CN109647439A - 一种用于光解水产氢的钙钛矿-固溶体复合光催化剂 - Google Patents
一种用于光解水产氢的钙钛矿-固溶体复合光催化剂 Download PDFInfo
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Abstract
本发明公开了一种用于光解水产氢的钙钛矿‑固溶体复合光催化剂,其采用共沉淀法合成钙钛矿材料LaNiO3,水热法制备CdxM(1‑x)S固溶体,再利用乙醇法将LaNiO3与CdxM(1‑x)S固溶体进行简单复合,制得LaNiO3/CdxM(1‑x)S复合光催化剂。该复合催化剂能够通过LaNiO3与CdxM(1‑x)S之间形成的复合结构,促进光生载流子的转移,抑制光生电子和空穴的复合,从而显著提高光解水产氢的效率,并能缓解传统光催化剂存在的光腐蚀现象。同时,该复合光催化剂制备方法简单易行,反应条件温和,在开发化石燃料的替代能源以及高效利用太阳能等方面具有广阔的应用前景。
Description
技术领域
本发明属于光解水产氢技术领域,具体涉及一种用于光解水产氢的钙钛矿-固溶体复合光催化剂。
背景技术
众所周知,能源是人类发展和进步的重要物质基础,对经济和社会的发展起着关键性的推动作用。但是随着经济的急速发展和人口的迅速增加,有限的传统化石能源的消耗速度迅猛增长,也带来了众多的环境问题。所以能源短缺问题和日益严重的环境问题将严重影响社会的正常发展。因此,开发新型可持续绿色能源是科学界急需解决的重大课题之一。氢能是一种新型清洁能源,其作为一种可再生的二次能源,不仅具有反应速度快捷以及燃烧热值高的特点,且燃烧产物只有水,能够同时缓解能源危机和环境污染问题。与传统的制氢方法相比,太阳能光解水产氢具有经济、清洁、安全等优势,因此,光催化分解水产氢被称为化学的“圣杯”。综上所述,重视太阳能光催化分解水的研究工作对国民经济的可持续发展和生态环境保护具有重要意义。
为了寻找有效的可见光响应催化剂,研究人员已经进行了大量的理论和实验研究。硫化物固溶体由于其独特的物理化学性质、简单的合成方法、非凡的可见光吸收能力等,受到了广泛的关注。但是,由于硫化物固溶体在光催化反应过程容易发生光腐蚀,催化剂稳定性差,因此不能满足生产需求。所以,希望通过将硫化物固溶体与其他催化剂复合,以提高其产氢性能。
钙钛矿型复合氧化物是一种具有独特物理性质和化学性质的新型无机非金属材料。理想的ABO3型钙钛矿是立方结构,具有高的结构稳定性。通常认为,在钙钛矿型复合氧化物中,A位一般是稀土或碱土元素离子,B位为过渡元素离子,A位金属可以起到稳定结构的作用,而B位金属为活性位。结构中A位和B位阳离子可被其它多种金属离子取代而形成多组分复合氧化物,从而产生其特殊的物理和化学性能。在钙钛矿氧化物的材料中,稀土钙钛矿材料LaNiO3已经被证明是光催化产氢的催化剂。因此,通过将稀土钙钛矿和固溶体复合以构筑复合结构,利用两者半导体导带和价带位置的不同,促进电子转移,抑制电子和空穴的复合,进而提高光反应的效率和固溶体催化剂的稳定性,有利于其实际应用。
发明内容
本发明的目的在于提供一种用于光解水产氢的钙钛矿-固溶体复合光催化剂,其针对现有材料的不足,合成出一种稳定性和活性更优的复合光催化剂,该复合光催化剂可以有效地促进光生载流子的分离,提高光反应效率,同时可以防止催化剂自身的氧化,解决了传统光催化剂稳定性差、活性低、量子效率低等缺点。该复合光催化剂合成方法简单易行,产量可观,同时其参与的光催化反应条件温和,有利于在光解水产氢反应中的推广应用。
为实现上述目的,本发明采用如下技术方案:
一种用于光解水产氢的钙钛矿-固溶体复合光催化剂,其是将钙钛矿材料LaNiO3作为助催化剂引入CdxM(1-x)S(M=Zn、Mn、Ni、Co等,0<x<1)固溶体中,制得LaNiO3/CdxM(1-x)S复合光催化剂。
所述钙钛矿-固溶体复合光催化剂的制备方法,是利用共沉淀法制备钙钛矿材料LaNiO3,水热法制备CdxM(1-x)S固溶体,再利用简单乙醇法制得LaNiO3/CdxM(1-x)S复合光催化剂。其具体步骤如下:
