CN110639531B - 一种TiO2-铜酸镧纳米催化粉体的制备方法 - Google Patents
一种TiO2-铜酸镧纳米催化粉体的制备方法 Download PDFInfo
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Abstract
本发明涉及光催化、电催化技术领域，公开了一种配位法制备TiO2‑铜酸镧纳米催化粉体的制备方法及其应用。本专利采用配位法制备纳米催化粉体，该方法制备的TiO2‑铜酸镧纳米光催化、电催化粉体纯度高，呈现片层状结构，比表面积大，不仅可以光催化降解有机物孔雀石绿还可以在电催化水解产氢、产氧方面具有潜在的应用空间。本发明提供的制备方法，简单易操作，成本低，片层薄且均匀，不会引入杂质或造成金属物料损失，配位法能保证析出物中金属离子的化学计量比，能推广应用于工业化生产。
Description
技术领域
本发明属于光催化、电催化材料技术领域，具体涉及一种配位法制备TiO2 包覆铜酸镧纳米催化粉体的制备方法。
近年来，随着人们生活水平的不断提高和科技的快速发展，环境污染和破坏问题越来越严重。通过各种方式进入人体的化学物质的种类和数量也在迅速增加，对水环境造成严重污染。一般来说，由于有机染料、卤化物、酚类和农药的存在，废水很难被降解。而且，相当一部分的有机污染物会引起癌症或引起基因突变，这对人类健康是一个巨大的威胁。环境污染和破坏问题已成为全球关注的问题，这已成为各国政府迫切需要解决的问题。
光催化氧化法是在光中使用催化剂，产生强氧化氢氧自由基和其他活性物质，有机分子中染料的氧化降解，将转化为水、二氧化碳和其他无机分子，最终达到脱色的目的。早在1972年，研究表明使用紫外线照射二氧化钛电极可以使水产生氢气和氧气。光催化氧化技术处理印染废水已成为一种新的发展前景。该技术能有效地破坏有机污染物的稳定和难以降解的结构，具有显著的效率和节能、降解等优点。几乎所有的有机物都可以在光催化的条件下完全转化为简单的无机物质、水和二氧化碳。
La2CuO4层和LaO层沿着c轴方向相互堆叠形成的类钙钛矿型复合氧化物 (A2BO4)。它是一种p型半导体材料，同时也是超导材料的母相材料。因LaCuO4内部有两种不同结构的交替组合，所以La2CuO4除了具有ABO3型钙钛矿的相似性能外，还有高温超导、催化等方面的性能。与ABO3相比的A2BO4中AO盐岩层的存在，使ABO3层中的BO6八面体发生畸变，所以在大的弹性范围内A2BO4的结构稳定。A2BO4型复合氧化物是一种非整比化合物，结构中可能存在氧空位，使其具有气敏性，成为优良的半导体传感器。此外，La2CuO4在有机物催化氧化、氨氮氧化物催化消除和汽车尾气催化净化等方面也具有良好的应用潜能。
本专利采用配位化合法制备TiO2-铜酸镧纳米催化粉体。利用金属阳离子与有机溶剂反应，使金属离子与配位体以配位键的形式相结合，从而形成具有一定组成或空间构型的配位离子。
目前，铜酸镧现有的制备方法并不令人满意，存在着制备过程复杂不易推广、所得产品性能不佳等问题。本发明所提供的制备方法，不仅可以解决上述问题，还将TiO2纳米粉体同时包覆在配位法制备的的La2CuO4纳米粉体上，制备出的粉体纯度高、粒度均匀、可控性好、性能优异。此外，本专利制备的纳米粉体，在降解水体中有害的有机物孔雀石绿有非常好的效果，并且在电催化水解产氢、产氧方面具有潜在的应用空间。
