CN112516990B - 一种层状钙钛矿型光催化剂的合成方法及其应用 - Google Patents
一种层状钙钛矿型光催化剂的合成方法及其应用 Download PDFInfo
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- 238000010189 synthetic method Methods 0.000 title description 2
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 19
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- 229910001631 strontium chloride Inorganic materials 0.000 claims abstract description 7
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- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical group Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种层状钙钛矿型光催化剂的合成方法,步骤为:(1)将SrCl2·6H2O、铋源和钛酸四丁酯溶于硝酸溶液,得到原料液;(2)将所得原料液滴加于氢氧化钠溶液中,然后进行水热合成,得到白色悬浊液;(3)将悬浊液冷却、过滤,取滤渣,将滤渣洗涤、干燥后获得层状钙钛矿型Sr2Bi4Ti5O18。还公开了上述层状钙钛矿型光催化剂在光催化反应中的应用。本申请的制备工艺简单,反应可控性好,所形成的层状钙钛矿型Sr2Bi4Ti5O18吸光能力强,吸光范围广,光生载流子活性高,光催化产氢能力强是传统TiO2的3.2倍以上,是固相烧结合成的2.8倍以上,是Bi4Ti3O12的2倍以上。
Description
技术领域
本发明涉及一种层状钙钛矿型光催化剂的合成方法及其应用,属于光催化剂领域。
背景技术
随着世界人口的持续增加和工业化的高速发展,能源消耗和能源需求居高不下,随之导致的能源危机和环境污染这两大问题越来越引起人们的注意。近几年来,光催化技术发展迅速,其污染物分解效率与产氢效率不断提升。然而目前绝大部分半导体材料的光生载流子寿命短、平均扩散长度短,其光生电子空穴对分离效率低,光催化活性较低,它们的光催化性能还远远不能满足实际应用的需求。
钙钛矿材料在可见光范围内表现出较高的光吸收率和能量转换效率,在光伏、光催化等可再生能源生产中显示出很好的应用前景。Sr2Bi4Ti5O18位于传统铁电、层状铋基半导体和钙钛矿结构晶体的交叉点,集诸多优点于一身,显示出巨大的光催化潜力。然而,目前对Sr2Bi4Ti5O18的研究主要集中在其在铁电陶瓷中的应用,并没有应用于光催化领域。
发明内容
为解决上述问题,本发明提出了一种层状钙钛矿型光催化剂的合成方法,该层状钙钛矿型光催化剂的化学式为:Sr2Bi4Ti5O18;该合成方法包括如下步骤:
(1)将SrCl2·6H2O、铋源和钛酸四丁酯溶于硝酸溶液,得到原料液;
(2)将所得原料液滴加于氢氧化钠溶液中,然后进行水热合成,得到白色悬浊液;
(3)将悬浊液冷却、过滤,取滤渣,将滤渣洗涤、干燥后获得层状钙钛矿型Sr2Bi4Ti5O18。
