CN112588317B - 一种共价三嗪基骨架催化剂及其制备方法和应用 - Google Patents
一种共价三嗪基骨架催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明提供一种共价三嗪基骨架催化剂及其制备方法,所述共价三嗪基骨架催化剂是一种具有B掺杂和氮缺陷的共价三嗪基骨架材料。本发明通过简便的烧结有效的将B掺杂和缺陷共同引入原始共价三嗪基骨架中,有效地改变了材料的电子能带结构,具有丰富的不饱和活性位点,拓展了光吸收范围,促进光生电子‑空穴对的有效分离。制得的具有掺杂和缺陷协同效应的共价三嗪基骨架材料在光驱动下极大地提升了激活过氧单硫酸盐的能力,可以高效降解BPA。在波长大于420nm的可见光照射下,1h内对20ppm双酚A的去除率高达98%。
Description
技术领域
本发明涉及一种具有掺杂和缺陷协同效应的共价三嗪基骨架催化剂及其制备方法和应用。
背景技术
酚类化合物是水环境中普遍存在的一类有机污染物,其中双酚A(BPA)是一种典型的内分泌干扰化合物,在自然条件下往往难以完全分解。基于PMS(过氧单硫酸盐)的AOPs因其高效降解难降解的污染物而受到越来越多的关注,这类系统依赖PMS激活,通过各种策略(包括紫外线照射、超声波、电化学方法和无机多相纳米催化剂)生成高反应性的硫种(如硫酸根(SO4 ·-))和氧种(ROS,如羟基自由基(·OH)和单线态氧(1O2))。为了找到一种高质量和绿色过硫酸盐活化剂,共价三嗪基骨架(CTFs)作为一种具有半导体特性、类似于g-C3N4、N4等三嗪单元的新型多孔聚合物,近年来在光催化领域引起了广泛的关注。但由于CTFs对于可见光的利用有限、电荷复合快和合成条件苛刻导致在太阳能驱动的AOP中应用很有限(P.Pachfule,A.Acharjya,J.Roeser,T.Langenhahn,M.Schwarze,R.Schomacker,A.Thomas,J.Schmidt,Diacetylene functionalized covalent organic framework(COF)for photocatalytic hydrogen generation,J.Am.Chem.Soc.140(4)(2018)1423–1427;b)Z.A.Lan,Y.X.Fang,Y.F.Zhang,X.C.Wang,Photocatalytic oxygen evolution fromfunctional triazine-based polymers with tunable bandstructures,Angew.Chem.Int.Ed.57(2)(2018)470–474;c)W.Huang,Z.J.Wang,B.C.Ma,S.Ghasimi,D.Gehrig,F.Laquai,K.Landfester,K.A.I.Zhang,Hollow nanoporous covalenttriazine frameworks via acid vapor-assisted solid phase synthesis forenhanced visible light photoactivity,J.Mater.Chem.A4(20)(2016)7555–7559.)。在原始共价三嗪基材料中引入硼掺杂和缺陷后,会产生丰富的不饱和活性位点,可以有效改变了电子能带结构拓展,扩展光吸收范围,促进光生电子-空穴对的有效分离。因此,制备一种具有掺杂和缺陷协同效应的共价三嗪基骨架材料至关重要。
发明内容
为了克服现有技术对于可见光的利用有限、电荷复合快和合成条件苛刻等缺陷,本发明提供一种具有掺杂和缺陷协同效应的共价三嗪基骨架催化剂及其制备方法和应用。
为解决上述技术问题,本发明采用如下技术方案:
