CN113680364B - 一种间氨基苯硼酸掺杂的石墨相氮化碳光催化剂、制备方法及其应用 - Google Patents
一种间氨基苯硼酸掺杂的石墨相氮化碳光催化剂、制备方法及其应用 Download PDFInfo
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Abstract
本发明公开了一种间氨基苯硼酸掺杂的石墨相氮化碳光催化剂、制备方法及其应用,属于光催化剂制备技术领域;本发明将尿素和间氨基苯硼酸的共融混合物在高温下热聚合获得间氨基苯硼酸掺杂的一体化多孔片状石墨相氮化碳光催化剂。间氨基苯硼酸掺杂到石墨相氮化碳中,增强了石墨相氮化碳对可见光的吸收,提升了光生载流子的分离和迁移效率,显著提高石墨相氮化碳光催化产氢和降解性能。该方法工艺简单、制备成本低、操作安全,制备的一体化石墨相氮化碳光催化剂纯度、稳定性及催化活性高。
Description
技术领域
本发明属于光催化剂制备技术领域,具体涉及一种间氨基苯硼酸掺杂的石墨相氮化碳光催化剂、制备方法及其应用。
背景技术
光催化技术因其高效、绿色和经济等优势,被认为是解决能源短缺和环境污染最有效的策略之一,在该技术中,开发可持续、高效的光催化剂至关重要。石墨相氮化碳(g-C3N4)作为一种典型的无金属有机半导体光催化剂,因其具有合成方便、无毒、成本低、带隙合适等吸引人的特点在光催化领域、材料领域、能源和环境领域受到了广泛的关注。遗憾的是,g-C3N4对可见光的响应范围较窄,活性位点暴露较少且光生载流子易快速复合,这使得纯g-C3N4材料的光生电子-空穴迁移距离长、迁移速率慢、在到达活性位点前就发生复合,严重制约了光催化性能的发挥。
目前,研究者主要通过掺杂、构建异质结、调控形貌、构建缺陷等策略来克服单一纯相g-C3N4存在的不足。虽然通过上述改性方法提升了g-C3N4催化性能,但是有些改性手段复杂、改性结果较为单一或改性后性能提升不明显。因此,非常有必要提出一种简单的g-C3N4光催化剂改性方法,通过该方法获得同时具有多种光催化效果且催化性能明显提升的新型g-C3N4光催化剂。
发明内容
针对上述现有技术存在的不足:g-C3N4光催化剂改性手段复杂、光催化功能较为单一、改性后性能提升不明显,本发明的目的在于提供一种简单将间氨基苯硼酸与尿素共聚构筑新型g-C3N4光催化剂的方法,本发明所制备的新型g-C3N4光催化剂增强了对可见光的吸收,抑制了光生电子-空穴的复合,光催化产氢和降解性能得到显著提高,目前该方法还未见报道。
本发明通过如下技术方案实现:
一种间氨基苯硼酸掺杂的g-C3N4光催化剂的制备方法,具体包括如下步骤:
(1)间氨基苯硼酸-尿素共融混合物的制备:
将尿素和间氨基苯硼酸按一定比例置于坩埚中,混合物加热获得均匀的澄清溶液,冷却至室温得到间氨基苯硼酸-尿素共融混合物;
(2)间氨基苯硼酸掺杂的g-C3N4光催化剂的制备:
将步骤(1)制备得到的间氨基苯硼酸-尿素共融混合物放入马弗炉中,以固定升温速率加热,并保持一段时间;自然冷却至室温后,将产物研磨成粉末获得间氨基苯硼酸掺杂的g-C3N4光催化剂。
优选地,步骤(1)中所述尿素与间氨基苯硼酸的质量比为1g:0.5~3.5mg。
优选地,步骤(1)中间氨基苯硼酸-尿素共融混合物的加热温度为140~170℃。
优选地,步骤(2)中间氨基苯硼酸-尿素共融混合物在马弗炉中的升温速率为4~6℃min-1。
优选地,步骤(2)中间氨基苯硼酸-尿素共融混合物在马弗炉中的保持温度为550~650℃。
优选地,步骤(2)中间氨基苯硼酸-尿素共融混合物在马弗炉中的保持时间为2.5~3.5h。
本发明的另一目的在于提供了一种间氨基苯硼酸掺杂的g-C3N4光催化剂在降解有机物方面的应用,具体包括如下步骤:使用一定瓦数的氙灯和一定波长的截止滤光片来滤除紫外光作为可见光光源,将一定质量光催化剂和一定浓度的有机污染物水溶液在黑暗处混合搅拌一定时间达到吸附-解吸平衡,开灯后每隔一段时间吸取混合液体离心,上清液使用UV-2700紫外-可见分光光度计在一定波长下分析吸光值(浓度)的变化。
