CN115193452A - 一种核壳结构上转换光催化材料及其制备与应用 - Google Patents
一种核壳结构上转换光催化材料及其制备与应用 Download PDFInfo
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Abstract
本发明公开了一种核壳结构上转换光催化材料及其制备与应用,首先,通过两步水热法制备了新型花苞状LuF3:Yb3+,Tm3+上转换纳米粒子。在980nm激光器激发下,该材料具有254nm的深紫外上转换发射。随后,通过溶剂热法在LuF3:Yb3+,Tm3+核外包覆上BiOCl壳层,形成了LuF3:Yb3+,Tm3+@BiOCl上转换光催化材料。LuF3:Yb3+,Tm3+强烈的蓝紫光发射及BiOCl壳有效的光谱重叠和良好的核壳结构使得LuF3:Yb3+,Tm3+@BiOCl可有效利用近红外光,具有优良的紫外‑可见‑近红外全光谱响应性能。
Description
技术领域
本发明属于光催化材料污染物降解技术领域,特别涉及一种核壳结构上转换光催化材料及其制备与应用。
背景技术
光催化技术作为一种绿色的太阳能转换技术,在环境污染物降解和能源转换等方面具有极大的应用前景,引起了人们的广泛关注和研究。现阶段应用的光催化剂多为紫外活性光催化剂,带隙较宽,如TiO2,ZnO,只能利用占太阳光谱5%的紫外光。为了扩大光催化剂的光谱吸收范围以充分利用太阳光,有很多改性方法,如金属离子和非金属离子掺杂,贵金属负载,二元或多元半导体复合。这些方法使得光催化剂可以利用可见光。为进一步扩大光催化剂的光谱吸收范围,上转换材料和光催化材料的结合引起了人们的关注。光催化剂和上转换纳米粒子的结合使得占太阳光谱55%的近红外光得以利用,已经成为扩大光催化剂吸收光谱的一个有吸引力的前景。
上转换发光是反斯托克斯发光,本质是通过多光子机制将低能量的光子转换为高能量光子的过程。在光催化过程中上转换材料可以作为中介,将吸收的近红外光转换为可被光催化剂吸收利用的可见和紫外光。光催化剂和不同的上转换材料,如:NaYF4:Yb3+,Er3+、CaF2:Yb3+,Er3+和YF3:Yb3+,Er3+的复合已被研究。由于它们上转换发射可见光,实验证明相比可见光,紫外光有更强的光催化性能,因此它们利用上转换提高光催化效率的优势不能被充分体现。上转换纳米粒子和传统的光催化剂如:TiO2、ZnS的复合被广泛研究。光催化剂较大的带隙宽度导致不匹配的光谱重叠,使得上转换光催化剂具有较低的量子产率。同时,良好的界面接触更加有利于上转换纳米粒子和光催化剂之间的能量转移过程。因此,获得强烈蓝紫光上转换发光纳米粒子并和光催化剂形成有效的光谱重叠和良好的核壳形态是提高近红外光照射下上转换光催化剂催化效率的关键目标。
发明内容
本发明所要解决的技术问题是,克服上转换材料较少的紫外发射以及它和光催化剂存在的光谱不重叠问题,本发明的目的在于提供一种核壳结构上转换光催化材料及其制备与应用,本发明的上转换发光核具有254nm、288nm的深紫外发射,346nm、362nm的紫外发射以及452nm、478nm的蓝光发射,光催化剂壳的吸收光谱和上转换发光核的发射光谱有效重叠,且核壳之间具有良好的界面接触,这些使得LuF3:Yb3+,Tm3+@BiOCl具有良好的近红外光响应性能,在NIR和Vis-NIR光照射下,10%LuF3:Yb3+,Tm3+@BiOCl的MB降解效率相比BiOCl分别提高了1.42和1.64倍。
为了实现上述目的,本发明采用的技术方案是:
一种核壳结构上转换光催化材料,以LuF3:Yb3+,Tm3+为核,BiOCl为壳,结构式为LuF3:Yb3+,Tm3+@BiOCl。
