CN105413699B - 一种可控修饰型钛酸锶光催化剂的制备方法 - Google Patents
一种可控修饰型钛酸锶光催化剂的制备方法 Download PDFInfo
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Abstract
本发明为一种可控修饰型钛酸锶光催化剂的制备方法,该方法包括以下步骤:1)将钛酸正四丁酯与冰乙酸混合;2)在搅拌下,向步骤1)得到的溶液中加入去离子水,搅拌形成溶液A,3)将碳酸锶、碳酸镍和碳酸镧分别加入到去离子水中,然后加入柠檬酸溶液,得到溶液B;4)将溶液B滴加到溶液A中并搅拌均匀,然后加入聚乙二醇,再向体系中加入琼脂,再加入可溶性无机盐,得到干凝胶粉末;5)利用双模板剂的性质不同对所构筑的孔道采用氧化、还原助催化剂进行分区域可控修饰,最后得到可控修饰型钛酸锶光催化剂。本发明所制备钛酸锶光催化剂结晶度好,热稳定性好及光催化性能稳定,光催化剂活性是较传统方法所制备钛酸锶光催化剂的5倍以上。
Description
技术领域
本发明涉及一种制备可控修饰型钛酸锶光催化剂的方法,属于光催化技术领域。
背景技术
虽然经过几十年的发展,光催化分解水技术已取得较大进展,但仍面临巨大挑战,特别是利用太阳光能分解水制清洁氢能源方面更是如此,其原因可能有:①催化剂可见光响应性能差、表面积小、透光率低,故而对可见光的捕获能力差,受可见光激发所产生的光生电子-空穴对数量少,导致其活性难以提高;②光生电子-空穴在催化剂本体的快速复合;③光分解水产生的氢气和氧气在催化剂表面的原位逆反应重新生成水分子。针对上述问题,李灿院士课题组(Nature Commun.,2013,4,1432)通过选择性沉积法将氧化、还原助催化剂分别担载在BiVO4的不同晶面,实现了助催化剂的分离,这种助催化剂空间分离结构提高了光生电荷分离效应,可将光催化性能提高两个数量级。Wang等(Angew.Chem.Int.Ed.,2013,52,11252)采用利于收集电子用以产氢的Pt助催化剂和利于富集空穴产氧的IrO2或CoOx助催化剂对球型催化剂内壁和外壁进行可控修饰,形成了助催化剂空间分离结构,使光生电子和空穴快速分离并传输到表面,抑制了电子-空穴对的复合,同时使产生的氢气和氧气分别在催化剂内外壳层富集,大大减小了逆反应,提高了光解水效率。因此,光催化剂中构筑多级孔结构,并对所构筑的孔道进行可控修饰,在有效提高催化剂表面积的同时实现催化剂的分区域可控修饰,构筑助催化剂空间分离结构,有利于明显改善光催化性能,有望突破当前可见光催化活性难以提高的瓶颈问题。钛酸锶以其独特的物化性质,展示了优良的液相光催化性能,是一种极具开发潜质的光催化材料,故该研究具有非常重要应用价值。
发明内容
本发明提供一种制备可控修饰型钛酸锶光催化剂的方法。本发明所述方法是通过以有机化合物和可溶性无机盐为双模板剂,采用改进的聚合诱导胶体聚集法使双模板在催化材料中的分布处于交替分布状态,在钛酸锶材料中构建多级孔结构,同时利用双模板剂的性质不同对所构筑的孔道采用氧化、还原助催化剂进行分区域可控修饰,从而得到氧化助催化剂与还原助催化剂空间分离的结构。这种助催化剂空间分离结构可加速光生电子和空穴分离和向表面传输,抑制了电子-空穴对的复合,提高量子效率,从而有效的改善其光催化活性。