优选地,所述氙灯的瓦数为300W;截止滤光片的波长为420nm;光催化剂质量与TC浓度比为1mg:0.1~4mg L-1;有机物溶液的体积为40~50mL;所述有机物为四环素;光催化剂和有机物的混合溶液达到吸附-解吸平衡的搅拌时间为10~50min;开灯后取样时间间隔为5~30min;开灯后每次取样的量为2mL;紫外-可见分光光度计的波长为355~358nm。
本发明的另一目的在于提供了一种间氨基苯硼酸掺杂的g-C3N4光催化剂在光催化产氢方面的应用,具体包括如下步骤:将一定量的催化剂均匀分散在一定量三乙醇胺(TEOA)的水溶液中,加入一定量的氯铂酸作为助催化剂光沉积Pt到催化剂上,利用一定瓦数和波长的氙灯作为可见光光源,光照前用氩气将反应系统内空气排出,并用循环水将整个反应温度维持在一定温度。
优选地,所述催化剂的量为28~32mg;TEOA量为2.5~3.5mL;氯铂酸用量为1mL;氙灯的瓦数和波长分别为350W和420nm;反应温度为15~20℃。
与现有技术相比,本发明的优点如下:
1、原料廉价易得、合成方法简单、易操作;
2、产物纯净,合成中不引入表面活性剂、模板及衬底等,极大的减少了杂质的含量,降低了杂质成分对目标产物结构、性质的影响;
3、一体化结构使得产物不存在相分离降低催化性能的情况;
4、原料仅为低成本的尿素和间氨基苯硼酸,不使用有机溶剂或保护性气体等昂贵或对环境有害的试剂,基本无风险因素;
5、产物可用于产氢和光催化降解,功能不单一;
6、所合成的间氨基苯硼酸掺杂的一体化氮化碳光催化剂为多孔纳米薄片结构,且具有活性位点暴露多、可见光利用率高、光生电子空穴复合率低和载流子迁移效率高等优势,因此较纯CN具备更加优异的光催化降解和析氢性能。
附图说明
为了更清楚地说明本发明具体实施方式,下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍。在所有附图中,类似的元件或部分一般由类似的附图标记标识。附图中,各元件或部分并不一定按照实际的比例绘制。
图1为实施例1-6所制备的CNx及纯g-C3N4(CN)的X-射线衍射图谱;
图2为实施例1-6所制备的CNx及CN的FT-IR图;
图3为实施例2和实施例6所制备的CN25(b)及CN(a)的透射电镜图;
图4为实施例2和实施例6所制备的CN25及CN的固体紫外漫反射图;
图5为实施例2和实施例6所制备的CN25及CN的PL光谱图;
图6为实施例2和实施例6所制备的CN25及CN的电化学阻抗谱图;
图7为实施例1-6所制备的CN25及CN降解水中四环素性能评价;
图8为实施例1-6所制备的CNx及CN的光催化产氢性能评价;
图9为实施例2所制备的CN25的稳定性分析。
具体实施方式
下面结合附图及实例对本发明作进一步描述:
实施例1
将20g尿素和0.01g间氨基苯硼酸置于坩埚中,混合物加热至150℃获得澄清溶液。冷却至室温后,将混合物置于马弗炉中,以升温速率为5℃min-1加热至600℃并保持3h。自然冷却至室温后,将黄色固体研磨成粉末并标记为CN10。
实施例2
将20g尿素和0.025g间氨基苯硼酸置于坩埚中,混合物加热至150℃获得澄清溶液。冷却至室温后,将混合物置于马弗炉中,以升温速率为5℃min-1加热至600℃并保持3h。自然冷却至室温后,将黄色固体研磨成粉末并标记为CN25。
实施例3
将20g尿素和0.04g间氨基苯硼酸置于坩埚中,混合物加热至150℃获得澄清溶液。冷却至室温后,将混合物置于马弗炉中,以升温速率为5℃min-1加热至600℃并保持3h。自然冷却至室温后,将黄色固体研磨成粉末并标记为CN40。
实施例4
