CN111036238B - 一种Fe2O3/WS2异质结光催化剂及其制备方法 - Google Patents
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Abstract
一种Fe2O3/WS2异质结光催化剂及其制备方法，属于光催化技术领域。本申请提供一种具有高效光化学能转换效率的光催化剂。本发明所述光催化剂由附载有Fe2O3纳米颗粒的WS2片层构成，呈花状结构；是通过水热反应耦合两种窄带半导体制备得到的一种具有异质结结构的复合材料。本发明制得的光催化剂具有较高的光生电子‑空穴对分离效率，在模拟太阳光光源照射下对亚甲基蓝指示剂溶液具有良好氧化降解效果的同时，对六价铬离子还具有较强的还原性。
Description
技术领域
本发明涉及一种Fe2O3/WS2异质结光催化剂及其制备方法，属于光催化技术领域。
背景技术
自Honda-Fujishima效应发现以来，光催化技术受到了科学界的极大关注。以半导体材料为核心的光催化技术可将太阳能作为光源驱动室温化学反应，即催化剂吸附催化目标物、催化剂吸收光能并受激发产生电子和空穴、电子和空穴迁移并和吸附目标物发生光化学反应。研究表明，制约半导体光催化剂效率的因素主要有以下三点：(1)太阳光谱利用率——常用的金属氧化物通常仅限紫外光激发，太阳光谱利用率尚不足<5％；(2)光生电荷分离转移效率——光生电荷在体相迅速复合，在迁移过程中也易被杂质或缺陷俘获；(3)表面化学反应效率——到达反应活性位点的电子与质子易于表面复合，逆反应的同时发生也大量消耗载流子。因此，提供一种具有高效光化学能转换效率的光催化剂及其制备方法是十分必要的。
发明内容
本发明目的是为了提供一种具有高效光化学能转换效率的Fe2O3/WS2异质结及其制备方法。
本发明中Fe2O3/WS2异质结光催化剂是由附载有Fe2O3纳米颗粒的WS2片层构成，呈花状结构；其制备方法是按下述步骤进行的：
步骤一、Fe2O3纳米颗粒的制备：将FeCl3·6H2O溶解于无水乙醇中，超声震荡后加入去离子水和醋酸钠，搅拌，然后水热反应，自然冷却至室温，再经洗涤、真空干燥后得到Fe2O3纳米颗粒；
步骤二、Fe2O3/WS2复合材料的制备：将步骤一制得的纳米颗粒加入去离子水中，搅拌，然后依次加入WCl6和CH4N2S，超声震荡同时磁力搅拌，再加热反应后自然冷却至室温，再经洗涤、干燥处理，得到花状Fe2O3/WS2异质结光催化剂。
进一步地限定，步骤一中FeCl3·6H2O与醋酸钠的摩尔比为(0.5～2.0)∶1。
进一步地限定，步骤一中搅拌速度为100rpm～500rpm，搅拌时间为1h。
进一步地限定，步骤一中水热反应温度为180℃～200℃，水热反应时间为20h～24h。
进一步地限定，步骤一中在60℃下真空干燥10h。
进一步地限定，步骤二中Fe2O3纳米颗粒、WCl6和CH4N2S的摩尔比为1∶(1～6)∶(6～36)。
进一步地限定，步骤二中搅拌速度为100rpm～500rpm，搅拌时间为30min。
进一步地限定，步骤二中180℃～220℃下保温24h～36h。
进一步地限定，步骤一中所述洗涤是先用无水乙醇洗涤3次后再用去离子水洗涤3次。
进一步地限定，步骤二中所述洗涤是先用无水乙醇洗涤3次后再用去离子水洗涤3次。
本发明具有以下有益效果：
本发明的方法制备得到的花状Fe2O3/WS2异质结光催化剂具有较高的光生电子-空穴对分离效率，在模拟太阳光光源下对亚甲基蓝指示剂溶液具有良好的氧化降解效果的同时，对六价铬离子还具有较强的还原性。