在一个实施例中,所述核,为直径300-500nm的花苞状上转换纳米粒子,在980nm激光器激发下,具有254nm的深紫外上转换发射;所述壳,为均匀包覆在LuF3:Yb3+,Tm3+表面的纳米薄片球状结构。
本发明还提供了所述核壳结构上转换光催化材料的制备方法,先采用两步水热法合成LuF3:Yb3+,Tm3+;随后通过溶剂热法在其外包覆上BiOCl壳层。
在一个实施例中,所述两步水热法的过程如下:
将Lu(NO3)3,Yb(NO3)3和Tm(NO3)3分散在去离子水中,并调节至碱性,之后在聚四氟乙烯衬里高压釜中180-200℃加热20-24h,自然冷却至室温,用去离子水和无水乙醇离心洗涤获得前驱体Ln4O(OH)9NO3,Ln=Lu,Yb,Tm;
向该前驱体中加入去离子水进行超声分散并加入NH4F溶液,之后在聚四氟乙烯衬里高压釜中180-200℃加热2-3h,自然冷却至室温,用去离子水和无水乙醇清洗所得样品数次,干燥后在450-600℃煅烧2-3h,得到LuF3:Yb3+,Tm3+;
所述溶剂热法的过程如下:
将1.5-2mmol Bi(NO3)3.5H2O溶于15-20mL有机溶剂中,标记为溶液A,1.5-2mmolKCl溶于15-20mL有机溶剂中,标记为溶液B,将溶液B与溶液A混合,随后加入LuF3:Yb3+,Tm3+,将所得混合物在聚四氟乙烯衬里高压釜中140-180℃下保存10-16h,自然冷却至室温后,用去离子水和无水乙醇洗涤数次,干燥即得LuF3:Yb3+,Tm3+@BiOCl上转换光催化材料。
在一个实施例中,所述干燥的条件为60-85℃下干燥8-16h
在一个实施例中,Lu(NO3)3,Yb(NO3)3和Tm(NO3)3的物质的量比为179:20:1,Ln和NH4F的物质的量比为0.07-0.2,LuF3:Yb3+,Tm3+和BiOCl的质量比为0.1-0.4。
在一个实施例中,所述两步水热法中,以NH3 .H2O将溶液PH调节至8-8.5。
在一个实施例中,所述有机溶剂为乙二醇。
本发明核壳结构上转换光催化材料可用于污染物降解。具体地,将所述核壳结构上转化光催化材料投入亚甲基蓝污染物中,在NIR和Vis-NIR光照射下实现对MB的降解,所述NIR是300W氙灯加<800nm滤光片,所述Vis-NIR是300W氙灯加<400nm滤光片。
与现有技术相比,本发明的有益效果是:
(1)本发明的上转换发光核LuF3:Yb3+,Tm3+在NIR激发下具有254nm(其他文献鲜有发现)、288nm的深紫外发射,346nm、362nm的紫外发射以及452nm、478nm的蓝光发射,更多的深紫外上转换发射促进了NIR光照射下污染物的高效降解。
(2)上转换发光核的发射光谱和光催化剂壳的吸收光谱有效重叠及核壳之间良好的界面接触为核壳之间有效的福斯特共振能量转移过程提供条件,从而进一步提高NIR光照射下污染物的降解效率。
(3)本发明制备方法简单且绿色无毒,制备的LuF3:Yb3+,Tm3+@BiOCl可实现UV-Vis-NIR全太阳光谱响应。
附图说明
图1是实施例1制备的BiOCl、LuF3:Yb3+,Tm3+和LuF3:Yb3+,Tm3+@BiOCl的XRD衍射谱图。
图2是实施例1制备的LuF3:Yb3+,Tm3+和LuF3:Yb3+,Tm3+@BiOCl的SEM,TEM,HRTEM和EDS-mapping图,其中,a、b分别为LuF3:Yb3+,Tm3+和LuF3:Yb3+,Tm3+@BiOCl的SEM图。c、d分别为LuF3:Yb3+,Tm3+@BiOCl的TEM和HRTEM图。e-l为LuF3:Yb3+,Tm3+@BiOCl的EDS-mapping图。
图3是实施例1制备的LuF3:Yb3+,Tm3+的光致发光(UCPL)谱图,激发光波长为980nm。
图4是实施例1制备的BiOCl和LuF3:Yb3+,Tm3+@BiOCl的UV-Vis漫反射光谱。
