CN112691689A - 一种单原子催化剂的蒸气辐照还原合成方法 - Google Patents
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Abstract
本发明提供了一种单原子催化剂的蒸气辐照还原合成方法，其特包括以下步骤：(1)将催化剂载体在贵金属催化剂前驱体水溶液中搅拌分散，催化剂在载体上的负载量以贵金属的质量分数计为1～10％；(2)使用碱溶液将步骤(1)所得溶液的pH调节到10；(3)将步骤(2)所得溶液冻干，得到干燥的负载催化剂前驱体的催化剂载体；(4)将步骤(3)所得物在乙醇蒸气环境中充分吸收乙醇蒸气；(5)使用伽马辐射源对催化剂在惰性气氛条件下辐照，辐照总强度100kGy，得到高分散单原子催化剂。本发明提供的合成方法能够得到分散度高、负载稳定且呈原子分散的单元子催化剂；并可实现单元子催化剂的规模化宏量制备。
Description
技术领域
本发明属于贵金属催化剂合成技术领域，具体涉及一种单原子催化剂的蒸气辐照还原合成方法。
背景技术
催化技术在石油化工、能源利用及环境保护等领域具有重要的作用。负载型的贵金属催化剂是应用最为广泛的催化剂类型之一，而且是一类环境友好型催化材料，其对CO低温氧化等许多反应具有优良的催化性能，在室内和工业气体的净化，封闭式CO2激光器、潜水艇、航天器等密闭环境，安全防毒面具，CO气体传感器，氢燃料电池等诸多方面已经得到广泛应用。
然而由于贵金属催化剂的价格昂贵和较低的储量，严重限制了这类催化剂的大规模商业化应用。目前普通的溶液浸渍还原等方法制备的催化剂贵金属原子利用率较低，直接影响了催化剂的活性和经济性。为了解决这个问题，研究者们利用降低贵金属基催化剂纳米粒子的尺寸，制备几个原子的纳米簇甚至于单个原子分散的催化剂等方法，来有效地提高了贵金属的利用率，从而降低了这类催化剂的成本。更重要的是，贵金属能够以原子形式均匀分散在碳材料或者过渡金属氧化物等载体上，从而表现出超高的催化性能。因此，制备单分散贵金属原子催化剂具有重要应用前景。
单原子催化剂具有较高的原子利用率，同时具有均相催化剂的“孤立活性位点”和多相催化剂的“稳定易于分离”的优点，具有优异的催化性能和良好的选择性，受到了研究者和工业界的广泛关注。
目前，可以用来制备贵金属单原子催化剂的方法主要有溶液化学法、原子层沉积法和光催化合成法等。然而，目前对于单原子催化剂的制备中不同程度的存在使用大量有机溶剂、分散度不高、不能宏量制备的问题，成为制约单原子催化剂实际应用的瓶颈之一。
专利文献CN 110961134 A报道了一种合成单原子催化剂的方法，其是在酸性条件下，以聚苯乙烯纳米球为牺牲模板，将氰胺类化合物，糠醛和金属源进行充分反应，得到高聚物；再在保护气体的氛围中，将高聚物进行高温热解，得到单原子催化剂。其合成过程就用到了大量的酸，需要进行酸液处理，并采用了氰胺类化合物和糠醛等毒性有机物质。
专利文献CN 108906113 A提供了一种高负载量的贵金属单原子催化剂的制备方法，该催化剂利用掺氮的碳材料作为载体，吸附贵金属酸根离子或盐离子，然后将获得的前驱体粉末，用一定强度的紫外线照射一段时间，最终得到高负载量的贵金属原子催化剂。但该方法获得的单原子催化剂分散并不均匀，负载稳定程度不高，虽然一定程度提高了负载量，但是其负载量在0.13wt％～9.8wt％范围内波动很大，贵金属催化剂在还原过程中的聚集问题仍较严重。
因此，亟待提供一种单原子催化剂的制备方法，以解决现有方法中贵金属催化剂在还原过程中容易聚集、分散度不高、负载量不稳定的问题，以及存在的大量使用有机溶剂、难以规模化宏量制备的问题。
发明内容
本发明的目的就是为了解决上述技术问题，而提供一种单原子催化剂的蒸气辐照还原合成方法。本发明提供的合成方法解决了贵金属催化剂在还原过程中的催化剂聚集问题，得到了分散度高、负载稳定且呈原子分散的单元子催化剂；并可实现单元子催化剂的规模化宏量制备。
为了实现上述目的，本发明提供了一种单原子催化剂的蒸气辐照还原合成方法，包括以下步骤：
(1)将催化剂载体在贵金属催化剂前驱体水溶液中搅拌分散，催化剂在载体上的负载量以贵金属的质量分数计为1～10％；