附图说明
图1为本发明Fe2O3/WS2异质结的合成过程示意图；
图2(a)是WS2纳米片和Fe2O3纳米颗粒的X射线衍射图谱；
图2(b)和图2(c)是对2WF在31～35°处以及37.5～42°处进行分峰拟合；
图3(a)是Fe2O3纳米颗粒、WS2纳米片、0.5WF、1WF、2WF和3WF的扫描电镜照片；
图3(b)是Fe2O3/WS2异质结的各元素分布图像；
图3(c)是Fe2O3/WS2异质结的透射电镜；
图3(d)是图3(c)选区高分辨透射电镜照片；
图4是Fe2O3/WS2异质结的X射线光电子能谱，(a)Fe元素，(b)W元素，(c)O元素，(d)S元素；
图5是Fe2O3纳米颗粒、WS2纳米片和2WF的光致发光光谱；
图6(a)是Fe2O3/WS2异质结对30mL 20mg/L的亚甲基蓝溶液的光催化降解情况比较；
图6(b)是Fe2O3/WS2异质结对30mL 40mg/L的重铬酸钾溶液的光催化还原情况比较；
图7是Fe2O3/WS2异质结的催化反应原理示意图。
具体实施方式
具体实施方式一：本实施例中Fe2O3/WS2异质结光催化剂的制备方法是按下述步骤进行的：
步骤一：Fe2O3纳米颗粒的制备：将5mmol FeCl3·6H2O溶于20mL无水乙醇中，超声震荡30min后加入3.4mL去离子水和5mmol醋酸钠，以500rpm的速度搅拌1h，转移至100mL反应釜中，在200℃条件下水热反应24h，自然冷却至室温，取出后先用无水乙醇洗涤3遍再用去离子水洗涤3遍，置于真空干燥箱中，在60℃下保温10h后获得 Fe2O3纳米颗粒；
步骤二：Fe2O3/WS2复合材料的制备：将0.5mmol步骤一制得的Fe2O3纳米颗粒加到40mL去离子水中，以500rpm的速度搅拌30min，然后依次加入2mmol的WCl6和12 mmol的CH4N2S，在超声频率为45KHz条件下超声震荡同时磁力搅拌30min，然后转移至50mL反应釜中，在200℃下保温24h，先用无水乙醇洗涤3遍再用去离子水洗涤3 遍，转移至真空干燥箱中，在60℃保温10h，得到花状Fe2O3/WS2异质结光催化剂，命名为2WF，合成路线如图1所示。
具体实施方式二：本实施方式与具体实施方式一不同的是：步骤二中Fe2O3纳米颗粒用量为2mmol，WCl6用量为2mmol，CH4N2S用量为12mmol，产品命名为0.5WF。其它步骤和参数与具体实施一相同。
具体实施方式三：本实施方式与具体实施方式一不同的是：步骤二中Fe2O3纳米颗粒用量为1mmol，WCl6用量为2mmol，CH4N2S用量为12mmol，命名为1WF。其它步骤和参数与具体实施一相同。
具体实施方式四：本实施方式与具体实施方式一不同的是：步骤二中Fe2O3纳米颗粒用量为0.3mmol，WCl6用量为2mmol，CH4N2S用量为12mmol，样品命名为3WF。其它步骤和参数与具体实施一相同。
对比例1：
将2mmol WCl6和12mmol CH4N2S，在超声频率为45KHz下超声震荡同时磁力搅拌30min后转移至50mL反应釜中，200℃下保温24h，然后先用无水乙醇洗涤3遍再用去离子水洗涤3遍，然后在60℃真空干燥箱中保温10h后，得到WS2纳米片。
对比例2：
将5mmol的FeCl3·6H2O溶于20mL无水乙醇中，在超声频率为45KHz下超声震荡30min后加入3.4mL去离子水和5mmol醋酸钠，以500rpm的速度搅拌1h，转移至 100mL反应釜中，200℃下水热反应24h，自然冷却至室温后取出，先用无水乙醇洗涤 3遍再用去离子水洗涤3遍，在60℃真空干燥箱中保温10h后，获得Fe2O3纳米颗粒。