图5是实施例1制备的LuF3:Yb3+,Tm3+和LuF3:Yb3+,Tm3+@BiOCl的光致发光(UCPL)谱图,激发光波长为980nm。
图6是实施例1制备的BiOCl和LuF3:Yb3+,Tm3+@BiOCl在NIR和Vis-NIR照射下的亚甲基蓝降解图,NIR照射下亚甲基蓝浓度为10mg/L,Vis-NIR照射下亚甲基蓝浓度为15mg/L。
具体实施方式
下面结合附图和实施例详细说明本发明的实施方式。本发明所采用的原料和设备若非特指,均可从市场购得或是本领域常用的,实施例中的方法,如无特别说明,均为本领域的常规方法。
本发明为一种核壳结构上转换光催化材料,该材料以LuF3:Yb3+,Tm3+为核,BiOCl为壳,结构式可表示为:LuF3:Yb3+,Tm3+@BiOCl。
优选地,该核,为直径300-500nm的新型花苞状LuF3:Yb3+,Tm3+上转换纳米粒子,在980nm激光器激发下,具有254nm的深紫外上转换发射。该壳,为均匀包覆在LuF3:Yb3+,Tm3+表面的BiOCl纳米薄片球状结构。由此,LuF3:Yb3+,Tm3+强烈的蓝紫光发射及BiOCl壳有效的光谱重叠和良好的核壳结构使得LuF3:Yb3+,Tm3+@BiOCl可有效利用近红外光,具有优良的紫外-可见-近红外全光谱响应性能,即形成近红外-深紫外光子上转换驱动的LuF3:Yb3+,Tm3+@BiOCl上转换光催化材料。
本发明核壳结构上转换光催化材料的制备方法可分为两步,第一步,先采用两步水热法合成LuF3:Yb3+,Tm3+;第二步,通过溶剂热法在LuF3:Yb3+,Tm3+外包覆上BiOCl壳层。
具体地步骤可描述如下:
步骤(1),将Lu(NO3)3,Yb(NO3)3和Tm(NO3)3分散在去离子水中,用NH3 .H2O将溶液PH调节至碱性,示例地,可调整至8-8.5。搅拌1h后,将溶液转移至50mL聚四氟乙烯衬里高压釜中,密封严密,200℃加热24h,待反应器自然冷却至室温后,用去离子水和无水乙醇离心洗涤以获得前驱体Ln4O(OH)9NO3(Ln=Lu,Yb,Tm);向上述制备的前驱体中加入去离子水进行超声分散并加入NH4F溶液,搅拌10min后,将溶液转移至50mL聚四氟乙烯衬里高压釜中200℃加热3h,待反应釜自然冷却至室温后,用去离子水和无水乙醇清洗所得样品数次,在60℃下干燥10h后在600℃的高温条件下煅烧2h,得到LuF3:Yb3+,Tm3+上转换纳米粒子。示例地,在本步骤中,Lu(NO3)3,Yb(NO3)3和Tm(NO3)3的物质的量比为179:20:1,Ln和NH4F的物质的量比为1:10。
步骤(2),将2mmol Bi(NO3)3.5H2O溶于20mL有机溶剂例如乙二醇中,标记为溶液A,将2mmol KCl溶于20mL有机溶剂例如乙二醇中,标记为溶液B,溶液B逐滴加入溶液A中并搅拌30min,随后,将LuF3:Yb3+,Tm3+加入溶液中,将混合物转移到50mL聚四氟乙烯衬里高压釜中,在160℃下保存12h,待反应器自然冷却至室温后,用去离子水和无水乙醇洗涤数次,60℃下干燥10h,得到LuF3:Yb3+,Tm3+@BiOCl上转换光催化材料(步骤2中不添加LuF3:Yb3+,Tm3+即获得BiOCl光催化材料)。示例地,在本步骤中,LuF3:Yb3+,Tm3+和BiOCl的质量比为1:9。
本发明核壳结构上转换光催化材料在污染物降解领域的应用也属于本发明的保护范围。优选的,所述应用的方法是将所述核壳结构上转换光催化材料投入亚甲基蓝水体中,在NIR(300W氙灯加<800nm滤光片)和Vis-NIR(300W氙灯加<400nm滤光片)光照下进行降解。优选的,所述在水体中的投加量为50mg,NIR光照下水体中亚甲基蓝的浓度为10mg/L,Vis-NIR光照下水体中亚甲基蓝的浓度为15mg/L。
