CN113231101A - 一种Cu-NM-101(Fe)光催化剂的制备及应用 - Google Patents
一种Cu-NM-101(Fe)光催化剂的制备及应用 Download PDFInfo
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
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Abstract
本发明公开了一种Cu‑NM‑101(Fe)光催化剂的制备及应用，属于光催化领域。金属有机框架(MOF)由于其多孔网络结构、良好的稳定性以及超高的比表面积受到越来越多的关注，但由于光生载流子的快速重组和低效的太阳能利用，其应用受到很大限制。本发明向带‑NH2的MOF中引入无贵金属铜元素，其中Cu物种与‑NH2形成新颖的从配体到连接体金属的电子转移途径，可抑制光生电子‑空穴对的复合以及提高电子的转移速率，改善光催化活性。通过调节醋酸铜的浓度，发现醋酸铜浓度为6mmol/L时，Cu‑NM‑101(Fe)光催化产氢效果最高。
Description
技术领域
本发明涉及光催化产氢技术领域，具体涉及一种Cu-NM-101(Fe)光催化剂的制备及应用。
背景技术
利用太阳能通过半导体催化剂分解水制氢是解决能源短缺和环境污染问题的绿色有效策略。在过去的几十年中，各种半导体催化剂，包括二氧化钛、石墨相氮化碳和异质结光催化剂，已经被广泛地设计和用于光催化析氢。然而，大多数半导体催化剂光吸收范围窄，电子转移速率慢，限制了其光催化活性。因此，研究催化材料对光催化产氢技术有着重要的意义。
近年来，金属有机骨架(MOF)是一种由多种有机配体和金属离子或团簇组成的新型多孔材料，具有比表面积大、结构稳定、孔结构丰富等优点，在光催化领域有着广泛的应用。MOF基材料，特别是MOFs衍生的磷化物或硫化物，通常可以作为助催化剂，实现光催化制氢的快速电子转移。然而，原始的MOF通常需要在高温下煅烧以进一步修饰金属节点，伴随着复杂的合成步骤和较低的原子利用效率。因此，如何寻找一种更方便、更有效的方法制备低成本、富稀土的MOFs光催化剂以提高其催化效果，是本领域技术人员研究的方向。
发明内容
本发明的目的在于提供一种Cu-NM-101(Fe)光催化剂的制备方法，该方法工艺简单、成本低廉，制备的Cu-NM-101(Fe)光催化剂催化活性较高
为了解决上述技术问题，本发明采用的技术方案是这样的：
一种Cu-NM-101(Fe)光催化剂的制备方法，包括如下步骤：
(1)将醋酸铜溶于乙醇溶液中，加入NH2-MIL-101(Fe)搅拌1h后，用乙醇离心洗涤三次；
(2)将所得固体在80℃下真空干燥12h后，得到所述Cu-NM-101(Fe)光催化剂。
其中，所述步骤(1)中醋酸铜的浓度为6mmol/L，NH2-MIL-101(Fe)质量为150mg。
进一步，NH2-MIL-101(Fe)采用如下方法制得：
1)将2-氨基对苯二甲酸溶于DMF中，再加入六水三氯化铁，搅拌10min将混合物置于烘箱中120℃保持20h后，静置冷却至室温；
2)将1)中离心得到的固体分别用DMF和甲醇离心洗涤三次；
3)将2)中得到的固体在100℃下真空干燥12h，即得NH2-MIL-101(Fe)。
其中所述步骤1)中，2-氨基对苯二甲酸与六水三氯化铁的摩尔比为：1:2
本发明还提供一种Cu-NM-101(Fe)材料的应用，将制得的Cu-NM-101(Fe)光催化剂用于光催化分解水制氢。
与现有技术相比，本发明具有如下优点：
1、本发明提供的Cu-NM-101(Fe)光催化剂的制备方法，采用金属有机骨架NH2-MIL-101(Fe)与醋酸铜在室温下搅拌即可制得Cu-NM-101(Fe)光催化剂，其中Cu物种与-NH2配位形成一种新颖的电子转移路径，加速电子转移，因而具有优异的电催化析氢效果。
2、与原始NH2-MIL-101(Fe)相比，在可见光照射下5小时内，Cu-NM-101(Fe)的产氢量提高了4.06倍。
3、本发明操作简单、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是本发明实施例1-5的NH2-MIL-101(Fe)和Cu-NM-101(Fe)的XRD谱图。
图2是本发明实施例1-5的NH2-MIL-101(Fe)和Cu-NM-101(Fe)的FT-IR谱图。
图3是本发明实施例3的Cu-NM-101(Fe)的Cu 2p2/3XPS谱图。
图4是本发明实施例1和3的NH2-MIL-101(Fe)和Cu-NM-101(Fe)的CV谱图。
图5是本发明实施例1-5的NH2-MIL-101(Fe)和Cu-NM-101(Fe)的光催化产氢图。
具体实施方式
下面将结合附图及实施例对本发明作进一步说明。
实施例1：
NH2-MIL-101(Fe)的制备方法，包括如下步骤：
1)将FeCl3·6H2O(541mg，2mmol)、2-氨基对苯二甲酸(181.2mg，1mmol)溶解于10mL无水N，N-二甲基甲酰胺中。然后将混合物搅拌10分钟，然后在不锈钢高压灭菌器中以120℃温度热处理20小时后，静置冷却至室温；
2)将1)中过滤得到的固体分别用DMF和甲醇离心洗涤各三次；
3)将2)中得到的固体在真空干燥，即得NH2-MIL-101(Fe)。
实施例2：
Cu-NM-101(Fe)光催化剂的合成，包括如下步骤：
(1)将NH2-MIL-101(Fe)(150mg)分散于20mL的Cu(OAc)2(3mM)乙醇溶液中，室温下搅拌1h；
(2)将上述产物用乙醇离心洗涤3次；
(3)得到的固体在80℃下干燥12h，即得3Cu-NM-101。
实施例3：
Cu-NM-101(Fe)光催化剂的合成，包括如下步骤：
(1)将NH2-MIL-101(Fe)(150mg)分散于20mL的Cu(OAc)2(6mM)乙醇溶液中，室温下搅拌1h；