发明内容
为解决上述技术问题，本发明提供了一种制备TiO2-铜酸镧纳米催化粉体的制备方法。本发明制备的粉体具有粉体纯度高、粒度均匀、可控性好、性能优异，制备的铜酸镧纳米粉体不仅可作为降解水体中有害的有机物孔雀石绿还可用于电解水产氢产氧的催化剂。
具体技术方案如下：
一种TiO2-铜酸镧纳米催化粉体的制备方法，包括以下步骤：
(1)按照铜酸钕La2CuO4中Cu与La的化学计量比称取Cu的可溶性盐和 La的可溶性盐，溶于去离子水中，混合均匀，得到溶液A；
(2)在溶液A中加入一定量的N,N-二甲基甲酰胺和一定量的3-4吡啶二羧酸，将溶液于60～90℃加热并搅拌2～3h，得到溶液B；
(3)用移液枪加入5-10mL浓度为1mol/L的碱液到溶液B中，搅拌直至溶解，制备成溶液C；
(4)将溶液C放进烘箱，在120℃-150℃的温度条件下，恒温反应3-6小时后，空气中冷却至室温；待溶液体系稳定后，将所得混合溶液进行过滤，所得固体用水洗涤2-4次，得到片状晶体，将得到的晶体放入液氮中进行粉化，将制得的粉体D取出；
(5)将粉体D和一定量的TiO2粉体放入去离子水中，喷雾器进行喷雾造粒， 60-90℃的温度条件下，烘箱烘干1-2h，制备出本专利需要的纳米片层粉体。
步骤(1)中所述的铜的可溶性盐可以为氯化铜、硝酸铜或醋酸铜，钕的可溶性盐可以为氯化镧、硝酸镧或醋酸镧。
步骤(1)中去离子水的体积用量为铜的可溶性盐和镧的可溶性盐总摩尔量的4～6倍。
步骤(2)(3)中所述的搅拌条件为机械搅拌或磁力搅拌，转子转数为500～ 1000r/min。
步骤(2)中所述N,N-二甲基甲酰胺的用量为铜盐摩尔量的3-4倍、3-4吡啶二羧酸用量为铜盐摩尔量的1-2倍。
步骤(5)中TiO2的用量为铜的可溶性盐和镧的可溶性盐总摩尔量的1～2 倍，去离子水的体积用量为铜的可溶性盐和镧的可溶性盐总摩尔量的4～6倍。
步骤(3)所述碱液的溶质为三乙胺，溶剂为乙醇。
TiO2-铜酸镧纳米催化粉体的应用，可以用于光催化降解有机物孔雀石绿及在电催化水解产氢、产氧方面具有潜在的应用。
本方法的优点是：
(1)本发明采用配位合成的方法，制备过程简单，金属原子匹配性好，不会造成金属的浪费，污染环境，节约成本；
(2)本发明在原有简单溶液制备的过程中，添加N,N-二甲基甲酰胺和3.4 吡啶二羧酸，有效的分散了铜离子和镧离子；在液氮中进行粉化，使得制备的粉体更为细小，有利于纳米化，具体为3.4吡啶二羧酸与铜离子进行有效的配位，可使铜和镧充分溶解在N,N-二甲基甲酰胺溶液中，而使用其他分散剂很难达到本专利要求的实验效果。
(3)本发明制备的粉体同时具有光催化和电催化效果，并且制备出的粉体纯度高、粒度均匀、可控性好、性能优异，目前还未见有该粉体对电解水催化的相关报道。开辟了电催化水解产氢、产氧方面具有潜在的应用空间，开拓了新的性能。
附图说明
图1为本发明实施例1制备得到的TiO2-铜酸镧纳米催化粉体的扫描电镜图；
图2为本发明实施例2制备得到的TiO2-铜酸镧纳米电催化粉体对孔雀石绿降解曲线；
图3为本发明实施例3制备得到的TiO2-铜酸镧纳米电催化粉体的析氢曲线；
图4为本发明实施例3制备得到的TiO2-铜酸镧纳米电催化粉体的析氧曲线；
图5为本发明对比例1制备得到的TiO2-铜酸镧纳米电催化粉体的扫描电镜图；
