CN112657515B - 3D花状Z型异质结光电催化剂Zn3In2S6@α-Fe2O3及其制备方法和应用 - Google Patents
3D花状Z型异质结光电催化剂Zn3In2S6@α-Fe2O3及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开3D花状Z型异质结光电催化剂Zn3In2S6@α‑Fe2O3及其制备方法和应用。所述3D花状Z型异质结光电催化剂是Zn3In2S6@α‑Fe2O3,按质量百分比,Fe2O3的负载量为3%‑7%。本发明提供的3D花状Z型异质结光电催化剂Zn3In2S6@α‑Fe2O3,用于高效还原高毒性的Cr(VI)为无毒的Cr(III),为含铬废水的处理提供理论基础,有助于推动光电催化技术在环境修复领域的应用。
Description
技术领域
本发明属于光电催化领域,特别涉及一种将Cr(VI)还原为Cr(III)的3D花状Z型异质结光电催化剂Zn3In2S6@α-Fe2O3及其制备方法和应用。
背景技术
近年来,快速工业化对环境造成了严重的威胁,特别是含重金属离子废水的排放已经成为人们担心的首要问题。铬是一种典型的重金属污染物,主要来源于皮革鞣制、纺织制造、钢铁制造等行业。与其他重金属相比,铬主要以Cr(VI)和Cr(III)两种价态存在,其中,Cr(VI)因其对生物体的急性毒性而被认为是致癌物,而Cr(III)无毒,是人体必需的微量金属。因此,将Cr(VI)还原为Cr(III)被认为是一种行之有效的水处理方法。
为解决Cr(VI)的还原问题,研究人员已经开展了各种研究工作:微生物还原、化学还原和光催化还原等等。光电催化技术是近年来发展起来的一种高效的催化技术,它利用取之不尽用之不竭的太阳光作为能源,具有节能、环保、高效等特性,在电驱动下可以加快光生载流子的分离,提高太阳能转换成化学能的转化效率。目前,该技术已被广泛应用在各种催化领域,包括析氢、加氢、析氧、CO2还原及合成氨等。该技术的关键是合理设计和构建性能优异的催化剂,它应具有良好的导电能力及高效的光吸收性能。
半导体异质结,特别是Z型电荷传导模式的异质结是公认的比较高效的光电催化剂。光激发使半导体中的电子从价带(VB)跃迁至导带(CB),形成电子/空穴对,并且,一种半导体CB位置的e-与另一半导体VB位置的h+优先结合,实现电荷分离的同时也在各自半导体上分别保留具有更强氧化/还原能力的光生电荷,保持了其原有的氧化/还原能力。
发明内容
为了解决上述技术问题,本发明提供一种3D花状Z型异质结光电催化剂Zn3In2S6@α-Fe2O3,用于高效还原高毒性的Cr(VI)为无毒的Cr(III),为含铬废水的处理提供理论基础,有助于推动光电催化技术在环境修复领域的应用。
本发明采用的技术方案是:一种3D花状Z型异质结光电催化剂Zn3In2S6@α-Fe2O3,所述3D花状Z型异质结光电催化剂是Zn3In2S6@α-Fe2O3,按质量百分比,Fe2O3的负载量为3-7%。
进一步的,按质量百分比,Fe2O3的负载量为5%。
一种3D花状Z型异质结光电催化剂Zn3In2S6@α-Fe2O3的制备方法,包括如下步骤:将硝酸铁和乙酸铵加入到乙醇和去离子水的混合溶液中,超声10-15min,使其均匀分散后,加入适量Zn3In2S6,搅拌30-40min后,在180℃下水热反应24h,产物洗涤干燥后,得Zn3In2S6@α-Fe2O3。
进一步的,上述的制备方法,按体积比,乙醇:去离子水=20:1。
进一步的,上述的制备方法,所述Zn3In2S6的制备方法,包括如下步骤:将InCl3·4H2O溶于去离子水,得InCl3水溶液;将ZnSO4·7H2O和硫代乙酰胺溶于去离子水中,搅拌均匀后,加入InCl3水溶液,继续搅拌30min后,转移至高压釜中,160℃水热反应12h,洗涤干燥后,得粉末状固体Zn3In2S6。
