CN107376964A - 一种以掺杂钙钛矿为载体的复合光催化剂制备及其应用 - Google Patents
一种以掺杂钙钛矿为载体的复合光催化剂制备及其应用 Download PDFInfo
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Abstract
提供了一种以掺杂钙钛矿为载体的复合光催化剂制备及其应用。首先以柠檬酸络合法制备位掺杂钙钛矿载体(LaCo(1‑x)BixO3),再采用原位沉淀法将半导体光催化材料(Ag3PO4)负载于掺杂钙钛矿载体(LaCo(1‑x)BixO3)表面得到Ag3PO4/LaCo(1‑x)BixO3复合光催化剂。掺杂可增大钙钛矿载体的比表面积,并促进更多氧空位的形成,延长复合光催化剂中光生电荷寿命,抑制光生电子‑空穴对的复合,有效提高光催化效率。将该复合光催化剂应用于处理双酚A(BPA)难生物降解有机废水,投加量为0.5g/L,40分钟时对BPA(10 mg/L)的去除率高达100%,矿化率可达80.7%。
Description
技术领域
本发明涉及一种以掺杂钙钛矿为载体的复合光催化剂制备及其应用,具体涉及:掺杂钙钛矿LaCo(1-x)BixO3载体的制备和可见光响应型复合光催化剂Ag3PO4/LaCo(1-x)BixO3的制备方法及应用,属于污水处理催化反应材料的制备与应用。
背景技术
在过去十年中,环境内分泌干扰物质(EDCs)带来的污染日益严重,其中应用广泛的双酚A(BPA)由于其难降解性在环境中积累,对人类健康和生态系统安全构成潜在威胁,因此如何有效去除BPA成为当今亟待解决的问题。
Ag3PO4是可见光响应型半导体光催化材料,但易于光腐蚀的缺陷对其光催化活性造成了极大影响。近年来,对于Ag3PO4光催化材料的研究越来越多的集中在将Ag3PO4与其他半导体材料复合,以改善其光腐蚀性问题,提高其光催化活性。
LaCoO3是ABO3型钙钛矿氧化物,这类材料制备方法简单、成本低廉。钙钛矿型氧化物传导电子能力强,稳定性较好,是一种优良的导电材料,也可作为光催化材料,但将其单独使用作为光催化剂降解有机物效果欠佳,而且大多必须在紫外光条件下进行反应。我们曾以LaCoO3作载体与Ag3PO4复合,研究证实ABO3型钙钛矿氧化物与Ag3PO4复合能有效提高Ag3PO4的光催化活性和稳定性。有研究表明,半导体材料(如TiO2、ZnS等)的掺杂可促使其具有更多的氧空位,能有效提高其光催化活性。钙钛矿载体掺杂后将同样具有更多的氧空位,从而促进复合光催化剂光生电子的捕获,抑制复合光催化剂光生电子-空穴对的复合,提高其光催化效率。目前还没有将掺杂钙钛矿型氧化物作为载体与其他半导体光催化剂复合用于光催化领域的报道。
发明内容
本发明的目的是为了解决Ag3PO4易于光腐蚀,以及对有机物光催化矿化率较低的问题,增强其光催化活性。为此,本发明提供了一种以掺杂钙钛矿作载体负载可见光响应型半导体光催化材料的复合光催化剂,即Ag3PO4/LaCo(1-x)BixO3的制备方法及其应用。
实现本发明所采用的技术解决方案为:提供一种复合光催化剂(Ag3PO4/LaCo(1-x)BixO3)的制备方法,按以下步骤进行:
(A)柠檬酸络合法制备掺杂钙钛矿载体(LaCo(1-x)BixO3)
(A1)取5mmol硝酸镧(La(NO3)3)·nH2O),以及一定摩尔比的硝酸钴((Co(NO3)2)·6H2O)和硝酸铋(Bi(NO3)3)·5H2O)溶解于100ml的蒸馏水中,搅拌10~120min,再加入一定量柠檬酸(C6H8O7·H2O)溶液,加热至45~70℃再继续搅拌30~60min;
(A2)向上述溶液加入一定量的醇溶液,于45~70℃继续搅拌15~60min,再次升温并搅拌30~120min后得到溶胶,再将溶胶放入真空干燥箱,经真空干燥8~16h后得到干凝胶;
(A3)将干凝胶移至程序升温炉,先煅烧1~4h,再升温煅烧2~6h,待自然冷却取出,经研磨,过80目筛,即可制备不同Bi掺杂含量的LaCo(1-x)BixO3。