图6为本发明对比例2制备得到的TiO2-铜酸镧纳米电催化粉体的扫描电镜图。
具体实施方式
下面结合附图对本发明进行详细说明，但本发明的保护范围不受实施例所限。
实施例1
(1)按照La2CuO4中Cu与La的化学计量比称取1mmol醋酸铜和2mmol醋酸镧，溶于去离子水中，去离子水的体积用量为醋酸铜和醋酸镧总摩尔质量的6 倍，混合均匀，得到溶液A；
(2)在溶液A中加入3mmolN,N-二甲基甲酰胺，加入2mmol 3.4吡啶二羧酸，在60℃下加热并700r/min磁力搅拌2h，得到溶液B；
(3)用移液枪加入浓度为1mol/L的碱液5ml(溶质为三乙胺，溶剂为乙醇)，至溶液B中，700r/min磁力搅拌20min至溶解，制备成溶液C。
(4)将溶液C放进烘箱，在120℃的温度条件下，恒温反应3小时后，空气中冷却至室温；待溶液体系稳定后，将所得混合溶液进行过滤，所得固体用水洗涤2次，将得到的晶体放入液氮中进行粉化，取出粉体D。
(5)将粉体D和3mmol的TiO2粉体放入去离子水中，去离子水的用量为TiO2摩尔量的4倍，喷雾器进行喷雾造粒，90℃的温度条件下，烘箱烘干1h，制备出TiO2-铜酸钕纳米催化粉体。
图1为本发明实施例1制备得到的TiO2-铜酸镧纳米催化粉体的扫描电镜图，从图1可以看出，制备的粉体呈现均匀的片层状形貌，片层厚度仅有20-30nm，分散性好，比表面积大，有利于催化反应进行。
实施例2
(1)按照La2CuO4中Cu与La的化学计量比称取1mmol硝酸铜和2mmol硝酸镧，溶于去离子水中，去离子水的体积用量为硝酸铜和硝酸镧总摩尔质量的6 倍，混合均匀，得到溶液A；
(2)在溶液A中加入3mmolN,N-二甲基甲酰胺，加入1mmol 3-4吡啶二羧酸，在60℃下加热并500r/min磁力搅拌2h，得到溶液B；
(3)用移液枪加入浓度为1mol/L的碱液5ml(溶质为三乙胺，溶剂为乙醇)，至溶液B中，500r/min磁力搅拌20min直至溶解，制备成溶液C。
(4)将溶液C放进烘箱，在120℃的温度条件下，恒温反应3小时后，空气中冷却至室温；待溶液体系稳定后，将所得混合溶液进行过滤，所得固体用水洗涤2次，将得到的晶体放入液氮中进行粉化，取出粉体D。
(5)将粉体D和6mmol的TiO2粉体放入去离子水中，去离子水的用量为TiO2摩尔量的6倍，喷雾器进行喷雾造粒，90℃的温度条件下，烘箱烘干1h，制备出TiO2-铜酸镧纳米催化粉体。
称量0.1g的孔雀石绿，制备成1g/L孔雀石绿溶液加水，取0.2g实施例2 制备的该粉体放入反应瓶中进行光催化实验，反应0min、30min、60min后，测量孔雀石绿的光催化效果，图2为本发明实施例2制备得到的TiO2-铜酸镧纳米电催化粉体对孔雀石绿降解曲线，从图2中可见，30min后对孔雀石绿的降解效率就达到60％，90min后达到90％，可见本专利制备的TiO2-铜酸镧纳米催化粉体对孔雀石绿有很好的光催化效果。
实施例3
(1)按照La2CuO4中Cu与La的化学计量比称取1mmol硝酸铜和2mmol硝酸镧，溶于去离子水中，去离子水的体积用量为硝酸铜和硝酸镧总摩尔质量的6 倍，混合均匀，得到溶液A；
(2)在溶液A中加入3mmolN,N-二甲基甲酰胺，加入1mmol 3-4吡啶二羧酸，在60℃下加热并1000r/min磁力搅拌2h，得到溶液B；
