CN115007207A - 一种BiNPs/TpBpy复合材料的制备及光催化二氧化碳还原 - Google Patents
一种BiNPs/TpBpy复合材料的制备及光催化二氧化碳还原 Download PDFInfo
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Abstract
本发明涉及一种BiNPs/TpBpy复合材料的制备及光催化二氧化碳还原。本发明提供一种新型BiNPs/TpBpy复合材料,目的是为了解决现有TpBpy光催化二氧化碳材料光利用率低和效率不高的问题。方法:一、BiNPs的制备;二、TpBpy的制备;三、BiNPs/TpBpy复合材料的制备。本发明制备过程简单,且具有较高的材料复合效率。本发明应用于光催化二氧化碳还原领域,实验表明该复合材料具有优异的光催化二氧化碳还原性能,在可见光照射下二氧化碳还原速率可达到217.3μmol·g‑1·h‑1,是TpBpy材料的15.5倍。
Description
技术领域
本发明涉及一种BiNPs/TpBpy复合材料的制备及光催化二氧化碳还原。
背景技术
随着经济的高速发展和人口数量的不断增长,人类社会发展对能源的依赖与日俱增,传统化石能源的快速消耗引发了严峻的能源危机,并导致严重的环境污染和生态破坏。另外,由于化石燃料大量燃烧,所产生的排放废物,如温室气体(主要是二氧化碳)持续在大气中积累,由此引发的一系列环境问题,如全球变暖、海平面升高、沙漠化、海洋酸化、物种多样性减少等,也威胁着人类社会的安定与发展。采用物理或化学等方式对二氧化碳进行处理转化从而减轻环境负担逐渐引起了各国研究人员的高度重视。因此,开发高效的能源存储和转换技术以便充分利用清洁能源及温室气体的捕获和处理尤为重要。
近几十年来,有效利用太阳能已成为实现能源和环境可持续能力的一项非常重要的战略。基本上,太阳能可以通过转化为电能、化学能和热能来进行人为利用。这些路径的效率最终取决于光活性材料的固有特性,包括它们的光捕获能力、电荷载流子分离和导电性等。着眼于这些因素,等离子金属纳米材料近年来被引入太阳能转换体系。等离子纳米结构可以通过激发局部表面等离子共振(LSPR)与入射光子相互作用,并表现出强大而独特的光学反应。这种共振过程使等离子体纳米结构能够捕获光能,将其集中在表面附近,并将光能转化为高能电荷载流子和热量。
共价有机骨架材料(COFs)是由C、B、O和N等轻元素通过共价键连接而成的多孔晶型材料,具有质量轻,密度低,高比表面积,结构规整,结构相对稳定,易功能化修饰等优点,使得COFs在气体贮存和分离、催化、传感、储能、光电转换等多个领域表现出极具潜力的应用前景。然而,单组分COFs光催化剂存在严重的光生电子-空穴复合问题,这极大地限制了COFs光催化二氧化碳还原的进一步提高。因此,研制一种光催化分解二氧化碳还原效率高的材料成为了研究热点。
发明内容
本发明的目的是要解决现有材料光催化二氧化碳还原效率不高的问题,而提供一种BiNPs/TpBpy复合材料的制备方法及光催化二氧化碳还原应用。
本发明的一种BiNPs/TpBpy复合材料的制备方法是按以下步骤完成的:
(1)在史朗克玻璃管中依次装入1,3,5-三醛基间苯三酚和[2,2'-联吡啶]-5,5'-二胺,随后加入邻二氯苯,N,N-二甲基乙酰胺组成的混合溶液,将该混合物超声处理30~40min以获得均匀的分散体,再加入乙酸水溶液。将史朗克管在77K(液氮浴)中快速冷冻,并通过三次冻融循环进行脱气,最后将管在真空密封状态下120℃加热72h。通过离心或过滤收集形成的深红色沉淀,依次用DMAc、水、丙酮洗涤多次,真空干燥得到TpBpy,将其分散在水中进行超声剥层处理60min形成粉末分散液,以备后续使用。
(2)将五水硝酸铋和聚乙烯吡咯烷酮溶解在甘油和乙醇的混合体系中,快速加入硼氢化钠搅拌然后离心,依次用乙醇和水洗涤,将其分散在水中形成BiNPs分散液,以备后续使用。
(3)将步骤(2)中得到的BiNPs分散液加入到步骤(1)所得到的TpBpy的分散液中,然后进行超声处理120min,最后通过冷冻干燥得到BiNPs/TpBpy复合材料。
步骤(1)中邻二氯苯和N,N-二甲基乙酰胺的体积比为1:3;
步骤(1)中乙酸浓度为6mol·L-1;
步骤(2)中甘油和乙醇的体积比为2:1;
步骤(2)中加入硼氢化钠搅拌1min;