(B)原位沉淀法制备复合光催化剂(Ag3PO4/LaCo(1-x)BixO3)
(B1)取一定量的LaCo(1-x)BixO3分散在超纯水中并经超声处理(超声时间优选10~60min),而后加入AgNO3溶液并机械搅拌6~18 h (优选8~12 h)得分散液;
(B2)将磷酸盐溶液缓慢滴加至上述分散液中,滴完后再继续反应0.5~2 h,反应所得沉淀物经超纯水反复洗涤后,将其分离、干燥、过80目筛,即得Ag3PO4/LaCo(1-x)BixO3。
优选的是:步骤(A1)中的硝酸镧、硝酸钴、硝酸铋与柠檬酸的摩尔比为1:(1-X) : X :0~10(其中0<X<1),优选1:(1-X) : X :0.6~8,进一步优选(1-X) : X :0.6~6(其中0.1≤X≤0.9)。
优选的是:步骤(A2)中醇溶液为C2~C6醇类有机溶剂,优选乙二醇。
优选的是:步骤(A2)中再次升温的温度区间应优选为70~100°C。
优选的是:步骤(A2)中真空干燥的温度区间应优选为40~120°C。
优选的是:步骤(A3)中程序升温炉内第一段煅烧温度应为300~450°C,第二段煅烧温度应为600~800°C。
优选的是:步骤(B1)中加入AgNO3 的质量与LaCo(1-x)BixO3的质量之比为1:0.05~0.5。
优选的是:步骤(B2)中碱金属磷酸盐溶液为磷酸氢二钠,且加入的 Na2HPO4·12H2O摩尔量与AgNO3的摩尔量之比为1:1~3.5,进一步优选1:2~3。
此外,本发明还提供以掺杂钙钛矿作载体的复合光催化剂(Ag3PO4/LaCo(1-x)BixO3)的应用,具体为:将该复合光催化剂应用于双酚A(BPA)难降解有机废水的处理。
另外,本发明还提供复合光催化剂Ag3PO4/LaCo(1-x)BixO3的应用方法,即:向BPA溶液中加入Ag3PO4/LaCo(1-x)BixO3,先进行暗吸附反应,待达到吸附平衡后进行可见光光照降解污染物的实验。
作为优选,废水中所含的双酚A与复合光催化剂Ag3PO4/LaCo(1-x)BixO3的质量之比为1:5~100,优选1:30~60。
本发明的有益技术效果在于:
1、本发明所提供的复合光催化剂(Ag3PO4/LaCo(1-x)BixO3)的制备方法简单、可操作性强、具有产业化前景,并创新性的提出了B位掺杂Bi的钙钛矿型氧化物载体,即LaCo(1-x)BixO3的制备。
2、本发明所制备的复合光催化剂(Ag3PO4/LaCo(1-x)BixO3)在短时间内对双酚A(BPA)的降解效率和矿化率相较纯Ag3PO4有显著提高,吸附性能和矿化率也比Ag3PO4/LaCoO3更好。同时,以掺杂钙钛矿作为载体也在很大程度上程度上解决了Ag3PO4易光腐蚀的问题,Ag3PO4/LaCo(1-x)BixO3的稳定性较Ag3PO4/LaCoO3也大大提高。
附图说明:
图1为本发明实施例1的复合光催化剂的SEM图。
图2为本发明实施例1的复合光催化剂的XRD图。
图3为本发明实施例1的复合光催化剂在可见光下对BPA催化降解性能图。
图4为本发明实施例1的复合光催化剂在可见光下对BPA的矿化率图。
图5为本发明实施例1的复合光催化剂重复利用性能示意图。
具体实施方式
为了进一步了解本发明,以下结合实施例对本发明作进一步的详细阐述,但,并非对本发明做任何形式上的限制。这些描述只是为了进一步说明本发明的特征和优点,而不是对本发明权利要求的限制。凡依照本发明公开内容所作的任何本领域的等同替换,均属于本发明的保护范围。
实施例1:
(1)复合光催化剂的制备:首先用柠檬酸络合法制备掺杂钙钛矿载体,即LaCo0.5Bi0.5O3。取5mmol硝酸镧(La(NO3)3)·nH2O),2.5mmol硝酸钴(Co(NO3)2)·6H2O)和2.5mmol硝酸铋(Bi(NO3)3)·5H2O)溶解于100ml的蒸馏水中,搅拌30min,再加入15~30 mmol柠檬酸溶液,加热至50℃下搅拌45min;向上述溶液加入25mmol乙二醇溶液,在50℃继续搅拌30min,再升温至80℃搅拌60min后得到溶胶,然后经80℃真空干燥12h得到干凝胶;将干凝胶移至程序升温炉,先400℃煅烧2h,再升温至700℃煅烧4h,待自然冷却取出,经研磨,过80目筛,即得LaCo0.5Bi0.5O3。不投入硝酸铋,以相同方法可制备出钴酸镧(LaCoO3)。