进一步的,上述的制备方法,按摩尔比,InCl3·4H2O:ZnSO4·7H2O:硫代乙酰胺=2:3:6。
本发明提供的3D花状Z型异质结光电催化剂Zn3In2S6@α-Fe2O3在光电催化Cr(VI)还原为Cr(III)中的应用。
进一步的,方法如下:将Zn3In2S6@α-Fe2O3涂覆在碳纸上作为工作电极,铂为对电极,Ag/AgCl为参比电极,形成三电极体系,将三电极体系置于电解质溶液中,加入含有Cr(VI)的废水,先在黑暗中搅拌60min,然后在光电催化下,进行还原反应。
进一步的,所述光电催化条件是:电压为-0.4~-0.7V,λ>420nm的可见光作为光源。
进一步的,所述电解质溶液为pH=3.0,浓度为0.1mol·L-1的Na2SO4。
本发明的有益效果是:本发明提供的3D花状Z型异质结光电催化剂Zn3In2S6@α-Fe2O3,可用于高效还原高毒性的Cr(VI)为无毒的Cr(III),为含铬废水的处理提供理论基础,有助于推动光电催化技术在环境修复领域的应用
附图说明
图1是实施例1制备的Zn3In2S6的SEM图。
图2是实施例1制备的Zn3In2S6@α-Fe2O3的SEM图。
图3是α-Fe2O3,Zn3In2S6和Zn3In2S6@α-Fe2O3的XRD图谱。
图4是Zn3In2S6@α-Fe2O3的XPS全谱图。
图5是放大的Fe元素XPS精细谱图。
图6是Zn3In2S6、α-Fe2O3和Zn3In2S6@α-Fe2O3的光电催化还原Cr(VI)性能对比。
图7是Zn3In2S6@α-Fe2O3在纯光、纯电及光电共同作用下的催化效果对比。
图8是Zn3In2S6@α-Fe2O3的催化反应动力学。
图9是自由基捕获图。
图10是Cr(VI)还原反应机理。
具体实施方式
实施例1 3D花状Z型异质结光电催化剂Zn3In2S6@α-Fe2O3
(一)制备方法
1、Zn3In2S6的制备:
0.5865g InCl3·4H2O溶于25mL去离子水,得InCl3水溶液。
0.8711g ZnSO4·7H2O和0.4545g硫代乙酰胺溶于45mL去离子水中,搅拌均匀后加入InCl3水溶液,继续搅拌30min后,转移至高压釜中160℃水热反应12h,洗涤干燥后,得黄色粉末状固体Zn3In2S6。
2、Zn3In2S6@α-Fe2O3的制备:
0.013g硝酸铁(Fe(NO3)3·9H2O)和0.012g乙酸铵(CH3COONH4)加入到60mL乙醇和3mL去离子水的混合溶液中,超声10min,使其均匀分散后,加入0.095g Zn3In2S6,搅拌30min,在180℃下水热反应24h,产物洗涤干燥后,得Fe2O3负载量为5%的Zn3In2S6@α-Fe2O3。
(二)材料表征
1、图1是Zn3In2S6的SEM图。由图1可见,Zn3In2S6展现了良好的3D分级花状结构。
2、图2是Zn3In2S6@α-Fe2O3的SEM图。由图2可见,负载α-Fe2O3之后,原本的3D花状分级结构没有明显的改变,花片上负载了大量纳米粒子。
3、图3是α-Fe2O3,Zn3In2S6和Zn3In2S6@α-Fe2O3的XRD图谱。由图3可见,纯的α-Fe2O3的谱图中,2θ=33.28,54.23,35.74,49.50,62.73,64.18处的衍射峰分别归因于Fe2O3的(104)、(116)、(110)、(024)、(214)、(300)晶面(JCPDS no.02-0919)。对于单独的Zn3In2S6样品,在2θ=28.23,46.92和32.73处的衍射峰归因于Zn3In2S6的(102)、(110)和(014)晶面(JCPDS no..80-0835)。在Zn3In2S6@α-Fe2O3复合材料中仅显示了较弱的α-Fe2O3的特征峰,这是因为α-Fe2O3在该复合材料中的含量较低。