本发明的技术方案为:
一种可控修饰型钛酸锶光催化剂的制备方法,包括以下步骤:
1)将钛酸丁酯与冰乙酸混合均匀得到体积浓度为20%~60%钛酸丁酯的乙酸溶液;
2)在搅拌下,向步骤1)得到的溶液中加入去离子水,搅拌形成澄清透明溶液A,其中,溶液A中Ti4+浓度为0.5-2.0mol/L;
3)将碳酸锶、碳酸镍和碳酸镧分别加入到去离子水中,形成质量浓度为10~40%悬浊溶液,然后将浓度为55%柠檬酸溶液搅拌下加入到上述碳酸盐的悬浊液中,得到溶液B;
其中,摩尔量镍和镧之和为锶的0.01~10%,摩尔比镍:镧=1:1;柠檬酸溶液的加入量为使溶液pH值为1~4;
4)将溶液B滴加到溶液A中并搅拌均匀,然后加入聚乙二醇,搅拌条件下水浴65℃恒温密闭搅拌4h,然后加入pH值调节剂使溶液pH值为5-10,再向体系中加入琼脂,再升温至95~100℃,待琼脂全部溶解后再加入可溶性无机盐,继续搅拌5~20分钟后停止加热,空气中冷却至室温得到块状含水胶体,干燥后研碎,得到干凝胶粉末;
其中,物料配比为:溶液A中元素锶、镍和镧的摩尔量之和,等于溶液B中钛元素Ti的摩尔量;琼脂的加入量为合成体系总含水量的1-10%,可溶性无机盐为熔点高于800℃的水溶性无机盐,其用量为合成体系总含水量的0.005-15%;所述的合成体系总含水量为溶液A、溶液B和pH调节剂中所含水量之和;聚乙二醇的质量为A溶液和B溶液总水量之和的10~70%;
5)将上述得到的干凝胶粉末,惰性气氛下800℃晶化5~7h后冷却,将所得到的黑色粉末用水洗涤,干燥后将所得到的粉末浸渍到还原助催化剂前驱体的水溶液中,室温搅拌0.4~0.6h,过滤、干燥后再380~420℃焙烧2~4h;重复“浸渍-过滤-干燥-焙烧”步骤1~6次,得到还原助催化剂;再将得到的还原助催化剂浸渍到无机盐溶液中静置10~20分钟,过滤、干燥;重复“无机盐溶液浸渍-过滤-干燥”步骤1~5次;然后430~480℃氧气氛下焙烧20~40min除去积碳硬模板,冷却后再将催化剂浸入到氧化助催化剂前驱体的有机溶液中,室温搅拌0.5h、干燥,然后再经过380~420℃焙烧2~4h;重复“氧化助催化剂前驱体的有机溶液浸渍-过滤-干燥-焙烧”过程1~6次,得到氧化助催化剂,经去离子水洗涤,最后得到可控修饰型钛酸锶光催化剂。
所述步骤4)中pH调节剂为碳酸铵溶液或者碳酸氢铵溶液;
所述步骤4)中合成体系的pH值范围最佳的为6-8;琼脂的最佳加入量为1.5-3.5%;所用无机盐为具有高熔点的水溶性无机盐,其最佳用量为0.01-10%;
所述的步骤4)中的干燥过程需在低于60℃条件下自然干燥或者冷冻干燥;
所述的步骤4)中的可溶性无机盐具体为NaCl、Na2SO4和KCl中的一种或几种;
所述的步骤5)中的无机盐具体为NaCl、Na2SO4、KCO3和KCl中的一种或几种;
所述步骤5)中还原助催化剂前驱体具体为氯铂酸、硝酸银或三氯化铑中的一种或几种;溶液浓度为0.5~5%;