(1)将硝酸镧和硝酸镍按摩尔比1:1超声分散在去离子水中,然后加入浓度为0.375mol/L的氢氧化钠溶液(氢氧化钠的用量为硝酸镧摩尔量的7.5倍),在60℃下回流4h,所得沉淀经洗涤、干燥后,于650℃空气气氛中煅烧2h,得LaNiO3;
(2)取乙酸镉、乙酸盐按比例溶于乙二胺和水的混合液(1:1,v/v)中,加入乙酸镉摩尔量1.25倍的硫代乙酰胺,搅拌30min,然后将溶液转移至100mL聚四氟乙烯的不锈钢高压反应釜中,在200℃水热反应24h,最后洗涤、干燥,即得到CdxM(1-x)S固溶体;
(3)将LaNiO3和CdxM(1-x)S按摩尔比1:1加入99.7wt%的乙醇溶液中,搅拌蒸干并烘干过夜,得到LaNiO3/CdxM(1-x)S;其中,LaNiO3的负载量为5-50wt%。
步骤(2)中所述乙酸盐为乙酸锌、乙酸锰、乙酸镍或乙酸钴。
所述钙钛矿-固溶体复合光催化剂可用于催化光解水产氢反应的进行。
本发明的显著效果在于:
(1)本发明将钙钛矿材料与固溶体结合形成复合结构,促进了光生电子的转移,抑制了光生载流子的复合,能够有效地提高光催化反应的效率。
(2)本发明复合光催化剂能够有效地缓解硫化物的光腐蚀现象,提高催化剂的稳定性。
(3)本发明制备方法简单易行,且合成材料产量较大,不含有贵金属,有利于其在光催化反应过程的应用。
附图说明
图1为实施例1(A)与实施例2(B)所得LaNiO3、CdxM(1-x)S及LaNiO3/CdxM(1-x)S的XRD对比图。
图2为实施例1(A)与实施例2(B)所得LaNiO3、CdxM(1-x)S及LaNiO3/CdxM(1-x)S的DRS对比图。
图3为实施例1(A)与实施例2(B)所得LaNiO3、CdxM(1-x)S及LaNiO3/CdxM(1-x)S光解水产氢活性的对比图。
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 LaNiO3/Cd0.9Zn0.1S复合催化剂的制备
将0.433g(1mmol)硝酸镧和0.290g(1mmol)六水硝酸镍溶解在80mL去离子水中,然后加入20mL含0.3g(7.5mmol)氢氧化钠的水溶液,在60℃下回流4h,所得沉淀经洗涤、干燥后,于650℃空气气氛中煅烧2h,即得LaNiO3。
取4.797g(21mmol)乙酸镉、0.439g(2.3mmol)乙酸锌溶于30mL乙二胺和30mL水的混合液中,加入1.972g(26mmol)硫代乙酰胺,搅拌30min,然后将溶液转移至100mL聚四氟乙烯的不锈钢高压反应釜中,并在200℃水热反应24h,最后用去离子水和乙醇洗涤,60℃干燥24h,即可得到Cd0.9Zn0.1S固溶体。
将LaNiO3和Cd0.9Zn0.1S按比例加入20mL乙醇溶液中,然后80℃搅拌蒸干,再在110℃真空烘箱中烘干过夜,得到负载量为5-50wt%的LaNiO3/Cd0.9Zn0.1S。
实施例2 LaNiO3/Cd0.8Mn0.2S复合催化剂的的制备
将0.433g(1mmol)硝酸镧和0.290g(1mmol)六水硝酸镍溶解在80mL去离子水中,然后加20mL含0.3g氢氧化钠(7.5mmol)的水溶液,在60℃下回流4h,所得沉淀经洗涤、干燥后,于650℃空气气氛中煅烧2h,即得LaNiO3。
取4.264g(18mmol)乙酸镉、0.7785g(4.5mmol)乙酸锰溶于30mL乙二胺和30mL水的混合液中,加入1.737g(23mmol)硫代乙酰胺,搅拌30min,然后将溶液转移至100mL聚四氟乙烯的不锈钢高压反应釜中,并在160℃水热反应24h,最后用去离子水和乙醇洗涤,60℃干燥24h,即可得到Cd0.8Mn0.2S固溶体。
将LaNiO3和Cd0.8Zn0.2S按比例加入20mL乙醇溶液中,然后80℃搅拌蒸干,再在110℃真空烘箱中烘干过夜,得到负载量为5-50wt%的LaNiO3/Cd0.8Mn0.2S。
图1为实施例1、2所得LaNiO3、CdxM(1-x)S、LaNiO3/CdxM(1-x)S的XRD对比图。如图1所示,LaNiO3/CdxM(1-x)S复合光催化剂的XRD图谱中包含了LaNiO3和CdxM(1-x)S的所有特征峰,这表明LaNiO3/CdxM(1-x)S复合光催化剂成功合成。
