CN109126828A - Z型花球状二硫化钼/硫化银/银复合光催化剂的制备方法及其应用 - Google Patents
Z型花球状二硫化钼/硫化银/银复合光催化剂的制备方法及其应用 Download PDFInfo
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Abstract
Z型花球状二硫化钼/硫化银/银复合光催化剂的制备方法及其应用，本发明涉及一种光催化剂的制备方法，它为了解决现有MoS2光催化剂的光催化效率较低的问题。制备方法：一、将(NH4)6Mo7O24·4H2O和硫脲分散在去离子水中，然后加入PVP，得到混合溶液，在180～220℃下水热反应，得到花球型MoS2；二、将花球型MoS2分散在离子水中，然后加入AgNO3在暗处搅拌反应，再滴加Na2S溶液，最后紫外灯下光照处理，得到该复合光催化剂。本发明以单质Ag作为电子传输体，加快了Ag2S导带上的电子向MoS2价带上传输，花球状MoS2褶皱边缘提供更多的活性位点，增加了复合催化剂的光催化效率。
Description
技术领域
本发明涉及一种MoS2/Ag2S/Ag复合光催化剂的制备方法及其应用。
背景技术
环境污染制约着人类社会的可持续发展，其中水体中有机污染物的降解问题仍是目前亟待解决的难题。而半导体光催化氧化技术具有反应条件温和，催化剂容易制备，无二次污染等优点，是解决环境污染问题的一条有效途径。目前，开发高效可见光响应的光催化剂，提高光量子效率，已成为光催化领域研究的重点课题。
随着石墨烯等二维材料研究热潮的兴起，MoS2的研究也引起了广泛的关注。MoS2层与层之间由相对薄弱的范德华力维持，因此表现出许多优异的性质。MoS2材料在润滑剂、催化剂和晶体管等领域都有广泛的应用。纳米MoS2的禁带宽度在1.20-1.9eV，具有在可见光下的光催化活性，同时MoS2片层边缘具有更多的活性位点，进而能提高它的催化活性，因此MoS2被广泛应用于加氢脱硫、光解水制氢和光催化降解有机污染物等催化反应。但是MoS2被可见光激发后，光生电子-空穴对易发生复合，致使单独的MoS2光催化效率低。硫化银的禁带宽度较窄，能够被可见光激发，与MoS2复合后能够有效降低光生电子空穴对复合几率同时拓宽吸收光范围。此外，当硫化银被紫外光照射时部分银离子会被还原为单质银，而单质银可以作为导电介质以加速电荷迁移速率。
发明内容
本发明的目的是为了解决现有MoS2光催化剂的光催化效率较低的问题，而提供一种Z型花球状MoS2/Ag2S/Ag复合光催化剂的制备方法及其应用。
本发明Z型花球状MoS2/Ag2S/Ag复合光催化剂的制备方法按下列步骤实现：
一、将(NH4)6Mo7O24·4H2O和硫脲分散在去离子水中，然后加入PVP，得到混合溶液，将混合溶液转移至聚四氟乙烯内胆，在180～220℃下水热反应8～12h，反应完毕后自然冷却至室温，固相产物经洗涤、干燥后得到花球型MoS2；
二、将花球型MoS2分散在去离子水中，然后加入AgNO3在暗处搅拌8～12h，再(缓慢)滴加Na2S溶液，继续搅拌，固相反应物经洗涤、干燥后得到MoS2/Ag2S复合物，将MoS2/Ag2S复合物在紫外灯下光照处理，干燥后得到Z型花球状MoS2/Ag2S/Ag复合光催化剂。
将本发明制备得到的Z型花球状MoS2/Ag2S/Ag复合光催化剂应用于(深度)净化有机污染水体和杀菌。
本发明Z型花球状MoS2/Ag2S/Ag复合光催化剂的制备方法包括以下有益效果：