本发明提供一种共价三嗪基骨架催化剂,所述共价三嗪基骨架催化剂是一种具有B掺杂和氮缺陷的共价三嗪基骨架催化剂,所述共价三嗪基骨架催化剂是以共价三嗪基骨架材料与NaBH4充分混合后在惰性气体的氛围下在250-350℃烧结,冷却后得到的物质。
本发明还提供上述共价三嗪基骨架催化剂的制备方法,所述方法为:共价三嗪基骨架材料与NaBH4充分混合后在惰性气体的氛围下250-350℃烧结0.5-1.5h,所得混合物经后处理即得所述共价三嗪基骨架催化剂,NaBH4的质量以B计,NaBH4与共价三嗪基骨架材料的质量比为2~10:100,优选为5:100。
进一步,所述共价三嗪基骨架材料按如下方法制备:在1,4-对苯二腈中加入三氟甲磺酸,在0℃下搅拌1.5h后放入100℃烘箱中20min,自然冷却后,用乙醇和水洗涤(优选乙醇洗3次后水洗3次),于60℃真空干燥后得到共价三嗪基骨架材料;所述三氟甲磺酸的体积以1,4-对苯二腈的质量计为4.8-5.2mL/g,优选5mL/g。
优选地,步骤(2)中所述惰性气体为氮气。
进一步,步骤(2)中共价三嗪基骨架材料与NaBH4在研钵中充分混合。
优选地,步骤(2)中所述烧结在管式炉中进行。
优选步骤(2)中所述烧结的条件为在300℃下烧结1h。特别优选以5℃/min升温至300℃后烧结1h。
进一步,步骤(2)中所述后处理为:所述混合物自然冷却后,用乙醇和水洗涤以去除多余的NaBH4,于60℃真空干燥后得到所述共价三嗪基骨架催化剂。
本发明尤其推荐步骤(2)为:将共价三嗪基骨架材料与NaBH4在研钵中充分混合后放于管式炉中,氮气氛围下以5℃/min升温至300℃后烧结1h,自然冷却后,用乙醇和水洗涤以去除多余的NaBH4,于60℃真空干燥后得到所述共价三嗪基骨架催化剂。
一种上述共价三嗪基骨架催化剂在降解双酚A中的应用。
本发明推荐所述应用为:共价三嗪基骨架催化剂在光照条件下激活过氧单硫酸盐以降解双酚A;
具体地,上述应用为:将所述共价三嗪基骨架催化剂分散于双酚A水溶液中,黑暗条件下搅拌至达吸附-解析平衡,加入过氧单硫酸盐继续搅拌,光照条件下(优选可见光,尤其是波长大于420nm的可见光)20-30℃(优选25℃)降解。
优选地,所述双酚A水溶液中双酚A的浓度为5-50ppm,优选20ppm。
优选地,所述共价三嗪基骨架催化剂的质量以双酚A水溶液的体积计为0.1-1.0g/L,优选0.3g/L。
优选地,所述过氧单硫酸盐为单过硫酸氢钾复合盐,化学式为2KHSO5·KHSO4·K2SO4。
进一步优选地,过氧单硫酸盐的物质的量以双酚A水溶液的体积计为0.15-1.0mM,优选0.3mM。
优选地,所述降解的时间为1.5h。
优选地,所述光选择截止波长为420nm的300W Xe灯作为光源。
与现有技术相比,本发明的有益效果在于:
1.本发明通过简便的烧结有效的将B掺杂和缺陷共同引入原始共价三嗪基骨架中,有效地改变了材料的电子能带结构,具有丰富的不饱和活性位点,拓展了光吸收范围,促进光生电子-空穴对的有效分离。
2.本发明制得的具有掺杂和缺陷协同效应的共价三嗪基骨架材料在光驱动下极大地提升了激活过氧单硫酸盐的能力,可以高效降解BPA。在波长大于420nm的可见光照射下,1h内对20ppm双酚A的去除率高达98%。
3.本发明所述的材料的制备过程简便且温和,属于非金属材料,经济环保,且材料性能稳定,具有良好的重复利用性。
附图说明
图1为实施例1制得的具有掺杂和缺陷协同效应的共价三嗪基骨架催化剂的扫描电子显微镜(SEM)图
图2为实施例1制得的具有掺杂和缺陷协同效应的共价三嗪基骨架催化剂的透射电子显微镜(TEM)图
图3为实施例1方法制得的具有掺杂和缺陷协同应的共价三嗪基骨架催化剂的能量色散X射线光谱(EDX)图。