所述步骤5)中氧化助催化剂前驱体具体为乙酸锌、乙酸镍、乙酸钴或乙酰丙酮钴中的一种或几种;溶液浓度为0.5~5%;
所述步骤5)中的有机溶液具体为无水乙醇、甲醇、碳酸二甲酯、石油醚和乙醚中的一种或几种。
本发明的有益效果为:
本发明实施方法开创性的采用改进的聚合诱导胶体聚集法有效的调控有机化合物模板剂和无机盐模板剂在催化剂凝胶前驱体中的分布,便利的实现双模板剂在前驱体中的交替分布,并进一步利用双模板剂的性质不同在催化剂内部构建孔道的同时实现对孔道结构的分区域修饰,从而得到氧化、还原助催化剂空间分离结构。与现有技术相比,该方法操作简便,工艺过程容易控制,易于得到的氧化、还原助催化剂分区域修饰的空间分离结构,且所制备钛酸锶光催化剂结晶度好,热稳定性好及光催化性能稳定,光催化剂活性是较传统方法所制备钛酸锶光催化剂的5倍以上。
附图说明
图1是本发明实施例1所制备的钛酸锶光催化剂的X射线衍射图谱。
图2是本发明实施例1制备的钛酸锶光催化剂的扫描电镜(SEM)照片。
图3是本发明实施例1所制备钛酸锶光催化剂光催化降解孔雀石绿性能对比图。
具体实施方式:
实施例1:
(1)将6.807g(0.02mol,约6.5mL)钛酸丁酯与10mL的冰乙酸混合均匀,然后边搅拌边加入10mL去离子水,搅拌形成澄清透明溶液A。
(2)将2.921g(0.0196mol)碳酸锶、0.060g(镧摩尔数为2×10-4mol)八水合碳酸镧和0.0248g(镍摩尔数为2×10-4mol)碱式碳酸镍加入到10g水中配制悬浊液,并向悬浊液中滴加23g浓度为55wt%的柠檬酸水溶液,使所有碳酸盐全部溶解得到溶液B(pH约为2)。
(3)将A、B溶液在常温下各自搅拌0.3~1h后,将溶液B在15~30min内滴加到溶液A中,并常温搅拌0.5h后加入聚乙二醇10.6g完全溶解后升温至65℃搅拌条件下恒温4h;采用20wt%的碳酸氢铵溶液调节系统pH=6,然后加入1.5g的琼脂粉,将合成体系升温至95℃使琼脂完全溶解并继续搅拌15分钟,然后加入2g NaCl搅拌至完全溶解,冷却得到块状的含水凝胶,自然干燥、研磨得到粉体,将粉体在800℃下晶化6h,制得黑色粉末。
(4)将所得到的黑色粉末用水洗涤去除NaCl,干燥后将催化剂粉末浸入到100mL浓度2wt%的氯铂酸水溶液中,室温搅拌0.5h,过滤、干燥,并400℃焙烧处理3h得到Pt负载修饰,重复以上“2wt%的氯铂酸水溶液浸渍-过滤-干燥-焙烧”步骤3次;然后将负载Pt后的催化剂浸渍到饱和NaCl溶液中静置15分钟,过滤、干燥,重复“饱和NaCl溶液浸渍-过滤-干燥”步骤4次使负载Pt的孔道得以填埋;然后450℃氧气氛焙烧0.5h除去积碳硬模板,冷却后再浸入到100mL浓度为5wt%的乙酸镍乙醇溶液浸渍中,室温搅拌0.5h,过滤、干燥后400℃焙烧3h进行氧化镍修饰,重复“乙酸镍乙醇溶液浸渍-过滤-干燥-焙烧”过程3次,然后用去离子水进行洗涤6次,将其中填埋孔道所用的NaCl全部移除,得到氧化、还原助催化剂分区域修饰的钛酸锶光催化材料。
