CN107243361B - 一种多酸基金属有机骨架纳米晶催化剂的制备方法和应用 - Google Patents
一种多酸基金属有机骨架纳米晶催化剂的制备方法和应用 Download PDFInfo
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Abstract
本发明提供一种多酸基金属有机骨架纳米晶催化剂的制备方法和应用。该纳米晶催化剂可以通过液体辅助研磨法合成,获得的纳米晶催化剂粒子尺度小,粒径在50~200纳米,并且形貌、尺寸均一,同时催化剂组成、结构确定。在温和条件下,以过氧化氢为氧化剂,这种纳米晶能够高效地催化苯酚降解,实现高的苯酚转化率和高矿化率。催化剂通过简单的离心操作即可完全分离、回收,经烘干处理即可重复使用,多次重复使用后仍能保持良好的催化活性。本发明提供的多酸基金属有机骨架纳米晶催化剂的制备方法简单,可有效的减少催化剂的粒子尺寸,从而减少催化反应中的扩散限制和“积炭”现象,提高材料的催化效率。
Description
技术领域
本发明属于催化材料技术领域,涉及一种多酸基金属有机骨架纳米晶催化剂的制备方法和应用。
背景技术
多金属氧酸盐(polyoxometalates,缩写为POMs),也称多酸化合物,是一类由处于最高氧化态的前过渡金属(Mo,W,V,Nb,Ta等)构成的金属—氧簇化合物。由于具有较强的酸性和丰富的氧化还原化学,多酸是一类性能优异的酸、氧化还原和双功能催化剂(酸催化和氧化催化)。多酸基金属有机骨架(POM-MOFs)是将多酸引入到金属有机骨架的孔道中,一方面可实现均相多酸催化剂的固载,另一方面,可将多酸和金属有机骨架两者的催化功能相结合,是设计新型高效多酸催化剂的一种重要途径。多酸基金属有机骨架材料在催化应用方面尽管取得一些进展,但还远没有达到理想水平,其进一步发展受到以下限制:1)多酸基金属有机骨架材料的孔径通常小于2nm,大分子无法进入其狭窄的孔道发生吸附或催化反应;2)常规方法(常规水溶液和水热合成)得到的多酸基金属有机骨架材料的晶体尺寸一般都在微米级,相对狭长的孔道对于可以进入微孔的反应物和产物分子也会造成扩散限制,并且在催化反应中容易发生“积炭”现象,导致催化剂失活。
粒子尺寸对材料性质有重要影响,将材料制成纳米尺寸是一种开发新材料的有效策略。纳米化多酸基金属有机骨架催化剂,制备小粒径的催化剂,由于其孔道短,晶内扩散阻力小,外表面积增大,暴露在外的原子增多,具有丰富的晶间隙和较强的吸附能力,不仅可以大大改善材料在大分子催化方面的活性,降低积炭可能性,而且提供了更多的有效反应活性位点,进而大大提高材料的催化效率。
机械化学合成法(Mechanochemical synthesis)是近年发展起来的新的固相反应法,是通过机械力,使不同元素或其化合物相互作用,形成超细粉体。机械化学合成法为纳米功能材料的制备提供了一种经济、温和、简单、无污染的新合成途径。液体辅助研磨法(Liquid-assisted grinding,LAG),是一种改进的机械化学合成法,其通过加入催化剂量的溶剂使反应组分具有一定的流动性,从而加速机械化学反应并增强产物的结晶性。目前,多酸基金属有机骨架材料的主要合成方法有常规水溶液合成和水热合成法,还没有应用液体辅助研磨法制备多酸基金属有机骨架材料的报道。
发明内容
本发明的目的之一是提供一种多酸基金属有机骨架纳米晶催化剂的制备方法。
本发明的目的之二是为多酸基金属有机骨架纳米晶催化剂提供一种用途。
本发明的目的是通过如下方法实现的:一种多酸基金属有机骨架纳米晶催化剂的制备方法,其特征在于,包括以下步骤:
1、将物质的量比为1~2:1的可溶性铜盐和Keggin型钨磷酸溶解在一定量水中,将溶液pH值调至4,蒸干溶剂,得到多酸与铜盐的混合物粉末。
2、称取与Keggin型钨磷酸物质的量之比为1~2:1的均苯三甲酸,与上述粉末在玛瑙研钵中混合,加入与固体粉末剂量比η=1.0~2.0μL mg-1的溶剂后研磨,反应物颜色逐渐变为蓝色,用水和乙醇分别超声洗涤数次后烘干产物,最后得到多酸基金属有机骨架纳米晶。
上述可溶性铜盐为硝酸铜、醋酸铜、氯化铜等;Keggin型钨磷酸为H3PW12O40;溶剂为甲醇,乙醇,DMF等。制得的多酸基金属有机骨架纳米晶催化剂的化学式为: Cu12(TMA)8H3PW12O40(TMA=均苯三甲酸)。