本发明通过简单的水热法和沉积法分别制备出MoS2花球状纳米球和MoS2/Ag2S复合材料，该方法具有简单、高效等优点。制备的MoS2/Ag2S/Ag复合光催化剂材料具有以下优势：1、单质Ag作为电子传输体，加快了Ag2S导带上的电子向MoS2价带上传输，有效提高了复合催化剂的电子传输速率；2、Z型结构使Ag2S导带上的电子与MoS2价带上的空穴复合，降低了此复合催化剂的光腐蚀效应，有效提高了光生电子空穴对的分离速率和复合催化剂的光降解能力；3、花球状MoS2褶皱边缘提供更多的活性位点，增加了复合催化剂的光催化效率。
附图说明
图1为不同沉积量的MoS2/Ag2S/Ag复合光催化剂的XRD图，其中◆代表MoS2，代表Ag2S，★代表Ag，1—实施例二，2—实施例三，3—实施例一，4—实施例四；
图2为实施例二得到的MoS2/Ag2S/Ag复合光催化剂的透射电镜图；
图3为实施例三得到的MoS2/Ag2S/Ag复合光催化剂的透射电镜图；
图4为实施例一得到的MoS2/Ag2S/Ag复合光催化剂的透射电镜图；
图5为实施例四得到的MoS2/Ag2S/Ag复合光催化剂的透射电镜图；
图6为不同光催化体系中刚果红的降解效率图，其中1代表刚果红，2代表Ag2S，3代表MoS2，4代表MoS2-Ag2S-0.5(实施例一中未经紫外灯光照处理的MoS2/Ag2S复合物)，5代表实施例二，6代表实施例三，7代表实施例四，8代表实施例一；
图7为不同光催化体系中盐酸四环素的降解效率图，其中A代表盐酸四环素，B代表
实施例一；
图8为光照前后刚果红和盐酸四环素体系中总有机碳的去除效率柱状图；
图9为MoS2/Ag2S/Ag复合光催化剂对铜绿假单胞菌的抗菌效率图，图中■代表在可见光下同时存在铜绿假单胞菌和实施例一得到的MoS2/Ag2S/Ag复合光催化剂，●代表只有铜绿假单胞菌在可见光下反应，▲代表在无可见光下同时存在铜绿假单胞菌和实施例一得到的MoS2/Ag2S/Ag复合光催化剂；
图10为不同光照时间铜绿假单胞菌的菌落数量照片。
具体实施方式
具体实施方式一：本实施方式Z型花球状MoS2/Ag2S/Ag复合光催化剂的制备方法按下列步骤实施：
一、将(NH4)6Mo7O24·4H2O和硫脲分散在去离子水中，然后加入PVP，得到混合溶液，将混合溶液转移至聚四氟乙烯内胆，在180～220℃下水热反应8～12h，反应完毕后自然冷却至室温，固相产物经洗涤、干燥后得到花球型MoS2；
二、将花球型MoS2分散在去离子水中，然后加入AgNO3在暗处搅拌8～12h，再滴加Na2S继续搅拌，固相反应物经洗涤、干燥后得到MoS2/Ag2S复合物，将MoS2/Ag2S复合物在紫外灯下光照处理，干燥后得到Z型花球状MoS2/Ag2S/Ag复合光催化剂。
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一中(NH4)6Mo7O24·4H2O和硫脲的摩尔比为1：1～35。
具体实施方式三：本实施方式与具体实施方式一或二不同的是步骤一中固相产物依次使用去离子水、无水乙醇进行交替洗涤多次。
具体实施方式四：本实施方式与具体实施方式一至三之一不同的是步骤一中固相产物的干燥温度为50℃。
具体实施方式五：本实施方式与具体实施方式一至四之一不同的是步骤二中花球型MoS2与AgNO3的摩尔比为1：0.1～0.7。
具体实施方式六：本实施方式与具体实施方式一至五之一不同的是步骤二中Na2S的加入量与AgNO3的摩尔比为1:1。
具体实施方式七：本实施方式与具体实施方式一至六之一不同的是步骤二中固相反应物使用去离子水、无水乙醇交替洗涤三次。
具体实施方式八：本实施方式与具体实施方式一至六之一不同的是步骤二中MoS2/Ag2S复合物在紫外灯下光照处理的时间为0.8～1.2h。
具体实施方式九：本实施方式与具体实施方式一至八之一不同的是步骤二得到的Z型花球状MoS2/Ag2S/Ag复合光催化剂的粒径为100～200nm。