由附图1可以看出本发明所制备的光催化剂具有较好的结晶度;由附图2可以看出所得到样品具有一定的大孔结构。图3为不同催化剂在催化用量为1g/L可见光降解20ppm的孔雀石绿的结果;由图3可以看出本发明所制备光催化剂的光催化活性明显高于未修饰镍镧掺杂钛酸锶光催化剂和商品钛酸锶,30min孔雀石绿的降解率为100%。
实施例2:
(1)将6.807g(0.02mol,约6.5mL)钛酸丁酯与10mL的冰乙酸混合均匀,然后边搅拌边慢慢加入10mL去离子水,搅拌形成澄清透明溶液A。
(2)将2.924g(0.0198mol)碳酸锶、0.030g(镧摩尔数为1×10-4mol)八水合碳酸镧和0.0248g(镍摩尔数为1×10-4mol)碱式碳酸镍加入到10g水中配制悬浊液,并向悬浊液中滴加23g浓度为55wt%的柠檬酸水溶液,使所有碳酸盐全部溶解得到溶液B(pH约为2)。
(3)将A、B溶液在常温下各自搅拌0.3-1h后,将溶液B在15~30min内滴加到溶液A中,并常温搅拌0.5h后加入聚乙二醇10.6g完全溶解后升温至65℃搅拌条件下恒温4h;采用50wt%碳酸铵水溶液调节系统pH=7,然后加入2.5g琼脂粉,将合成体系升温至95℃使琼脂完全溶解并继续搅拌15分钟,然后加入4g NaCl搅拌至完全溶解,冷却得到块状含水凝胶,自然干燥、研磨得到粉体,将粉体在800℃下晶化6h,制得黑色粉末。
(4)将所得到的黑色粉末用水洗涤去除NaCl,干燥后将催化剂粉末浸入到100mL浓度1wt%的三氯化铑水溶液中,室温搅拌0.5h,过滤、干燥,并400℃焙烧处理3h得到Rh负载修饰,重复以上“1wt%的三氯化铑水溶液浸渍-过滤-干燥-焙烧”步骤3次;然后将负载Rh后的催化剂浸入饱和NaCl溶液中静置15分钟,过滤、干燥,重复“饱和NaCl溶液浸渍-过滤-干燥”步骤4次使负载Rh的孔道得以填埋;然后450℃氧气氛焙烧0.5h除去积碳硬模板,冷却后再浸入到100mL浓度为5wt%的乙酸锌乙醇溶液浸渍中,室温搅拌0.5h,过滤、干燥后400℃焙烧3h进行氧化锌修饰,重复“乙酸锌乙醇溶液浸渍-过滤-干燥-焙烧”3次,,然后用去离子水进行洗涤6次,将其中填埋孔道所用的NaCl全部移除,得到氧化、还原助催化剂分区域修饰的钛酸锶光催化材料;30min孔雀石绿的降解率为100%。
实施例3:
(1)将6.807g(0.02mol,约6.5mL)钛酸丁酯与10mL的冰乙酸混合均匀,然后边搅拌边慢慢加入10mL去离子水,搅拌形成澄清透明溶液A。
(2)将2.805g(0.019mol)碳酸锶、0.150g(镧摩尔数为5×10-4mol)八水合碳酸镧和0.062g(镍摩尔数为5×10-4mol)碱式碳酸镍加入到10g水中配制悬浊液,并向悬浊液中滴加26g浓度为55wt%的柠檬酸水溶液,使所有碳酸盐全部溶解得到溶液B(pH约为1)。
(3)将A、B溶液在常温下各自搅拌0.3~1h后,将溶液B在15~30min内滴加到溶液A中,并常温搅拌0.5h后加入聚乙二醇10.6g完全溶解后升温至65℃搅拌条件下恒温4h;采用50wt%碳酸铵水溶液调节系统pH=7,然后加入3.0g琼脂粉,将合成体系升温至95℃使琼脂完全溶解并继续搅拌15分钟,然后加入4g K2CO3搅拌至完全溶解,冷却得到块状含水凝胶,自然干燥、研磨得到粉体,将粉体在800℃下晶化6h,制得黑色粉末。
