CN108636454A - 一种基于金属有机骨架材料uio-66(nh2)复合光催化剂的制备方法 - Google Patents
一种基于金属有机骨架材料uio-66(nh2)复合光催化剂的制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 24
- 239000013207 UiO-66 Substances 0.000 title claims description 44
- 239000012621 metal-organic framework Substances 0.000 title abstract description 11
- 239000000463 material Substances 0.000 title abstract description 5
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims abstract description 35
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 18
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
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- 239000000843 powder Substances 0.000 claims description 6
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- 238000002156 mixing Methods 0.000 claims description 5
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
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- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 3
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- 229940012189 methyl orange Drugs 0.000 description 7
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- 239000003795 chemical substances by application Substances 0.000 description 4
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- YARHASAHCGKZOB-UHFFFAOYSA-M [Ag]Br.[S] Chemical compound [Ag]Br.[S] YARHASAHCGKZOB-UHFFFAOYSA-M 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
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- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
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- 229940107698 malachite green Drugs 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
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Abstract
本发明涉及一种金属有机骨架材料UIO‑66(NH2)掺杂掺杂颗粒状Ag/AgBr复合光催化剂的制备,包括步骤:颗粒状Ag/AgBr的制备、UIO‑66(NH2)的制备和UIO‑66(NH2)掺杂掺杂颗粒状Ag/AgBr复合光催化剂的制备。本发明的有益效果是:该制备方法较为简单,制备条件容易控制,所制备的UIO‑66(NH2)掺杂颗粒状Ag/AgBr复合催化剂具有无二次污染,光催化效率高等优点,具有一定的应用价值。
Description
技术领域
本发明属于纳米材料制备及应用技术领域,涉及一种金属有机骨架材料 UIO-66(NH2)掺杂颗粒状Ag/AgBr复合光催化剂的制备方法。
背景技术
光催化技术逐渐成为治理环境污染以及能源短缺问题的最关键的技术之一,并引发了国内外科学家的广泛研究。许多研究工作集中在高效光催化剂的搜索和适当设计上,因为直接使用太阳辐射来驱动反应已被证明是一种科学,有效和绿色的方法。