WS2和Fe2O3的X射线衍射图谱如图2(a)所示。由图2(a)图可知，Fe2O3/WS2异质结各衍射峰分别在33.0°,36.2°,40.0°,41.2°,43.6°,54.4°,64.1°和66.3°对应赤铁矿相α-Fe2O3的(104),(110),(113),(202),(116),(214),(300)和(125)晶面，在14.2°,28.7°,33.7°, 39.2°,49.6°,56.1°和58.6°对应辉钨矿相2H-WS2的(002),(004),(101),(103),(105),(106) 和(110)晶面。图2(b)和图2(c)是对2WF在31～35°处以及37.5～42°处进行分峰拟合，确定该试样在33.7°，39.2°以及39.6°分别对应2H-WS2的(101)、(103)晶面，以及α-Fe2O3的(006)晶面。并且当Fe/W元素占比较多时(如0.5WF和1.0WF)，复合材料中存在杂质相FeWO4，但当WS2含量比重增加时(如2.0WF和3.0WF)，该杂质相消失。这是因为在水热反应中，依靠S源(CH4N2S)分解释放的H2S还原W源(WCl6)中的W6+。当Fe2O3较多时，因Fe3+的氧化性强于W6+，更易被还原，故而生成副产物FeWO4。当 WS2较多时，复合材料表现为纯净的α-Fe2O3和2H-WS2相。
Fe2O3纳米颗粒、WS2纳米片、0.5WF、1WF、2WF和3WF的扫描电镜照片如图3 (a)所示。由图3(a)可知，单一组分的Fe2O3纳米颗粒和WS2纳米片分别呈现零维圆角纳米颗粒和二维纳米片层形貌。合成的Fe2O3/WS2异质结中，WS2片层依附Fe2O3粒子生长，随着WS2含量的增加，Fe2O3逐渐被WS2片层包覆，并形成稳定的三维花状结构。 WS2片层形似花瓣，Fe2O3粒子形似露珠覆于其表面。这种特殊的形貌使得复合材料二组分紧密结合，有利于形成大量的异质结构。
对具体实施方式一制得的2WF进行各元素能谱分析，测试结果如图3(b)所示。由图3(b)可知，Fe、W、O、S四种元素均匀分布于材料表面，进一步说明该复合材料是由Fe2O3和WS2二组分构成。
具体实施方式一制得的Fe2O3/WS2异质结(2WF)的透射电镜如图3中(c)图所示，并对图3(c)中图的选区进行高分辨透射电镜测试，测试结果如图3(d)所示。由图3 (d)可知，选区部分的HRTEM照片清楚显示由Fe2O3的(104)晶面和WS2的(002) 晶面形成的异质结结构。
对具体实施方式一制得的2WF进行X射线光电子能谱测试，测试结果如图4所示，其中图4中(a)为Fe元素、(b)为W元素、(c)为O元素、(d)为S元素。由图4可知，进一步证明Fe、W、O、S四种元素分布于材料表面，进一步说明该复合材料是由 Fe2O3和WS2二组分构成。
对Fe2O3纳米颗粒、WS2纳米片和2WF进行光致发光测试(PL)光谱测试，获得光致发光谱线，如图5所示。由图5可知，2WF的光致发光强度与WS2和Fe2O3相比显著降低，说明花状Fe2O3/WS2的异质结构能够降低复合材料中光生电子-空穴对复合几率，有效促进光生载流子寿命的增加。
对具体实施方式一制得的2WF进行光催化性能测试，具体测试条件为：选用300W的氙灯加AM1.5滤镜模拟太阳光光源。测试过程为：在100mL的烧杯中放入30mL的 20mg/L的亚甲基蓝溶液和10mg光催化剂，将烧杯置于光源前方搅拌台上，并固定烧杯与光源的距离为5cm，降解反应过程中保持匀速的磁力搅拌。每10min对反应液进行吸光度检测，以此绘制光照时间与降解率变化曲线，如图6(a)所示。