将20g尿素和0.055g间氨基苯硼酸(mb)置于坩埚中,混合物加热至150℃获得澄清溶液。冷却至室温后,将混合物置于马弗炉中,以升温速率为5℃min-1加热至600℃并保持3h。自然冷却至室温后,将黄色固体研磨成粉末并标记为CN55。
实施例5
将20g尿素和0.07g间氨基苯硼酸(mb)置于坩埚中,混合物加热至150℃获得澄清溶液。冷却至室温后,将混合物置于马弗炉中,以升温速率为5℃min-1加热至600℃并保持3h。自然冷却至室温后,将黄色固体研磨成粉末并标记为CN70。
实施例6
对比例:将20g尿素置于坩埚中,混合物加热至150℃获得澄清溶液。冷却至室温后,将混合物置于马弗炉中,以升温速率为5℃min-1加热至600℃并保持3h。自然冷却至室温后,将黄色固体研磨成粉末并标记为CN。
实施例7
一种间氨基苯硼酸掺杂的g-C3N4光催化剂在降解四环素方面的应用,具体如下:使用300W氙灯和420nm截止滤光片来滤除紫外光(λ<420nm)作为可见光光源,以TC为目标污染物探究制备的一系列光催化剂的降解效果。将含有10mg光催化剂的TC(40mg L-1,50mL)混合溶液在黑暗处搅拌40min达到吸附-解吸平衡,开灯后每隔10min吸取2mL液体,离心取上清液,使用UV-2700紫外-可见分光光度计在358nm下分析TC吸光值(浓度)的变化。
实施例8
一种间氨基苯硼酸掺杂的g-C3N4光催化剂在产氢方面的应用,具体如下:将30mg催化剂均匀分散在29mL TEOA水溶液中(其中TEOA为3mL),加入1mL氯铂酸作为助催化剂光沉积铂到催化剂上,利用350W氙灯(λ>420nm)作为可见光光源,光照前用氩气将反应系统内空气排出,并用循环水将整个反应温度维持在18.5℃。
如图1所示,通过XRD分析了CN和CNx的晶相结构。所有样品在13.1°(100)和27.5°(002)左右出现两个明显的g-C3N4特征峰,表明g-C3N4的晶体结构被很好地保留。
如图2所示,通过FT-IR对CN和CNx进行官能团分析。CN和CNx在3000-3600cm-1、1200-1700cm-1和810cm-1处的典型峰值分别对应O-H和N-H、芳香CN杂环单元和三嗪单元的伸缩振动峰。相似的FT-IR光谱表明,mb引入后g-C3N4的骨架结构被很好地保留。
如图3所示,相比于CN(图3a),CN25的TEM图像(图3b)呈现出明显的多孔结构,该多孔结构的产生可能是由于尿素与mb共聚过程产生的气体所致,这非常有利于光催化活性位点的暴露及光生载流子的快速迁移。
如图4所示,采用固体紫外漫反射对制备光催化剂的光吸收特性进行分析。由图可知,与CN相比,合成的CN25表现出明显的红移且可见光响应明显提升,表明mb的掺杂能有效提高g-C3N4催化剂对可见光的响应能力。
如图5CN和CN25的PL光谱所示,与CN相比,CN25显示出显著猝灭的光致发光强度,表明mb的掺杂可以加速电荷的转移,有效的抑制载流子的复合。
从图6看出,CN25的电化学阻抗半径明显小于CN,表明CN25电阻较低,这非常有利于结构间电荷的分离和转移。
如图7为CN和CNx在可见光照射下对TC的光催化降解效果图。由图可知,CN在100min内对TC的降解率为64.1%,而CNx对TC明显高于CN,性能最优的CN25对TC的降解率达到81.3%。表明mb的掺杂可显著提升g-C3N4材料对TC光催化降解性能。
由图8不同催化剂的光催化产氢效果图可知,相比CN(497.36μmol h-1g-1),CNx光催化产氢速率明显提高,性能最优的CN25产氢速率达到了1914.33μmol h-1g-1,表明mb的掺杂有助于提升g-C3N4材料的光催化产氢性能。这可能由于mb的掺杂使得CNx呈现多孔的片状结构、更强和更宽的可见光吸收、更有效的电子空穴对分离效率和更快速的载流子迁移率。
如图9a所示,CN25经过四个连续的光催化循环降解实验,对TC的降解率略有降低(可能是由于循环过程催化剂回收损失所致),但依然较为稳定;图9b循环前后CN25的典型峰位置和峰强度未见变化,再次证明CN25具有较高的循环稳定性,这可能得益于通过简单共混共聚构筑的氮化碳是一体化共轭骨架结构。