4、图4是Zn3In2S6@α-Fe2O3的XPS全谱。由图4可见,除了Zn、In、S等元素之外,还有Fe元素的存在。
5、图5是放大的Fe元素XPS精细谱。由图5可见,证明Fe元素为三价,说明Fe2O3被成功负载在Zn3In2S6上。
实施例2Zn3In2S6@α-Fe2O3在光电催化Cr(VI)还原为Cr(III)中的应用
方法如下:将Zn3In2S6@α-Fe2O3涂覆在碳纸上作为工作电极,铂为对电极,Ag/AgCl为参比电极,形成三电极体系。将三电极体系置于50mL浓度为0.1mol·L-1的Na2SO4(pH=3.0)电解质溶液(含有10mg·L-1的K2Cr2O7)中,电/光开始前,在黑暗中搅拌60min以达吸附和解吸平衡。然后在光电催化(电压为-0.6V,光源为300W,氙灯(λ>420nm),平均光强为100mW·cm-2)下进行还原反应120min,采用显色法在540nm处紫外可见吸收,进行定量分析,每隔30min测定一次目标物Cr(VI)浓度,评价Zn3In2S6@α-Fe2O3的催化活性。
(一)不同光电催化剂对Cr(VI)还原为Cr(III)的影响
工作电极分别采用涂覆了Zn3In2S6,α-Fe2O3和Zn3In2S6@α-Fe2O3(实施例1)的碳纸。结果如图6。由图6可见,反应120min后,Zn3In2S6,α-Fe2O3和Zn3In2S6@α-Fe2O3对Cr(VI)的还原率分别为30%、13%和78%,可见,相比于单独的Zn3In2S6和α-Fe2O3,Zn3In2S6@α-Fe2O3复合材料展现了明显增强的光电催化还原Cr(VI)性能。
(二)不同催化条件对Cr(VI)还原为Cr(III)的影响
方法如下:将Zn3In2S6@α-Fe2O3(实施例1)涂覆在碳纸上作为工作电极,铂为对电极,Ag/AgCl为参比电极,形成三电极体系。将三电极体系置于50ml浓度为0.1mol·L-1的Na2SO4(pH=3.0)电解质溶液(含有10mg·L-1的K2Cr2O7)中,先在黑暗中搅拌60min以达吸附和解吸平衡。然后分别在纯光(光源为300W,氙灯(λ>420nm),平均光强为100mW·cm-2)、纯电(电压为-0.6V)和光电催化(电压为-0.6V,光源为300W,氙灯(λ>420nm),平均光强为100mW·cm-2)下进行还原反应120min,采用显色法在540nm处紫外可见吸收,进行定量分析,每隔30min测定一次目标物Cr(VI)浓度。结果如图7。
由图7可见,反应120min后,纯光、纯电和光/电协同的Cr(VI)还原率分别为36%,18%和78%,可见,相比于单纯的光催化和电催化,光电催化展示了明显增强的催化活性,证明了光电的协同作用。
(三)Fe2O3的负载率对Cr(VI)还原为Cr(III)的影响
Zn3In2S6@α-Fe2O3的制备:分别将0.0078g、0.013g、0.018g硝酸铁(Fe(NO3)3·9H2O)和0.012g乙酸铵(CH3COONH4)加入到60mL乙醇和3mL去离子水的混合溶液中,超声10min,使其均匀分散后,加入0.095g Zn3In2S6,搅拌30min,在180℃下水热反应24h,产物洗涤干燥后,分别得Fe2O3负载量为3%、5%、7%的Zn3In2S6@α-Fe2O3。