步骤(2)中,在完成原料液到氢氧化钠溶液的滴加后,要继续搅拌30-120分钟,在使反应充分进行的同时,还可以将反应热及时地排出,避免酸碱中和反应时所释放出的热量过大,影响后续水热反应的顺利进行。浓氢氧化钠溶液的强碱性使钛酸四丁酯水解成溶解的钛酸盐,均匀的反应溶液有利于纳米结构的形成。进一步水热反应使反应物溶解—再结晶达到原子级别的均匀混合。
具体地,铋源为硝酸铋或硫酸铋。
本申请的制备工艺简单,反应可控性好,所形成的层状钙钛矿型Sr2Bi4Ti5O18吸光能力强,吸光范围广,光生载流子活性高,光催化产氢能力强是传统TiO2的3.2倍以上,是固相烧结合成的2.8倍以上,是Bi4Ti3O12的2倍以上。
Sr2Bi4Ti5O18是典型的铋层状钙钛矿结构铁电材料,其基本结构特点是5层钙钛矿层中被***了一层萤石结构的铋氧层(Bi2O2)2+,由于铋氧层的***,该材料体系表现出明显的各向异性,这种各向异性使得材料体系在合成制备的过程中倾向于形成高表面积的纳米片形貌;其价带能级由高度离散的Bi 6s和O 2p杂化轨道组成,这种高度离散的轨道能级更利于光生空穴的迁移和相应的光催化氧化反应。并且由于铋氧层的存在,使得Sr2Bi4Ti5O18具有非常高的结构和性能可调性。合理利用掺杂等手段或许能够一定程度上提高其铁电性能,这对有效分离光生载流子、提高光催化活性非常有利,但是现有的Sr2Bi4Ti5O18产品却无法作为光催化剂使用。
经试验发现,现有的Sr2Bi4Ti5O18产品由于主要应用于铁电陶瓷,Sr2Bi4Ti5O18的生产均是通过高温固相反应合成,这导致产品的粒径较大,有效反应点位不足,无法有效地吸收光子,并产生光生载流子。而采用水热合成法所生产的Sr2Bi4Ti5O18产品,具有合适的禁带宽度和纳米结构,能够最大限度地有效吸收光子,并产生光生载流子,从而具有光催化剂的功能。水热合成相比于固相烧结晶体的生长缺陷少、取向好,合适的尺寸大小有效减少了光生电子与空穴的复合,Sr2Bi4Ti5O18的自发铁电极化进一步促进了光生电子与空穴的分离与迁移,大大增加了其光催化性能。
具体地,水热合成的温度为180-240℃,时间为24-72h。在该条件下,所合成的Sr2Bi4Ti5O18呈现片状形貌。在该温度与时间范围内,利于Sr2Bi4Ti5O18的合成并减少杂项的产生,并随着温度的增加与时间的延长,提高结晶度。
具体地,硝酸溶液的浓度为4-5mol/L,氢氧化钠溶液的浓度为6-9mol/L。硝酸溶液与氢氧化钠溶液的体积比为1:1-1:1.2。
在上述硝酸溶液浓度下,可以快速而充分的溶解金属离子,但是层状钙钛矿型Sr2Bi4Ti5O18在酸性条件下无法合成,为弥补这一缺陷,利用上述浓度的氢氧化钠来提供反应所需要的强碱环境,以获得所希望的产品。在上述硝酸溶液浓度、氢氧化钠溶液浓度以及硝酸溶液与氢氧化钠溶液的体积比的限定下,可获得所希望的产品。在碱浓度不够或者过碱的时候,产物杂质过多,不利于纯相产物的获得。
上述的硝酸溶液与氢氧化钠溶液的体积比在保证提高有效碱浓的情况下,还起到及时吸收反应热的功能,足量的溶液体积,能够及时吸收反应热,避免在滴加过程中,由于溶液温度急剧升高,而导致溶液挥发以及溶液中的一些前驱物高温分解。
进一步,滤渣的干燥温度为60-80℃,干燥时间为7-10h。在水热合成后,自然冷却到室温后,再进行过滤。在上述温度下,可以使水热反应后产物快速干燥而不影响产物结构。
上述任一项所述的层状钙钛矿型Sr2Bi4Ti5O18作为光催化剂应用。
根据本发明提供的层状钙钛矿型Sr2Bi4Ti5O18光催化剂的制备方法,制备得到均为纯相,呈现规则片状形貌,提供了光催化反应的活性位点,而且,制得的光催化剂材料的分解水性能均比传统光催化剂优异,且合成条件温和、产物纯度高、晶粒发育完整、粒径小且分布均匀、形貌可控性强,合成路线和装置简单,有利于实现规模化生产。