图2为实施例1、2所得LaNiO3、CdxM(1-x)S、LaNiO3/CdxM(1-x)S的DRS对比图。从图2中可知LaNiO3/CdxM(1-x)S复合材料可以通过可见光激发,产生电子空穴对。
实施例3 LaNiO3/CdxM(1-x)S光解水产氢活性评价
实施例1和2所得LaNiO3/CdxM(1-x)S复合光催化剂的光解水产氢效率评价实验在泊菲莱光解水装置上进行,采用岛津8A型气相色谱检测H2的产量。实验过程为:将20mg所得复合光催化剂加入100mL去离子水中,并加入0.35M Na2S/0.25M Na2SO3作为空穴牺牲剂,以氙灯为光源,并加上420nm的截止滤波片,在光解水装置上进行光解水反应,系统抽真空,反应温度10℃,然后以λ>420nm的可见光对系统进行光照,每隔1h检测系统中H2的含量,5h后结束反应。
图3为实施例1、2所得CdxM(1-x)S、LaNiO3/CdxM(1-x)S光解水产氢的活性对比图。从图3中可以看出,反应经过五小时后,纯的Cd0.9Zn0.1S和Cd0.8Mn0.2S的产氢量分别为1025μmol和118μmol,复合后的LaNiO3/Cd0.9Zn0.1S和LaNiO3/Cd0.8Mn0.2S的产氢量分别为4950μmol和1190μmol,大约为Cd0.9Zn0.1S和Cd0.8Mn0.2S的产氢量的5倍和10倍。相较于纯的CdxM(1-x)S,LaNiO3/CdxM(1-x)S复合光催化剂能够有效地提高光解水产氢的效率,这主要是由于LaNiO3和CdxM(1-x)S二者之间形成的复合结构能够有效地转移光生电子,抑制电子和空穴的复合,从而延长光生电子的寿命,以促进光催化反应;同时,随着反应的进行,CdxM(1-x)S的反应效率逐渐降低,而LaNiO3/CdxM(1-x)S则仍能够保持较高的反应速率,这主要是由于CdxM(1-x)S存在着光腐蚀的缺陷,因而随着反应的进行,反应效率逐渐降低,而LaNiO3/CdxM(1-x)S形成的复合结构可以抑制CdxM(1-x)S的光腐蚀效应,从而使光催化反应一直保持较高的速率进行。
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 (7)
1.一种用于光解水产氢的钙钛矿-固溶体复合光催化剂,其特征在于:将钙钛矿材料LaNiO3作为助催化剂引入CdxM(1-x)S固溶体中,制得LaNiO3/CdxM(1-x)S复合光催化剂;其中,M为金属元素Zn、Mn、Ni或Co,0<x<1。
2.一种如权利要求1所述的钙钛矿-固溶体复合光催化剂的制备方法,其特征在于:利用共沉淀法制备钙钛矿材料LaNiO3,水热法制备CdxM(1-x)S固溶体,再利用简单乙醇法制得LaNiO3/CdxM(1-x)S复合光催化剂。
3.根据权利要求2所述的钙钛矿-固溶体复合光催化剂的制备方法,其特征在于:具体步骤如下:
(1)将硝酸镧和硝酸镍超声分散在去离子水中,然后加入氢氧化钠溶液,在60℃下回流4h,所得沉淀经洗涤、干燥后,于650℃空气气氛中煅烧2h,得LaNiO3;
(2)将乙酸镉、乙酸盐按比例溶于乙二胺和水的混合液中,加入硫代乙酰胺,搅拌,然后在200℃水热反应24h,最后洗涤、干燥,即得到CdxM(1-x)S固溶体;
(3)将LaNiO3和CdxM(1-x)S按比例加入99.7wt%的乙醇溶液中,搅拌蒸干并烘干过夜,得到LaNiO3/CdxM(1-x)S。
4.根据权利要求3所述的钙钛矿-固溶体复合光催化剂的制备方法,其特征在于:步骤(1)中所用硝酸镧和硝酸镍的摩尔比为1:1;
所用氢氧化钠的加入量为硝酸镧摩尔量的7.5倍。
5.根据权利要求3所述的钙钛矿-固溶体复合光催化剂的制备方法,其特征在于:步骤(2)中所述乙酸盐为乙酸锌、乙酸锰、乙酸镍或乙酸钴;
所用乙二胺和水的混合液中乙二胺与水的体积比为1:1;
所用硫代乙酰胺的加入量为乙酸镉摩尔量的1.25倍。
6.根据权利要求3所述的钙钛矿-固溶体复合光催化剂的制备方法,其特征在于:步骤(3)所得LaNiO3/CdxM(1-x)S中LaNiO3的负载量为5-50wt%。
7.一种如权利要求1所述钙钛矿-固溶体复合光催化剂在光解水产氢反应中的应用。
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