众所周知,AgBr可以部分转化为等离子体银纳米粒子,它们的界面可以是明确的。这些性能最近被用于光催化***的设计和制造,结果表明不同形状的 AgBr或Ag@AgBr杂化物可以作为可见光驱动的光催化剂用于有机污染物的降解,具有高稳定活性。在吸收光子时,卤化银颗粒在CB中产生电子并在VB中产生空穴;随后,光生电子被Ag+俘获形成卤化银颗粒内的AgO原子簇。因此,纯的卤化银可以在光照下光解,其很少用作光催化剂。然而,最近的研究表明, AgBr可以表现出高稳定性,在连续的紫外照射下在表面上形成Ag纳米颗粒。AgX/Ag异质结构比其他异质结构更有优势,因为在没有添加额外的前体,还原剂和稳定剂的情况下,Ag NPs可以在AgX表面上容易地形成。因为它们具有可见光吸收能力和银纳米粒子的局域表面等离子体共振效应。目前已经开发出了作为等离子体光催化剂的AgX/Ag组合(AgBr/Ag,AgCl/Ag,AgI/Ag)的品种,引起了人们的广泛兴趣。除了AgX/Ag异质结构外,还有与其他半导体的混合 (TiO2,ZnO,WO3,CeO2,Fe3O4,Bi2O3)在光催化应用中也有报道。在各种 AgX/Ag基异质结构中,AgBr/Ag和AgCl/Ag纳米颗粒在光催化领域应用最多,合成过程简单,稳定性好,光催化性能较好。在光催化中,也观察到AgBr/Ag 比AgCl/Ag更具活性,因为Br-的较低电子亲和力使得与Cl-相比更容易与空穴结合。尽管AgBr/Ag混合结构具有一些优点,Ag的SPR仅覆盖可见光区域的一小部分,这限制了其在光催化应用中的适用性。
由金属离子和有机配体的自组装形成的金属有机骨架(MOFs),因其独特的物理化学性质如高孔体积,高比表面积,结构适应性和灵活性而具有广泛的应用,包括气体吸附,分离,化学感应,线性光学性质以及催化。MOFs本身可以作为催化剂,其是光催化的极好候选物,研究表明一些MOFs可以作为半导体,并通过有机接触体或金属簇的光激发来传输电子。此外,还可以在光活性金属物质和半导体纳米颗粒的活性位点引入金属有机框架。与传统的半导体光催化剂相比,MOFs的优越性在于具有超高的表面积,并且窄的微孔分布在MOFs 上形成单分散光活性物质,有利于其催化活性和选择性。更重要的是,作为光催化反应的有机多孔材料,它们还可为光致电子的迁移提供途径,从而促进电荷分离,提高光催化效率。据我们所知,目前还没有关于UIO-66(NH2)/Ag/AgBr 异质结构作为高效可见光活性等离子体光催化剂以更好地利用太阳能和大量光激发电荷载体的报道。因此,研究和开发这种新型的复合光催化剂是十分有意义的。
发明内容
本发明要解决的技术问题是:基于上述问题,本发明提供一种金属有机骨架材料UIO-66(NH2)/Ag/AgBr复合光催化剂的制备方法。
本发明解决其技术问题所采用的一个技术方案是:一种UIO-66(NH2)掺杂颗粒状Ag/AgBr复合光催化剂的制备方法,包括以下步骤:
(1)颗粒状Ag/AgBr的制备:将AgNO3避光溶解在30mL去离子水中,搅拌1h,将NaBr溶解于30mL去离子水,逐滴加入上述避光搅拌的硝酸银水溶液中,在避光的条件下将混合溶液搅拌3h,将所得淡黄色粉末用水和乙醇洗涤以除去杂质,离心干燥得产品;
(2)UIO-66(NH2)的制备:将ZrCl4和2-氨基-对苯二甲酸溶解在DMF(50 mL)中,然后溶液转移到100mL高压釜中,将高压釜密封并在120℃的烘箱中加热24h。得到的样品用无水甲醇清洗几次,以确保封闭的DMF分子除去,然后在真空(100℃,12h)下干燥;
(3)UIO-66(NH2)掺杂颗粒状Ag/AgBr复合光催化剂的制备:将步骤(2) 中干燥后的一定质量的UIO-66(NH2)放入40mL去离子水中,超声30min至混匀浑浊状态,在避光条件下逐滴加入硝酸银水溶液,剧烈搅拌一小时,使Ag+最大程度吸附在UIO-66(NH2)表面上,然后在避光条件下逐滴加入溴化钠水溶液,搅拌3h。将所得淡黄色粉末用水和乙醇洗涤以除去杂质,离心干燥得产品;
进一步地,所述的步骤(1)中AgNO3与NaBr的摩尔比为1:1;
进一步地,所述的步骤(2)中ZrCl4和2-氨基-对苯二甲酸的摩尔比为1:1;
进一步地,所述的步骤(3)中UIO-66(NH2):Ag/AgBr质量比分别为1:1, 1:2,1:3,分别标记为UIO-66(NH2)/Ag/AgBr-1,UIO-66(NH2)/Ag/AgBr-2, UIO-66(NH2)/Ag/AgBr-3。
进一步地,所述的步骤(3)中AgNO3与NaBr的摩尔比为1:1.1以确保附着在UIO-66(NH2)上的Ag+完全反应。
UIO-66(NH2)/Ag/AgBr复合催化剂的应用,用于光催化降解甲基橙(MO) 溶液,按照下述步骤进行:
称取25mg催化剂放入试管中,加入50mL 12.5mg/L MO溶液,用带有420 nm滤光片的500W氙灯作为光源,进行光催化降解反应。暗反应时间为30min,光照后,依次5min,5min,5min,10min,10min,10min,20min取7次样,进行离心,进而测其吸光度。
本发明的有益效果是:该制备方法较为简单,制备条件容易控制,所制备的 UIO-66(NH2)/Ag/AgBr复合光催化剂具有无污染,催化效率高等优点,具有一定的应用价值。
附图说明
下面结合附图对本发明进一步说明。
图1是本发明实施例1制备得到的UIO-66(NH2)的扫描电镜图(a)和 UIO-66(NH2)/Ag/AgBr复合光催化剂的扫描电镜图(b);
图2是本发明实施例1制备得到的UIO-66(NH2)/Ag/AgBr复合光催化剂的X 射线衍射图;
