CN107262153A - 一种Pd/MIL‑100(Fe)光催化剂的制备方法 - Google Patents
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Abstract
本发明公开了一种Pd/MIL‑100(Fe)光催化剂的制备方法,其是将MIL‑100(Fe)分散在乙醇‑水溶液中,然后在不断搅拌的条件下加入聚乙烯吡咯烷酮与H2PdCl4,随后于90 ℃油浴回流3 h,使Pd2+被乙醇逐渐还原,而得到Pd/MIL‑100(Fe)光催化剂。本发明利用简单、温和的乙醇还原贵金属方法,在具有超大比表面积的MIL‑100(Fe)上生长高分散的贵金属Pd纳米颗粒,在这个过程中,不需要惰性气氛、强还原剂和热处理过程,且制备的Pd纳米颗粒分散性好,利用率高,使所得Pd/MIL‑100(Fe)光催化剂具有高效光催化降解水环境中的药物、个人护理用品或者染料的性能。
Description
技术领域
本发明属于能源、环境治理中的催化技术领域,具体涉及一种Pd/MIL-100(Fe)光催化剂的制备方法和应用。
背景技术
金属有机骨架(Metal-Organic Frameworks,MOFs)材料是对一类以金属阳离子为节点、具有多齿配位的有机配体为连接体的微孔-介孔金属有机配位聚合物的总称。MOFs材料作为多孔材料的生力军,在气体储存分离,药物输送,光、电、磁学以及催化等等诸多方面拥有巨大的应用前景。近年来,以MOFs材料为基础的光催化技术受到人们的广泛关注。在众多已知的MOFs材料中,几种过渡金属形成的MOFs材料具有较高的水热稳定性和化学稳定性,其中,介孔MIL-100(Fe)就是典型的一种。MIL-100(Fe)为刚性沸石型晶体结构,具有较高的化学与热稳定性。Fe作为一种生命元素廉价易得,且含Fe化合物在光催化上有着广泛应用。基于以上因素,MIL-100(Fe)成为了众多MOFs中最具应用潜力的材料之一。
然而,结合光催化应用的实际情况,我们发现目前MIL-100(Fe)光催化材料仍然存在着光生载流子分离效率低与太阳能利用率较低的许多问题。已有研究表明,将具有优良的电学、催化等性能的贵金属纳米粒子均匀分散到MOFs材料表面或者孔道中制成复合材料,不仅能增强MOFs材料的可见光吸收性能,提高光生载流子分离的效率,而且可能产生一些新颖的协同效应。而传统的用于贵金属复合的手段,如化学还原、化学气相沉积和电化学还原等方法通常比较耗时、反应条件苛刻,并且反应过程中通常需要加入还原剂比如硼氢化钠,而MIL-100(Fe)是对外界环境敏感的一类材料,强还原剂在反应过程中有可能会对载体本身的结构造成一定的影响。此外,贵金属颗粒在还原过程中易造成颗粒的大量团聚,粒子平均粒径过大,不利于高效转移和分离光生载流子。因此,有必要开发一种简单而有效的方法将贵金属粒子沉积在MIL-100(Fe)的表面,而不需要复杂的设备、惰性气氛与昂贵有机配体。
发明内容
本发明的目的在于针对现有技术中的不足,提供一种Pd/MIL-100(Fe)光催化剂的制备方法和应用,其通过温和、简单的乙醇还原方法将钯离子还原成原子沉积在载体的表面,具有制备方法简单易行,不需要复杂昂贵的设备与惰性气氛、合成条件温和等特点,解决了现有技术中制备贵金属/MOFs复合催化剂耗时、不能普遍适用等问题,且其还可以拓展到其它贵金属的负载应用上。
为实现上述目的,本发明采用如下技术方案:
一种Pd/MIL-100(Fe)光催化剂的制备方法,其是以乙醇为还原剂,将Pd2+还原为Pd纳米颗粒,并使其负载在金属有机骨架材料MIL-100(Fe)上,制得所述Pd/MIL-100(Fe)光催化剂;其中, Pd纳米颗粒的含量为0.5 wt%-3 wt %,其颗粒粒径为6-8nm。
其具体制备方法是将MIL-100(Fe)分散在乙醇-水溶液中,然后在不断搅拌的条件下加入聚乙烯吡咯烷酮与H2PdCl4,加完后搅拌30 min,再于90 ℃油浴回流3 h,离心,用去离子水洗去多余离子后,60 ℃真空干燥,即得。其中,所用乙醇-水溶液中乙醇与水的体积比为1:1。
