CN109078636A - 一种等离子体光催化剂、其制备方法及其在制氢中的应用 - Google Patents
一种等离子体光催化剂、其制备方法及其在制氢中的应用 Download PDFInfo
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Abstract
本发明涉及一种等离子体光催化剂、其制备方法及其在制氢中的应用,等离子体光催化剂的制备方法,具体步骤为:将柠檬酸溶解在100‑200℃的乙二醇中,搅拌直到形成透明凝胶,然后加入摩尔比为1:1的银源及坦源和/或摩尔比为1:1的锶源及钛源,搅拌进行聚合,得到无定形的金属氧化物前驱体;将金属氧化物前驱体煅烧以去除有机物质并研磨成粉末,用压片机将所得粉末压成颗粒,之后在马弗炉中煅烧,再将高温煅烧的颗粒研磨成粉末,即得到等离子体光催化剂。为进一步将固溶体的吸收边缘扩展到可见区域,通过乙二醇还原,可以在固溶体表面原位生长具有等离子体效应的银纳米粒子,进一步提高样品在可见光和全范围照射下的光催化产氢性能。
Description
技术领域
本发明属于光催化材料技术领域,具体涉及一种等离子体光催化剂、其制备方法及其在制氢中的应用。
背景技术
氢气作为一种清洁能源,可用于燃料电池以及化学工业中,如在工业氨合成中需要消耗大量的氢气。目前,氢气主要由化石燃料如天然气通过蒸汽重整生成,在这个过程中,消耗化石燃料并排放二氧化碳。如果考虑到能源和环境问题,氢气必须使用诸如太阳光等自然能源从水中生产。其中,使用半导体和太阳能光的光催化技术已经引起了极大的关注,光催化分解水产氢使我们有机会从无尽的可再生能源中生产清洁燃料。
最近,新型可见光光催化剂的开发近年来受到越来越多的关注。其中,构建固溶体半导体具有对能带结构进行连续可调谐的特点,此外,其优异的能量转换效率是其中的单个材料无法实现的。在众多半导体材料中,钙钛矿氧化物(ABO3)由于其灵活的化学组成和优异的结构稳定性而成为制备固溶体光催化剂的热门材料。
例如罗文俊课题组通过热氨解法制备了(SrTiO3)1-x(LaTiO2N)x固溶体,其在可见光照射下显示出优异光催化活性,参阅Physical Chemistry Chemical Physics,2008年,10期,6717–6723页;孙小军课题组用ZnO和ZnGa2O4的混合物成功地制备了(Ga1-xZnx)(N1- xOx)的固溶体,用作在可见光驱动下进行纯水分解的光催化剂,参阅Applied Catalysis AGeneral,2007年,327期,114–121页。
然而上述报道的固溶体催化剂在合成过程中均需要先合成氧化物的前驱体,再通过氨气来氨化进而转化为氮氧化物。从原子经济性的角度上考虑,这不能最大限度的利用资源。此外,上述固溶体并不具备等离子体纳米结构。通常构建等离子体纳米结构方法是将金属纳米粒子通过沉积或浸渍技术带到半导体表面。尽管这些方法具有广泛的应用,但是其沉积的金属纳米颗粒通常局限于半导体的暴露表面,并且沉积过程中通常包括合成金属纳米颗粒这一耗时的步骤。
发明内容
本发明的目的就是为了解决上述问题而提供一种等离子体光催化剂、其制备方法及其在制氢中的应用。
本发明的目的通过以下技术方案实现:
一种等离子体光催化剂的制备方法,包括以下步骤:
(1)将柠檬酸溶解在100-200℃的乙二醇中,搅拌直到形成透明凝胶,然后加入摩尔比为1:1的银源及坦源和/或摩尔比为1:1的锶源及钛源,搅拌进行聚合,得到无定形的金属氧化物前驱体;
(2)将金属氧化物前驱体煅烧以去除有机物质并研磨成粉末,用压片机将所得粉末压成颗粒,之后在马弗炉中煅烧,再将高温煅烧的颗粒研磨成粉末,即得到等离子体光催化剂。
进一步地,所述金属氧化物前驱体的分子式为(AgTaO3)1-x(SrTiO3)x,其中0≤x≤1。