再采用原位沉淀法制备Ag3PO4/LaCo(1-x)BixO3复合光催化剂(Ag3PO4/LaCo0.5Bi0.5O3)。将0.1 g LaCo0.5Bi0.5O3分散在散在超纯水中,并经超声处理30 min,而后向上述向经超声分散的LaCo0.5Bi0.5O3水溶液中加入50 mLAgNO3溶液(0.129 mol/L)并机械搅拌12 h;再将60mL Na2HPO4·12H2O溶液(0.043 mol/L)缓慢滴加至上述分散液中,滴完后继续搅拌1 h待反应完全,反应所得沉淀物经超纯水反复洗涤后,将其干燥、研磨过80目筛,即得所述LaCo0.5Bi0.5O3与Ag3PO4质量比为1:9的复合催化剂Ag3PO4/LaCo0.5Bi0.5O3。不投入LaCo0.5Bi0.5O3,以相同方法可制备出纯磷酸银(Ag3PO4)。
Ag3PO4/LaCo(1-x)BixO3复合光催化剂(Ag3PO4/LaCo0.5Bi0.5O3)的SEM与XRD表征结果分别见图1与图2。由SEM可看到复合催化剂的形貌和结构,图1中(a)、(b)分别为LaCo0.5Bi0.5O3和复合光催化剂Ag3PO4/LaCo0.5Bi0.5O3。由图1(a)明显地观察到经过Bi元素的掺杂,LaCo0.5Bi0.5O3表面变得粗糙,并且出现许多孔洞,从图1(b)可以看出纳米颗粒Ag3PO4均匀分散在LaCo0.5Bi0.5O3的表面,并与其紧密结合在一起。图2中LaCo0.5Bi0.5O3的特征峰较LaCoO3的特征峰向小角度方向偏移,经XRD分析可证明是Bi进入到LaCoO3的晶格中导致晶格间距变大;而且复合材料的成分仅包括LaCo0.5Bi0.5O3和Ag3PO4,没有其它物质的衍射峰,这说明复合光催化剂中组成成分之间只是通过物理作用相互复合,并没有发生化学反应。
(2)复合光催化剂应用于去除水中BPA的性能测试:在10 mg/L 的BPA溶液中,投加0.5g/L上述复合光催化剂,先进行暗吸附反应30 min达到吸附平衡后,再在300 W氙灯照射条件下光催化反应40 min,并在不同反应时间点测定上清液中BPA残余浓度和TOC值,可得该复合光催化剂及磷酸银在可见光照射下对有机污染物BPA的光催化降解效率曲线和矿化率图,分别见图3、图4。测试结果可知,光照40 min,Ag3PO4/LaCo0.5Bi0.5O3对BPA的去除效率和矿化率分别达到100%和80.7%,远远高于纯磷酸银对BPA的去除效率(72%)及矿化率(58.3%),也高于相同时间呢Ag3PO4/LaCoO3复合光催化剂对BPA的矿化率(77%)。
实施例2:
(1)复合光催化剂的制备:首先用柠檬酸络合法制备制备掺杂钙钛矿载体,,即LaCo0.9Bi0.1O3。取5mmol硝酸镧(La(NO3)3)·nH2O),4.5mmol硝酸钴(Co(NO3)2)·6H2O)和0.5mmol硝酸铋(Bi(NO3)3)·5H2O)溶解于100ml的蒸馏水中,搅拌30min,再加入25mmol柠檬酸溶液,加热至50℃下搅拌45min;向上述溶液加入15~30 mmol乙二醇溶液,在50℃继续搅拌30min,再升温至80℃搅拌60min后得到溶胶,然后经80℃真空干燥12h得到干凝胶;将干凝胶移至程序升温炉,先400℃煅烧2h,再升温至700℃煅烧4h,待自然冷却取出,经研磨,过80目筛,即得LaCo0.9Bi0.1O3。
再采用原位沉淀法制备Ag3PO4/LaCo(1-x)BixO3复合光催化剂(Ag3PO4/ LaCo0.9Bi0.1O3)。将0.1 g LaCo0.9Bi0.1O3分散在散在超纯水中,并经超声处理30 min,而后向上述向经超声分散的LaCo0.9Bi0.1O3水溶液中加入50 mLAgNO3溶液(0.129 mol/L)并机械搅拌12 h;再将60mL Na2HPO4·12H2O溶液(0.043 mol/L)缓慢滴加至上述分散液中,滴完后继续搅拌1 h待反应完全,反应所得沉淀物经超纯水反复洗涤后,将其干燥、研磨过80目筛,即得所述LaCo0.9Bi0.1O3与Ag3PO4质量比为1:9的复合催化剂Ag3PO4/ LaCo0.9Bi0.1O3。
