CN114471727B - 一种Au@NH2-MIL-125(Cu/Ti)光催化剂及其制备方法和应用 - Google Patents
一种Au@NH2-MIL-125(Cu/Ti)光催化剂及其制备方法和应用 Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
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- 150000001879 copper Chemical class 0.000 claims abstract description 9
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Abstract
本发明提供一种Au@NH2‑MIL‑125(Cu/Ti)光催化剂及其制备方法和应用,该光催化剂的制备是以2‑氨基对苯二甲酸为原料,先和铜盐、钛酸四丁酯反应获得NH2‑MIL‑125(Cu/Ti)中间体;NH2‑MIL‑125(Cu/Ti)中间体再在溶剂中与金离子复合形成Au3+@NH2‑MIL‑125(Cu/Ti)光催化剂。本申请的光催化剂与原始NH2‑MIL‑125(Ti)相比,在可见光照射下5小时内,Au@NH2‑MIL‑125(Cu/Ti)的产氢量是NH2‑MIL‑125(Ti)的至少7.9倍,是现有光催化产氢材料15BTC的至少2.4倍。在NO去除率方面,Au@NH2‑MIL‑125(Cu/Ti)是NH2‑MIL‑125(Ti)去除率的至少1.7倍,是现有P25材料去除率的至少1.45倍。并且制备方法操作简单、条件温和、设备要求低,是一种环保简易的制备方法。
Description
技术领域
本发明属于光催化剂技术领域,具体涉及一种Au@NH2-MIL-125(Cu/Ti)光催化剂及其制备方法和应用。
背景技术
随着社会的发展,化石燃料的过度开采和耗竭造成能源问题,化石燃料燃烧释放的温室气体造成环境问题。我们迫切需要寻找可再生替代能源或者开发环境友好型技术来解决上述问题。在可再生替代能源中,氢能是最有前景的一种。在目前的研究中,光催化技术是获取氢能最为常见的方法。此外,光催化技术还用于去除NO和其他污染物,以解决环境恶化问题。在光催化技术中,光催化剂至关重要。目前的光催化剂存在光利用率低,光生载流子易复合等缺点,导致其光催化产氢或NO去除效率低,并且目前能同时用于光催化产氢和 NO去除的光催化剂甚少。因此,寻找一种既能分解水氢,又能去除NO的高效光催化剂仍然是一个巨大的挑战。
发明内容
针对现有技术存在的问题,本发明提供一种Au@NH2-MIL-125(Cu/Ti)光催化剂及其制备方法和应用,该光催化剂具有优异的光催化特性和NO降解性能。本发明的技术方案为:
第一方面,本发明提供一种Au@NH2-MIL-125(Cu/Ti)光催化剂的制备方法,是以2-氨基对苯二甲酸为原料,先和铜盐、钛酸四丁酯反应获得 NH2-MIL-125(Cu/Ti)中间体;NH2-MIL-125(Cu/Ti)中间体再在溶剂中与金离子复合形成Au3+@NH2-MIL-125(Cu/Ti)光催化剂。
进一步的,所述制备方法具体包括以下步骤:
(1)将2-氨基对苯二甲酸溶于溶剂一中,再加入铜盐溶液混合均匀,最后加入钛酸四丁酯混合均匀;将混合物于110~160℃保温搅拌20~24h后,静置冷却至室温,离心得到固体;将固体采用溶剂一洗涤,并于80~100℃下真空干燥10~12h,获得NH2-MIL-125(Cu/Ti)中间体;
(2)将NH2-MIL-125(Cu/Ti)中间体溶于蒸馏水中,加入氯金酸溶液搅拌5-8 h后,用蒸馏水离心洗涤;将所得固体在50~80℃下真空干燥6~12h,得到 Au3+@NH2-MIL-125(Cu/Ti)粗品;
(3)将Au3+@NH2-MIL-125(Cu/Ti)粗品分散于蒸馏水中,加入葡萄糖搅拌 1~6h后用蒸馏水离心洗涤,并将所得固体在50~80℃下真空干燥6~12h,即得。
进一步地,所述步骤(1)中2-氨基对苯二甲酸、铜盐、钛酸四丁酯的摩尔比为(3~5):(0.5%-2%):1。