(4)将所得到的黑色粉末用水洗涤去除NaCl,干燥后将催化剂粉末浸入到100mL浓度1wt%的三氯化铑水溶液中,室温搅拌0.5h,过滤、干燥,并400℃焙烧处理3h得到Rh负载修饰,重复以上“1wt%的三氯化铑水溶液浸渍-过滤-干燥-焙烧”步骤3次;然后将负载Rh后的催化剂浸入饱和NaCl溶液中静置15分钟,过滤、干燥,重复“饱和NaCl溶液浸渍-过滤-干燥”步骤4次使负载Rh的孔道得以填埋;然后450℃氧气氛焙烧0.5h除去积碳硬模板,冷却后再浸入到100mL浓度为2wt%的乙酸锌碳酸二甲酯溶液浸渍中,室温搅拌0.5h,过滤、干燥后400℃焙烧3h进行氧化锌修饰,重复“乙酸锌碳酸二甲酯溶液浸渍-过滤-干燥-焙烧”3次,然后用去离子水进行洗涤6次,将其中填埋孔道所用的NaCl全部移除,得到氧化、还原助催化剂分区域修饰的钛酸锶光催化材料;30min孔雀石绿的降解率为100%。
实施例4:
(1)将6.807g(0.02mol,约6.5mL)钛酸丁酯与10mL的冰乙酸混合均匀,然后边搅拌边慢慢加入10mL去离子水,搅拌形成澄清透明溶液A。
(2)将2.921g(0.0196mol)碳酸锶、0.060g(镧摩尔数为2×10-4mol)八水合碳酸镧和0.0248g(镍摩尔数为2×10-4mol)碱式碳酸镍加入到10g水中配制悬浊液,并加入20g浓度为55%的柠檬酸溶液,使所有碳酸盐全部溶解得到溶液B(pH约为2)。
(3)将A、B溶液在常温下各自搅拌0.3~1h后,将溶液B在15~30min内滴加到溶液A中,并常温搅拌0.5h后加入聚乙二醇10.6g完全溶解后升温至65℃搅拌条件下恒温4h;采用20wt%碳酸氢铵溶液调节系统pH=6,然后加入2.0g的琼脂粉,将合成体系升温至95℃使琼脂完全溶解并继续搅拌15分钟,然后加入2g K2SO4搅拌至完全溶解,冷却得到块状的含水凝胶,自然干燥、研磨得到粉体,将粉体在800℃下晶化6h,制得黑色粉末。
(4)将所得到的黑色粉末用水洗涤去除K2SO4,干燥后将催化剂粉末浸入到100mL浓度2wt%的氯铂酸水溶液中,室温搅拌0.5h,过滤、干燥,并400℃焙烧处理3h得到Pt负载修饰,重复以上“2wt%的氯铂酸水溶液浸渍-过滤-干燥-焙烧”步骤3次;然后将负载Pt后的催化剂浸渍到饱和K2CO3溶液中静置15分钟,过滤、干燥,重复“饱和NaCl溶液浸渍-过滤-干燥”步骤4次使负载Pt的孔道得以填埋;然后450℃氧气氛焙烧0.5h除去积碳硬模板,冷却后再浸入到100mL乙酸钴饱和乙醇溶液(约1.5wt%)中,室温搅拌0.5h,过滤、干燥后400℃焙烧3h进行氧化锌修饰,“乙酸钴饱和乙醇溶液浸渍-过滤-干燥-焙烧”浸渍3次,然后用去离子水进行洗涤6次,将其中填埋孔道所用的K2CO3全部移除,得到氧化、还原助催化剂分区域修饰的钛酸锶光催化材料;20min孔雀石绿的降解率为99%。
本发明未尽事宜为公知技术。
Claims (2)
1.一种可控修饰型钛酸锶光催化剂的制备方法,其特征为包括以下步骤:
1)将钛酸丁酯与冰乙酸混合均匀得到体积浓度为20%~60%钛酸丁酯的乙酸溶液;
