CN109444106B - 一种基于表面增强拉曼光谱的光催化原位监测*** - Google Patents
一种基于表面增强拉曼光谱的光催化原位监测*** Download PDFInfo
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Abstract
本发明公开一种基于表面增强拉曼光谱的光催化原位监测***。监测***包括:拉曼激发光光源、激光耦合透镜、窄带滤光片、全反射镜、二向色镜、聚焦耦合透镜、表面增强拉曼散射光纤探针、液相光催化反应器、光催化光源、拉曼收集透镜和光谱仪。表面增强拉曼散射光纤探针的公共检测部的一端分别延伸出第一分叉部和第二分叉部,第一分叉部的延伸端与聚焦耦合透镜耦合连接,第二分叉部的延伸端与光催化光源耦合连接,公共检测部的另一端设置在液相光催化反应器内,拉曼激发光和光催化光共路传输,极大地降低了实验难度,而且可有效避免由于聚焦点不完全重合导致的监测误差,进而有效提高拉曼动态监测的准确度,监测***的结构紧凑,便携性好。
Description
技术领域
本发明涉及光催化原位监测领域,特别是涉及一种基于表面增强拉曼光谱的光催化原位监测***。
背景技术
光催化化学反应是指光催化材料(如TiO2)在紫外或可见光照射下进行的一类化学反应,如光催化水解制氢、光催化有机物降解等,在能源、环境等领域具有重要应用。光催化反应机理及光催化剂选取对化学反应速度、效率等具有重要影响。而对光催化化学反应过程进行动态监测是理解光催化反应机理及设计高效光催化剂的前提,成为当前的研究热点。
光催化化学反应包括固相、液相、气相等多种反应相,其中液相光催化化学反应是当前研究较多、应用较为广泛的一类。近年来,利用表面增强拉曼散射(Surface-enhancedRaman Scattering,SERS)光谱技术进行液相光催化化学反应过程监测吸引了科研人员的广泛关注。目前,利用SERS进行液相光催化过程监测的现有技术主要包括以下两种:
1、在光催化反应过程的不同阶段分别取出部分反应液,将其滴至固态SERS基底表面,干燥后利用拉曼光谱仪进行SERS检测。这种分立取点检测方法通常难以遍历整个反应过程,且操作过程复杂,检测误差较大。
2、借助一微反应器,将固态SERS基底置于微反应器底部,在其上表面覆盖一薄层反应液,将微反应器置于拉曼光谱仪焦点处,实现SERS光谱检测。这种拉曼原位监测方法由于固态SERS基底表面的薄层反应液在拉曼激发光的照射下易挥发,引起反应液浓度发生变化,从而影响监测过程的准确性。
上述两种方法由于光催化光源的入射光路与拉曼激发光路不共路,为了实现光催化过程的监测,需调节两路光的聚焦点重合,这不仅极大地增加了实验难度,而且存在由于聚焦点不完全重合导致的监测误差。
发明内容
本发明的目的是提供一种基于表面增强拉曼光谱的光催化原位监测***,拉曼激发光和光催化光能够共路传输,进行光催化监测时无需进行聚焦点重合调整,这不仅极大地降低了实验难度,而且能够有效避免由于聚焦点不完全重合导致的监测误差,进而有效提高拉曼动态监测的准确度,监测***的结构紧凑,便携性好。
为实现上述目的,本发明提供了如下方案:
一种基于表面增强拉曼光谱的光催化原位监测***,所述光催化原位监测***包括:拉曼激发光光源、激光耦合透镜、窄带滤光片、全反射镜、二向色镜、聚焦耦合透镜、表面增强拉曼散射光纤探针、液相光催化反应器、光催化光源、拉曼收集透镜和光谱仪,其中,
所述表面增强拉曼散射光纤探针包括公共检测部,在所述公共检测部的一端分别延伸出第一分叉部和第二分叉部;
