本发明的目的在于提供一种生产工艺简单、生产过程安全、易于实现工业化生产、产品稳定性高和可见光光催化活性高的由纳米片构成的硫化铜锌花状微米球超结构可见光催化剂的制备方法。
本发明的目的是通过如下方式实现的:
一种由纳米片构成的硫化铜锌花状微米球超结构可见光催化剂,其化学式为ZnxCu1-xS,其中,0.05≤x≤0.3,制备方法包括如下步骤:
(a)按ZnxCu1-xS中锌与铜的物质的量之比即x:(1-x)将锌盐与铜盐分别加入到邻羟基二醇中,搅拌溶解,邻羟基二醇的用量为每毫升邻羟基二醇中加入Zn2+与Cu2+总物质的量为0.05~0.1mmol;然后加入硫脲,加入硫脲的物质的量为Zn2+与Cu2+总物质的量的2~4倍,继续搅拌至硫脲完全溶解,得混合溶液;
(b)在混合溶液中加入聚乙烯吡咯烷酮,其用量为每毫升邻羟基二醇中加入0.5~3mg聚乙烯吡咯烷酮,搅拌均匀;然后,在120~160℃搅拌回流1~3小时;
(c)反应完成后,自然冷却到室温,离心分离,将所得沉淀分别用去离子水和无水乙醇交替超声洗涤,干燥后得由纳米片构成的硫化铜锌花状微米球超结构可见光催化剂。
进一步地,所述的邻羟基二醇是乙二醇或1,2-丙二醇。
进一步地,所述的铜盐是氯化铜、硫酸铜或硝酸铜。
进一步地,所述的锌盐是硫酸锌、硝酸锌或氯化锌。
本发明的有益效果在于:
(1)本发明通过回流法制备由纳米片构成的花状微米球超结构可见光催化剂ZnxCu1-xS(0.05≤x≤0.3),具有生产工艺简单、生产过程安全、反应参数容易控制和易于实现工业化生产的优点。
(2)本发明制备的由纳米片构成的硫化铜锌花状微米球超结构材料,一方面其比表面积大,对可见光的吸收能力强,且纳米尺寸的薄片可以抑制光生电子与空穴的复合,另一方面在六角相的CuS中掺杂Zn2+提高了其能带间隙、增加了其对污染物的氧化降解能力,因此,其可见光光催化活性高,能充分利用太阳光对环境污染物进行光催化降解,效率高,成本低。且本发明制备的产品属多元金属硫化物,在光催化过程中抗光腐蚀能力强,稳定性高。
附图说明
图1为实施例1制备的由纳米片构成的花状微米球超结构可见光催化剂Zn0.2Cu0.8S的扫描电子显微镜(SEM)图。
图2为制备的由纳米片构成的花状微米球超结构可见光催化剂ZnxCu1-xS(0.05≤x≤0.3)的X-射线衍射(XRD)谱图。其中a、b、c、d分别为实施例3、实施例2、实施例1、实施例4制备的光催化剂的X-射线衍射谱图。
图3为制备的由纳米片构成的花状微米球超结构可见光催化剂ZnxCu1-xS(0.05≤x≤0.3)的光催化效果图。其中a、b、c、d分别为实施例4、实施例1、实施例3、实施例2制备的产品对亚甲基蓝溶液的光催化降解曲线,横坐标表示降解时间,纵坐标表示降解率。
具体实施方式
下面结合实施例对本发明作进一步的说明,但本发明并不限于此。
实施例1
(a)称取0.82g CuCl2·2H2O和0.35g ZnSO4·7H2O分别加入到120mL乙二醇中(相当于每毫升乙二醇中加入Zn2+与Cu2+总物质的量为0.05mmol),搅拌溶解;然后加入1.83g硫脲(其物质的量为Zn2+与Cu2+总物质的量的4倍),继续搅拌至硫脲完全溶解,得混合溶液;
(b)在混合溶液中加入60mg聚乙烯吡咯烷酮(相当于每毫升乙二醇中加入0.5mg聚乙烯吡咯烷酮),搅拌均匀;然后,在130℃搅拌回流1小时;