分别将不同Fe2O3负载量的Zn3In2S6@α-Fe2O3涂覆在碳纸上作为工作电极,铂为对电极,Ag/AgCl为参比电极,分别形成三电极体系。将三电极体系置于50mL浓度为0.1mol·L-1的Na2SO4(pH=3.0)电解质溶液(含有10mg·L-1的K2Cr2O7)中,电/光开始前,在黑暗中搅拌60min以达吸附和解吸平衡。然后在光电催化(电压为-0.6V,光源为300W,氙灯(λ>420nm),平均光强为100mW·cm-2)下进行还原反应120min,采用显色法在540nm处紫外可见吸收,进行定量分析,测定目标物Cr(VI)浓度。结果如表1,当Fe2O3负载量为5%时,Zn3In2S6@α-Fe2O3展示了更高的催化活性。
表1不同Fe2O3负载量对还原效率的影响
(四)Zn3In2S6@α-Fe2O3催化过程的动力学曲线
图8为Zn3In2S6@α-Fe2O3催化过程的动力学曲线。由图8可见,本发明提供的方法中,反应过程符合准一级动力学,相比于单独的Zn3In2S6和α-Fe2O3,Zn3In2S6@α-Fe2O3复合材料展现了更高的速率常数,常温下反应速率常数为k=0.01187min-1。
(五)Zn3In2S6@α-Fe2O3催化机理
在催化过程中,通常存在着多种活性粒子,包括h+和·O2 -等。为进一步研究Zn3In2S6@α-Fe2O3复合材料光电催化还原Cr(VI)的机理,进行了捕获实验(图9)。当在反应体系中通入O2时,材料对Cr(VI)的还原效率明显降低,这是由于O2竞争电子而产生了·O2 -;N2通入反应体系中用以除去溶液中的溶解O2,材料对Cr(VI)的还原效率明显提升,这是由于溶解氧的去除,使更多的电子参与了Cr(VI)的还原;将柠檬酸(h+捕获剂)加入反应体系中时,Zn3In2S6@α-Fe2O3复合材料对Cr(VI)的催化还原效率明显提升,这可能是由于h+的消耗延长了电子的寿命,从而加速了Cr(VI)的还原。
基于产生活性粒子的标准电极电位(O2/·O2 -(-0.33eV vs.NHE)),结合捕获实验结果及带隙结构,Zn3In2S6@α-Fe2O3传导被认为是该异质结的电荷传导模式(图10)。
Claims (4)
1.3D 花状Z型异质结光电催化剂Zn3In2S6@α-Fe2O3在光电催化Cr(VI)还原为Cr(III)中的应用,其特征在于,方法如下:将Zn3In2S6@α-Fe2O3涂覆在碳纸上作为工作电极,铂为对电极,Ag/AgCl为参比电极,形成三电极体系,将三电极体系置于电解质溶液中,加入含有Cr(VI)的废水,先在黑暗中搅拌60 min,然后在光电催化下,进行还原反应;所述光电催化的条件是:电压为-0.4~-0.7V,λ > 420 nm的可见光作为光源;
所述3D 花状Z型异质结光电催化剂Zn3In2S6@α-Fe2O3,按质量百分比,Fe2O3的负载量为5%,制备方法包括如下步骤:
1)将InCl3·4H2O溶于去离子水,得InCl3水溶液;将ZnSO4·7H2O和硫代乙酰胺溶于去离子水中,搅拌均匀后,加入InCl3水溶液,继续搅拌30 min后,转移至高压釜中,160℃水热反应12 h,洗涤干燥后,得粉末状固体Zn3In2S6;
2)将硝酸铁和乙酸铵加入到乙醇和去离子水的混合溶液中,超声10-15 min,使其均匀分散后,加入适量Zn3In2S6,搅拌30-40 min后,在180℃下水热反应24 h,产物洗涤干燥后,得Zn3In2S6@α-Fe2O3。
2.根据权利要求1所述的应用,其特征在于,所述电解质溶液为pH = 3.0,浓度为0.1mol·L-1的Na2SO4 。
3.根据权利要求1所述的应用,其特征在于,步骤2)中,按体积比,乙醇:去离子水 =20:1。
4.根据权利要求1所述的应用,其特征在于,步骤1)中,按摩尔比,InCl3·4H2O:ZnSO4·7H2O:硫代乙酰胺= 2: 3 : 6。
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