进一步地,所述银源为可溶性银盐,所述坦源为可溶性钽盐,所述锶源为可溶性锶盐,所述钛源为钛酸四丁酯或钛酸异丙酯,进一步优选,所述银源为硝酸银,所述坦源为五氯化钽,所述锶源为硝酸锶,所述钛源为钛酸四丁酯,所述五氯化钽溶于无水乙醇,所述硝酸锶与硝酸银溶于去离子水中。
进一步地,步骤(1)聚合时,在250-350℃下搅拌3-6h。
进一步地,步骤(2)去除有机物质煅烧温度为450-650℃,煅烧时间为10-20h,在马弗炉中煅烧温度为900-1200℃,煅烧时间为8-12h。
进一步地,将步骤(2)得到的等离子体光催化剂加入120-200℃的乙二醇溶液中进行还原,还原时间控制在15-30min,使等离子体光催化剂表面原位生长Ag纳米颗粒。进一步地,通过将乙二醇溶液转移到冰水中终止还原过程。
所述等离子体光催化剂与产氢助催化剂或产氧助催化剂混合,用于光催化分解水制备氢气或氧气,具体方法为将等离子体光催化剂与助催化剂前驱物(产氢助催化剂:氯铂酸;产氧助催化剂:硝酸钴)溶液混合,超声得到悬浊液,烘干,高温加热数小时。
催化剂应用于光催化分解水制备氢气时,其反应条件为:将100毫克样品加入到100毫升去离子水中,以亚硫酸钠为牺牲剂,在光照下研究产氢速率。H2PtCl6助催化剂的沉积方式可以用光沉积替代,即将适量的H2PtCl6添加到样品粉末悬浮液中,随后使用500W高压汞灯作为光源,将悬浮液全光谱照射30分钟以将H2PtCl6转化为铂纳米颗粒,硝酸钴助催化剂可用三氯化铑或乙酰丙酮钌代替。
本发明中,先通过聚合复合法合成了一系列(AgTaO3)1-x(SrTiO3)x(0≤x≤1)固溶体作为支撑半导体,再通过乙二醇一步还原工艺在(AgTaO3)1-x(SrTiO3)x表面上原位生长银纳米颗粒,与传统不具备等离子体纳米结构的固溶体相比,该方法从固溶体内部晶体中生长金属纳米颗粒,从而产生分布良好的银纳米颗粒,促进了该结构光催化材料的应用。在常规的等离子体纳米结构制备方法中,金属纳米粒子通常通过沉积或浸渍技术被带到半导体表面,其中浸渍方法对金属纳米粒子的分布和锚定的控制很差;沉积方法通常包括耗时的合成金属纳米颗粒的步骤,并且在操纵金属纳米颗粒和半导体衬底之间的接触方面很差;溅射方法成本高,金属纳米颗粒的沉积通常局限于半导体的暴露表面。本发明通过调控硝酸银,五氯化坦与硝酸锶,钛酸四丁酯的计量比,可以有效调控该材料对太阳光的吸收能力,吸收太阳光光子范围可在380纳米至430纳米内连续调控。本发明通过乙二醇一步还原过程,可以在(AgTaO3)1-x(SrTiO3)x(0≤x≤1)固溶体表面原位生长具有等离子体效应的银纳米粒子,银纳米粒子的溶出在可见光范围内引起广泛的等离子体共振吸收,进一步提高样品在可见光和全范围照射下的光催化产氢性能。
附图说明
图1是钙钛矿型固溶体(AgTaO3)1-x(SrTiO3)x(0≤x≤1)的XRD图谱。
图2是钙钛矿型固溶体(AgTaO3)1-x(SrTiO3)x(0≤x≤1)的吸光率与x的关系。
图3是实施例6和实施例7样品的紫外可见吸收图谱。
图4是实施例7样品的扫描电镜图片。
图5是实施例7样品的透射电镜图片。
图6是实施例1-7样品在紫外和可见光照射下的光催化分解水产氢性能图。
图7是实施例7样品沉积不同助催化剂的光催化分解水产氧性能图。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。
实施例1
先将1克五氯化钽溶于5毫升的无水乙醇中。再称取0.4752克的硝酸银,加入少量去离子水超声使其完全溶解。将6.7179克柠檬酸溶解在7毫升的乙二醇中,在150摄氏度下磁力搅拌直到形成透明凝胶。再将溶解好的五氯化钽和硝酸银加入到上述凝胶溶液中,升温到300摄氏度继续搅拌3小时以促进聚合。然后将所得树脂在550摄氏度下煅烧15小时以除去有机物质并研磨成粉末。用压片机将所得粉末压成颗粒,转移到氧化铝坩埚中,并在900摄氏度马弗炉中煅烧10小时,然后将高温煅烧的颗粒研磨成粉末并收集,得到的粉末即为AgTaO3。