(2)使用碱溶液将步骤(1)所得溶液的pH调节到10；
(3)将步骤(2)所得溶液冻干，得到干燥的负载催化剂前驱体的催化剂载体；
(4)将步骤(3)所得物在乙醇蒸气环境中充分吸收乙醇蒸气；
(5)使用伽马辐射源对催化剂在惰性气氛条件下辐照，辐照总强度100kGy，得到高分散单原子催化剂。
本发明提供了一种单原子催化剂的蒸气辐照还原合成方法，不同于常见的溶液浸渍还原方法，本发明方法是在乙醇蒸气气氛环境下，再结合辐照还原方法来制备单原子催化剂。本发明人研究发现，通过将催化剂载体吸附乙醇蒸气，乙醇蒸气在辐照条件下能够电离产生具有强还原性的自由基将催化剂前驱体还原。该方法合成温度为室温，还原温度温和；且有机溶剂使用量少，更加环保；所得催化剂高度分散并呈现单原子级别分散；且该制备工艺稳定性高，可以宏量制备单原子催化剂。
需要指出的是，本发明中采用的乙醇蒸气还原氛围是必要的，如对比例所示，当不采用乙醇蒸气，直接将贵金属催化剂溶于乙醇溶液中进行辐照还原，得到的是纳米颗粒和少量单原子催化剂的混合物，而无法得到高分散性的单原子催化剂。
进一步的是，步骤(1)中所述贵金属包括铂、钯、金、银、钌、铱、钨。
进一步的是，步骤(1)中所述贵金属催化剂前驱体包括氯铂酸、氯化钯、HAuCl6、AgCl、RuCl3、IrCl3·H2O、WCl6。
进一步的是，所述贵金属催化剂前驱体水溶液的浓度为5～20mg/mL。
进一步的是，步骤(1)中所述催化剂载体包括无机分子筛、多孔氧化铝、多孔碳或C3N4。
进一步的是，步骤(2)中所述碱溶液包括氢氧化钾溶液或氢氧化钠溶液，碱溶液的浓度无限制，可根据需要配制来调节pH。
进一步的是，步骤(3)中所述冻干步骤采用冷冻干燥机进行，其步骤为：使用液氮对溶液进行冷冻，使得溶液快速成为固体，将固体转移至冷冻干燥机中的真空腔室，低温真空干燥，得到冻干的样品。
进一步的是，步骤(4)中进行乙醇蒸气处理时间为24h。
进一步的是，步骤(5)中所述伽马辐射源包括钴源，所述钴源为Co-60。
进一步的是，步骤(5)中所述惰性气氛包括氮气、氩气或氦气。
本发明的有益效果如下：
(1)本发明使用伽马辐照源进行原位辐照还原，可以实现单原子催化剂的公斤级宏量制备，解决了现有合成方法难以规模化宏量制备的问题；
(2)本发明使用的蒸气辐照还原方法适用于不同的催化剂载体，如碳载体、多孔氧化铝、分子筛等载体，均可稳定制备得到单原子催化剂；
(3)本发明使用乙醇蒸气提供还原气氛，使用的有机溶剂较少，更加环保，且能够促进催化剂在载体上的负载和分散。
附图说明
图1中，(A)为普通的Pt纳米粒子催化剂的影像图；(B)为实施例1采用的蒸气辐照还原法得到的Pt单原子催化剂影像图；(C)为实施例2采用氯化钯制备的Pd单原子催化剂影像图；(D)为将实施例1中的载体替换为C3N4、碳材料等载体制备得到的单原子催化剂；(E)为实施例1的Pt单原子催化剂同步辐射光源的XAFS数据；(F)为实施例1的Pt单原子催化剂同步辐射光源的XANFS图谱。图2为对比例1所得到纳米颗粒催化剂的影像图，其中A和B分别为对不同批次的催化剂进行影像拍照。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例对本发明进行具体描述，有必要指出的是，以下实施例仅仅用于对本发明进行解释和说明，并不用于限定本发明。本领域技术人员根据上述发明内容所做出的一些非本质的改进和调整，仍属于本发明的保护范围。
实施例1
(一)材料成分说明
贵金属催化剂前驱体：氯铂酸。
还原性气氛：乙醇。
用于调节溶液酸碱度的碱性溶液：氢氧化钾溶液，浓度1mol/L。
催化剂载体：无机分子筛(或多孔碳，C3N4)。
辐照源：来自钴源(Co-60)伽马射线，辐照总强度100kGy。
(二)材料配方
催化剂前驱体水溶液的浓度为20mg/mL。以氯铂酸中铂的质量进行计量，在催化剂载体的负载量为10％。
(三)材料制备方案
(1)催化剂载体在20mg/mL的贵金属催化剂前驱体水溶液中搅拌分散，催化剂的负载量以贵金属计量的质量分数为1～10％；
(2)使用碱溶液将前驱体溶液的酸碱度pH调节到10；
