CN115532297A - 一种异核双原子光催化材料及其制备方法 - Google Patents
一种异核双原子光催化材料及其制备方法 Download PDFInfo
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Abstract
本发明提供一种异核双原子催化材料,所述异核双原子催化材料以PCN纳米片作为载体,掺杂金属双原子。本发明提供了一个异核双原子催化材料及其便捷简单的合成方法,采用两种金属盐与尿素溶液混合干燥后直接烧结得到,不需要预先合成存在金属键的异核有机金属前体。
Description
技术领域
本发明属于光催化技术领域。涉及了一种异核双原子光催化材料及其制备方法。
背景技术
甲烷(CH4)是天然气的主要成分,其产生的全球变暖效应是CO2的20倍以上,而且在大气中的滞留时间长达10年,属于强温室气体;并且CH4易燃易爆,当空气中的CH4溶度 在5%~15%之间时,有爆炸的可能性,具有重大的安全隐患。由于甲烷中C-H键的固有惰性,传统上CH4向氧化合物的转化需要多个步骤和苛刻的反应条件,对于甲烷的活化反应常被称 为催化界的“圣杯”。因此,开发出结构明确的非贵金属基催化剂并通过简单的方法驱动CH4选择性的转化为醇。
PCN是一种经典的聚合物半导体材料,其形貌类似于石墨烯状呈二维纳米片层结构,其 中的C、N原子通过sp2杂化形成高度离域的π共轭体系。CN中的反键π轨道能够与某些金 属相互作用,接收金属d轨道的电子,从而形成反馈π键。基于前期研究工作,我们将金属Bi与W中心同时引入到PCN中,通过不同金属原子之间的电荷互补策略有效提高了W、Bi 双金属原子的负载量并实现了对W-Bi双原子催化剂的精准构筑。
本发明提供一种基于异核双原子的简易制备方法,在不添加氧化剂H2O2或O2的条件 下,水蒸气条件下成功将甲烷光氧化为液体燃料甲醇。
经检索发现一篇与本发明申请相似的专利文献,公开号为CN113782756A的中国专利提供 了一种二维材料担载单原子掺杂Au24M(Pt,Au,Pd)双金属团簇电催化剂,该催化剂优势在 于:本发明用于燃料电池阴极催化剂,该催化剂为单分散的Au25、Au24Pt、Au24Pd以团簇形 式负载于多孔二维材料,合成高效稳定的担载型单原子调控的双金属团簇催化剂;探索单原 子调控双金属团簇中掺杂原子种类、掺杂数目、掺杂位点等对其氧还原性能的影响,明确其 催化性能的差异,运用计算化学的手段,结合它们的具体结构,阐明催化机理,揭示团簇内 金属间协同作用对催化效果影响的规律,建立起单原子掺杂-团簇结构-电催化性能三者之间 的关联。该催化剂具有高效的电催化性能,为燃料电池提供了一种新的阴极催化材料,具有 良好的应用前景。
经对比,该方案与本案用途以及原料使用上存在一定差异。
发明内容
本发明旨在至少解决现有技术中存在的技术问题之一。为此,提供一种异核双原子光催 化剂的一锅、批量制备方法。该催化剂温和条件下,不添加额外的H2O2或O2实现水蒸气中CH4的高效光氧化,显著降低成本。
一种异核双原子催化材料,所述异核双原子催化材料以PCN纳米片作为载体,掺杂金属 双原子。
而且,所述金属双原子包括第一金属源和第二金属源,其中第一金属源在W、Cu、Fe的 结晶盐任选其一,其中第二金属源在Bi、In、Zn的结晶盐任选其一。
而且,所述第一金属源的结晶盐包括:Na2WO4·2H2O、Cu(NO3)2·3H2O、Fe(NO3)3·9H2O, 所述二金属源的结晶盐包括:Bi(NO3)3·5H2O、In(NO3)3·xH2O、Zn(NO3)2·6H2O。
本发明还提供一种异核双原子催化材料的制备方法,其制备方法是将尿素与第一金属源 中的任一结晶盐和第二金属源中的任一结晶盐在水中混合,搅拌均匀,旋蒸后烧结得到异核 双原子催化材料。
而且,所述尿素和第一金属源中的任一结晶盐和第二金属源中的任一结晶盐的摩尔比为 12500:1~2:1~2。