附图说明
图1为实施例4所合成的Sr2Bi4Ti5O18的X射线衍射(XRD)图。
图2为实施例4所合成的Sr2Bi4Ti5O18的扫描电镜(SEM)图。
具体实施方式
实施例1
1、量取30mL 4mol/L硝酸溶液倒于烧杯中,按Sr2Bi4Ti5O18的化学计量比称取1.5mmol SrCl2·6H2O、1.5mmol Bi2(SO4)3、3.75mmol钛酸四丁酯溶于硝酸溶液中,搅拌10min,得到原料液。
2、称7.2g NaOH溶于30mL去离子水中,搅拌5min,待其冷却至室温,得到氢氧化钠溶液。
3、边搅拌边用滴管将原料液滴于氢氧化钠溶液中,滴加完成后,再搅拌30min使其混合均匀后移入100mL水热反应釜,在180℃条件下保温72h。反应完成后,将反应液冷却到常温,然后离心取沉淀,用乙醇和去离子水各洗涤3次,60℃烘箱干燥10h,研磨成粉,制得Sr2Bi4Ti5O18光催化剂1#。
检测:
将40mg Sr2Bi4Ti5O18光催化剂1#、40mg传统光催化剂TiO2、40mg光催化剂Bi4Ti3O12和40mg固相烧结Sr2Bi4Ti5O18分别投入甲醇溶液中,制成四种测试溶液,然后将四种测试溶液在500W中压汞灯照射5h后,测得Sr2Bi4Ti5O18光催化剂1#催化生成16μmol H2,Bi4Ti3O12光催化剂催化生成7.9μmol H2,而固相烧结合成的Sr2Bi4Ti5O18催化生成H2 5.6μmol,TiO2光催化剂催化生成H2只有5μmol。甲醇溶液由3ml甲醇和30ml去离子水混合而成。
实施例2
1、量取28.4mL 4.3mol/L硝酸溶液倒于烧杯中,按Sr2Bi4Ti5O18的化学计量比称取1.5mmol SrCl2·6H2O、3mmol Bi(NO3)3·5H2O、3.75mmol钛酸四丁酯溶于硝酸溶液中,搅拌10min,得到原料液。
2、称8.4g NaOH溶于30mL去离子水中,搅拌5min,待其冷却至室温,得到氢氧化钠溶液。
3、边搅拌边用滴管将原料液滴于氢氧化钠溶液中,滴加完成后,再搅拌60min使其混合均匀后移入100mL水热反应釜,在200℃条件下保温56h。反应完成后,将反应液冷却到常温,然后离心取沉淀,用乙醇和去离子水各洗涤3次,67℃烘箱干燥9h,研磨成粉,制得Sr2Bi4Ti5O18光催化剂2#。
检测:
将40mg Sr2Bi4Ti5O18光催化剂2#、40mg传统光催化剂TiO2、40mg光催化剂Bi4Ti3O12和40mg固相烧结Sr2Bi4Ti5O18分别投入甲醇溶液中,制成四种测试溶液,然后将四种测试溶液在500W中压汞灯照射5h后,测得Sr2Bi4Ti5O18光催化剂2#催化生成15.4μmol H2,Bi4Ti3O12光催化剂催化生成7.9μmol H2,而固相烧结合成的Sr2Bi4Ti5O18催化生成H2 5.6μmol,TiO2光催化剂催化生成H2只有5μmol。甲醇溶液由3ml甲醇和30ml去离子水混合而成。
实施例3
1、量取26.7mL 4.6mol/L硝酸溶液倒于烧杯中,按Sr2Bi4Ti5O18的化学计量比称取1.5mmol SrCl2·6H2O、1.5mmol Bi2(SO4)3、3.75mmol钛酸四丁酯溶于硝酸溶液中,搅拌10min,得到原料液。
2、称9.6g NaOH溶于30mL去离子水中,搅拌5min,待其冷却至室温,得到氢氧化钠溶液。
3、边搅拌边用滴管将原料液滴于氢氧化钠溶液中,滴加完成后,再搅拌90min使其混合均匀后移入100mL水热反应釜,在220℃条件下保温40h。反应完成后,将反应液冷却到常温,然后离心取沉淀,用乙醇和去离子水各洗涤3次,73℃烘箱干燥8h,研磨成粉,制得Sr2Bi4Ti5O18光催化剂3#。