进一步地,所述溶剂一为DMF与甲醇按照体积比为(0.5~1):1的混合溶液。
进一步地,所述铜盐溶液选自硝酸铜或醋酸铜的水溶液。
进一步地,所述步骤(2)中氯金酸加入量为NH2-MIL-125(Cu/Ti)中间体质量的0.25%~1%。
进一步地,所述Au3+@NH2-MIL-125(Cu/Ti)与葡萄糖的质量比为(0.5~0.8): 1。
第二方面,本发明提供一种Au@NH2-MIL-125(Cu/Ti)光催化剂,是采用上述制备方法获得。
第三方面,本发明提供上述Au@NH2-MIL-125(Cu/Ti)光催化剂用于光催化产氢或光催化NO去除。
与现有技术相比,本发明具有以下突出优点和积极效果:
1、本发明提供的制备方法采用金属有机骨架NH2-MIL-125(Cu/Ti)与氯金酸在室温下搅拌制得Au3+@NH2-MIL-125(Cu/Ti),再通过葡萄糖还原制得 Au@NH2-MIL-125(Cu/Ti)光催化剂。在Au@NH2-MIL-125(Cu/Ti)光催化剂中, Cu离子部分取代NH2-MIL-125(Ti)中的Ti离子形成混合中心金属簇,可改变 MOF的电子结构,扩大其光吸收范围。等离子体Au纳米粒子被约束在 NH2-MIL-125(Cu/Ti)的框架中,可以抑制纳米粒子的团聚,同时等离子体效应在光照下能在Au表面产生大量的热电子,加速电荷分离,抑制光生电子和空穴的复合,从而提升光催化析氢效果和光催化NO去除效果。
2、与原始NH2-MIL-125(Ti)相比,在可见光照射下5小时内, Au@NH2-MIL-125(Cu/Ti)的产氢量是NH2-MIL-125(Ti)的至少7.9倍,是现有光催化产氢材料15BTC的至少2.4倍。在NO去除率方面, Au@NH2-MIL-125(Cu/Ti)是NH2-MIL-125(Ti)去除率的至少1.7倍,是现有P25 材料去除率的至少1.45倍。
3、本发明提供的制备方法操作简单、条件温和、设备要求低,是一种环保简易的制备方法。
附图说明
图1为本发明对比例1的NH2-MIL-125(Ti)、实施例1的NH2-MIL-125(Cu/Ti)和Au@NH2-MIL-125(Cu/Ti)的XRD谱图。
图2为本发明对比例1的NH2-MIL-125(Ti)、实施例1的NH2-MIL-125(Cu/Ti)和 Au@NH2-MIL-125(Cu/Ti)的FT-IR谱图。
图3为本发明实施例1制备的Au@NH2-MIL-125(Cu/Ti)的Cu2p3/2XPS谱图。
图4为本发明实施例1制备的Au@NH2-MIL-125(Cu/Ti)的Au4fXPS谱图。
图5为本发明对比例1的NH2-MIL-125(Ti)、实施例1的NH2-MIL-125(Cu/Ti)和 Au@NH2-MIL-125(Cu/Ti)的光催化产氢图。
图6为本发明对比例1的NH2-MIL-125(Ti)、实施例1的NH2-MIL-125(Cu/Ti)和 Au@NH2-MIL-125(Cu/Ti)的光催化NO去除图。
具体实施方式
在本发明的描述中,需要说明的是,实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
下面结合附图和具体实施方式对本发明作进一步详细的说明,以帮助本领域的技术人员对本发明的发明构思、技术方案有更完整、准确和深入的理解,本发明的保护范围包括但不限于以下实施例,在不偏离本申请的精神和范围的前提下任何对本发明的技术方案的细节和形式所做出的修改均落入本发明的保护范围内。
实施例1
本实施例提供一种Au@NH2-MIL-125(Cu/Ti)光催化剂的制备方法,具体如下:
Au@NH2-MIL-125(Cu/Ti)光催化剂的制备:
S1、制备NH2-MIL-125(Cu/Ti)。
1)将2-氨基对苯二甲酸(1.086g,6mmol)溶解于20mL无水N,N-二甲基甲酰胺和无水甲醇(v=1:1)混合溶液中,搅拌20min。再加入4.425mL的硝酸铜溶液(0.023mmol),搅拌30min,然后加入钛酸四丁酯(0.52mL,1.5 mmol),搅拌10min,将混合物置于烘箱中150℃保持20h后,静置冷却至室温,离心得到固体;