对具体实施方式一制得的2WF进行光催化性能测试，具体测试条件为：选用300W的氙灯加AM1.5滤镜模拟太阳光光源。测试过程为：在100mL的烧杯中放入30mL的 40mg/L重铬酸钾溶液，加入20mg乙二胺四乙酸EDTA作为空穴牺牲剂，并加入20mg 的2WF作为光催化剂，然后将烧杯置于光源前方搅拌台上，并固定烧杯与光源的距离为 5cm，降解反应过程中保持匀速的磁力搅拌。每10min对反应液进行吸光度检测，以此绘制光照时间与降解率变化曲线，如图6(b)所示。
由图6可知，2WF与WS2纳米片和Fe2O3纳米颗粒相比对指示剂的降解效率有了较大幅度的提高，说明复合材料独特的三维花状结构促进形成大量的异质结构，进而说明本方法制得的光催化剂在模拟太阳光光源下在具有较强的光催化性能，即表现为光催化氧化同时还具有可观的光催化还原性能。Fe2O3/WS2异质结的催化反应原理示意图如图7所示，在水环境中，光诱导产生的电子和空穴分别与吸附的溶解氧和水分子作用产生具有强氧化性的羟基自由基(·OH)和超氧离子自由基(·O2-)，这类活性基团具有无选择性的氧化降解有机污染物(MB)的能力；另一方面，光生电子还可用以还原有毒无机重金属Cr6+离子。
Claims (8)
1.一种Fe2O3/WS2异质结光催化剂的制备方法，其特征在于：该方法是按下述步骤进行的：
步骤一、Fe2O3纳米颗粒的制备：将FeCl3·6H2O溶解于无水乙醇中，超声震荡后加入去离子水和醋酸钠，搅拌，然后水热反应，自然冷却至室温，再经洗涤、真空干燥后得到Fe2O3纳米颗粒；
步骤二、Fe2O3/WS2复合材料的制备：将步骤一制得的Fe2O3纳米颗粒加入去离子水中，搅拌，然后依次加入WCl6和CH4N2S，超声震荡同时磁力搅拌，再加热反应后自然冷却至室温，再经洗涤、干燥处理，得到花状Fe2O3/WS2异质结光催化剂；
所述的步骤二中Fe2O3纳米颗粒、WCl6和CH4N2S的摩尔比为1∶4∶24；
所述异质结光催化剂由附载有Fe2O3纳米颗粒的WS2片层构成，呈花状结构。
2.根据权利要求1所述的一种Fe2O3/WS2异质结光催化剂的制备方法，其特征在于：所述的步骤一中FeCl3·6H2O与醋酸钠的摩尔比为(0.5～2.0)∶1。
3.根据权利要求1所述的一种Fe2O3/WS2异质结光催化剂的制备方法，其特征在于：所述的步骤一中搅拌速度为100rpm～500rpm，搅拌时间为1h。
4.根据权利要求1所述的一种Fe2O3/WS2异质结光催化剂的制备方法，其特征在于：所述的步骤一中水热反应温度为180℃～200℃，水热反应时间为20h～24h。
5.根据权利要求1所述的一种Fe2O3/WS2异质结光催化剂的制备方法，其特征在于：所述的步骤一中在60℃下真空干燥10h。
6.根据权利要求1所述的一种Fe2O3/WS2异质结光催化剂的制备方法，其特征在于：所述的步骤二中搅拌速度为100rpm～500rpm，搅拌时间为30min。
7.根据权利要求1所述的一种Fe2O3/WS2异质结光催化剂的制备方法，其特征在于：所述的步骤二中所述加热反应是在180℃～220℃下保温24h～36h。
8.根据权利要求1所述的一种Fe2O3/WS2异质结光催化剂的制备方法，其特征在于：所述的步骤一和步骤二中洗涤是先用无水乙醇洗涤3次后再用去离子水洗涤3次。
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