CN116532159A - 一种Keggin型过渡金属杂多酸盐修饰的光催化剂的制备方法及应用 - Google Patents
一种Keggin型过渡金属杂多酸盐修饰的光催化剂的制备方法及应用 Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract
本发明公开了一种Keggin型过渡金属杂多酸盐修饰的光催化剂的制备方法及应用,具体为通过制备不同种过渡金属杂多酸盐,并将一定量的不同种过渡金属杂多酸盐与单体光催化剂研磨后,经过煅烧增强异质结结构,可以实现将过渡金属杂多酸盐在单体光催化剂表面负载,使复合材料能够拓宽光吸收范围和强度,促进载流子分离和转移,从而改善其光催化降解环境水体有机染料、抗生素和酚类污染物性能。本发明具有效率高、方法简单、经济环保等优点。
Description
技术领域
本发明属于材料合成技术领域,特别涉及一种Keggin型过渡金属杂多酸盐修饰的光催化剂的制备方法及应用。
背景技术
随着现代社会工业进程的快速发展,环境污染问题逐渐被社会各界所关注,尤其是水体污染已经成为人类社会可持续发展必须面对的严肃问题。水体中的有机染料,内分泌干扰物,农药等,即使浓度很低也对生态环境和人类造成极大的损害。然而,常规的水处理技术与方法已不能满足有效水净化的需求。半导体材料已经成为科学研究和工业应用中最重要的材料之一,被广泛应用于光催化、太阳能电池等多个领域。
g-C3N4、TiO2、SiO2等是光催化中广泛使用的半导体材料。但由于单体光催化剂存在比表面积小、可见光利用率低、光生载流子复合快和导电性差等缺点,影响光催化技术的发展和性能的提升。因此,探寻具有高导电性、强光吸收能力、低光生载流子复合率和优异光催化性能的光催化材料已经成为一件迫切要做的事情。大量的改性方法:如形貌调控、缺陷工程、元素掺杂、半导体复合等,被用来修饰单体光催化剂以达到克服上述问题并改善其光催化性能的目的。
Keggin型过渡金属杂多酸盐是一种用途广泛的n型半导体催化剂,其原因是特殊的几何结构和电子结构。Keggin型杂多酸分子是由一个中心四面体配位原子(如P、Si、Ge或B),十二个相同的八面体配位原子(如W或Mo)紧密包围组成。在溶液酸度改变条件下,形成Keggin型缺位杂多酸阴离子,该缺位阴离子具有很强的配位能力,能与绝大多数过渡金属阳离子形成Keggin型过渡金属取代杂多酸盐,这种化合物具有良好的光催化活性,可以增强导带上电子转移速率,从而延缓电荷重组,是一种新型光催化材料。但目前尚不存在适合量产化的方法制备Keggin型过渡金属杂多酸盐,限制了其进一步广泛应用。
发明内容
本发明的目的在于克服现有技术中的不足,提供一种Keggin型过渡金属杂多酸盐修饰的光催化剂的制备方法及应用。
本发明解决上述技术问题的技术方案如下:
本发明的第一个方面提供了一种Keggin型过渡金属杂多酸盐修饰的光催化剂的制备方法,其特征在于,包括如下步骤:
(1)称取Na2HPO4 .12H2O和Na2WO4 .2H2O溶于去离子水中,用浓硝酸调节pH值,搅拌加热至溶液体积蒸发一半,冷却后加入丙酮,静置后吸去上层丙酮,重复此操作2~3次,干燥下层溶液后得到纯白色固体NaxPWyOz;
(2)称取步骤(1)所得NaxPWyOz溶于去离子水,称取金属无机盐溶于水,加热条件下,将金属无机盐溶液逐滴加入NaxPWyOz溶液中,直至出现浑浊即停止滴加,冷却后加入丙酮,过滤至无沉淀出现,完全蒸除丙酮,经烘干、研磨后,得到NaxPWyOzM;
(3)将步骤(2)所得NaxPWyOzM溶于水,加入CsCl,过滤得CsxPWyOzM沉淀物,烘干后得到CsxPWyOzM;
(4)称取步骤(3)所得CsxPWyOzM与单体光催化剂,研磨充分后形成混合物粉末;
(5)将步骤(4)所得混合物粉末在一定条件下进行煅烧,得到CsxPWyOzM修饰的复合光催化剂;
其中,所述M选自Co、Cr、Fe、Cu或Mn;