而且,所述搅拌稳定为室温,搅拌时间0.5~3h,旋蒸温度为70℃,混合烧结温度为450℃,时间4h。
一种异核双原子催化材料在光催化CH4的应用,在密封反应器中进行CH4氧化光催化, 采用气固反应,水在反应体系下层,异核双原子催化材料在反应体系上层,在光照下进行甲 烷光氧化反应,生成甲醇。
而且,所述水和异核双原子催化材料的用量比为5000:1~5。
而且,所述光照条件波长为全光谱模拟太阳光,用300W氙灯照射,光强为200mW·cm-2, 光照5h。
相对于现有技术,本发明具有如下有益效果:
(1)本发明开发了一个便捷简单的合成方法,采用两种金属盐与尿素溶液混合干燥后直 接烧结得到,不需要预先合成存在金属键的异核有机金属前体。
(2)能够实现甲烷光氧化为液态产物醇。催化过程中不需要使用牺牲剂与额外加入氧化 剂。
(3)本发明的异核双原子催化材料不含贵金属,合成成本低,安全性高。
(4)本发明可以实现双原子催化剂的大批量合成,同时不损害催化剂本身催化效率。
附图说明
图1为W-Bi-PCN的XRD图。
图2为W-Bi-PCN原子级分辨的HAADF-STEM图。
具体实施方式
以下结合具体的实施例进一步说明本发明的技术方案。
实施例1
本发明提供一种异核双原子催化剂材料,其制备方法包括如下步骤:
1)将7.5g尿素和0.2mL 0.1mol L-1Na2WO4·2H2O溶解在纯水中搅拌均匀;
2)将0.2mL 0.1mol L-1Bi(NO3)3·5H2O溶液缓慢滴加到上述溶液中,持续搅拌;
3)将混合液通过旋蒸去除水分,得到白色结晶固体;
4)将固体转移到氧化铝坩埚中,在马弗炉中加热至450℃,保持4h,升温速率 为5℃min-1;
5)将烧结好样品分散在1M HCl中搅拌,并多次用超纯水离心洗涤(离心机转速 为9000rpm,离心时间为5min);
6)将洗涤好样品进行冷冻干燥,得到催化剂样品(标记为W-Bi-PCN)。
结构表征:
对步骤6)制得的W-Bi-PCN进行结构表征,结果如下:
1)W-Bi-PCN纳米片
W-Bi-PCN纳米片的XRD图如图1所示。由图1可知,W-Bi-PCN纳米片出现了PCN的 特征峰,不存在金属单质和金属氧化物的特征峰,证明了W-Bi-PCN中金属中心没有团聚生 成纳米颗粒。
2)W-Bi-PCN纳米片
W-Bi-PCN纳米片的HAADF-STEM图如图2所示。HAADF-STEM图像显示出W-Bi-PCN 上有许多孤立的亮点,每个亮点对应一个W或Bi原子。在HAADF-STEM放大图像中可以 观察到W和Bi以明显的原子对形式存在。
综上所述:异核W和Bi金属中心以双原子形式均匀分布在PCN上,W-Bi-PCN被成功制备。
实施例2
根据此方法合成W-In-PCN异核光催化剂包括如下步骤制备方法:
1)将7.5g尿素和0.2mL 0.1mol L-1Na2WO4·2H2O溶解在纯水中搅拌均匀;
2)将0.2mL 0.1mol L-1In(NO3)3·xH2O溶液缓慢滴加到上述溶液中,持续搅拌;
3)将混合液通过旋蒸去除水分,得到白色结晶固体;
4)将固体转移到氧化铝坩埚中,在马弗炉中加热至450℃,保持4h,升温速率为 5℃min-1;
5)将烧结好样品分散在1M HCl中搅拌,并多次用超纯水离心洗涤(离心机转速为9000rpm,离心时间为5min);
6)将洗涤好样品进行冷冻干燥,得到催化剂样品(标记为W-In-PCN)。
实施例3
根据此方法合成W-Zn-PCN异核光催化剂包括如下步骤制备方法:
1)将7.5g尿素和0.2mL 0.1mol L-1Na2WO4·2H2O溶解在纯水中搅拌均匀;
2)将0.2mL 0.1mol L-1Zn(NO3)2·6H2O溶液缓慢滴加到上述溶液中,持续搅拌;
3)将混合液通过旋蒸去除水分,得到白色结晶固体;
4)将固体转移到氧化铝坩埚中,在马弗炉中加热至450℃,保持4h,升温速率为 5℃min-1;