具体实施方式十：本实施方式将具体实施方式一得到的Z型花球状MoS2/Ag2S/Ag复合光催化剂应用于(深度)净化有机污染水体和杀菌。
实施例一：本实施例Z型花球状MoS2/Ag2S/Ag复合光催化剂的制备方法按下列步骤实施：
一、将0.210g(NH4)6Mo7O24·4H2O和0.456g硫脲分散在30mL去离子水中，磁力搅拌10min后，加入0.1g PVP，继续搅拌20min，得到混合溶液，将混合溶液转移至聚四氟乙烯内胆，在200℃下水热反应10h，反应完毕后自然冷却至室温，固相产物用去离子水、乙醇交替洗涤三次，在50℃下干燥12h，得到花球型MoS2(黑色固体)；
二、将1mmol花球型MoS2分散在50mL去离子水中超声20min，然后加入0.5mmolAgNO3在暗处搅拌12h，再滴加50mLNa2S(0.35mmol)继续搅拌1h，固相反应物用去离子水、乙醇交替洗涤三次，在50℃下干燥12h，得到MoS2/Ag2S复合物，将MoS2/Ag2S复合物在紫外灯下光照处理1h，离心干燥后得到Z型花球状MoS2/Ag2S/Ag复合光催化剂。
本实施例得到的MoS2/Ag2S/Ag复合光催化剂的透射电镜图如图4所示。
实施例二：本实施例与实施例一不同的是步骤二加入0.1mmol AgNO3在暗处搅拌12h。其他步骤及参数与实施例一相同。
本实施例得到的MoS2/Ag2S/Ag复合光催化剂的透射电镜图如图2所示。
实施例三：本实施例与实施例一不同的是步骤二加入0.3mmol AgNO3在暗处搅拌12h。其他步骤及参数与实施例一相同。
本实施例得到的MoS2/Ag2S/Ag复合光催化剂的透射电镜图如图3所示。
实施例四：本实施例与实施例一不同的是步骤二加入0.7mmol AgNO3在暗处搅拌12h。其他步骤及参数与实施例一相同。
本实施例得到的MoS2/Ag2S/Ag复合光催化剂的透射电镜图如图5所示。
图1为实施例一至实施例四不同沉积量的MoS2/Ag2S/Ag复合光催化剂的XRD图，从XRD图上可以看出当Ag+沉积量为0.1和0.3mmol时，Ag2S与Ag的XRD衍射峰都较弱，当Ag+沉积量为0.5和0.7mmol时，Ag2S与Ag的XRD衍射峰都相对较强，且都与标准卡片相对应，说明MoS2与Ag2S/Ag已经成功复合。
图2-5分别为Ag2S/Ag为0.1-0.7mmol时得到的复合光催化剂的透射电镜图。从图中我们可以看出随着Ag2S/Ag沉积量的增加，MoS2花球上的覆盖面积逐渐增大。但是当Ag2S/Ag沉积量超过0.5mmol时，Ag2S/Ag纳米粒子在MoS2花球上逐渐形成团聚现象。
应用实施例一：本实施例称取40mg上述实施例制得的MoS2/Ag2S/Ag复合光催化剂，加入到50mL刚果红溶液(C0＝30mg/L)，首先在暗处搅拌60min，然后在可见光下120min进行光催化降解，计算其降解效率达到97.0％，其中TOC去除率为81.88％。
应用实施例二：本实施例称取40mg上述实施例制得的MoS2/Ag2S/Ag复合光催化剂，加入到50mL盐酸四环素溶液(C0＝5mg/L)，首先在暗处搅拌60min，然后在可见光下120min进行光催化降解，计算其降解效率达到92.6％，其中TOC去除率为65.34％。
应用实施例三：本实施例称取40mg上述实施例制得的MoS2/Ag2S/Ag复合光催化剂，加入到50mL铜绿假单胞菌悬浮液中(C0＝1×106CFU/mL)，首先在暗处搅拌60min，然后在可见光下180min进行光催化杀菌，计算其抗菌效率达到100％。