2)将1)中离心得到的固体分别用DMF和甲醇离心洗涤3~4次,并在80℃下真空干燥10h,即得NH2-MIL-125(Cu/Ti)。
S2、制备Au3+@NH2-MIL-125(Cu/Ti)。
将NH2-MIL-125(Cu/Ti)(100mg)分散于10mL蒸馏水中,在加入0.5mg氯金酸,室温下搅拌6h后,用蒸馏水离心洗涤四次;将所得固体在80℃下真空干燥12h,即得Au3+@NH2-MIL-125(Cu/Ti)。
S3、将80mgAu3+@NH2-MIL-125(Cu/Ti)分散于10mL蒸馏水中,加入100 mg葡萄糖搅拌4h后用蒸馏水离心洗涤,并将所得固体在80℃下真空干燥12 h,得到所述Au@NH2-MIL-125(Cu/Ti)光催化剂。
实施例2
本实施例提供一种Au@NH2-MIL-125(Cu/Ti)光催化剂的制备方法,与实施例1不同的是:硝酸铜与钛酸四丁酯的摩尔比为0.5%,其它同实施例1。
实施例3
本实施例提供一种Au@NH2-MIL-125(Cu/Ti)光催化剂的制备方法,与实施例1不同的是:硝酸铜与钛酸四丁酯的摩尔比为2%,其它同实施例1。
实施例4
本实施例提供一种Au@NH2-MIL-125(Cu/Ti)光催化剂的制备方法,与实施例1不同的是:氯金酸与NH2-MIL-125(Cu/Ti)的质量比为1%,其它同实施例1。
实施例5
本实施例提供一种Au@NH2-MIL-125(Cu/Ti)光催化剂的制备方法,与实施例1不同的是:Au3+@NH2-MIL-125(Cu/Ti)与葡萄糖的质量比为0.5:1,其它同实施例1。
实施例6
本实施例提供一种Au@NH2-MIL-125(Cu/Ti)光催化剂的制备方法,与实施例1不同的是:采用醋酸铜水溶液,并且醋酸铜与钛酸四丁酯的摩尔比为3:1,其它同实施例1。
对比例1
本对比例提供一种Au@NH2-MIL-125(Cu/Ti)光催化剂的制备方法,具体如下:
NH2-MIL-125(Ti)的制备:
将2-氨基对苯二甲酸(1.086g,6mmol)溶解于20mL无水N,N-二甲基甲酰胺和无水甲醇(v=1:1)混合溶液中,将混合物搅拌20min,向其加入钛酸四丁酯(0.52mL,1.5mmol),然后在不锈钢高压灭菌器中150℃热处理20h 后,静置冷却至室温;过滤得到的固体分别用DMF和甲醇离心洗涤各3-4次,并在真空干燥,即得NH2-MIL-125(Ti)。
性能测试及分析
将实施例1制备的NH2-MIL-125(Cu/Ti)和Au@NH2-MIL-125(Cu/Ti)以及对比例制备的NH2-MIL-125(Ti)三种材料进行分析测试。
三种材料的XRD谱图如图1所示,FT-IR谱图(傅里叶变换红外光谱仪) 如图2所示。Au@NH2-MIL-125(Cu/Ti)材料的Cu 2p3/2XPS谱图如图3所示,以及Au 4fXPS谱图如图4所示。结合XRD和FT-IR可以证实掺杂Cu以及负载 Au纳米粒子后,NH2-MIL-125(Ti)的晶体结构未被破坏。XPS显示了Cu和Au 存在的价态,说明Cu离子与Au纳米粒子的成功加入。以上表征结果,证明了 Au@NH2-MIL-125(Cu/Ti)材料的成功制备。Cu离子的加入使NH2-MIL-125(Ti) 中形成混合中心金属簇,可改变MOF的电子结构,扩大其光吸收范围。等离子体Au纳米粒子被约束在NH2-MIL-125(Cu/Ti)的框架中,可以抑制纳米粒子的团聚,同时等离子体效应在光照下能在Au表面产生大量的热电子,可以抑制光生电子和空穴的复合,从而提升光催化析氢效果和光催化NO去除效果。
1、光催化产氢性能测试
向石英反应器中分别加入2.5mL三乙醇胺作为牺牲剂、10mg的实施例 1~6制备的NH2-MIL-125(Cu/Ti)和Au@NH2-MIL-125(Cu/Ti)材料以及对比例1 制备的NH2-MIL-125(Ti)以及文献报道的15BTC材料、12.6mL乙腈0.4mL作为质子源、0.5mL氯铂酸溶液作为助催化剂前驱体,再将石英反应器加盖并通入氮气鼓泡,脱氧20分钟。然后接入产氢光催化系统中,循环冷凝水保持 6℃。将接有石英反应器的产氢光催化系统抽真空。在石英反应器上部5cm处放置氙灯光源,开启光源,待反应半小时后,在光源处加入420nm截止滤光片。每半个小时取一次样通过产氢光催化系统进入气相色谱中,检测氢气的量。这几种MOF材料的产氢量(单位为μmol/g)如表1所示和图5所示。