图4为实施例1方法制得的具有掺杂和缺陷协同效应的共价三嗪基骨架催化剂(BCTFs-5)与原始共价三嗪基材料(CTFs)的X射线粉末衍射(XRD)图。
图5为实施例1方法制得的具有掺杂和缺陷协同效应的共价三嗪基骨架催化剂(BCTFs-5、BCTF-2、BCTF-10)与原始共价三嗪基材料(CTFs)的傅里叶变换红外光谱(FT-IR)图
图6为实施例1方法制得的具有掺杂和缺陷协同效应的共价三嗪基骨架催化剂(BCTFs-5、BCTF-2、BCTF-10)与原始共价三嗪基骨架材料(CTFs)在光驱动下激活过氧单硫酸盐以催化降解BPA的对比效果图
图7为实施例1方法制得的具有掺杂和缺陷协同效应的共价三嗪基骨架催化剂的光催化降解BPA循环实验效果图
具体实施方式
下面结合附图和实施例对本发明做进一步阐述,以便本领域技术人员更好地理解本发明的实质。本发明中试剂或材料,若无特殊说明,均为市售产品。
实施例1 BCTF-5的制备方法:
1)原始共价三嗪基材料的制备:在2.0g 1,4-对苯二腈中加入10.0mL三氟甲磺酸,在0℃下搅拌1.5h后放入100℃烘箱中20min,自然冷却后,用水洗三遍后,乙醇洗三遍,于60℃真空干燥后得到原始共价三嗪基骨架材料1.6g。
2)BCTF-5的制备:将0.5g原始共价三嗪基材料与84mg NaBH4在研钵中充分混合后放于管式炉中,氮气氛围下以5℃/min升温至300℃后烧结1h,自然冷却后,用乙醇洗涤两遍后,水洗涤两遍以去除多余的NaBH4,于60℃真空干燥后得到具有掺杂和缺陷协同效应的共价三嗪基骨架催化剂0.49g。
实施例2 BCTF-2的制备
操作同实施例1,不同之处仅在于0.5g原始共价三嗪基材料与35.6mgNaBH4在研钵中充分混合,最终得到具有掺杂和协同效应的共价三嗪基骨架催化剂0.45g。
实施例3 BCTF-10的制备
操作同实施例1,不同之处仅在于0.5g原始共价三嗪基材料与168mgNaBH4在研钵中充分混合,最终得到具有掺杂和协同效应的共价三嗪基骨架催化剂0.56g。
实施例4本发明所述具有掺杂和缺陷协同效应的共价三嗪基骨架材料的结构表征。
1)形貌表征
SEM和TEM图像(图1-2)显示了原来的有序层状结构有所破坏。EDX图像(图3)清楚地表明,C、N、B元素均匀分布在共价三嗪基骨架材料表面,证明了B的成功掺杂。
2)晶形表征
通过(图4)可见,在掺杂前后,共价三嗪基骨架下料都有两个明显的衍射峰,分别位于14.5°和25.7°,前者对应于聚合物网的远程分子序的(100)晶面,而后者对应于共轭芳族体系的层间堆叠的(002)晶面。随着B的掺杂,衍射峰的强度有所减弱,属于(002)晶面的衍射峰从原来的25.7°偏移至25.4°,表明B掺杂后原始共价三嗪基骨架材料有序结构被破坏。
3)官能团表征
傅里叶变换红外光谱显示,在B掺杂前后,共价三嗪基骨架材料显示出详细的特征FT-IR振动带(图5)。在750-810cm-1和1330-1600cm-1附近的峰分别对应于三嗪单元典型的呼吸模式和三嗪环中芳族C=N键的拉伸模式。值得注意的是,在引入B掺杂后,出现了一个位于2180cm-1的新峰这可以归因于是氰基基团。该现象表明有缺陷产生。
实施例5本发明所述具有掺杂和缺陷协同效应的共价三嗪基骨架材料在可见光下激活过氧单硫酸盐以降解BPA。
具有掺杂和缺陷协同效应的共价三嗪基骨架材料制备过程同实例1。
实验方法:
1.光催化降解BPA实验:将30mg的材料粉末(BCTF-2、BCTF-5、BCTF-10)分散在100mL的反应液中,反应液为20ppm的BPA水溶液,在黑暗条件下搅拌30min以达吸附-解析平衡。30min后取的样作为初始样,加入18.4mg PMS(单过硫酸氢钾复合盐2KHSO5·KHSO4·K2SO4,0.3mM)继续搅拌。选择截止波长为420nm的300W Xe灯(PLS-SXE300;ShanghaiPerfect Light Co.,Ltd,Beijing,China)作为光源。经测量,反应器上的实际辐照强度约为60.2mW·cm-2。反应温度保持25℃。总反应时间为1.5h,在一定时间点取样1mL置于装有0.5mL甲醇的液相小瓶中,经液相色谱仪(Waters e2695)确定BPA的浓度。其中,流动相为甲醇:水=70:30,波长为225nm,流速为1mL/min,进样体积为10uL。