上述方法制得的多酸基金属有机骨架纳米晶催化剂的结构通过X射线粉末衍射(PXRD,见附图1)进行表征。通过对比可以发现,在PXRD谱图中,纳米晶与文献中报道的水热方法合成的晶体(J.Am.Chem.Soc.2009,131,1883–1888)在峰位置和峰强度上均一致,这证明了用上述方法合成的纳米晶和文献中报道的水热方法合成的晶体具有相同的结构。同时,通过扫描电子显微镜图像可以确定,上述方法制得的纳米晶形貌、尺寸均一,纳米晶粒径在 50~200纳米之间(见附图2)。
本发明提供的多酸基金属有机骨架纳米晶催化剂在苯酚降解中的应用,其反应条件如下:
配置苯酚浓度为200mg/L的水溶液作为苯酚废水模拟物,过氧化氢为氧化剂,多酸基金属有机骨架纳米晶Cu12(TMA)8H3PW12O40作为催化剂。将0.05mmol催化剂和15mL过氧化氢(30wt%)加入50mL苯酚水溶液中,反应温度为40摄氏度。反应1小时后,苯酚转化率可达97%,矿化率为87%。上述反应的转化率通过气相色谱监测,矿化率通过TOC分析仪监测。
本发明中提供的多酸基金属有机骨架纳米晶催化剂具有以下特点:
1、催化剂粒子尺度小,粒径在50~200纳米,并且形貌、尺寸均一,同时催化剂组成、结构确定。
2、催化剂对苯酚降解具有高的催化活性,表现在苯酚转化率和矿化率高,催化反应条件温和。
3、催化剂通过简单的离心操作即可完全分离、回收,经烘干处理即可重复使用,多次重复使用后仍能保持良好的催化活性。
附图说明
图1是多酸基金属有机骨架Cu12(TMA)8H3PW12O40的X射线粉末衍射图:a)根据单晶X射线衍射数据,用Mercury软件模拟的XRD(J.Am.Chem.Soc.2009,131,1883–1888);b) 水热合成的晶体的X射线粉末衍射图;c)液体辅助研磨法合成的纳米晶的X射线粉末衍射图。
图2是液体辅助研磨法合成的多酸基金属有机骨架纳米晶的扫描电镜图。
图3是催化苯酚降解反应中的苯酚转化率随时间的变化曲线。
具体实施方式
为了进一步说明本发明,列举下列实施实例,但它并不限制各附加权利要求所定义的发明范围。
具体实施例1:Cu12(TMA)8H3PW12O40的液体辅助研磨法合成
取0.24g Cu(NO3)2·3H2O和0.28g H3PW12O40溶于10mL去离子水中,用NaOH将溶液pH值调至4,烘干溶液,得到混合物粉末。将得到的粉末和0.14g均苯三甲酸在玛瑙研钵中混合,并加入1mL甲醇,进行研磨,混合粉末逐渐变为蓝色。将蓝色粉末用水洗涤两次,乙醇洗涤两次,离心分离后在烘箱中60℃烘干24h,得到多酸基金属有机骨架纳米晶催化剂。具体实施例2:Cu12(TMA)8H3PW12O40的催化苯酚降解应用
将10mg苯酚溶于50mL去离子水中,配成浓度为200mg/L的苯酚水溶液。然后向苯酚水溶液中加入0.05mmol的催化剂和15mL过氧化氢(30wt%),反应温度为40℃。反应1 小时后,通过气相色谱监测,苯酚转化率已达97%,TOC检测显示矿化率达到87%。上述反应的转化率通过气相色谱监测,矿化率通过TOC分析仪监测。苯酚转化率随时间的变化关系见附图3。
Claims (3)
1.一种多酸基金属有机骨架纳米晶催化剂在苯酚降解中的应用,其特征在于,所述多酸基金属有机骨架纳米晶催化剂的组成为:Cu12(TMA)8H3PW12O40,TMA为均苯三甲酸的英文缩写,可采用液体辅助研磨法合成,具体为:将物质的量比为1~2:1的可溶性铜盐和Keggin型钨磷酸溶解在一定量水中,将溶液pH值调至4,蒸干溶剂,得到多酸与铜盐的混合物粉末;称取与Keggin型钨磷酸物质的量之比为1~2:1的均苯三甲酸,与上述粉末在玛瑙研钵中混合,加入与固体粉末剂量比η=1.0~2.0μL mg-1的溶剂后研磨,反应物颜色逐渐变为蓝色,用水和乙醇分别超声洗涤数次后烘干产物,最后得到多酸基金属有机骨架纳米晶催化剂;催化剂粒子尺度小,粒径在50~200纳米,并且形貌、尺寸均一,同时催化剂组成、结构确定;催化剂对苯酚降解具有高的催化活性,表现在苯酚转化率和矿化率高,催化反应条件温和;催化剂通过简单的离心操作即可完全分离、回收,经烘干处理即可重复使用,多次重复使用后仍能保持良好的催化活性。
2.按照权利要求1所述的一种多酸基金属有机骨架纳米晶催化剂在苯酚降解中的应用,其特征在于:所述的铜盐为硝酸铜、氯化铜或醋酸铜;所述的Keggin型钨磷酸为H3PW12O40;溶剂为甲醇,乙醇或DMF。
3.按照权利要求1所述的一种多酸基金属有机骨架纳米晶催化剂在苯酚降解中的应用,其特征在于:在温和条件下,以过氧化氢作为氧化剂,催化降解苯酚水溶液。
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