2)在搅拌下,向步骤1)得到的溶液中加入去离子水,搅拌形成澄清透明溶液A,其中,溶液A中Ti4+浓度为0.5-2.0mol/L;
3)将碳酸锶、碳酸镍和碳酸镧分别加入到去离子水中,形成质量浓度为10~40%悬浊溶液,然后将质量百分浓度为55%柠檬酸溶液搅拌下加入到上述碳酸盐的悬浊液中,得到溶液B;
其中,摩尔量镍和镧之和为锶的0.01~10%,摩尔比镍:镧=1:1;柠檬酸溶液的加入量为使溶液pH值为1~4;
4)将溶液B滴加到溶液A中并搅拌均匀,然后加入聚乙二醇,搅拌条件下水浴65 ℃恒温密闭搅拌4h,然后加入pH值调节剂使溶液pH值为5-10,再向体系中加入琼脂,再升温至95~100 ℃,待琼脂全部溶解后再加入可溶性无机盐,继续搅拌5~20分钟后停止加热,空气中冷却至室温得到块状含水胶体,干燥后研碎,得到干凝胶粉末;
其中,物料配比为:溶液A中元素锶、镍和镧的摩尔量之和,等于溶液B中钛元素Ti的摩尔量;琼脂的加入量为合成体系总含水量的1-10%,可溶性无机盐为熔点高于800℃的水溶性无机盐,其用量为合成体系总含水量的0.005-15%;所述的合成体系总含水量为溶液A、溶液B和pH调节剂中所含水量之和;聚乙二醇的质量为A溶液和B溶液总水量的10~70%;
5)将上述得到的干凝胶粉末,惰性气氛下800℃晶化5~7h后冷却,将所得到的黑色粉末用水洗涤,干燥后将所得到的粉末浸渍到还原助催化剂前驱体的水溶液中,室温搅拌0.4~0.6h,过滤、干燥后再380~420℃焙烧2~4h;重复“浸渍-过滤-干燥-焙烧”步骤1~6次,得到还原助催化剂;再将得到的还原助催化剂浸渍到无机盐溶液中静置10~20分钟,过滤、干燥;重复“无机盐溶液浸渍-过滤-干燥”步骤1~5次;然后430~480℃氧气氛下焙烧20~40min除去积碳硬模板,冷却后再将催化剂浸入到氧化助催化剂前驱体的有机溶液中,室温搅拌0.5h、干燥,然后再经过380~420℃焙烧2~4h;重复“氧化助催化剂前驱体的有机溶液浸渍-过滤-干燥-焙烧”过程1~6次,得到氧化助催化剂,经去离子水洗涤,最后得到可控修饰型钛酸锶光催化剂;
所述步骤4)中pH调节剂为碳酸铵溶液或者碳酸氢铵溶液;
所述步骤4)中合成体系的pH值范围为6-8;琼脂的加入量为1.5-3.5%;所用无机盐为具有高熔点的水溶性无机盐,其用量为0.01-10%;
所述的步骤4)中的可溶性无机盐具体为NaCl、Na2SO4和KCl中的一种或几种;
所述的步骤5)中的无机盐具体为NaCl、Na2SO4、KCO3和KCl中的一种或几种;
所述步骤5)中还原助催化剂前驱体具体为氯铂酸、硝酸银或三氯化铑中的一种或几种;溶液质量百分浓度为0.5~5%;
所述步骤5)中氧化助催化剂前驱体具体为乙酸锌、乙酸镍、乙酸钴或乙酰丙酮钴中的一种或几种;溶液质量百分浓度为0.5~5%;
所述步骤5)中的有机溶剂具体为无水乙醇、甲醇、碳酸二甲酯、石油醚和乙醚中的一种或几种。
2.如权利要求1所述的可控修饰型钛酸锶光催化剂的制备方法,其特征为所述的步骤4)中的干燥过程需在低于60℃条件下自然干燥或者冷冻干燥。
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