上述钽酸银氧化物样品进行光催化分解水:
助催化剂纳米铂的沉积:将100毫克上述样品加入到100毫升去离子水中,将1毫升氯铂酸溶液(1mg/mL)加入上述粉末悬浮液中,随后使用500W高压汞灯作为光源,将悬浮液全光谱照射30分钟以将H2PtCl6转化为铂纳米颗粒。
光催化分解水制氢反应:在沉积好助催化剂的样品溶液中加入0.64克的亚硫酸钠做牺牲剂,以500W高压汞灯为光源,与UV截止滤光器(λ≥400nm)耦合以产生可见光照射,在真空条件下测试光催化产氢速率。
实施例2
称取2.4707克硝酸锶,加入少量去离子水超声使其完全溶解。将26.8719克柠檬酸溶解在28毫升的乙二醇中,在150摄氏度下磁力搅拌直到形成透明凝胶。再将溶解好的硝酸锶加入到上述凝胶溶液中,升温到300摄氏度继续搅拌3小时以促进聚合。然后将所得树脂在550摄氏度下煅烧15小时以除去有机物质并研磨成粉末。用压片机将所得粉末压成颗粒,转移到氧化铝坩埚中,并在900摄氏度马弗炉中煅烧10小时,然后将高温煅烧的颗粒研磨成粉末并收集,得到的粉末即为SrTiO3。
实施例3
先将1克五氯化钽溶于5毫升的无水乙醇中。再称取0.4752克硝酸银和2.4707克硝酸锶,加入少量去离子水超声使其完全溶解。将3.8389克钛酸四丁酯,29.3936克柠檬酸溶解在35毫升乙二醇中,在150摄氏度下磁力搅拌直到形成透明凝胶。再将溶解好的五氯化钽,硝酸锶和硝酸银加入到上述凝胶溶液中,升温到300摄氏度继续搅拌3小时以促进聚合。然后将所得棕色树脂在550摄氏度下煅烧15小时以除去有机物质并研磨成粉末。用压片机将所得粉末压成颗粒,转移到氧化铝坩埚中,并在900摄氏度马弗炉中煅烧10小时,然后将高温煅烧的颗粒研磨成粉末并收集,得到的粉末即为(AgTaO3)0.2(SrTiO3)0.8固溶体。
实施例4
先将1克五氯化钽溶于5毫升的无水乙醇中。再称取0.4752克硝酸银和1.4411克硝酸锶,加入少量去离子水超声使其完全溶解。将2.2394克钛酸四丁酯,22.3933克柠檬酸溶解在23毫升乙二醇中,在150摄氏度下磁力搅拌直到形成透明凝胶。再将溶解好的五氯化钽,硝酸锶和硝酸银加入到上述凝胶溶液中,升温到300摄氏度继续搅拌3小时以促进聚合。然后将所得棕色树脂在550摄氏度下煅烧15小时以除去有机物质并研磨成粉末。用压片机将所得粉末压成颗粒,转移到氧化铝坩埚中,并在900摄氏度马弗炉中煅烧10小时,然后将高温煅烧的颗粒研磨成粉末并收集,得到的粉末即为(AgTaO3)0.3(SrTiO3)0.7固溶体。
实施例5
先将1克五氯化钽溶于5毫升的无水乙醇中。再称取0.4752克硝酸银和0.6176克硝酸锶,加入少量去离子水超声使其完全溶解。将0.9597克钛酸四丁酯,13.4359克柠檬酸溶解在14毫升乙二醇中,在150摄氏度下磁力搅拌直到形成透明凝胶。再将溶解好的五氯化钽,硝酸锶和硝酸银加入到上述凝胶溶液中,升温到300摄氏度继续搅拌3小时以促进聚合。然后将所得棕色树脂在550摄氏度下煅烧15小时以除去有机物质并研磨成粉末。用压片机将所得粉末压成颗粒,转移到氧化铝坩埚中,并在900摄氏度马弗炉中煅烧10小时,然后将高温煅烧的颗粒研磨成粉末并收集,得到的粉末即为(AgTaO3)0.5(SrTiO3)0.5固溶体。
实施例6
先将1克五氯化钽溶于5毫升的无水乙醇中。再称取0.4752克硝酸银和0.1544克硝酸锶,加入少量去离子水超声使其完全溶解。将0.2399克钛酸四丁酯,8.3974克柠檬酸溶解在8毫升乙二醇中,在150摄氏度下磁力搅拌直到形成透明凝胶。再将溶解好的五氯化钽,硝酸锶和硝酸银加入到上述凝胶溶液中,升温到300摄氏度继续搅拌3小时以促进聚合。然后将所得棕色树脂在550摄氏度下煅烧15小时以除去有机物质并研磨成粉末。用压片机将所得粉末压成颗粒,转移到氧化铝坩埚中,并在900摄氏度马弗炉中煅烧10小时,然后将高温煅烧的颗粒研磨成粉末并收集,得到的粉末即为(AgTaO3)0.8(SrTiO3)0.2固溶体。