(3)用移液枪加入浓度为1mol/L的碱液5ml(溶质为三乙胺，溶剂为乙醇)，至溶液B中，1000r/min磁力搅拌20min直至溶解，制备成溶液C。
(4)将溶液C放进烘箱，在120℃的温度条件下，恒温反应3小时后，空气中冷却至室温；待溶液体系稳定后，将所得混合溶液进行过滤，所得固体用水洗涤2次，将得到的晶体放入液氮中进行粉化，取出粉体D。
(5)将粉体D和6mmol的TiO2粉体放入去离子水中，去离子水的用量为TiO2摩尔量的5倍，喷雾器进行喷雾造粒，90℃的温度条件下，烘箱烘干1h，制备出TiO2-铜酸镧纳米催化粉体。
采用三电极体系对TiO2-铜酸镧纳米催化粉体的电催化析氢析氧性能进行测试，以Pt片为对电极，饱和甘汞电极(SCE)为参比电极，工作电极为表面滴涂有铜酸稀土电催化材料的ITO电极；测试仪器为PARSTAT 2273电化学工作站；测试溶液为1mol/L的KOH。
采用滴涂法制备工作电极，具体工艺如下：称取0.04g的TiO2-铜酸镧纳米催化粉体，置于小玻璃瓶中，加入500ml乙醇，500ml去离子水和30μl质量分数为5％的杜邦溶液，将上述混合物超声20min以上形成催化剂溶液。以ITO为电极时，需要先将ITO依次使用丙酮，乙醇和去离子水清洗，再向ITO导电面底涂20μl上述催化剂溶液，于干燥箱中以60℃烘干1h，待测。
测试参数：LSV测试时扫描速率5mV/s。
图3为本发明实施例3制备得到的TiO2-铜酸镧纳米电催化粉体的析氢曲线，图4为本发明实施例3制备得到的TiO2-铜酸镧纳米电催化粉体的析氧曲线，如图所示：图3为HER曲线，曲线向下弯曲的起始点代表还原产氢的起始电位，越小越好。弯曲的斜率代表还原速度与过电位的关系，越大越好。图4为OER 曲线，曲线向上弯曲的起始点代表氧化产氢的起始电位，越小越好。弯曲的斜率代表还原速度与过电位的关系，越大越好。
对比例1(未在液氮中粉化)
(1)按照La2CuO4中Cu与La的化学计量比称取1mmol醋酸铜和2mmol醋酸镧，溶于去离子水中，去离子水的体积用量为醋酸铜和醋酸镧总摩尔质量的4 倍，混合均匀，得到溶液A；
(2)在溶液A中加入3mmolN，N-二甲基甲酰胺，加入1mmol 3-4吡啶二羧酸，在60℃下加热并700r/min磁力搅拌3h，得到溶液B；
(3)用移液枪加入浓度为1mol/L的碱液5ml(溶质为三乙胺，溶剂为乙醇)，至溶液B中，700r/min磁力搅拌20min直至溶解，制备成溶液C。
(4)将溶液C放进烘箱，在120℃的温度条件下，恒温反应3小时后，空气中冷却至室温；待溶液体系稳定后，将所得混合溶液进行过滤，所得固体用水洗涤2次，得到片状晶体D。
(5)将粉体D和3mmol的TiO2粉体放入去离子水中，去离子水的用量为 TiO2摩尔量的4倍，喷雾器进行喷雾造粒，60℃的温度条件下，烘箱烘干1h，制备出本专利需要的纳米粉体。
图5为本发明对比例1制备得到的TiO2-铜酸镧纳米电催化粉体的扫描电镜图，如图5所示，粉体未在液氮中粉化，所制备的粉体呈现片层厚度不均匀，很多片层黏在一起，尺度为100nm，虽然形貌较为一致，但比表面积较小，不利于光催化及电催化反应进行。
对比例2(未在液氮中粉化、未加3-4吡啶二羧酸)