以下为本发明的若干实施例。
实施例1
步骤1:将稀土氧化物溶解在稀硝酸溶液中,加热得到0.1mol/LLn(NO3)3(Ln=Lu,Yb,Tm)溶液。
步骤2:在35mL去离子水中添加1.79mmol Lu(NO3)3,0.2mmol Yb(NO3)3和0.01mmolTm(NO3)3,用NH3 .H2O将溶液的PH值调节至8-8.5后搅拌1h。
步骤3:将搅拌后的溶液转移至50mL聚四氟乙烯衬里高压釜中,密封严密,200℃加热24h。反应器自然冷却至室温后,用去离子水和无水乙醇离心洗涤三次去除污染物以获得前驱体Ln4O(OH)9NO3(Ln=Lu,Yb,Tm)。
步骤4:向上述制备的前驱体中加入去离子水进行超声分散,并以Ln:F=1:10的比例加入NH4F溶液,搅拌10min。
步骤5:将搅拌后的溶液转移至50mL聚四氟乙烯衬里高压釜中200℃加热3h。反应釜自然冷却至室温后,用去离子水和无水乙醇离心洗涤三次,并在60℃下干燥10h。最后在600℃下煅烧2小时得到LuF3:Yb3+,Tm3+。
步骤6:2mmolBi(NO3)3.5H2O溶于20mL乙二醇中,标记为溶液A。2mmolKCl溶于20mL乙二醇中,标记为溶液B。溶液B逐滴加入溶液A中并搅拌30min,标记为溶液C。
步骤7:将10%质量分数的LuF3:Yb3+,Tm3+加入溶液C后将混合液转移到50mL聚四氟乙烯衬里高压釜中,在160℃下保存12h。反应器自然冷却至室温后,用去离子水和无水乙醇洗涤3次,60℃干燥10h后得到LuF3:Yb3+,Tm3+@BiOCl(不添加LuF3:Yb3+,Tm3+,将溶液C直接转移到50mL聚四氟乙烯衬里高压釜中,后续操作和上述一致即获得纯相BiOCl)。
首先,实施例1制备的LuF3:Yb3+,Tm3+和LuF3:Yb3+,Tm3+@BiOCl进行了XRD衍射,其结果如图1所示。从图中可以看到,LuF3:Yb3+,Tm3+在2θ处显示出24.6°、26.3°、28.0°、31.9°、36.3°、47.5°、50.1°和52.3°的强衍射峰,分别对应于正交相LuF3(JCPDS No.32-0612)的(101)、(020)、(111)、(210)、(121)、(131)、(230)和(212)晶面。这表明正交相LuF3的成功合成且Yb3+和Tm3+离子在产物中掺杂较好。LuF3:Yb3+,Tm3+@BiOCl的XRD图谱不仅能够与正交相LuF3:Yb3+,Tm3+一一对应,其在12.0°、25.9°、32.5°、33.4°、40.9°、46.6°和58.6°等位置的衍射峰还能够与四方相BiOCl(JCPDS No.06-0249)的(001)、(101)、(110)、(102)、(112)、(200)和(212)晶面一一对应,没有杂峰,表明LuF3:Yb3+,Tm3+@BiOCl的成功合成且该复合材料具有较高的晶体纯度。
随后,将实施例1制备的LuF3:Yb3+,Tm3+和LuF3:Yb3+,Tm3+@BiOCl进行了SEM,TEM,HRTEM和EDS-mapping扫描。图2中a为合成的正交相LuF3:Yb3+,Tm3+纳米粒子的SEM图。样品形态为直径300-500nm的花苞状。据了解,这种特殊形态的LuF3是首次合成的。该结构具有较少的表面缺陷,减少了能量的交叉弛豫,更有利于强蓝紫光的上转换发射。LYT(10)@BiOCl核壳结构的SEM图像如图2中b所示。花状球形的BiOCl由密集的纳米薄片组成。这种结构具有较高的比表面积,不仅增加了光催化反应位点,而且有助于污染物在催化剂表面的吸附。组合后,LuF3:Yb3+,Tm3+被BiOCl部分包裹,裸露的部分有利于将NIR传输到上转换纳米粒子核心,这对光催化应用中有效的光子上转换至关重要。同时,形成的良好核壳包覆有利于光催化过程中上转换纳米颗粒与光催化剂之间高效的能量传递。