图3是本发明实施例1制备得到的UIO-66(NH2)/Ag/AgBr复合光催化剂降解甲基橙(MO)的活性图。
具体实施方式
现在结合具体实施例对本发明作进一步说明,以下实施例旨在说明本发明而不是对本发明的进一步限定。
实施例1
(1)颗粒状Ag/AgBr的制备:将AgNO3(0.1699g,1mmol)避光溶解在 30mL去离子水中,搅拌1h,将NaBr(0.1029g,1mmol)溶解于30mL去离子水,逐滴加入上述避光搅拌的硝酸银水溶液中,在避光的条件下将混合溶液搅拌3h,将所得淡黄色粉末用水和乙醇洗涤以除去杂质,离心干燥得产品;
(2)UIO-66(NH2)的制备:将ZrCl4(0.2332g,1.0mmol)和2-NH2-对苯二甲酸(0.1812g,1.0mmol)溶解在DMF(50mL)中,然后溶液转移到100 mL高压釜中,将高压釜密封并在120℃的烘箱中加热24h。得到的样品用无水甲醇清洗几次,以确保封闭的DMF分子除去,然后在真空(100℃,12h)下干燥;
(3)UIO-66(NH2)掺杂颗粒状Ag/AgBr复合光催化剂的制备:将步骤(2) 中干燥后的0.1g的UIO-66(NH2)放入40mL去离子水中,超声30min至混匀浑浊状态,在避光条件下逐滴加入AgNO3(0.0904g,0.53mmol)10mL水溶液,剧烈搅拌1h,使Ag+最大程度吸附在UIO-66(NH2)表面上,然后在避光条件下逐滴加入NaBr(0.0603g,0.58mmol)10mL水溶液,搅拌3h。将所得淡黄色粉末用水和乙醇洗涤以除去杂质,离心干燥得产品;
扫描电镜图如图1所示,从图(a)可以看出,本实施方式制备的UIO-66(NH2) 为片层状,从图(b)可以看出,本实施方式制备的UIO-66(NH2)掺杂颗粒状硫溴化银复合光催化剂的形貌为片层状UIO-66(NH2)表面负载颗粒状溴化银,且分布较为均匀。
X射线衍射图谱如图2所示,由图可知,制备的UIO-66(NH2)掺杂颗粒状溴化银复合光催化剂XRD衍射图中可看到在7.3°,8.36°出现UIO-66(NH2)的特征衍射峰,26.62°,30.84°,44.28°,55.12°,64.48°与73.2°是颗粒状溴化银的特征衍射峰。因此,可以证明UIO-66(NH2)与颗粒状溴化银复合在一起,并且未改变自身晶型,这与电镜的结果一致。
(4)光催化降解甲基橙(MO)
分别称取25mg不同催化剂放入试管中,加入50ml 12.5mg/L MO溶液,用带有420nm滤光片的500W氙灯作为光源,进行光催化降解反应。暗反应时间为30min,光照以后,依次5min,5min,5min,10min,10min,10min, 20min取7次样,并在5000rpm条件下高速离心,取上层清液用紫外可见分光光度计测其浓度变化。由图3可见,在65分钟内孔雀石绿降解率以达到96%,可见所制备的UIO-66(NH2)/Ag/AgBr复合光催化剂具有较高的光催化活性。
Claims (5)
1.一种UIO-66(NH2)掺杂颗粒状Ag/AgBr复合光催化剂的制备方法,其特征在于,包括以下步骤:
(1)颗粒状Ag/AgBr的制备:将AgNO3避光溶解在30mL去离子水中,搅拌1h,将NaBr溶解于30ml去离子水,逐滴加入上述避光搅拌的硝酸银水溶液中,在避光的条件下将混合溶液搅拌3h,将所得淡黄色粉末用水和乙醇洗涤以除去杂质,离心干燥得产品;
(2)UIO-66(NH2)的制备:将ZrCl4和2-氨基-对苯二甲酸溶解在DMF(50mL)中,然后溶液转移到100mL高压釜中,将高压釜密封并在120℃的烘箱中加热24h。得到的样品用无水甲醇清洗几次,以确保封闭的DMF分子除去,然后在真空(100℃,12h)下干燥;
(3)UIO-66(NH2)掺杂颗粒状Ag/AgBr复合光催化剂的制备:将步骤(2)中干燥后的一定质量的UIO-66(NH2)放入40ml去离子水中,超声30min至混匀浑浊状态,在避光条件下逐滴加入硝酸银水溶液,剧烈搅拌一小时,使Ag+最大程度吸附在UIO-66(NH2)表面上,然后在避光条件下逐滴加入溴化钠水溶液,搅拌3h。将所得淡黄色粉末用水和乙醇洗涤以除去杂质,离心干燥得产品。
2.根据权利要求1所述的一种UIO-66(NH2)掺杂颗粒状Ag/AgBr复合光催化剂的制备方法,其特征是:所述的步骤(1)中AgNO3与NaBr的摩尔比为1:1。
3.根据权利要求1所述的一种UIO-66(NH2)掺杂颗粒状Ag/AgBr复合光催化剂的制备方法,其特征是:所述的步骤(2)中ZrCl4和2-氨基-对苯二甲酸的摩尔比为1:1。
4.根据权利要求1所述的一种UIO-66(NH2)掺杂颗粒状Ag/AgBr复合光催化剂的制备方法,其特征是:所述的步骤(3)中颗粒状Ag/AgBr的质量为0~2g,且UIO-66(NH2):Ag/AgBr的质量比分别为1:1,1:2,1:3,分别标记为UIO-66(NH2)/Ag/AgBr-1,UIO-66(NH2)/Ag/AgBr-2,UIO-66(NH2)/Ag/AgBr-3。
5.根据权利要求1所述的一种UIO-66(NH2)掺杂颗粒状Ag/AgBr复合光催化剂的制备方法,其特征是:沉淀法常温避光制备。
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