图6和图7分别为在不同光催化体系条件下刚果红和盐酸四环素的降解效率曲线，从图中可以看出，复合光催化剂对刚果红和盐酸四环素表现出很好的光催化活性，其性能优于纯的二硫化钼、硫酸银。图8中表明硫酸银/银沉积量为0.5mmol时得到的光催化剂对刚果红和盐酸四环素体系中的总有机碳具有一定的去除效率。经过120min光照后，刚果红的TOC去除率为81.88％，盐酸四环素的TOC去除率为65.34％。
图9为在不同光催化体系条件下对铜绿假单胞菌的抗菌效率曲线，通过试验结果得知，在可见光光照180min时，复合催化剂对铜绿假单胞菌的抗菌效率达到100％。图10随着光照时间的延长，铜绿假单胞菌的菌落数逐渐减少，180min时，没有铜绿假单胞菌的菌落生长。
本实施例MoS2/Ag2S/Ag复合催化剂形成的Z型机理如下：在此体系中，Ag作为电子传输体，在可见光照射下，Ag2S导带上的电子优先传递给Ag，Ag迅速把电子传输到MoS2价带上，并与MoS2价带上空穴复合，形成Z型电子传输机制，有效分离了的光生电子-空穴对。抑制了MoS2和复合催化剂的光腐蚀。MoS2导带上的电子把溶液中的O2还原成·O2 -，同时，价带上的空穴具有强还原能力，最后，·O2 -，Ag2S价带上的h+共同参与光催化反应降解有机物和抗菌。
Claims (10)
1.Z型花球状二硫化钼/硫化银/银复合光催化剂的制备方法，其特征在于该方法是按下列步骤实现：
一、将(NH4)6Mo7O24·4H2O和硫脲分散在去离子水中，然后加入PVP，得到混合溶液，将混合溶液转移至聚四氟乙烯内胆，在180～220℃下水热反应8～12h，反应完毕后自然冷却至室温，固相产物经洗涤、干燥后得到花球型MoS2；
二、将花球型MoS2分散在去离子水中，然后加入AgNO3在暗处搅拌8～12h，再滴加Na2S溶液，继续搅拌，固相反应物经洗涤、干燥后得到MoS2/Ag2S复合物，将MoS2/Ag2S复合物在紫外灯下光照处理，干燥后得到Z型花球状MoS2/Ag2S/Ag复合光催化剂。
2.根据权利要求1所述的Z型花球状二硫化钼/硫化银/银复合光催化剂的制备方法，其特征在于步骤一中(NH4)6Mo7O24·4H2O和硫脲的摩尔比为1：1～35。
3.根据权利要求1所述的Z型花球状二硫化钼/硫化银/银复合光催化剂的制备方法，其特征在于步骤一中固相产物依次使用去离子水、无水乙醇进行交替洗涤多次。
4.根据权利要求1所述的Z型花球状二硫化钼/硫化银/银复合光催化剂的制备方法，其特征在于步骤一中固相产物的干燥温度为50℃。
5.根据权利要求1所述的Z型花球状二硫化钼/硫化银/银复合光催化剂的制备方法，其特征在于步骤二中花球型MoS2与AgNO3的摩尔比为1：0.1～0.7。
6.根据权利要求1所述的Z型花球状二硫化钼/硫化银/银复合光催化剂的制备方法，其特征在于步骤二中Na2S的加入量与AgNO3的摩尔比为1:1。
7.根据权利要求1所述的Z型花球状二硫化钼/硫化银/银复合光催化剂的制备方法，其特征在于步骤二中固相反应物使用去离子水、无水乙醇交替洗涤三次。
8.根据权利要求1所述的Z型花球状二硫化钼/硫化银/银复合光催化剂的制备方法，其特征在于步骤二中MoS2/Ag2S复合物在紫外灯下光照处理的时间为0.8～1.2h。
9.根据权利要求1所述的Z型花球状二硫化钼/硫化银/银复合光催化剂的制备方法，其特征在于步骤二得到的Z型花球状MoS2/Ag2S/Ag复合光催化剂的粒径为100～200nm。
10.如权利要求1所述的Z型花球状二硫化钼/硫化银/银复合光催化剂的应用，其特征在于Z型花球状MoS2/Ag2S/Ag复合光催化剂作为光催化剂应用于净化有机污染水体和杀菌。
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