采用TEM和HRTEM研究了LuF3:Yb3+,Tm3+@BiOCl复合材料的界面连接和晶体特征。图2中c为LuF3:Yb3+,Tm3+@BiOCl结构TEM图像。LuF3:Yb3+,Tm3+核与BiOCl壳之间的紧密连接进一步证明了良好的核壳结构的形成。图2中d的HRTEM图显示了LuF3:Yb3+,Tm3+(10)@BiOCl中两种不同类型的晶格条纹。0.28nm的晶格条纹间距对应于LuF3的(210)面,而较大的晶格条纹间距表明四方相BiOCl(101)面的存在。HRTEM结果与XRD结果一致,证实了复合材料的高结晶性。LuF3:Yb3+,Tm3+(10)@BiOCl的元素映射图如图2中e-l所示。可以清楚地看到,Bi、O和Cl元素均匀分布在壳中,Lu、F、Yb和Tm元素均匀分布在核中。所有这些结果都表明核-壳纳米粒子的成功制备。
为证明所合成的上转换纳米粒子具有较好的蓝紫光上转换输出,在980nm激光器激发下,我们测试了LuF3:Yb3+,Tm3+的上转换光致发光光谱,如图3所示。它包括两个中心位于254和288nm的深紫外发射带、两个中心位于346和362nm的紫外发射带、两个中心位于452和478nm的蓝带和一个中心位于645nm的弱红色发射带。这些上转换带分别对应于Tm3+离子的3P2-3H6、1I6-3H6、1I6-3F4、1D2-3H6、1G4-3H6和1F4-3F4跃迁。与低能红光相比,LuF3:Yb3+,Tm3+上转换纳米粒子主要发射高能深紫外光和蓝光,更有利于光催化反应。Tm3+离子中980nm近红外光激发的254nm强烈UVC上转换发射在其他文献中鲜有发现。
实施例1制备的LuF3:Yb3+,Tm3+@BiOCl的紫外-可见漫反射光谱如图4所示。结果表明,随着上转换材料的加入,催化剂的吸收边没有明显变化,但紫外-可见区部分的吸收强度增加。LuF3:Yb3+,Tm3+@BiOCl在紫外-可见区都表现出很强的吸收,吸收边约为480nm,这和上转换纳米粒子的发射光谱具有有效重叠。根据Kubelka-Munk函数与光能之间的关系模式(插图所示),对应的带隙能量均为3eV。LuF3:Yb3+,Tm3+@BiOCl的低带隙能量和高紫外-可见吸收表明它可以利用广谱光子以提高光反应的量子产率。
实施例1制备的LuF3:Yb3+,Tm3+和不同质量比的LuF3:Yb3+,Tm3+@BiOCl的光致发光谱图如图5所示。LuF3:Yb3+,Tm3+的发光强度最强,随着BiOCl壳层的加入,发光强度降低,表明LuF3:Yb3+,Tm3+@BiOCl可以吸收NIR光并上转换发射强烈蓝紫光,发射的蓝紫光被包覆在LuF3:Yb3+,Tm3+表面的BiOCl壳层吸收利用以产生光催化效应。
实施例2
取实施例1制备的LuF3:Yb3+,Tm3+、BiOCl和LuF3:Yb3+,Tm3+@BiOCl进行光催化降解实验。以亚甲基蓝(MB)作为模拟污染物来评估所制备样品的光催化性能。将50mg催化剂分散在100mL MB溶液(近红外光催化实验浓度为10mg/L,可见-近红外光催化实验浓度为15mg/L)中,在黑暗条件下搅拌30分钟,以达到吸附-解吸平衡。使用300W氙灯作为光源(在<800nm的滤光片上进行NIR光催化实验,在<420nm的滤光片上进行Vis-NIR光催化实验)。在辐照过程中,按一定时间间隔提取4mL悬浮液并离心,使用紫外-可见分光光度计分析上清液。实验过程中通过循环冷却水将反应装置保持在室温下。使用公式:η=(1-Ct/C0)×100%计算样品的降解效率,其中C0和Ct分别为初始浓度和时间浓度。