作为对比实验,将原始共价三嗪基骨架材料粉末用上述相同的方法进行实验。如图6所示,原始共价三嗪基骨架材料在1.5h内只能降解20%的BPA,表明原始共价三嗪基骨架材料没有足够的能力来激活PMS,从而有效降解BPA。
2.光催化降解循环实验:进行过光催化降解BPA实验的粉末通过用乙醇和去离子水洗涤的方法回收后,在60℃真空条件在干燥12h,再将回收的粉末取30mg的材料粉末分散在100mL的反应液中,反应液为20ppm的BPA水溶液,在黑暗条件下搅拌30min以达吸附-解析平衡。30min后取的样作为初始样,加入18.4mg继续搅拌。选择截止波长为420nm的300W Xe灯(PLS-SXE300;Shanghai Perfect Light Co.,Ltd,Beijing,China)作为光源。经测量,反应器上的实际辐照强度约为60.2mW·cm-2。反应温度保持25℃。总反应时间为1.5h,在一定时间点取样1mL于装有0.5mL甲醇的液相小瓶中,经液相色谱仪(Waters e2695)确定BPA的浓度。其中,流动相为甲醇:水=70:30,波长为225nm,流速为1mL/min,进样体积为10uL。循环实验共进行4组,每组进行1.5h。
如图7所示,在进行4轮循环光催化降解BPA后,本发明所述的材料降解效率只表现出轻微下降,证明材料具有较高的稳定性和重复利用性。
本说明书所述的内容仅仅是对发明构思实现形式的列举,本发明的保护范围不应当被视为仅限于实施例所陈述的具体形式。
Claims (8)
1.一种共价三嗪基骨架催化剂在降解双酚A中的应用,其特征在于:所述共价三嗪基骨架催化剂是一种具有B掺杂和氮缺陷的共价三嗪基骨架催化剂,
所述的共价三嗪基骨架催化剂按如下方法制备:共价三嗪基骨架材料与NaBH4充分混合后在惰性气体的氛围下300-350℃烧结0.5-1.5h,所得混合物经后处理即得所述共价三嗪基骨架催化剂,NaBH4的质量以B计,NaBH4与共价三嗪基骨架材料的质量比为5~10:100。
2.如权利要求1所述的应用,其特征在于:NaBH4的质量以B计,NaBH4与共价三嗪基骨架材料的质量比为5:100。
3.如权利要求1所述的应用,其特征在于所述共价三嗪基骨架材料按如下方法制备:在1,4-对苯二腈中加入三氟甲磺酸,在0℃下搅拌1.5h后放入100℃烘箱中20min,自然冷却后,用乙醇与水洗涤,于60℃真空干燥后得到共价三嗪基骨架材料;所述三氟甲磺酸的体积以1,4-对苯二腈的质量计为4.8-5.2mL/g。
4.如权利要求1所述的应用,其特征在于:所述烧结的条件为在300℃下烧结1h。
5.如权利要求1所述的应用,其特征在于所述后处理为:所述混合物自然冷却后,用乙醇和水洗涤以去除多余的NaBH4,于60℃真空干燥后得到所述共价三嗪基骨架催化剂。
6.如权利要求1所述的应用,其特征在于:所述共价三嗪基骨架催化剂在光照条件下激活过氧单硫酸盐以降解双酚A。
7.如权利要求6所述的应用,其特征在于:将所述共价三嗪基骨架催化剂分散于双酚A水溶液中,黑暗条件下搅拌至达吸附-解析平衡,加入过氧单硫酸盐继续搅拌,光照条件下20-30℃降解双酚A。
8.如权利要求6所述的应用,其特征在于:所述光为可见光。
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