(2)复合光催化剂应用于去除水中BPA的性能测试:在10 mg/L 的BPA溶液中,投加0.5g/L上述复合光催化剂,先进行暗吸附反应30 min达到吸附平衡后,再在300 W氙灯照射条件下光催化反应40 min,并在不同反应时间点测定上清液中BPA残余浓度和TOC值,可得该复合光催化剂及磷酸银在可见光照射下对有机污染物BPA的光催化降解效率曲线和矿化率图,分别见图3、图4。由测试结果可知,光照40 min,Ag3PO4/ LaCo0.9Bi0.1O3对BPA的去除效率和矿化率分别达到70.6%和62.3%。
实施例3:
(1)复合光催化剂的制备:首先用柠檬酸络合法制备掺杂钙钛矿载体,即LaCo0.1Bi0.9O3。取5mmol硝酸镧(La(NO3)3)·nH2O),0.5mmol硝酸钴(Co(NO3)2)·6H2O)和4.5mmol硝酸铋(Bi(NO3)3)·5H2O)溶解于100ml的蒸馏水中,搅拌30min,再加入15~30 mmol柠檬酸溶液,加热至50℃下搅拌45min;向上述溶液加入25mmol乙二醇溶液,在50℃继续搅拌30min,再升温至80℃搅拌60min后得到溶胶,然后经80℃真空干燥12h得到干凝胶;将干凝胶移至程序升温炉,先400℃煅烧2h,再升温至700℃煅烧4h,待自然冷却取出,经研磨,过80目筛,即得LaCo0.1Bi0.9O3。
再采用原位沉淀法制备Ag3PO4/LaCo(1-x)BixO3复合光催化剂(Ag3PO4/ LaCo0.1Bi0.9O3)。将0.1 g LaCo0.1Bi0.9O3分散在散在超纯水中,并经超声处理30 min,而后向上述向经超声分散的LaCo0.1Bi0.9O3水溶液中加入50 mLAgNO3溶液(0.129 mol/L)并机械搅拌12 h;再将60mL Na2HPO4·12H2O溶液(0.043 mol/L)缓慢滴加至上述分散液中,滴完后继续搅拌1 h待反应完全,反应所得沉淀物经超纯水反复洗涤后,将其干燥、研磨过80目筛,即得所述LaCo0.1Bi0.9O3与Ag3PO4质量比为1:9的复合催化剂Ag3PO4/ LaCo0.1Bi0.9O3。
(2)复合光催化剂应用于去除水中BPA的性能测试:在10 mg/L 的BPA溶液中,投加0.5g/L上述复合光催化剂,先进行暗吸附反应30 min达到吸附平衡后,再在300 W氙灯照射条件下光催化反应40 min,并在不同反应时间点测定上清液中BPA残余浓度和TOC值,可得该复合光催化剂及磷酸银在可见光照射下对有机污染物BPA的光催化降解效率曲线和矿化率图,分别见图3、图4。由测试结果可知,光照40 min,Ag3PO4/ LaCo0.1Bi0.9O3对BPA的去除效率和矿化率分别达到65.5%和51.5%。
实施例4:
(1)复合光催化剂的制备:复合光催化剂的制备过程与实施例1相同。
(2)复合光催化剂重复应用于去除水中BPA的性能测试:在10 mg/L的BPA溶液中,投加0.5g/L上述复合光催化剂,先进行暗吸附反应30 min达到吸附平衡后,再在300 W氙灯照射条件下光催化反应40 min,并在不同反应时间点测定上清液中BPA残余浓度和TOC值。回收的复合光催化剂经超纯水洗涤数次、在60 ℃真空干燥箱中干燥后,研磨,过80目筛,再次应用于BPA废水处理,处理过程同上,测定反应后上清液中BPA残余浓度和TOC值,可得图5。复合光催化剂重复利用第三次时,其对BPA的降解效率仍可达87.4%,矿化率可达69.7%。
Claims (12)