所得Pd/MIL-100(Fe)光催化剂可应用于光催化降解水中药物、个人护理用品或染料等领域。
本发明提出一种通用、快速的Pd/MIL-100(Fe)光催化剂的制备方法,其利用具有一定还原能力的乙醇作为还原剂,在加热条件下与具有氧化能力的贵金属阳离子反应,从而在不需要复杂的设备、惰性气氛与昂贵的有机配体的条件下,制得Pd/MIL-100(Fe)光催化剂。
本发明的显著优点在于:
1)与常规在载体表面通过浸渍还原法、沉积沉淀法制备贵金属复合催化剂的操作不同,本发明采用温和简单的乙醇还原方法制备复合光催化材料,其不需要复杂的设备、惰性气氛与昂贵的有机配体,并解决了传统方法中采用强还原剂还原贵金属时,会造成载体结构破坏的问题。
2)本发明制得的光催化剂中钯颗粒小、均匀,其粒径约为6-8 nm,在载体表面分散性好,没有团聚现象,且贵金属与载体之间具有紧密的界面接触。因此,MIL-100(Fe)导带上的电子可以顺利转移到钯颗粒上,促进光生电子-空穴对的分离,从而使制备的催化剂具有很好的催化活性。
3)本发明制备方法简单易行,有利于大规模的推广,具有很大的普适性。许多贵金属(如金、银、铂、铜、镍等)都可以成功地采用该技术负载到载体上,因此,可以通过加入两种或两种以上的贵金属盐,制备出贵金属合金负载型催化剂,并且可以通过改变贵金属盐的加入量在很大程度上改变贵金属的负载量。
4)本发明制备的催化剂可以应用于室温光催降化解水环境中的药物、个人护理用品或者染料,且该催化剂可以方便地进行分离处理,重复利用效率高,具有很高的实用价值和应用前景。此外,该催化剂还可应用于降解有机污染物,例如室内空气和水的处理;和能源方面,比如光解水制备氢气等领域。
附图说明
图1为本发明实施例1所得Pd/MIL-100(Fe)催化剂的XRD图。
图2为本发明实施例1所得Pd/MIL-100(Fe)催化剂的EDS图。
图3为本发明实施例1所得Pd/MIL-100(Fe)催化剂的TEM图。
图4为本发明实施例1所得Pd/MIL-100(Fe)催化剂室温光催催化降解茶碱的活性情况图。
图5为本发明实施例1所得Pd/MIL-100(Fe)催化剂室温光催催化降解布洛芬的活性情况图。
图6为本发明实施例1所得Pd/MIL-100(Fe)催化剂室温光催催化降解双酚A的活性情况图。
图7为本发明实施例1所得Pd/MIL-100(Fe)催化剂室温光催降化降解甲基橙的活性情况图。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
实施例1 Pd/MIL-100(Fe)光催化剂的制备
(1)MIL-100(Fe)的制备:按摩尔比n(Fe):n(H3BTC):n(HF):n(HNO3):n(H2O)=1:0.67:2:0.6:277分别称取一定量的铁粉(Fe)、均苯三甲酸(H3BTC)和一定体积的氢氟酸(HF)、浓硝酸(HNO3)和水(H2O),混合搅拌约5 min后将混合液转移至聚四氟乙烯水热反应釜中,于密闭条件下升温至150 ℃后恒温保持24 h;反应结束后将水热反应釜静置冷却至室温,将样品过滤,用蒸馏水洗去附着于沉淀上的多余离子后,放入干燥箱中恒温干燥数小时,得到淡橘黄色块状晶体,即为MIL-100(Fe)粗品;
(2)MIL-100(Fe)的纯化:将1.0 g所得MIL-100(Fe)粗品溶于350 mL乙醇中,在60 ℃条件下恒温搅拌3h,过滤,60℃真空干燥,制得MIL-100(Fe);
(3)Pd/MIL-100(Fe)光催化剂的制备:将0.1g MIL-100(Fe)分散于10mL乙醇-水溶液(1:1,v/v)中,然后在不断搅拌的条件下加入0.333g聚乙烯吡咯烷酮与294μL H2PdCl4(10mg/mL),加完后搅拌30 min使之分散均匀,再于90 ℃油浴回流3 h,离心,用去离子水洗去多余离子后,60℃真空干燥,得到Pd/MIL-100(Fe)光催化剂。
图1为所合成的Pd/MIL-100(Fe)光催化剂的XRD图。由图1可见,Pd的掺入对MIL-100(Fe)没有影响,证明其是负载在MIL-100(Fe)上的。