表1多种材料的光催化产氢量比较
注:15BTC产氢量的文献出处为F.Li,D.Wang,Q.Xing,G.Zhou,S.Liu,Y.Li,L.Zheng,P.Ye,J.Zou,Design and Syntheses of MOF/COF Hybrid Materials viaPostsynthetic Covalent Modification:An Efficient Strategy to Boost theVisible-Light-DrivenPhotocatalytic Performance,Appl.Catal.B Environ.243(2019)621-628.
从表1和图5可知,NH2-MIL-125(Ti)表现出低的H2产氢量,而本发明制备的Au@NH2-MIL-125(Cu/Ti)具有最大产氢量为5193.4μmol/g(实施例1),是 NH2-MIL-125(Ti)产氢量的11.8倍,是NH2-MIL-125(Cu/Ti)最高产氢量的1.76 倍,是现有光催化产氢材料15BTC的3.6倍;Au@NH2-MIL-125(Cu/Ti)最低产氢量为3459.1μmol/g(实施例6),是NH2-MIL-125(Ti)产氢量的7.9倍,是 NH2-MIL-125(Cu/Ti)最高产氢量的1.17倍,是现有光催化产氢材料15BTC的2.4 倍。
2、光催化NO性能测试
称取200mg实施例1~6制备的NH2-MIL-125(Cu/Ti)和Au@NH2-MIL-125(Cu/Ti)材料以及对比例1制备的NH2-MIL-125(Ti)以及现有的 P25材料,将这几种材料都均分为两份,并分别放入两个玻璃皿中,然后加入 10mL乙醇进行超声分散,然后在60℃下干燥玻璃皿,直到所有溶剂蒸发。冷却至室温后,将这两个干燥皿用于光催化NO去除实验。该反应在连续流动反应器中进行,反应器上方垂直放置两个普通LED灯(12W)。在每次试验期间,首先通入NO(初始浓度为100ppm),然后打开空气发生器将NO浓度稀释至 530ppb。待气体达到吸附-解吸平衡后,开灯进行光照反应,每个样品光照反应半小时。通过NO-NO2-NOx分析仪(ThermoScientific,42iTL)进行测试。这几种材料的NO去除率如表2和图6所示。
表2多种材料的光催化去除NO性能比较
材料 | 去除率(%) |
NH2-MIL-125(Ti)(对比例1) | 17.4 |
NH2-MIL-125(Cu/Ti)(实施例1/实施例4/实施例5) | 25.2 |
NH2-MIL-125(Cu/Ti)(实施例2) | 20.2 |
NH2-MIL-125(Cu/Ti)(实施例3) | 19.8 |
NH2-MIL-125(Cu/Ti)(实施例6) | 23.4 |
Au@NH2-MIL-125(Cu/Ti)(实施例1) | 43 |
Au@NH2-MIL-125(Cu/Ti)(实施例2) | 33.6 |
Au@NH2-MIL-125(Cu/Ti)(实施例3) | 31.2 |
Au@NH2-MIL-125(Cu/Ti)(实施例4) | 30.5 |
Au@NH2-MIL-125(Cu/Ti)(实施例5) | 34.3 |
Au@NH2-MIL-125(Cu/Ti)(实施例6) | 29.4 |
P25 | 20.2 |
注:P25去除NO性能数据参考文献:B.Lei,W.Cui,J.Sheng,H.Wang,P.Chen,J. Li,Y.Sun,F.Dong,Synergistic effects of crystal structure and oxygen vacancy onBi2O3 polymorphs:intermediates activation,photocatalytic reaction efficiency,and conversionpathway,Sci.Bull.65(2020)467-476.