以上结合附图详细描述了本发明的优选实施方式,但是,本发明并不限于上述实施方式中的具体细节,在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,这些简单变型均属于本发明的保护范围。
另外需要说明的是,在上述具体实施方式中所描述的各个具体技术特征,在不矛盾的情况下,可以通过任何合适的方式进行组合,为了避免不必要的重复,本发明对各种可能的组合方式不再另行说明。
此外,本发明的各种不同的实施方式之间也可以进行任意组合,只要其不违背本发明的思想,其同样应当视为本发明所公开的内容。
Claims (8)
1.一种间氨基苯硼酸掺杂的g-C3N4光催化剂的制备方法,其特征在于,具体包括如下步骤:
(1)间氨基苯硼酸-尿素共融混合物的制备:
将尿素和间氨基苯硼酸按一定比例置于坩埚中,混合物加热获得均匀的澄清溶液,冷却至室温得到间氨基苯硼酸-尿素共融混合物;
(2)间氨基苯硼酸掺杂的g-C3N4光催化剂的制备:
将步骤(1)制备得到的间氨基苯硼酸-尿素共融混合物放入马弗炉中,以固定升温速率加热并保持一段时间;自然冷却至室温后,将产物研磨成粉末获得间氨基苯硼酸掺杂的g-C3N4光催化剂;
步骤(1)中所述尿素与间氨基苯硼酸的质量比为1g:0.5~3.5mg;
步骤(2)中间氨基苯硼酸-尿素共融混合物在马弗炉中的保持温度为550~650℃。
2.如权利要求1所述的一种间氨基苯硼酸掺杂的g-C3N4光催化剂的制备方法,其特征在于,步骤(1)中间氨基苯硼酸-尿素共融混合物的加热温度为140~170℃。
3.如权利要求1所述的一种间氨基苯硼酸掺杂的g-C3N4光催化剂的制备方法,其特征在于,步骤(2)中间氨基苯硼酸-尿素共融混合物在马弗炉中的升温速率为4~6℃min-1。
4.如权利要求1所述的一种间氨基苯硼酸掺杂的g-C3N4光催化剂的制备方法,其特征在于,步骤(2)中间氨基苯硼酸-尿素共融混合物在马弗炉中的保持时间为2.5~3.5h。
5.一种间氨基苯硼酸掺杂的g-C3N4光催化剂,其特征在于,由权利要求1-4任意一项所述的方法制备得到。
6.如权利要求5所述的一种间氨基苯硼酸掺杂的g-C3N4光催化剂在降解有机物方面的应用,其特征在于,具体包括如下步骤:使用一定瓦数的氙灯和一定波长的截止滤光片来滤除紫外光作为可见光光源,将一定质量光催化剂和一定浓度的有机污染物水溶液在黑暗处混合搅拌一定时间达到吸附-解吸平衡,开灯后每隔一段时间吸取部分液体,上清液使用UV-2700紫外-可见分光光度计在一定波长下分析吸光值的变化。
7.如权利要求6所述的一种间氨基苯硼酸掺杂的g-C3N4光催化剂在降解有机物方面的应用,其特征在于,所述氙灯的瓦数为300W;截止滤光片的波长为420nm;光催化剂质量与TC浓度比为1mg:0.1~4mg L-1;有机物溶液的体积为40~50mL;所述有机物为四环素;光催化剂和有机物的混合溶液达到吸附-解吸平衡的搅拌时间为10~50min;开灯后取样时间间隔为5~30min;开灯后每次取样的量为2mL;紫外-可见分光光度计的波长为355~358nm。
8.如权利要求5所述的一种间氨基苯硼酸掺杂的g-C3N4光催化剂光催化产氢方面的应用,其特征在于,具体包括如下步骤:将一定量的催化剂均匀分散在一定量三乙醇胺(TEOA)的水溶液中,加入一定量的氯铂酸作为助催化剂光沉积Pt到催化剂上,利用一定瓦数和波长的氙灯作为可见光光源,光照前用氩气将反应系统内空气排出,并用循环水将整个反应温度维持在一定温度;所述催化剂的量为28~32mg;TEOA量为2.5~3.5mL;氯铂酸用量为1mL;氙灯的瓦数和波长分别为350W和420nm;反应温度为15~20℃。
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