所述拉曼激发光光源通过输入光纤与所述激光耦合透镜连接,所述窄带滤光片设置在所述激光耦合透镜的透射光路上,所述全反射镜设置在所述窄带滤光片的透射光路上,所述二向色镜设置在所述全反射镜的反射光路上,且所述二向色镜与所述全反射镜平行设置,所述聚焦耦合透镜设置在所述二向色镜的反射光路上,所述第一分叉部的延伸端与所述聚焦耦合透镜耦合连接,所述第二分叉部的延伸端与所述光催化光源耦合连接,所述公共检测部的另一端设置在所述液相光催化反应器内,所述拉曼收集透镜设置在所述二向色镜的透射光路上,且所述拉曼收集透镜的出射端通过输出光纤与所述光谱仪耦合连接。
可选的,所述光催化原位监测***还包括设置在所述拉曼收集透镜与所述二向色镜之间的高通滤光片,所述高通滤光片用于滤除透过所述二向色镜的所述拉曼激发光光源发出的拉曼激发光。
可选的,所述光催化原位监测***还包括设置在所述拉曼收集透镜与所述二向色镜之间的带阻滤光片,所述带阻滤光片的中心波长与所述光催化光源的波长相等,所述带阻滤光片用于滤除透过所述二向色镜的光催化光源发出的光催化光。
可选的,所述光催化原位监测***还包括依次设置在所述拉曼收集透镜与所述二向色镜之间的高通滤光片和带阻滤光片,所述高通滤光片用于滤除透过所述二向色镜的所述拉曼激发光光源发出的拉曼激发光,所述带阻滤光片用于滤除透过所述二向色镜的光催化光源发出的光催化光。
可选的,所述全反射镜的入射光路的光轴与所述全反射镜的夹角为45°。
可选的,所述拉曼激发光光源与所述输入光纤的入光端通过FC/PC光纤接口或FC/APC光纤接口直接连接,所述输入光纤的出光端设于所述激光耦合透镜的入射光焦点处。
可选的,所述输出光纤的入光端置于所述拉曼收集透镜的出射光焦点处,所述输出光纤的出光端通过SMA905光纤接口与所述光谱仪连接。
可选的,所述公共检测部的设于所述液相光催化反应器内的一端设置有表面增强拉曼散射敏感单元,所述表面增强拉曼散射敏感单元为贵金属纳米结构。
可选的,所述贵金属纳米结构包括金纳米结构和银纳米结构中至少一者。
可选的,所述表面增强拉曼散射光纤探针的光纤为Y型光纤或双分叉光纤束。
根据本发明提供的具体实施例,本发明公开了以下技术效果:
本发明提供的一种基于表面增强拉曼光谱的光催化原位监测***包括:拉曼激发光光源、激光耦合透镜、窄带滤光片、全反射镜、二向色镜、聚焦耦合透镜、表面增强拉曼散射光纤探针、液相光催化反应器、光催化光源、拉曼收集透镜和光谱仪。表面增强拉曼散射光纤探针包括公共检测部、第一分叉部和第二分叉部。公共检测部的一端、所述第一分叉部的一端和所述第二分叉部的一端连接,第一分叉部的另一端与拉曼激发光路上的聚焦耦合透镜耦合连接,第二分叉部的另一端与光催化光源耦合连接,公共检测部的另一端设置在液相光催化反应器内,从而实现光催化光源的入射光路与拉曼激发光路共路。由于拉曼激发光和光催化光能够共路传输,可有效避免现有技术中光路不共路引起的聚焦点重合困难的问题,进行光催化监测时无需进行聚焦点重合调整,这不仅极大地降低了实验难度,而且能够有效避免由于聚焦点不完全重合导致的监测误差,进而有效提高拉曼动态监测的准确度,监测***的结构紧凑,便携性好。
本发明将波导型表面增强拉曼散射光纤探针直接浸入液相光催化反应器中即可实现光催化过程中SERS光谱的原位实时监测,避免了当前拉曼原位监测技术中薄层液体挥发引起的反应液浓度变化的问题,能够提高拉曼动态监测的准确度。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其它的附图。