实施例7
在磁力搅拌下将40毫升乙二醇倒入烧杯中并加热至160摄氏度,再将约1克实例6中的(AgTaO3)0.8(SrTiO3)0.2粉末迅速加入上述乙二醇溶液中进行还原。在几分钟内可以看出烧杯中的悬浮液从白色变为黄色,表明乙二醇还原过程非常快。为了确保银纳米粒子的完全生长,我们将还原时间控制在30分钟。通过将热的烧杯快速转移到冰水中进行冷却来实现还原过程的终止。还原过程完成后,将沉淀物离心并用去离子水洗涤三次,然后在70摄氏度下干燥24小时,得到的粉末即为Ag@(AgTaO3)0.8(SrTiO3)0.2。
上述钙钛矿型固溶体(AgTaO3)1-x(SrTiO3)x(0≤x≤1)的光催化产氢性能测试步骤与实例1中相同。实例7的产氧测试是在300W氙灯加400纳米滤光片条件下进行。
图1-7为测试结果的相关图,从图中可知,(AgTaO3)1-x(SrTiO3)x(0≤x≤1)吸收太阳光光子范围可在380纳米至430纳米内连续调控。相应的能带结构也具有连续可调制的特性,当x值从1.0下降到0.2时,带隙宽度从3.26降低到2.97eV。经过乙二醇一步还原,成功地在(AgTaO3)0.8(SrTiO3)0.2的表面原位生长了粒径约为20-30nm的银纳米粒子,乙二醇还原后的(AgTaO3)0.8(SrTiO3)0.2在在可见光和全范围照射下均表现出较高的光催化产氢效率。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (10)
1.一种等离子体光催化剂的制备方法,其特征在于,包括以下步骤:
(1)将柠檬酸溶解在100-200℃的乙二醇中,搅拌直到形成透明凝胶,然后加入摩尔比为1:1的银源及坦源和/或摩尔比为1:1的锶源及钛源,搅拌进行聚合,得到无定形的金属氧化物前驱体;
(2)将金属氧化物前驱体煅烧以去除有机物质并研磨成粉末,用压片机将所得粉末压成颗粒,之后在马弗炉中煅烧,再将高温煅烧的颗粒研磨成粉末,即得到等离子体光催化剂。
2.根据权利要求1所述的一种等离子体光催化剂的制备方法,其特征在于,所述金属氧化物前驱体的分子式为(AgTaO3)1-x(SrTiO3)x,其中0≤x≤1。
3.根据权利要求1所述的一种等离子体光催化剂的制备方法,其特征在于,所述银源为可溶性银盐,所述坦源为可溶性钽盐,所述锶源为可溶性锶盐,所述钛源为钛酸四丁酯或钛酸异丙酯。
4.根据权利要求3所述的一种等离子体光催化剂的制备方法,其特征在于,所述银源为硝酸银,所述坦源为五氯化钽,所述锶源为硝酸锶,所述钛源为钛酸四丁酯,所述五氯化钽溶于无水乙醇,所述硝酸锶与硝酸银溶于去离子水中。
5.根据权利要求1所述的一种等离子体光催化剂的制备方法,其特征在于,步骤(1)聚合时,在250-350℃下搅拌3-6h。
6.根据权利要求1所述的一种等离子体光催化剂的制备方法,其特征在于,步骤(2)去除有机物质煅烧温度为450-650℃,煅烧时间为10-20h,在马弗炉中煅烧温度为900-1200℃,煅烧时间为8-12h。
7.根据权利要求1所述的一种等离子体光催化剂的制备方法,其特征在于,将步骤(2)得到的等离子体光催化剂加入120-200℃的乙二醇溶液中进行还原,还原时间控制在15-30min,使等离子体光催化剂表面原位生长Ag纳米颗粒。
8.根据权利要求7所述的一种等离子体光催化剂的制备方法,其特征在于,通过将乙二醇溶液转移到冰水中终止还原过程。
9.一种等离子体光催化剂,其特征在于,采用如权利要求1-8任一项所述的制备方法制备得到。