1.一种以掺杂钙钛矿为载体的复合光催化剂制备及其应用,其特征在于:该复合光催化剂是以掺杂钙钛矿作为载体,负载可见光响应型半导体光催化材料所得到高矿化率的复合光催化剂。首先,通过柠檬酸络合法制备掺杂钙钛矿载体(即B位掺杂Bi的LaCoO3,即LaCo(1-x)BixO3),再通过原位沉淀法将半导体光催化材料Ag3PO4负载于LaCo(1-x)BixO3表面,使两者紧密结合,形成一种光催化效率高的复合光催化剂,并将其应用于双酚A(BPA)废水的处理。
2.根据权利要求1所述的以掺杂钙钛矿作为载体的复合光催化剂Ag3PO4/LaCo(1-x)BixO3,其特征在于复合光催化剂中掺杂钙钛矿载体LaCo(1-x)BixO3的质量分数为2~50%。
3.根据权利要求1或2所述一种复合光催化剂Ag3PO4/LaCo(1-x)BixO3的制备方法,其特征在于所述方法包括以下步骤:
(A)柠檬酸络合法制备掺杂钙钛矿载体(LaCo(1-x)BixO3)
(A1)取5mmol硝酸镧(La(NO3)3)·nH2O),以及一定摩尔比的硝酸钴(Co(NO3)2)·6H2O)和硝酸铋(Bi(NO3)3)·5H2O)溶解于100ml的蒸馏水中,搅拌10~120min,再加入一定量柠檬酸(C6H8O7·H2O)溶液,加热至45~70℃再继续搅拌30~60min;
(A2)向上述溶液加入一定量的醇溶液,于45~70℃继续搅拌15~60min,再次升温并搅拌30~120min后得到溶胶,再将溶胶放入真空干燥箱,经真空干燥8~16h后得到干凝胶;
(A3)将干凝胶移至程序升温炉,先煅烧1~4h,再升温煅烧2~6h,待自然冷却取出,经研磨,过80目筛,即可制备不同Bi掺杂含量的LaCo(1-x)BixO3;
(B)原位沉淀法制备复合光催化剂(Ag3PO4/LaCo(1-x)BixO3)
(B1)取一定量的LaCo(1-x)BixO3分散在超纯水中并经超声处理(超声时间优选10~60min),而后加入AgNO3溶液并机械搅拌6~18 h (优选8~12 h)得分散液;
(B2)将磷酸盐溶液缓慢滴加至上述分散液中,滴完后再继续反应0.5~2 h,反应所得沉淀物经超纯水反复洗涤后,将其分离、干燥、过80目筛,即得Ag3PO4/LaCo(1-x)BixO3。
4.根据权利要求3所述的制备方法,其特征在于:步骤(A1)中的硝酸镧、硝酸钴、硝酸铋与柠檬酸的摩尔比为1:(1-X) : X :0~10(其中0<X<1),优选1:(1-X) : X :0.6~8(其中0<X<1),进一步优选(1-X) : X :0.6~6(其中0.1≤X≤0.9)。
5.根据权利要求3所述的制备方法,其特征在于:步骤(A2)中醇溶液为C2~C6醇类有机溶剂,优选乙二醇。
6.根据权利要求3所述的制备方法,其特征在于:步骤(A2)中再次升温的温度区间应优选为70~100°C。
7.根据权利要求3所述的制备方法,其特征在于:步骤(A2)中真空干燥的温度区间应优选为40~120°C。
8.根据权利要求3所述的制备方法,其特征在于:步骤(A3)中程序升温炉内第一段煅烧温度应为300~450°C,第二段煅烧温度应为600~800°C。
9.根据权利要求3-8中任一项所述的制备方法,其特征在于:步骤(B1)中加入AgNO3 的质量与LaCo(1-x)BixO3的质量之比为1:0.05~0.5。
和/或
步骤(B2)中碱金属磷酸盐溶液为磷酸氢二钠,且加入的 Na2HPO4·12H2O摩尔量与AgNO3的摩尔量之比为1:1~3.5,进一步优选1:2~3。
10.根据权利要求1所述的掺杂钙钛矿作为载体的复合光催化剂的应用,其特征在于:将Ag3PO4/LaCo(1-x)BixO3应用于含有双酚A废水的处理。
11.根据权利要求10所述的应用,其特征在于:向含有双酚A的废水中加入Ag3PO4/LaCo(1-x)BixO3,先进行暗吸附反应,待达到平衡后进行可见光光照。
12.根据权利要求11所述的应用,其特征在于:Ag3PO4/LaCo(1-x)BixO3的用量是:废水中所含的双酚A与Ag3PO4/LaCo(1-x)BixO3的质量之比为1:5~100,优选1:30~60。
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