(1)按照La2CuO4中Cu与La的化学计量比称取1mmo硝酸铜和2mmol硝酸镧，溶于去离子水中，去离子水的体积用量为硝酸铜和硝酸镧总摩尔质量的4 倍，混合均匀，得到溶液A；
(2)在溶液A中加入3mmolN，N-二甲基甲酰胺，在60℃下加热并800r/min 磁力搅拌2h，得到溶液B；
(3)用移液枪加入浓度为1mol/L的碱液5ml(溶质为三乙胺，溶剂为乙醇)，至B溶液中，800r/min磁力搅拌20min直至溶解，制备成溶液C。
(4)将溶液C放进烘箱，在130℃的温度条件下，恒温反应3小时后，空气中冷却至室温；待溶液体系稳定后，将所得混合溶液进行过滤，所得固体用水洗涤3次，得到片状晶体D。
(5)将粉体D和3mmol的TiO2粉体放入去离子水中，去离子水的用量为TiO2 摩尔量的6倍，喷雾器进行喷雾造粒，80℃的温度条件下，烘箱烘干1.5h，制备出本专利需要的纳米粉体。
图6为本发明对比例2制备得到的TiO2-铜酸镧纳米电催化粉体的扫描电镜图，从图6可以看出，未加入3-4吡啶二羧酸的粉体，呈现较大块状，包覆的 TiO2也没有很好的分散在块状粉体表面。制备的粉体呈现大的颗粒形貌且边缘不分明，比表面积小，不利于催化反应进行。
Claims (7)
1.一种TiO2-铜酸镧纳米催化粉体的制备方法，其特征在于，包括以下步骤：
（1）按照铜酸镧La2CuO4中Cu与La的化学计量比称取Cu的可溶性盐和La的可溶性盐，溶于去离子水中，混合均匀，得到溶液A；
（2）在溶液A中加入一定量的N,N-二甲基甲酰胺和一定量的3-4吡啶二羧酸，将溶液于60～90℃加热并搅拌2～3h，得到溶液B；
（3）用移液枪加入5-10mL浓度为1mol/L的碱液到溶液B中，搅拌直至溶解，制备成溶液C；
（4）将溶液C放进烘箱，在120℃-150℃的温度条件下，恒温反应3-6小时后，空气中冷却至室温；待溶液体系稳定后，将所得混合溶液进行过滤，所得固体用水洗涤2-4次，得到片状晶体，将得到的晶体放入液氮中进行粉化，将制得的粉体D取出；
（5）将粉体D和一定量的TiO2粉体放入去离子水中，喷雾器进行喷雾造粒，60-90℃的温度条件下，烘箱烘干1-2h，制备出纳米片层粉体。
2.根据权利要求1所述的TiO2-铜酸镧纳米催化粉体的制备方法，其特征在于：步骤（1）中所述的铜的可溶性盐为氯化铜、硝酸铜或醋酸铜，镧的可溶性盐为氯化镧、硝酸镧或醋酸镧。
3.根据权利要求1所述的TiO2-铜酸镧纳米催化粉体的制备方法，其特征在于：步骤（2）（3）中所述的搅拌条件为机械搅拌或磁力搅拌，转子转速为500～1000r/min。
4.根据权利要求1所述的TiO2-铜酸镧纳米催化粉体的制备方法，其特征在于：步骤（2）中所述N,N-二甲基甲酰胺的用量为铜盐摩尔量的3-4倍、3-4吡啶二羧酸用量为铜盐摩尔量的1-2倍。
5.根据权利要求1所述的TiO2-铜酸镧纳米催化粉体的制备方法，其特征在于：步骤（5）中TiO2的用量为铜的可溶性盐和镧的可溶性盐总摩尔量的1～2倍。
6.根据权利要求1所述的TiO2-铜酸镧纳米催化粉体的制备方法，其特征在于：步骤（3）所述碱液的溶质为三乙胺，溶剂为乙醇。
7.根据权利要求1所述的制备方法制备的TiO2-铜酸镧纳米催化粉体的应用，其特征在于：用于光催化降解有机物孔雀石绿及在电催化水解产氢、产氧方面。
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