(2)将上述产物用乙醇离心洗涤3次；
(3)得到的固体在80℃下干燥12h，即得6Cu-NM-101。
实施例4：
Cu-NM-101(Fe)光催化剂的合成，包括如下步骤：
(1)将NH2-MIL-101(Fe)(150mg)分散于20mL的Cu(OAc)2(9mM)乙醇溶液中，室温下搅拌1h；
(2)将上述产物用乙醇离心洗涤3次；
(3)得到的固体在80℃下干燥12h，即得9Cu-NM-101。
实施例5：
Cu-NM-101(Fe)光催化剂的合成，包括如下步骤：
(1)将NH2-MIL-101(Fe)(150mg)分散于20mL的Cu(OAc)2(12mM)乙醇溶液中，室温下搅拌1h；
(2)将上述产物用乙醇离心洗涤3次；
(3)得到的固体在80℃下干燥12h，即得12Cu-NM-101。
将实施例1-5得到的NH2-MIL-101(Fe)与Cu-NM-101(Fe)材料进行分析测试，其中，NH2-MIL-101(Fe)与Cu-NM-101(Fe)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(FT-IR))如图2所示，Cu 2p2/3的XPS谱图如图3所示，CV谱图如图4所示。结合XRD和FT-IR可以证实Cu物种的引入未破坏NH2-MIL-101(Fe)的晶体结构。XPS和CV证明了Cu物种混合价态的存在。
实施例6：
光催化产氢性能测试
向石英反应器中分别加入3mL三乙醇胺作为牺牲剂、10mg的实施例1～5中所得的NH2-MIL-101(Fe)或Cu-NM-101(Fe)材料、17mLH2O作为质子源、30mg曙红作为光敏剂，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10℃。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，每个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。实施例1～5制备的MOF材料的产氢量(单位为mmol/g/h)如表1所示。
| 实施例 | 产氢量(mmol/g/h) |
| 实施例1 | 1.42003 |
| 实施例2 | 3.56749 |
| 实施例3 | 5.77098 |
| 实施例4 | 4.37413 |
| 实施例5 | 4.61429 |
参见图5，实施例1表现出低的H2产氢量，而实施例3的催化剂的最大产氢量为5.77098mmol/g/h，是实施例1的4.06倍。优异的性能可归因于增强的可见光吸收和新颖的电子转移路径的形成。然而，从实施例4看出，随着Cu物种的浓度的增加，光催化活性降低，这可能时由于Cu物种过多，遮住了活性中心，从而降低光催化效率。
最后需要说明的是，以上实施例仅用以说明本发明的技术方案而非限制技术方案，本领域的普通技术人员应当理解，那些对本发明的技术方案进行修改或者等同替换，而不脱离本技术方案的宗旨和范围，均应涵盖在本发明的权利要求范围当中。
Claims (5)
1.一种Cu-NM-101(Fe)光催化剂的制备方法，其特征在于，包括如下步骤：
(1)将醋酸铜溶于乙醇溶液中，加入NH2-MIL-101(Fe)搅拌1h后，用乙醇离心洗涤三次；
(2)将所得固体在80℃下真空干燥12h后，得到所述Cu-NM-101(Fe)光催化剂。
2.根据权利要求1所述的Cu-NM-101(Fe)光催化剂的制备方法，其特征在于，所述步骤(1)中，所述醋酸铜的浓度为6mmol/L，NH2-MIL-101(Fe)质量为150mg。
3.根据权利要求1所述的Cu-NM-101(Fe)光催化剂的制备方法，其特征在于，所述NH2-MIL-101(Fe)采用如下方法制得：
1)将2-氨基对苯二甲酸溶于DMF中，再加入六水三氯化铁，搅拌10min将混合物置于烘箱中120℃保持20h后，静置冷却至室温；
2)将1)中离心得到的固体分别用DMF和甲醇离心洗涤三次；
3)将2)中得到的固体在100℃下真空干燥12h，即得NH2-MIL-101(Fe)。
4.根据权利要求3所述的Cu-NM-101(Fe)光催化剂的制备方法，其特征在于，所述步骤1)中，2-氨基对苯二甲酸与六水三氯化铁的摩尔比为：1:2。
5.Cu-NM-101(Fe)光催化剂的应用，其特征在于，将权利要求1-4任一项制备方法制得的Cu-NM-101(Fe)光催化剂用于光催化分解水制氢。
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| CN114768871A (zh) * | 2022-02-25 | 2022-07-22 | 武汉工程大学 | PANI/NH2-MIL-101(Fe)复合材料及其制备方法和应用 |
| CN115518690A (zh) * | 2022-07-28 | 2022-12-27 | 广东工业大学 | 一种Cu7S4-MOF复合材料及其制备方法和应用 |
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| CN114768871B (zh) * | 2022-02-25 | 2023-10-13 | 武汉工程大学 | PANI/NH2-MIL-101(Fe)复合材料及其制备方法和应用 |
| CN115518690A (zh) * | 2022-07-28 | 2022-12-27 | 广东工业大学 | 一种Cu7S4-MOF复合材料及其制备方法和应用 |
| CN115518690B (zh) * | 2022-07-28 | 2023-11-10 | 广东工业大学 | 一种Cu7S4-MOF复合材料及其制备方法和应用 |
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