10.如权利要求9所述的一种等离子体光催化剂的应用,其特征在于,所述等离子体光催化剂与产氢助催化剂混合,用于光催化分解水制备氢气。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006256901A (ja) * | 2005-03-17 | 2006-09-28 | Nissan Motor Co Ltd | 水素発生装置、水素発生方法及び水素発生システム |
CN101254462A (zh) * | 2008-03-21 | 2008-09-03 | 西安交通大学 | 一种纳米钽酸镉光催化剂的制备方法 |
CN104086181A (zh) * | 2014-07-18 | 2014-10-08 | 渤海大学 | Slmton钙钛矿型氮氧化物固溶体粉末的制备方法 |
CN104163627A (zh) * | 2014-07-15 | 2014-11-26 | 华南理工大学 | 一种光学带隙可调的KNbO3纳米固溶体的制备方法 |
-
2018
- 2018-08-02 CN CN201810870548.XA patent/CN109078636B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006256901A (ja) * | 2005-03-17 | 2006-09-28 | Nissan Motor Co Ltd | 水素発生装置、水素発生方法及び水素発生システム |
CN101254462A (zh) * | 2008-03-21 | 2008-09-03 | 西安交通大学 | 一种纳米钽酸镉光催化剂的制备方法 |
CN104163627A (zh) * | 2014-07-15 | 2014-11-26 | 华南理工大学 | 一种光学带隙可调的KNbO3纳米固溶体的制备方法 |
CN104086181A (zh) * | 2014-07-18 | 2014-10-08 | 渤海大学 | Slmton钙钛矿型氮氧化物固溶体粉末的制备方法 |
Non-Patent Citations (3)
Title |
---|
WEIRONG ZHAO,ET AL: "Visible-light-driven photocatalytic H2 evolution from water splitting with band structure tunable solid solution (AgNbO3)1-x(SrTiO3)x", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
XIAOXIANG XU,ET AL: "Visible light photocatalysis by in situ growth of plasmonic Ag nanoparticles upon AgTaO3", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
蒋勤等: "溶胶-凝胶法制备钛酸锶粉体及其光催化性能的研究", 《工业催化》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110667019A (zh) * | 2019-09-06 | 2020-01-10 | 山东大学 | 等离子体共振可逆调控银纳米颗粒薄膜及其制备方法与应用 |
CN110667019B (zh) * | 2019-09-06 | 2021-07-16 | 山东大学 | 等离子体共振可逆调控银纳米颗粒薄膜及其制备方法与应用 |
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