(c)反应完成后,自然冷却到室温,离心分离,将所得沉淀分别用去离子水和无水乙醇交替超声洗涤各3次,干燥后得由纳米片构成的花状微米球超结构可见光催化剂Zn0.2Cu0.8S。
实施例1所得产品的扫描电子显微镜(SEM)图如图1所示。由图1可见,产品是由厚度为20~80nm(纳米)的纳米片构成的花状微米球,纳米片形貌规则、表面光滑,相互交错而组装成微米球超结构,微米球大小较均匀、分散性良好,直径为0.8~2.8μm(微米)。
实施例2
(a)称取1.42g CuSO4·5H2O和0.041g ZnCl2分别加入到60mL 1,2-丙二醇中(相当于每毫升1,2-丙二醇中加入Zn2+与Cu2+总物质的量为0.1mmol),搅拌溶解;然后加入1.37g硫脲(其物质的量为Zn2+与Cu2+总物质的量的3倍),继续搅拌至硫脲完全溶解,得混合溶液;
(b)在混合溶液中加入180mg聚乙烯吡咯烷酮(相当于每毫升1,2-丙二醇中加入3mg聚乙烯吡咯烷酮),搅拌均匀;然后,在150℃搅拌回流2小时;
(c)反应完成后,自然冷却到室温,离心分离,将所得沉淀分别用去离子水和无水乙醇交替超声洗涤各3次,干燥后得由纳米片构成的花状微米球超结构可见光催化剂Zn0.05Cu0.95S。
实施例3
(a)称取1.30g Cu(NO3)2·3H2O和0.17g ZnSO4·7H2O分别加入到100mL乙二醇中(相当于每毫升乙二醇中加入Zn2+与Cu2+总物质的量为0.06mmol),搅拌溶解;然后加入0.91g硫脲(其物质的量为Zn2+与Cu2+总物质的量的2倍),继续搅拌至硫脲完全溶解,得混合溶液;
(b)在混合溶液中加入200mg聚乙烯吡咯烷酮(相当于每1毫升乙二醇中加入2mg聚乙烯吡咯烷酮),搅拌均匀;然后,在160℃搅拌回流3小时;
(c)反应完成后,自然冷却到室温,离心分离,将所得沉淀分别用去离子水和无水乙醇交替超声洗涤各3次,干燥后得由纳米片构成的花状微米球超结构可见光催化剂Zn0.1Cu0.9S。
实施例4
(a)称取0.72g CuCl2·2H2O和0.54g Zn(NO3)2·6H2O分别加入到80mL 1,2-丙二醇中(相当于每毫升1,2-丙二醇中加入Zn2+与Cu2+总物质的量为0.075mmol),搅拌溶解;然后加入1.83g硫脲(其物质的量为Zn2+与Cu2+总物质的量的4倍),继续搅拌至硫脲完全溶解,得混合溶液;
(b)在混合溶液中加入80mg聚乙烯吡咯烷酮(相当于每1毫升1,2-丙二醇中加入1mg聚乙烯吡咯烷酮),搅拌均匀;然后,在140℃搅拌回流1.5小时;
(c)反应完成后,自然冷却到室温,离心分离,将所得沉淀分别用去离子水和无水乙醇交替超声洗涤各3次,干燥后得由纳米片构成的花状微米球超结构可见光催化剂Zn0.3Cu0.7S。
可见光光催化性能测试:
将0.1g光催化剂加入到100mL 20mg/L的亚甲基蓝(MB)溶液中,然后加入5mL质量分数为30%的H2O2,避光超声分散5分钟,再在暗处磁力搅拌30分钟,使亚甲基蓝在催化剂表面达到吸附平衡。取3mL样液离心分离除去催化剂粉末后,用紫外-可见分光光度计测试其在664nm(亚甲基蓝的最大吸收波长)处的吸光度并作为被降解液的初始吸光度A0。随后,以35W氙灯为光源进行可见光光催化降解实验(氙灯的顶端距液面15cm),同时磁力搅拌,每隔5分钟取样液3mL,离心分离去掉催化剂固体后,取上层清液在相同波长处测试其吸光度Ax,并据此计算出亚甲基蓝的降解率。