5)将烧结好样品分散在1M HCl中搅拌,并多次用超纯水离心洗涤(离心机转速为9000rpm,离心时间为5min);
6)将洗涤好样品进行冷冻干燥,得到催化剂样品(标记为W-Zn-PCN)。
实施例4
根据此方法合成Cu-Bi-PCN异核光催化剂包括如下步骤制备方法:
1)将7.5g尿素和0.2mL 0.1mol L-1Cu(NO3)2·3H2O溶解在纯水中搅拌均匀;
2)将0.2mL 0.1mol L-1Bi(NO3)3·5H2O溶液缓慢滴加到上述溶液中,持续搅拌;
3)将混合液通过旋蒸去除水分,得到白色结晶固体;
4)将固体转移到氧化铝坩埚中,在马弗炉中加热至450℃,保持4h,升温速率为 5℃min-1;
5)将烧结好样品分散在1M HCl中搅拌,并多次用超纯水离心洗涤(离心机转速为9000rpm,离心时间为5min);
6)将洗涤好样品进行冷冻干燥,得到催化剂样品(标记为Cu-Bi-PCN)。
实施例5
根据此方法合成Cu-In-PCN异核光催化剂包括如下步骤制备方法:
1)将7.5g尿素和0.2mL 0.1mol L-1Cu(NO3)2·3H2O溶解在纯水中搅拌均匀;
2)将0.2mL 0.1mol L-1In(NO3)3·xH2O溶液缓慢滴加到上述溶液中,持续搅拌;
3)将混合液通过旋蒸去除水分,得到白色结晶固体;
4)将固体转移到氧化铝坩埚中,在马弗炉中加热至450℃,保持4h,升温速率为 5℃min-1;
5)将烧结好样品分散在1M HCl中搅拌,并多次用超纯水离心洗涤(离心机转速为9000rpm,离心时间为5min);
6)将洗涤好样品进行冷冻干燥,得到催化剂样品(标记为Cu-In-PCN)。
实施例6
根据此方法合成Cu-Zn-PCN异核光催化剂包括如下步骤制备方法:
1)将7.5g尿素和0.2mL 0.1mol L-1Cu(NO3)2·3H2O溶解在纯水中搅拌均匀;
2)将0.2mL 0.1mol L-1Zn(NO3)2·6H2O溶液缓慢滴加到上述溶液中,持续搅拌;
3)将混合液通过旋蒸去除水分,得到白色结晶固体;
4)将固体转移到氧化铝坩埚中,在马弗炉中加热至450℃,保持4h,升温速率为 5℃min-1;
5)将烧结好样品分散在1M HCl中搅拌,并多次用超纯水离心洗涤(离心机转速为9000rpm,离心时间为5min);
6)将洗涤好样品进行冷冻干燥,得到催化剂样品(标记为Cu-Zn-PCN)。
实施例7
根据此方法合成Fe-Bi-PCN异核光催化剂包括如下步骤制备方法:
1)将7.5g尿素和0.1mL 0.1mol L-1Fe(NO3)3·9H2O溶解在纯水中搅拌均匀;
2)将0.1mL 0.1mol L-1Bi(NO3)3·5H2O溶液缓慢滴加到上述溶液中,持续搅拌;
3)将混合液通过旋蒸去除水分,得到淡黄色结晶固体;
4)将固体转移到氧化铝坩埚中,在马弗炉中加热至450℃,保持4h,升温速率为 5℃min-1;
5)将烧结好样品分散在1M HCl中搅拌,并多次用超纯水离心洗涤(离心机转速为9000rpm,离心时间为5min);
6)将洗涤好样品进行冷冻干燥,得到催化剂样品(标记为Fe-Bi-PCN)。
实施例8
根据此方法合成Fe-In-PCN异核光催化剂包括如下步骤制备方法:
1)将7.5g尿素和0.1mL 0.1mol L-1Fe(NO3)3·9H2O溶解在纯水中搅拌均匀;
2)将0.1mL 0.1mol L-1In(NO3)3·xH2O溶液缓慢滴加到上述溶液中,持续搅拌;
3)将混合液通过旋蒸去除水分,得到淡黄色结晶固体;
4)将固体转移到氧化铝坩埚中,在马弗炉中加热至450℃,保持4h,升温速率为 5℃min-1;
5)将烧结好样品分散在1M HCl中搅拌,并多次用超纯水离心洗涤(离心机转速为9000rpm,离心时间为5min);
6)将洗涤好样品进行冷冻干燥,得到催化剂样品(标记为Fe-In-PCN)。
实施例9
根据此方法合成Fe-Zn-PCN异核光催化剂包括如下步骤制备方法:
1)将7.5g尿素和0.1mL 0.1mol L-1Fe(NO3)3·9H2O溶解在纯水中搅拌均匀;
2)将0.1mL 0.1mol L-1Zn(NO3)2·6H2O溶液缓慢滴加到上述溶液中,持续搅拌;
3)将混合液通过旋蒸去除水分,得到淡黄色结晶固体;
4)将固体转移到氧化铝坩埚中,在马弗炉中加热至450℃,保持4h,升温速率为 5℃min-1;
5)将烧结好样品分散在1M HCl中搅拌,并多次用超纯水离心洗涤(离心机转速为9000rpm,离心时间为5min);
检测实施例
将实施例1制备得到的W-Bi-PCN应用于光催化甲烷氧化制备甲醇。具体方法如下:
在1mL去离子水中加入1mg的W-Bi-PCN,超声后分散在100mg石英棉上,用275W温灯烘干。在高压釜内衬中加入去离子水5mL,将石英棉固定在纯水上方。用氮气(99.999%)连续 冒泡30分钟去除釜中空气,然后密封反应器,用CH4气体(99.999%)加压至0.5MPa,用300W 氙灯照射,光强为200mW·cm-2,光照5h后。以氩气为载气,用岛津GC-2014测定CO与CH4的产量。以氮气为载气,用岛津GC-2014定量测量CH3OH的产量,甲醇产量为250.8μmol·gcat -1。 用离子色谱法(DX-120,DIONEX)分析HCOOH的含量。
W-Bi-PCN用于光催化氧化CH4制备CH3OH。W-Bi-PCN对于光催化活化甲烷制备甲醇具有良好的光催化活性。对于单纯的PCN而言,缺少活化甲烷的活性位点,甲醇产率仅为 45μmol·gcat -1,不利于光催化甲烷活化。
本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原 理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保 护范围之内。
Claims (9)
1.一种异核双原子催化材料,其特征在于:所述异核双原子催化材料以PCN纳米片作为载体,掺杂金属双原子。
2.根据权利要求1所述的异核双原子催化材料,其特征在于:所述金属双原子包括第一金属源和第二金属源,其中第一金属源在W、Cu、Fe的结晶盐任选其一,其中第二金属源在Bi、In、Zn的结晶盐任选其一。
3.根据权利要求2所述的异核双原子催化材料,其特征在于:所述第一金属源的结晶盐包括:Na2WO4·2H2O、Cu(NO3)2·3H2O、Fe(NO3)3·9H2O,所述二金属源的结晶盐包括:Bi(NO3)3·5H2O、In(NO3)3·xH2O、Zn(NO3)2·6H2O。
4.一种如权利要求2所述的异核双原子催化材料的制备方法,其特征在于:其制备方法是将尿素与第一金属源中的任一结晶盐和第二金属源中的任一结晶盐在水中混合,搅拌均匀,旋蒸后烧结得到异核双原子催化材料。
5.根据权利要求4所述的异核双原子催化材料的制备方法,其特征在于:所述尿素和第一金属源中的任一结晶盐和第二金属源中的任一结晶盐的摩尔比为12500:1~2:1~2。
6.根据权利要求4所述的异核双原子催化材料的制备方法,其特征在于:所述搅拌稳定为室温,搅拌时间0.5~3h,旋蒸温度为70℃,混合烧结温度为450℃,时间4h。
7.一种如权利要求2所述的异核双原子催化材料在光催化CH4的应用,其特征在于:在密封反应器中进行CH4氧化光催化,采用气固反应,水在反应体系下层,异核双原子催化材料在反应体系上层,在光照下进行甲烷光氧化反应,生成甲醇。
8.根据权利要求7所述的异核双原子催化材料在光催化CH4的应用,其特征在于:所述水和异核双原子催化材料的用量比为5000:1~5。
9.根据权利要求7所述的异核双原子催化材料在光催化CH4的应用,其特征在于:所述光照条件波长为全光谱模拟太阳光,用300W氙灯照射,光强为200mW·cm-2,光照5h。
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