图2为所合成的Pd/MIL-100(Fe)光催化剂的EDS图。由图中也证实了所得Pd@MIL-100(Fe)光催化剂中含有Fe、C、O和Pd元素,进一步证明了本发明乙醇回流的方法可以实现贵金属的高效负载,且Pd的质量分数为0.867 wt%,与理论值的1 wt%十分接近。
图3为所合成的Pd/MIL-100(Fe)光催化剂的TEM图。由图3中可以看出,通过简单的一步乙醇回流方法得到的贵金属颗粒较小,其密实地分布在底物MIL-100(Fe)的表面上,形成高分散状态(图3A),其中Pd纳米颗粒的平均粒径大约为6-8 nm(图3B)。从高分辨透射电镜图(图3C-3D)上可观察到清晰的晶格条纹,晶面间距d=0.221 nm,与Pd纳米颗粒的(111)晶面相匹配。这种高分散的金属纳米Pd颗粒的形成一方面可能由于在反应中添加的高聚物PVP能够在Pd的表面形成稳定的保护膜,从而极大地抑制金属颗粒的团聚;另一方面,由于MIL-100(Fe)的超高比表面积与孔隙率的协同作用,有益于形成高分散纳米颗粒。
实施例2 Pd/MIL-100(Fe)光催化剂催化降解药物与个人护理用品的活性
实验选用了茶碱、布洛芬与双酚A这三种典型的药物与个人护理用品作为模拟污染物。具体实验步骤如下:取5 mg制备得的催化剂分散于40 mL溶解有药物与个人护理用品的溶液中(20 mg/L),然后加入40 μL的H2O2,并且调节溶液pH值为4。将上述分散液在暗处放置3h以达到吸附脱附平衡后,开灯进行光照(波长大于等于420 nm),并间隔一段时间量取3 mL的反应溶液,经离心分离后,取上层清液进行高效液相色谱分析,以计算茶碱、布洛芬与双酚A的去除率,其计算公式如下:
去除率(%)=[(C0-Ct)/C0]×100%,
其中C0是污染物的初始浓度,Ct是污染物在反应一段时间后的浓度。茶碱、布洛芬与双酚A的反应情况分别如图4-图6所示。
由图中可见,经过240 min的反应,大部分茶碱、布洛芬与双酚A都被降解,表明本发明Pd/MIL-100(Fe)光催化剂具有较高水相常温下光催化降解的药物与个人护理用品的活性。
实施例3 Pd/MIL-100(Fe)光催化剂催化降解甲基橙的活性
具体实验步骤如下:取5 mg制备得的催化剂分散于40 mL溶解有甲基橙的溶液中(20mg/L),然后加入40 μL的H2O2,并且调节溶液pH值为4。将上述分散液在暗处放置3h以达到吸附脱附平衡后,开灯进行光照(波长大于等于420 nm),并间隔一段时间量取3 mL的反应溶液,经离心分离后,取上层清液进行紫外−可见光谱分析。由其最大吸收波长(460 nm)处的强度变化计算甲基橙的降解率,结果如图7所示。
由图7可见,经过150 min的反应,大部分甲基橙可以被降解,表明本发明Pd/MIL-100(Fe) 光催化剂具有较高水相常温下光催化降解活性。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (4)
1.一种Pd/MIL-100(Fe)光催化剂的制备方法,其特征在于:以乙醇为还原剂,将Pd2+还原为Pd纳米颗粒,并使其负载在金属有机骨架材料MIL-100(Fe)上,制得所述Pd/MIL-100(Fe)光催化剂;
所得光催化剂中Pd纳米颗粒的含量为0.5 wt%-3 wt %,其颗粒粒径为6-8nm。
2. 根据权利要求1所述Pd/MIL-100(Fe)光催化剂的制备方法,其特征在于:其具体是将MIL-100(Fe)分散在乙醇-水溶液中,然后在不断搅拌的条件下加入聚乙烯吡咯烷酮与H2PdCl4,加完后继续搅拌30 min,再于90 ℃油浴回流3 h,离心、洗涤,60 ℃真空干燥,制得Pd/MIL-100(Fe)光催化剂。
3.根据权利要求2所述Pd/MIL-100(Fe)光催化剂的制备方法,其特征在于:所用乙醇-水溶液中乙醇与水的体积比为1:1。
4.一种如权利要求1所述方法制得的Pd/MIL-100(Fe)光催化剂在光催化降解水中药物、个人护理用品或染料上的应用。
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