(3)使用冷冻干燥机将溶液冻干，得到干燥的负载催化剂前驱体的催化剂载体；
(4)干燥的负载催化剂前驱体的催化剂载体在乙醇蒸气环境中充分吸收乙醇蒸气；
(5)使用Co-60辐射源对催化剂在惰性气氛条件下辐照，辐照总强度100kGy，得到高分散催化剂。
实施例2
按照实施例1的方法，采用氯化钯为贵金属催化剂前驱体，碱液采用氢氧化钠溶液，催化剂载体采用C3N4，氯化钯中钯的质量在催化剂载体的负载量为1％，进行实施例1的乙醇蒸气辐照还原，得到钯的单原子催化剂。
实施例3
按照实施例1的方法，采用氯金酸为贵金属催化剂前驱体，碱液采用氢氧化钠溶液，催化剂载体采用多孔碳，氯金酸中金的质量在催化剂载体的负载量为5％，进行实施例1的乙醇蒸气辐照还原，得到金的单原子催化剂。
对比例1
按照实施例1的方法，不使用乙醇蒸气，使用的是乙醇溶液，处理步骤为步骤(1)中前驱体选用氯铂酸的乙醇溶液，将溶液的pH值调到10，进行辐照还原，得到催化剂。因为乙醇溶液中的铂的前驱体可以自由的移动，在辐照还原的同时会进行聚集，最终得到的是Pt的纳米颗粒和少量单原子催化剂的混合物。
实验例
对上述实施例和对比例中的催化剂进行表征，包括普通纳米颗粒催化剂和单原子催化剂，采用双球差矫正高分辨透射电镜(型号为FEI Themis Z)进行HAADF-STEM表征，即高角环形暗场-扫描透射显微镜成像；使用北京同步辐射光源得到X射线吸收精细结构谱图(XAFS)，相应的表征结果见图1(实施例)和图2(对比例)。
图1中(A)可以看出普通的Pt纳米粒子催化剂呈颗粒状，一般粒径为几纳米；(B)可以看出采用蒸气辐照还原法，得到的催化剂为原子级别分散；(C)表明本发明的方法具有一定普适性，Pd单原子的催化剂制备也同样适用；(D)表明本发明的制备方法所用的载体具有一定普适性，C3N4、碳材料等载体都可以作为载体；(E)表明实施例1得到的原子分散的Pt催化剂与用作对比的Pt箔有明显不同，呈现出典型单原子分散特征；(F)表明Pt原子的配位方式主要是Pt-N配位，和普通催化剂的Pt-Pt相互作用明显不同，进一步佐证了该催化剂为单原子催化剂。
从图2可以看出，对比例1中制备的催化剂为Pt的纳米颗粒和少量单原子催化剂的混合物，其中大块亮点为纳米颗粒，分散的小亮点为单原子催化剂。
Claims (10)
1.一种单原子催化剂的蒸气辐照还原合成方法，其特征在于，包括以下步骤：
(1)将催化剂载体在贵金属催化剂前驱体水溶液中搅拌分散，催化剂在载体上的负载量以贵金属的质量分数计为1～10％；
(2)使用碱溶液将步骤(1)所得溶液的pH调节到10；
(3)将步骤(2)所得溶液冷冻干燥，得到干燥的负载催化剂前驱体的催化剂载体；
(4)将步骤(3)所得物在乙醇蒸气环境中充分吸收乙醇蒸气；
(5)使用伽马辐射源对催化剂在惰性气氛条件下辐照，辐照总强度100kGy，得到高分散单原子催化剂。
2.根据权利要求1所述的合成方法，其特征在于，步骤(1)中所述贵金属包括铂、钯、金、银、钌、铱或钨。
3.根据权利要求1所述的合成方法，其特征在于，步骤(1)中所述贵金属催化剂前驱体包括H2PtCl6、PdCl2、HAuCl6、AgCl、RuCl3、IrCl3·H2O或WCl6。
4.根据权利要求1或3所述的合成方法，其特征在于，所述贵金属催化剂前驱体水溶液的浓度为5～20mg/mL。
5.根据权利要求1所述的合成方法，其特征在于，步骤(1)中所述催化剂载体包括无机分子筛、多孔氧化铝、多孔碳或C3N4。
6.根据权利要求1所述的合成方法，其特征在于，步骤(2)中所述碱溶液包括氢氧化钾溶液或氢氧化钠溶液。
7.根据权利要求1所述的合成方法，其特征在于，步骤(3)中所述冷冻干燥步骤采用冷冻干燥机进行。
8.根据权利要求1所述的合成方法，其特征在于，步骤(4)中进行乙醇蒸气处理时间为24h。
9.根据权利要求1所述的合成方法，其特征在于，步骤(5)中所述伽马辐射源包括钴源，所述钴源为Co-60。
10.根据权利要求1所述的合成方法，其特征在于，步骤(5)中所述惰性气氛包括氮气、氩气或氦气。
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