所制备的由纳米片构成的花状微米球超结构可见光催化剂ZnxCu1-xS(0.05≤x≤0.3)的X-射线衍射(XRD)谱图如图2所示。其中a、b、c、d分别为实施例3、实施例2、实施例1、实施例4制备产品的X-射线衍射谱图。将图2与CuS的标准谱图(JCPDS No.78-0876)对照知,其所有衍射峰都与六方相CuS的标准谱图相吻合,没有ZnS或其它杂质的衍射峰,因此产品纯度高。由于与的离子半径相近,掺杂的Zn2+部分取代了CuS中Cu2+的位置形成了六方相的取代固溶体ZnxCu1-xS。另外,谱图的衍射峰明显宽化,这是由于纳米片的尺寸较小的原因。由(110)和(102)晶面的衍射峰计算得出Zn0.05Cu0.95S、Zn0.1Cu0.9S、Zn0.2Cu0.8S、Zn0.3Cu0.7S的晶胞参数分别为a=0.3785nm,c=1.6378nm;a=0.3787nm,c=1.6392nm;a=0.3790nm,c=1.6495nm;a=0.3795nm,c=1.6632nm,由此可以看出,随着锌所占摩尔比的增加,晶胞参数有所增加,这是由于所形成的固溶体中的离子半径比的离子半径稍大的缘故。
将花状微米球超结构可见光催化剂ZnxCu1-xS(0.05≤x≤0.3)进行可见光光催化降解实验,结果如图3所示。由图3可见,实施例1、实施例2、实施例3、实施例4制备的产品都具有优异的可见光光催性性能(其降解效果分别用曲线b、d、c、a表示),其中实施例4制备的产品的可见光光催化活性最高(曲线a),在35W氙灯下,经50分钟降解,其对亚甲基蓝的光催化降解率可达99.6%。
Claims (4)
1.一种由纳米片构成的硫化铜锌花状微米球超结构可见光催化剂的制备方法,该可见光催化剂的化学式为ZnxCu1-xS,其中,0.05≤x≤0.3,其特征在于,制备方法包括如下步骤:
(a)按ZnxCu1-xS中锌与铜的物质的量之比即x:(1-x)将锌盐与铜盐分别加入到邻羟基二醇中,搅拌溶解,邻羟基二醇的用量为每毫升邻羟基二醇中加入Zn2+与Cu2+总物质的量为0.05~0.1mmol;然后加入硫脲,加入硫脲的物质的量为Zn2+与Cu2+总物质的量的2~4倍,继续搅拌至硫脲完全溶解,得混合溶液;
(b)在混合溶液中加入聚乙烯吡咯烷酮,其用量为每毫升邻羟基二醇中加入0.5~3mg聚乙烯吡咯烷酮,搅拌均匀;然后,在120~160℃搅拌回流1~3小时;
(c)反应完成后,自然冷却到室温,离心分离,将所得沉淀分别用去离子水和无水乙醇交替超声洗涤,干燥后得由纳米片构成的硫化铜锌花状微米球超结构可见光催化剂。
2.根据权利要求1所述的一种由纳米片构成的硫化铜锌花状微米球超结构可见光催化剂的制备方法,其特征在于,所述的邻羟基二醇是乙二醇或1,2-丙二醇。
3.根据权利要求1所述的一种由纳米片构成的硫化铜锌花状微米球超结构可见光催化剂的制备方法,其特征在于,所述的铜盐是氯化铜、硫酸铜或硝酸铜。
4.根据权利要求1所述的一种由纳米片构成的硫化铜锌花状微米球超结构可见光催化剂的制备方法,其特征在于,所述的锌盐是硫酸锌、硝酸锌或氯化锌。
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