结果如图6所示,空白反应中MB的浓度在整个过程中没有显著变化,表明MB降解过程中光催化而非光解发挥了重要作用。同时,纯LuF3:Yb3+,Tm3+仅作为UC发光材料,对MB的光催化降解没有影响。通过NIR光辐射降解MB,验证了光子上转换及其对光催化活性的增强作用。由于BiOCl中形成了氧空位,它可以吸收和利用部分近红外光。在NIR照射下,BiOCl在4h内对MB的降解率为50%。同时,LuF3:Yb3+,Tm3+@BiOCl的降解率达到71%,这归因于上转换过程。在Vis-NIR照射下,BiOCl在60min内降解58%MB。当使用LYT(10)@BiOCl复合材料时,降解率达到95%。从BiOCl到LYT(10)@BiOCl的额外37%的增长归因于将未使用的近红外光子向上转换为活跃的紫外-蓝光光子来增强对太阳光的使用。上述数值结果表明,构建LuF3:Yb3+,Tm3+@BiOCl核壳结构可实现对近红外光的有效利用从而提高光催化性能。
Claims (10)
1.一种核壳结构上转换光催化材料,以LuF3:Yb3+,Tm3+为核,BiOCl为壳,结构式为LuF3:Yb3+,Tm3+@BiOCl。
2.根据权利要求1所述核壳结构上转换光催化材料及其制备与应用,其特征在于,所述核,为直径300-500nm的花苞状上转换纳米粒子,在980nm激光器激发下,具有254nm的深紫外上转换发射;所述壳,为均匀包覆在LuF3:Yb3+,Tm3+表面的纳米薄片球状结构。
3.权利要求1所述核壳结构上转换光催化材料的制备方法,其特征在于,先采用两步水热法合成LuF3:Yb3+,Tm3+;随后通过溶剂热法在其外包覆上BiOCl壳层。
4.根据权利要求3所述制备方法,其特征在于,所述两步水热法的过程如下:
将Lu(NO3)3,Yb(NO3)3和Tm(NO3)3分散在去离子水中,并调节至碱性,之后在聚四氟乙烯衬里高压釜中180-200℃加热20-24h,自然冷却至室温,用去离子水和无水乙醇离心洗涤获得前驱体Ln4O(OH)9NO3,Ln=Lu,Yb,Tm;
向该前驱体中加入去离子水进行超声分散并加入NH4F溶液,之后在聚四氟乙烯衬里高压釜中180-200℃加热2-3h,自然冷却至室温,用去离子水和无水乙醇清洗所得样品数次,干燥后在450-600℃煅烧2-3h,得到LuF3:Yb3+,Tm3+;
所述溶剂热法的过程如下:
将1.5-2mmol Bi(NO3)3.5H2O溶于15-20mL有机溶剂中,标记为溶液A,1.5-2mmol KCl溶于15-20mL有机溶剂中,标记为溶液B,将溶液B与溶液A混合,随后加入LuF3:Yb3+,Tm3+,将所得混合物在聚四氟乙烯衬里高压釜中140-180℃下保存10-16h,自然冷却至室温后,用去离子水和无水乙醇洗涤数次,干燥即得LuF3:Yb3+,Tm3+@BiOCl上转换光催化材料。
5.根据权利要求4所述制备方法,其特征在于,所述干燥的条件为60-85℃下干燥8-16h。
6.根据权利要求4所述制备方法,其特征在于,Lu(NO3)3,Yb(NO3)3和Tm(NO3)3的物质的量比为179:20:1,Ln和NH4F的物质的量比为0.07-0.2,LuF3:Yb3+,Tm3+和BiOCl的质量比为0.1-0.4。
7.根据权利要求4所述制备方法,其特征在于,所述两步水热法中,以NH3 .H2O将溶液PH调节至8-8.5。
8.根据权利要求4所述制备方法,其特征在于,所述有机溶剂为乙二醇。
9.权利要求1或2所述核壳结构上转换光催化材料或权利要求2~8所述制备方法制备的核壳结构上转换光催化材料在污染物降解中的应用。
10.根据权利要求9所述应用,其特征在于,将所述核壳结构上转化光催化材料投入亚甲基蓝污染物中,在NIR和Vis-NIR光照射下实现对MB的降解,所述NIR是300W氙灯加<800nm滤光片,所述Vis-NIR是300W氙灯加<400nm滤光片。
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