进一步的,所述步骤(1)中Na2HPO4 .12H2O和Na2WO4 .2H2O的摩尔比为1~10:10~120;
进一步的,所述步骤(1)中pH调至4.5~4.8,加热温度为50~100℃;
进一步的,所述步骤(2)中的金属无机盐包括Co(NO3)2 .6H2O、Cr(NO3)3 .9H2O、Fe(NO3)3 .9H2O、Cu(NO3)2 .3H2O或MnSO4 .H2O 中的一种或几种,所述金属无机盐与NaxPWyOz的摩尔比为1~10:1~10;
进一步的,所述步骤(2)的加热温度为90~100℃,烘干温度为50~60℃;
进一步的,所述步骤(3)中CsCl与NaxPWyOzM的质量比为0.2~1:0.8~1;
进一步的,所述步骤(4)中单体光催化剂选自g-C3N4、TiO2、单晶硅、氧化铝或金属有机框架中的一种或几种;
进一步的,所述步骤(4)中CsxPWyOzM与单体光催化剂的质量比为1~10:100;
进一步的,所述步骤(5)中煅烧条件为:温度选自200~300℃,煅烧的气氛为氮气或氩气,升温速率为2~5℃/min,恒温时间为1~2h。
本发明的第二个方面提供了一种上述方法制备得到的Keggin型过渡金属杂多酸盐修饰的光催化剂在光催化降解有机染料、抗生素或酚类污染物上的应用。
本发明中化合物的中文命名与结构式有冲突的,以结构式为准;结构式有明显错误的除外。
与现有技术相比,本发明提供了一种Keggin型过渡金属杂多酸盐修饰的光催化剂的制备方法及其应用,将结构形貌可控、性能优异的单体光催化剂与不同种Keggin型过渡金属杂多酸盐复合,通过两者之间的相互作用,形成CsxPWyOzM与单体光催化剂异质结结构,改善原始单体光催化剂可见光响应有限和活性位点较少的缺点,加速电荷分离,产生更多的光生载流子,改善单体光催化剂的光谱响应范围,从而实现高效的可见光催化氧化活性,并进一步提高光催化降解环境水体有机染料、抗生素或酚类污染物性能,具有效率高,简单,经济等优点。
附图说明
图1:Keggin型过渡金属取代杂多阴离子结构
图2:实施例1制备的Cs5PW11Co/g-C3N4的复合光催化剂及其单体光催化剂降解RhB的活性图;
图3:实施例2制备的Cs4PW11Fe/g-C3N4的复合光催化剂及其单体光催化剂降解RhB的活性图。
具体实施方式
以下结合实例说明本发明,但不限制本发明。在本领域内,技术人员对本发明所做的简单替换或改进均属于本发明所保护的技术方案内。
实施例1:
首先分别称取0.02mol Na2HPO4 .12H2O和0.225mol Na2WO4 .2H2O,溶解于150mL去离子水中,用浓硝酸调节pH值至4.8,后置于磁力搅拌油浴上加热至85℃,在此温度下搅拌加热直至溶液体积蒸发一半,冷却后加入丙酮80mL,在通风橱内静止,吸去上层丙酮,重复此操作2~3次即可,下层溶液置于烘箱中50℃干燥,得到纯白色固体Na7PW11O39。
称取0.002 mol白色固体溶于去离子水,称取0.002 mol Co(NO3)2 .6H2O溶于水,并且油浴加热95℃,将Co(NO3)2溶液逐滴加入溶液中,直到出现浑浊立即停止滴加,冷却后加入丙酮,过滤3~4次至无沉淀出现,随即利用油浴锅加热蒸发直至丙酮完全去除。放入50℃烘箱中蒸干得产品并研磨,所得产品为粉红色粉末Na5PW11O39Co(Ⅱ)。
将0.87g Na5PW11O39Co(Ⅱ)溶于水,加入0.20g CsCl,过滤得Cs5PW11O39Co (H2O)沉淀。将滤纸放入干净得烧杯置于70℃的烘箱中烘干,得到粉红色固体Cs5PW11O39Co(Ⅱ)。
取3mg Cs5PW11O39Co(Ⅱ)与100mg g-C3N4放置于研钵中,研磨20min充分混合,形成混合物粉末,将混合物粉末置于带盖的坩埚中,管式炉中氩气气氛下煅烧200℃,起始温度为30℃,升温速率为2℃/min, 恒温1h,所得的样品即为Cs5PW11Co修饰的g-C3N4复合光催化剂(此样品为3wt.% Cs5PW11Co/g-C3N4)。