图1为本发明实施例提供的一种基于表面增强拉曼光谱的光催化原位监测***的结构示意图;
图2为本发明实施例提供的表面增强拉曼散射光纤探针的结构示意图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
本发明的目的是提供一种基于表面增强拉曼光谱的光催化原位监测***,拉曼激发光和光催化光能够共路传输,进行光催化监测时无需进行聚焦点重合调整,这不仅极大地降低了实验难度,而且能够有效避免由于聚焦点不完全重合导致的监测误差,进而有效提高拉曼动态监测的准确度,监测***的结构紧凑,便携性好。
为使本发明的上述目的、特征和优点能够更加明显易懂,下面结合附图和具体实施方式对本发明作进一步详细的说明。
图1为本发明实施例提供的一种基于表面增强拉曼光谱的光催化原位监测***的结构示意图。图2为本发明实施例提供的表面增强拉曼散射光纤探针的结构示意图。如图1和图2所示,一种基于表面增强拉曼光谱的光催化原位监测***,所述光催化原位监测***由拉曼激发光路、拉曼收集光路和光催化光路组成。其中,拉曼激发光路包括拉曼激发光光源1、输入光纤2、激光耦合透镜3、窄带滤光片4、全反射镜5、二向色镜6、聚焦耦合透镜7、表面增强拉曼散射光纤探针8和液相光催化反应体系9。拉曼收集光路包括表面增强拉曼散射光纤探针8、聚焦耦合透镜7、二向色镜6、带阻滤光片10、高通滤光片11、拉曼收集透镜12、输出光纤13和光谱仪14。光催化光路包括光催化光源15、表面增强拉曼散射光纤探针8和液相光催化反应体系9。
所述表面增强拉曼散射光纤探针8包括公共检测部80,在所述公共检测部80的一端分别延伸出第一分叉部81和第二分叉部82。
所述拉曼激发光光源1通过输入光纤2与所述激光耦合透镜3连接。具体地,所述拉曼激发光光源1与所述输入光纤2的入光端通过FC/PC光纤接口或FC/APC光纤接口直接连接,所述输入光纤2的出光端设于所述激光耦合透镜3的入射光焦点处。所述激光耦合透镜3用于将从输入光纤中出射的激光变为平行光。所述窄带滤光片4设置在所述激光耦合透镜3的透射光路上,即窄带滤光片4置于所述激光耦合透镜3后方,用于对透过激光耦合透镜3的激光进行空间滤波,提高拉曼激发光的边摸抑制比。所述全反射镜5设置在所述窄带滤光片4的透射光路上,所述二向色镜6设置在所述全反射镜5的反射光路上,且所述二向色镜6与所述全反射镜5平行设置。所述全反射镜5的入射光路的光轴与所述全反射镜5的夹角为45°。所述聚焦耦合透镜7设置在所述二向色镜6的反射光路上。所述表面增强拉曼散射光纤探针8的所述第一分叉部81的延伸端置于所述聚焦耦合透镜7的后焦点处,与所述聚焦耦合透镜7耦合连接,所述第二分叉部82的延伸端通过FC/PC或SMA905等光纤接口16与所述光催化光源15耦合连接,所述公共检测部81的另一端设置在所述液相光催化反应器9内进行SERS光谱的动态监测。经过窄带滤光片4的拉曼激发光先后经全反射镜5、二向色镜6反射后,垂直入射至聚焦耦合透镜7,由聚焦耦合透镜7耦合至表面增强拉曼散射光纤探针8中。本实施例中,表面增强拉曼散射光纤探针8的光纤可以为Y型光纤或双分叉光纤束,Y型光纤SERS探针的结构如图2所示。所述拉曼收集透镜12设置在所述二向色镜6的透射光路上,且所述拉曼收集透镜12的出射端通过输出光纤13与所述光谱仪14耦合连接。
优选地,所述光催化原位监测***还包括设置在所述拉曼收集透镜12与所述二向色镜6之间的带阻滤光片10,所述带阻滤光片10的中心波长与所述光催化光源15的波长相等,所述带阻滤光片10用于滤除透过所述二向色镜6的光催化光源15发出的光催化光。