从表2和图6可知,NH2-MIL-125(Ti)的NO去除率是最低的,本发明制备的Au@NH2-MIL-125(Cu/Ti)的NO去除率在这几种材料中都很显著,是 NH2-MIL-125(Ti)去除率的至少1.7倍,是现有P25材料去除率的至少1.45倍。
综上,本发明制备的Au@NH2-MIL-125(Cu/Ti)表现出优异的光催化产氢性能和光催化去除NO性能,可归因于掺杂的Cu离子改变了中心金属簇的构成,导致电子结构的变化,提高了电荷分离速率,其次Au纳米粒子的表面等离子体效应有利于光催化性能的提升。
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,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。因此,本发明专利的保护范围应以所附权利要求为准。
Claims (8)
1.一种Au@NH2-MIL-125(Cu/Ti)光催化剂的制备方法,其特征在于:是以2-氨基对苯二甲酸为原料,先和铜盐、钛酸四丁酯反应获得NH2-MIL-125(Cu/Ti)中间体;NH2-MIL-125(Cu/Ti)中间体再在溶剂中与金离子复合形成Au3+@NH2-MIL-125(Cu/Ti)光催化剂;所述制备方法具体包括以下步骤:
(1)将2-氨基对苯二甲酸溶于溶剂一中,再加入铜盐溶液混合均匀,最后加入钛酸四丁酯混合均匀;将混合物于110~160℃保温搅拌20~24h后,静置冷却至室温,离心得到固体;将固体采用溶剂一洗涤,并于80~100℃下真空干燥10~12h,获得NH2-MIL-125(Cu/Ti)中间体;
(2)将NH2-MIL-125(Cu/Ti)中间体溶于蒸馏水中,加入氯金酸溶液搅拌5-8h后,用蒸馏水离心洗涤;将所得固体在50~80℃下真空干燥6~12h,得到Au3+@NH2-MIL-125(Cu/Ti)粗品;
(3)将Au3+@NH2-MIL-125(Cu/Ti)粗品分散于蒸馏水中,加入葡萄糖搅拌1~6h后用蒸馏水离心洗涤,并将所得固体在50~80℃下真空干燥6~12h,即得。
2.根据权利要求1所述的一种Au@NH2-MIL-125(Cu/Ti)光催化剂的制备方法,其特征在于:所述步骤(1)中2-氨基对苯二甲酸、铜盐、钛酸四丁酯的摩尔比为(3~5):(0.5%-2%):1。
3.根据权利要求1所述的一种Au@NH2-MIL-125(Cu/Ti)光催化剂的制备方法,其特征在于:所述溶剂一为DMF与甲醇按照体积比为(0.5~1):1的混合溶液。
4.根据权利要求2所述的一种Au@NH2-MIL-125(Cu/Ti)光催化剂的制备方法,其特征在于:所述铜盐溶液选自硝酸铜或醋酸铜的水溶液。
5.根据权利要求1所述的一种Au@NH2-MIL-125(Cu/Ti)光催化剂的制备方法,其特征在于:所述步骤(2)中氯金酸加入量为NH2-MIL-125(Cu/Ti)中间体质量的0.25%~1%。
6.根据权利要求1所述的一种Au@NH2-MIL-125(Cu/Ti)光催化剂的制备方法,其特征在于:所述Au3+@NH2-MIL-125(Cu/Ti)与葡萄糖的质量比为(0.5~0.8):1。
7.一种Au@NH2-MIL-125(Cu/Ti)光催化剂,其特征在于:是采用权利要求1~6任意一项所述的制备方法获得。
8.权利要求7所述的Au@NH2-MIL-125(Cu/Ti)光催化剂用于光催化产氢或光催化NO去除。
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