实施例2:
首先分别称取0.02mol Na2HPO4 .12H2O和0.225mol Na2WO4 .2H2O,溶解于150mL去离子水中,用浓硝酸调节pH值至4.8,后置于磁力搅拌油浴上加热至85℃,在此温度下搅拌加热直至溶液体积蒸发一半,冷却后加入丙酮80mL,在通风橱内静止,吸去上层丙酮,重复此操作2~3次即可,下层溶液置于烘箱中50℃干燥,得到纯白色固体Na7PW11O39。
称取0.002mol白色固体溶于去离子水,称取0.002mol Fe(NO3)3 .9H2O溶于水,并且油浴加热95℃,将Fe(NO3)3溶液逐滴加入溶液中,直到出现浑浊立即停止滴加,冷却后加入丙酮,过滤3~4次至无沉淀出现,随即利用油浴锅加热蒸发直至丙酮完全去除。放入50℃烘箱中蒸干得产品并研磨,所得产品为黄色粉末Na4PW11O39Fe(Ⅲ)。
将0.87g Na4PW11O39Fe(Ⅲ)溶于水,加入0.20g CsCl,过滤得Cs4PW11O39Fe (H2O)沉淀。将滤纸放入干净得烧杯置于70℃的烘箱中烘干,得到黄色固体Cs4PW11O39Fe(Ⅲ)。
取3mg Cs5PW11O39Fe(Ⅲ)与100mg TiO2放置于研钵中,研磨20 min充分混合,形成混合物粉末,将混合物粉末置于带盖的坩埚中,管式炉中氩气气氛下煅烧200℃,起始温度为30℃,升温速率为2℃/min, 恒温1h,所得的样品即为Cs4PW11Fe修饰的TiO2复合光催化剂(此样品为3wt.% Cs4PW11Fe/ TiO2)。
实施例3:
首先分别称取0.02mol Na2HPO4 .12H2O和0.225mol Na2WO4 .2H2O,溶解于150mL去离子水中,用浓硝酸调节pH值至4.8,后置于磁力搅拌油浴上加热至85℃,在此温度下搅拌加热直至溶液体积蒸发一半,冷却后加入丙酮80mL,在通风橱内静止,吸去上层丙酮,重复此操作2~3次即可,下层溶液置于烘箱中50℃干燥,得到纯白色固体Na7PW11O39。
称取0.002mol白色固体溶于去离子水,称取0.002mol Cu(NO3)2 .3H2O溶于水,并且油浴加热95℃,将Cu(NO3)2溶液逐滴加入溶液中,直到出现浑浊立即停止滴加,冷却后加入丙酮,过滤3~4次至无沉淀出现,随即利用油浴锅加热蒸发直至丙酮完全去除。放入50℃烘箱中蒸干得产品并研磨,所得产品为蓝色粉末Na5PW11O39Cu(Ⅱ)。
将0.87g Na5PW11O39Cu(Ⅱ)溶于水,加入0.20g CsCl,过滤得Cs5PW11O39Cu (H2O)沉淀。将滤纸放入干净得烧杯置于70℃的烘箱中烘干,得到蓝色固体Cs5PW11O39Cu(Ⅱ)。
取3mg Cs5PW11O39Cu(Ⅱ)与100mg 单晶硅放置于研钵中,研磨20min充分混合,形成混合物粉末,将混合物粉末置于带盖的坩埚中,管式炉中氩气气氛下煅烧200℃,起始温度为30℃,升温速率为2℃/min, 恒温1h,所得的样品即为Cs5PW11Cu修饰的单晶硅复合光催化剂(此样品为3 wt.% Cs5PW11Cu/Si)。
试验例:
性能检测
降解RhB(罗丹明B的缩写,属于有机染料)的步骤如下:
以10mg/L RhB为目标污染物,评价CsxPW11M/g-C3N4 (M=Co、Cr、Fe、Cu、Mn)的光催化活性。将15mg的材料置于光催化反应器中,在250W在氙灯下光降解50mL RhB(λ>400nm)。采用流动冷却水系统使温度维持在30℃以避免热催化。氙灯照射前,将溶液磁搅拌30min,使光催化剂在材料表面达到吸附-脱附平衡。开灯后,在一定的时间间隔内(实例中间隔时间为15min),取3mL溶液,离心并通过0.2 μm聚醚砜过滤去除颗粒,用于后续分析。用紫外-可见分光光度计在最大吸收波长554nm下测定目标污染物的浓度变化。