优选地,所述光催化原位监测***还包括设置在所述拉曼收集透镜12与所述二向色镜6之间的高通滤光片11,所述高通滤光片11用于滤除透过所述二向色镜6的所述拉曼激发光光源发出的拉曼激发光。
本实施例中,所述光催化原位监测***还包括依次设置在所述拉曼收集透镜12与所述二向色镜6之间的高通滤光片11和带阻滤光片10,所述高通滤光片11用于滤除透过所述二向色镜6的拉曼激发光,所述带阻滤光片10用于滤除透过所述二向色镜的光催化光。
由Y型光纤SERS探针收集到的光信号,先经聚焦耦合透镜7变成平行光。聚焦耦合透镜7收集的光信号中除了待测拉曼信号光外还包含少量后向反射的拉曼激发光及光催化光。其中,拉曼激发光和光催化光经过二向色镜6后先被发射,透过的拉曼激发光由高通滤光片11滤除;透过的光催化光则由中心波长位于光催化光波长处的带阻滤光片10实现滤除。先后通过二向色镜6、带阻滤光片10、高通滤光片11等分别进行分光和滤波,能够尽可能滤除聚焦耦合透镜7出射的光信号中的拉曼激发光及光催化光。最终剩余的拉曼信号光由拉曼收集透镜12聚焦至输出光纤13中。所述输出光纤13的入光端置于所述拉曼收集透镜12的出射光焦点处,所述输出光纤13的出光端通过SMA905光纤接口与所述光谱仪14连接。
如图2所示,所述公共检测部80的设于所述液相光催化反应器9内的一端为敏感端,敏感端为平端面或者锥面,在敏感端设置有表面增强拉曼散射敏感单元83,所述表面增强拉曼散射敏感单元83为贵金属纳米结构。所述贵金属纳米结构包括金纳米结构和银纳米结构中至少一者。所述光纤SERS探针的制备方法可以为激光诱导法、化学修饰固定法、模板法等。
光催化光源15的功率、波长等对催化反应的速度、中间产物等具有较大影响,通过原位实时拉曼光谱的监测可为光催化反应的机理研究提供可靠数据。本实施例中,所述输入光纤2的参数为105/125μm、NA=0.22;所述输出光纤13的参数为200/225μm、NA=0.22;所述Y型光纤SERS探针8所用光纤参数为200/225μm、NA=0.22。所述拉曼激发光光源1发出的光信号的中心波长为532nm,线宽为0.1nm。所述光催化光源15发出的光信号为波长365nm的紫外LED光或者紫外激光。
本实施例提供的基于表面增强拉曼光谱的光催化原位监测***的实施过程如下:(1)在Y型光纤的公共检测部的敏感端制备贵金属纳米结构,形成Y型光纤SERS探针;(2)配制液相光催化反应器中的液相光催化反应体系,并将Y型光纤SERS探针浸入配制好的液相光催化反应体系中;(3)打开拉曼激发光光源,利用拉曼激发光路实现Y型光纤SERS探针附近液体拉曼信号的有效激发;(4)启动光谱仪,设置数据保存路径,利用拉曼收集光路实现拉曼信号的有效收集;(5)打开光催化光源,利用光催化光路诱导Y型光纤SERS探针的敏感端发生光催化反应;结合拉曼激发与拉曼收集光路,记录整个光催化反应过程中反应液的动态SERS光谱,从而实现对光催化反应过程的实时原位监测。
本发明通过将波导型光纤SERS探针直接浸入液相光催化反应体系中,即可实现光催化过程中SERS光谱的原位实时监测,避免了当前拉曼原位监测技术中薄层液体挥发引起的反应液浓度变化的问题,能够提高拉曼动态监测的准确度。同时,本发明中利用Y型光纤实现拉曼激发光和光催化光的共路传输,可有效避免现有技术中光路不共路引起的聚焦点重合困难的问题,极大降低了光催化原位监测装置的设计难度,利于构建紧凑型、便携式光催化原位监测仪器,在光催化研究领域具有重要的应用前景。
本说明书中各个实施例采用递进的方式描述,每个实施例重点说明的都是与其他实施例的不同之处,各个实施例之间相同相似部分互相参见即可。