本发明的有益效果:
本发明成功合成了BiNPs/TpBpy复合材料,通过将具有等离子体效应的BiNPs与TpBpy纳米片复合,该材料有效的提高了光催化二氧化碳还原性能,BiNPs/TpBpy复合材料的光催化二氧化碳还原效率为217.3μmol·h-1·g-1。
附图说明
图1为BiNPs/TpBpy复合材料的X-射线粉末衍射图;
图2为BiNPs/TpBpy复合材料的SEM图;
图3为BiNPs/TpBpy复合材料的光催化二氧化碳还原性能图。
具体实施方式
下面用实施例对本发明进行进一步说明,这些实施例仅对本发明的方法进行说明,对本发明的适用范围无任何限制。
实施例1:本实施方式的一种BiNPs/TpBpy复合材料的制备是按以下步骤完成的:
一、BiNPs的制备:将300mg的聚乙烯吡咯烷酮(PVP)和100mg Bi(NO3)3·5H2O加入到10mL甘油和5mL的乙醇混合溶液中,温和加热溶解,然后快速加入50mg NaBH4搅拌1min后离心,依次用乙醇和蒸馏水多次洗涤,分散在水中得到BiNPs分散液;
二、TpBpy的制备:在史朗克玻璃管中依次装入42mg 1,3,5-三醛基间苯三酚和55.8mg[2,2'-联吡啶]-5,5'-二胺,1mL邻二氯苯(o-DCB),3mL DMAc组成的混合溶液。将该混合物超声处理30~40min以获得均匀的分散体,再加入0.4mL 6.0M乙酸水溶液。将史朗克管在77K(液氮浴)中快速冷冻,并通过三次冻融循环进行脱气,最后将管在真空密封状态下120℃加热72小时。通过离心或过滤收集形成的深红色沉淀,依次用DMAc、水、丙酮洗涤多次,真空干燥得到TpBpy,将其分散在水中进行超声剥层处理60min形成粉末分散液。
三、BiNPs/TpBpy复合材料的制备:将BiNPs分散液加入到TpBpy分散液中,然后进行超声处理120min,最后通过冷冻干燥得到BiNPs/TpBpy复合材料
为验证本发明的有益效果进行以下试验:
为了考察该复合物的光催化二氧化碳还原效果,按以下方法对其光催化二氧化碳还原性能进行测试。测试过程如下:分别将10mg的BiNPs/TpBpy复合材料分散在0.5mL丙酮中,滴涂在玻璃片上,制成一层均匀的膜并置于反应装置底部,然后向装置持续通入二氧化碳,30min后停止通气,并将光源打开开始光催化二氧化碳还原反应;如图3所示,在氙灯光照下,BiNPs/TpBpy复合材料的还原产物均为一氧化碳,BiNPs/TpBpy复合材料的平均产量为217.3μmol·g-1·h-1,是TpBpy材料的15.5倍。
Claims (5)
1.一种BiNPs/TpBpy复合材料的制备,其特征在于该方法按以下步骤进行:
(1)在史朗克玻璃管中依次装入1,3,5-三醛基间苯三酚和[2,2'-联吡啶]-5,5'-二胺,随后加入邻二氯苯,N,N-二甲基乙酰胺组成的混合溶液,将该混合物超声处理30~40min以获得均匀的分散体,再加入乙酸水溶液。将史朗克管在77K(液氮浴)中快速冷冻,并通过三次冻融循环进行脱气,最后将管在真空密封状态下120℃加热72h。通过离心或过滤收集形成的深红色沉淀,依次用DMAc、水、丙酮洗涤多次,真空干燥得到TpBpy,将其分散在水中进行超声剥层处理60min形成粉末分散液,以备后续使用。
(2)将五水硝酸铋和聚乙烯吡咯烷酮溶解在甘油和乙醇的混合体系中,快速加入硼氢化钠搅拌然后离心,依次用乙醇和水洗涤,将其分散在水中形成BiNPs分散液,以备后续使用。
(3)将步骤(2)中得到的BiNPs分散液加入到步骤(1)所得到的TpBpy的分散液中,然后进行超声处理120min,最后通过冷冻干燥得到BiNPs/TpBpy复合材料。
2.根据权利要求1所述的一种BiNPs/TpBpy复合材料的制备,其特征在于步骤(1)中邻二氯苯和N,N-二甲基乙酰胺的体积比为1:3。
3.根据权利要求1所述的一种BiNPs/TpBpy复合材料的制备,其特征在于步骤(1)中乙酸水溶液浓度为6mol·L-1。
4.根据权利要求1所述的一种BiNPs/TpBpy复合材料的制备,其特征在于步骤(2)中甘油和乙醇的体积比为2:1。
5.根据权利要求1所述的一种BiNPs/TpBpy复合材料的制备,其特征在于步骤(2)中加入硼氢化钠搅拌1min。
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