上述测试,结果如图1和图2所示。从图1和图2中可以看出,与g-C3N4单体和CsxPW11M单体相比,将Keggin型过度金属杂多酸盐修饰g-C3N4得到的复合光催化剂,更能有效的提高其光催化降解污染物的性能。其中,实施例1和实施例2制备得到的3wt.% Cs5PW11Co/g-C3N4、3wt.% Cs4PW11Fe/g-C3N4降解RhB降解率分别可以达到92.3%、89.1%。
以上所述的仅是本发明的优选实施方式,应当指出,对于本领域的普通技术人员来说,在不脱离本发明创造构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。
Claims (10)
1.一种Keggin型过渡金属杂多酸盐修饰的光催化剂的制备方法,其特征在于,包括如下步骤:
(1)称取Na2HPO4 .12H2O和Na2WO4 .2H2O溶于去离子水中,用浓硝酸调节pH值,搅拌加热至溶液体积蒸发一半,冷却后加入丙酮,静置后吸去上层丙酮,重复此操作2~3次,干燥下层溶液后得到纯白色固体NaxPWyOz;
(2)称取步骤(1)所得NaxPWyOz溶于去离子水,称取金属无机盐溶于水,加热条件下,将金属无机盐溶液逐滴加入NaxPWyOz溶液中,直至出现浑浊即停止滴加,冷却后加入丙酮,过滤至无沉淀出现,完全蒸除丙酮,经烘干、研磨后,得到NaxPWyOzM;
(3)将步骤(2)所得NaxPWyOzM溶于水,加入CsCl,过滤得CsxPWyOzM沉淀物,烘干后得到CsxPWyOzM;
(4)称取步骤(3)所得CsxPWyOzM与单体光催化剂,研磨充分后形成混合物粉末;
(5)将步骤(4)所得混合物粉末在一定条件下进行煅烧,得到CsxPWyOzM修饰的复合光催化剂;
其中,所述M选自Co、Cr、Fe、Cu或Mn。
2.根据权利要求1所述的Keggin型过渡金属杂多酸盐修饰的光催化剂的制备方法,其特征在于,所述步骤(1)中Na2HPO4 .12H2O和Na2WO4 .2H2O的摩尔比为1~10:10~120。
3.根据权利要求1所述的Keggin型过渡金属杂多酸盐修饰的光催化剂的制备方法,其特征在于,所述步骤(1)中pH调至4.5~4.8,加热温度为50~100℃。
4.根据权利要求1所述的 Keggin型过渡金属杂多酸盐修饰的光催化剂的制备方法,其特征在于,所述步骤(2)中的金属无机盐包括Co(NO3)2 .6H2O、Cr(NO3)3 .9H2O、Fe(NO3)3 .9H2O、Cu(NO3)2 .3H2O或MnSO4 .H2O 中的一种或几种,所述金属无机盐与NaxPWyOz的摩尔比为1~10:1~10。
5.根据权利要求1所述的 Keggin型过渡金属杂多酸盐修饰的光催化剂的制备方法,其特征在于,所述步骤(2)的加热温度为90~100℃,烘干温度为50~60℃。
6.根据权利要求1所述的 Keggin型过渡金属杂多酸盐修饰的光催化剂的制备方法,其特征在于,所述步骤(3)中CsCl与NaxPWyOzM的质量比为0.2~1:0.8~1。
7.根据权利要求1所述的 Keggin型过渡金属杂多酸盐修饰的光催化剂的制备方法,其特征在于,所述步骤(4)中单体光催化剂选自g-C3N4、TiO2、单晶硅、氧化铝或金属有机框架中的一种或几种。
8.根据权利要求1所述的 Keggin型过渡金属杂多酸盐修饰的光催化剂的制备方法,其特征在于,所述步骤(4)中CsxPWyOzM与单体光催化剂的质量比为1~10:100。
9.根据权利要求1所述的 Keggin型过渡金属杂多酸盐修饰的光催化剂的制备方法,其特征在于,所述步骤(5)中煅烧条件为:温度选自200~300℃,煅烧的气氛为氮气或氩气,升温速率为2~5℃/min,恒温时间为1~2h。
10.根据权利要求1~9任一项所述的方法制备得到的Keggin型过渡金属杂多酸盐修饰的光催化剂在光催化降解有机染料、抗生素或酚类污染物上的应用。
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