本文中应用了具体个例对本发明的原理及实施方式进行了阐述,以上实施例的说明只是用于帮助理解本发明的方法及其核心思想;同时,对于本领域的一般技术人员,依据本发明的思想,在具体实施方式及应用范围上均会有改变之处。综上所述,本说明书内容不应理解为对本发明的限制。
Claims (10)
1.一种基于表面增强拉曼光谱的光催化原位监测***,其特征在于,所述光催化原位监测***包括:拉曼激发光光源、激光耦合透镜、窄带滤光片、全反射镜、二向色镜、聚焦耦合透镜、表面增强拉曼散射光纤探针、液相光催化反应器、光催化光源、拉曼收集透镜和光谱仪,其中,
所述表面增强拉曼散射光纤探针包括公共检测部,在所述公共检测部的一端分别延伸出第一分叉部和第二分叉部;
所述拉曼激发光光源通过输入光纤与所述激光耦合透镜连接,所述窄带滤光片设置在所述激光耦合透镜的透射光路上,所述全反射镜设置在所述窄带滤光片的透射光路上,所述二向色镜设置在所述全反射镜的反射光路上,且所述二向色镜与所述全反射镜平行设置,所述聚焦耦合透镜设置在所述二向色镜的反射光路上,所述第一分叉部的延伸端与所述聚焦耦合透镜耦合连接,所述第二分叉部的延伸端与所述光催化光源耦合连接,所述公共检测部的另一端设置在所述液相光催化反应器内,所述拉曼收集透镜设置在所述二向色镜的透射光路上,且所述拉曼收集透镜的出射端通过输出光纤与所述光谱仪耦合连接。
2.根据权利要求1所述的光催化原位监测***,其特征在于,所述光催化原位监测***还包括设置在所述拉曼收集透镜与所述二向色镜之间的高通滤光片,所述高通滤光片用于滤除透过所述二向色镜的所述拉曼激发光光源发出的拉曼激发光。
3.根据权利要求1所述的光催化原位监测***,其特征在于,所述光催化原位监测***还包括设置在所述拉曼收集透镜与所述二向色镜之间的带阻滤光片,所述带阻滤光片的中心波长与所述光催化光源的波长相等,所述带阻滤光片用于滤除透过所述二向色镜的光催化光源发出的光催化光。
4.根据权利要求1所述的光催化原位监测***,其特征在于,所述光催化原位监测***还包括依次设置在所述拉曼收集透镜与所述二向色镜之间的高通滤光片和带阻滤光片,所述高通滤光片用于滤除透过所述二向色镜的所述拉曼激发光光源发出的拉曼激发光,所述带阻滤光片用于滤除透过所述二向色镜的光催化光源发出的光催化光。
5.根据权利要求1所述的光催化原位监测***,其特征在于,所述全反射镜的入射光路的光轴与所述全反射镜的夹角为45°。
6.根据权利要求1所述的光催化原位监测***,其特征在于,所述拉曼激发光光源与所述输入光纤的入光端通过FC/PC光纤接口或FC/APC光纤接口直接连接,所述输入光纤的出光端设于所述激光耦合透镜的入射光焦点处。
7.根据权利要求1所述的光催化原位监测***,其特征在于,所述输出光纤的入光端置于所述拉曼收集透镜的出射光焦点处,所述输出光纤的出光端通过SMA905光纤接口与所述光谱仪连接。
8.根据权利要求1所述的光催化原位监测***,其特征在于,所述公共检测部的设于所述液相光催化反应器内的一端设置有表面增强拉曼散射敏感单元,所述表面增强拉曼散射敏感单元为贵金属纳米结构。
9.根据权利要求8所述的光催化原位监测***,其特征在于,所述贵金属纳米结构包括金纳米结构和银纳米结构中至少一者。
10.根据权利要求1所述的光催化原位监测***,其特征在于,所述表面增强拉曼散射光纤探针的光纤为Y型光纤或双分叉光纤束。
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