检测:
将40mg Sr2Bi4Ti5O18光催化剂3#、40mg传统光催化剂TiO2、40mg光催化剂Bi4Ti3O12和40mg固相烧结Sr2Bi4Ti5O18分别投入甲醇溶液中,制成四种测试溶液,然后将四种测试溶液在500W中压汞灯照射5h后,测得Sr2Bi4Ti5O18光催化剂3#催化生成15.7μmol H2,Bi4Ti3O12光催化剂催化生成7.9μmol H2,而固相烧结合成的Sr2Bi4Ti5O18催化生成H2 5.6μmol,TiO2光催化剂催化生成H2只有5μmol。甲醇溶液由3ml甲醇和30ml去离子水混合而成。
实施例4
1、量取25mL 5mol/L硝酸溶液倒于烧杯中,按Sr2Bi4Ti5O18的化学计量比称取1.5mmol SrCl2·6H2O、3mmol Bi(NO3)3·5H2O、3.75mmol钛酸四丁酯溶于硝酸溶液中,搅拌10min,得到原料液。
2、称10.8g NaOH溶于30mL去离子水中,搅拌5min,待其冷却至室温,得到氢氧化钠溶液。
3、边搅拌边用滴管将原料液滴于氢氧化钠溶液中,滴加完成后,再搅拌120min使其混合均匀后移入100mL水热反应釜,在240℃条件下保温24h。反应完成后,将反应液冷却到常温,然后离心取沉淀,用乙醇和去离子水各洗涤3次,80℃烘箱干燥7h,研磨成粉,制得Sr2Bi4Ti5O18光催化剂4#。
检测:
将40mg Sr2Bi4Ti5O18光催化剂4#、40mg传统光催化剂TiO2、40mg光催化剂Bi4Ti3O12和40mg固相烧结Sr2Bi4Ti5O18分别投入甲醇溶液中,制成四种测试溶液,然后将四种测试溶液在500W中压汞灯照射5h后,测得Sr2Bi4Ti5O18光催化剂4#催化生成16.1μmol H2,Bi4Ti3O12光催化剂催化生成7.9μmol H2,而固相烧结合成的Sr2Bi4Ti5O18催化生成H2 5.6μmol,TiO2光催化剂催化生成H2只有5μmol。甲醇溶液由3ml甲醇和30ml去离子水混合而成。
上述各实施例表明,本申请所制备的层状钙钛矿型Sr2Bi4Ti5O18光催化剂分解水的性能大大优于传统光催化剂TiO2、Bi4Ti3O12光催化剂与固相烧结合成的Sr2Bi4Ti5O18。
Claims (6)
1.一种层状钙钛矿型光催化剂的合成方法,其特征在于,
该层状钙钛矿型光催化剂的化学式为:Sr2Bi4Ti5O18;
该合成方法包括如下步骤:
(1)将SrCl2·6H2O、铋源和钛酸四丁酯溶于硝酸溶液,得到原料液;
(2)将所得原料液滴加于氢氧化钠溶液中,然后进行水热合成,得到白色悬浊液;
(3)将悬浊液冷却、过滤,取滤渣,将滤渣洗涤、干燥后获得层状钙钛矿型Sr2Bi4Ti5O18;
水热合成的温度为180-240℃,时间为24-72h;氢氧化钠溶液的浓度为6-9mol/L。
2.根据权利要求1所述的合成方法,其特征在于,硝酸溶液的浓度为4-5mol/L。
3.根据权利要求2所述的合成方法,其特征在于,硝酸溶液与氢氧化钠溶液的体积比为1:1-1:1.2。
4.根据权利要求1所述的合成方法,其特征在于,铋源为硝酸铋或硫酸铋。
5.根据权利要求1所述的合成方法,其特征在于,滤渣的干燥温度为60-80℃,干燥时间为7-10h。
6.权利要求1-5任一项所述的层状钙钛矿型光催化剂在光催化反应中的应用。
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