CN110404532B - 一种湿化学研磨法制备贵金属团簇或单原子催化剂的方法 - Google Patents
一种湿化学研磨法制备贵金属团簇或单原子催化剂的方法 Download PDFInfo
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Abstract
本发明涉及一种湿化学研磨法制备贵金属纳米团簇或单原子催化剂的方法，属于材料科学与工程技术和化学领域。本发明方法制备的催化剂为以介孔金属氧化物(Co3O4、MnO2、NiCoO2以及TiO2)、氮掺杂介孔碳、导电炭黑XC72R等载体负载的团簇或原子级分散金属Pt、Ir。首先配置一定浓度的载体分散溶液A，分散均匀后加入贵金属前驱体溶液B，将溶液B加入到溶液A中均匀搅拌后用力研磨至粉末状态并干燥。部分载体的催化剂可通过退火处理得到单原子形态的贵金属。本发明具有大密度、高产量、高效率、适用性强等优点，相对于传统方法具有显著的优势。
Description
(1)发明名称:一种湿化学研磨法制备贵金属纳米团簇或单原子催化剂的方法。
(2)技术领域
本发明涉及湿化学研磨法制备贵金属纳米团簇或单原子催化剂的方法，属于材料科学与工程技术和化学领域。
(3)背景技术
目前，金属纳米结构(例如颗粒、团簇、单原子)负载的非均相纳米催化剂是材料科学与催化领域中的热点问题。与传统的纳米级催化剂相比，金属纳米结构能够作为在催化过程中的活性位点，提高催化剂的效率和活性；而且合理的金属与载体界面之间的结合也往往带来更好的催化选择性与稳定性。在纳米级金属负载型催化剂的研究中，保证金属活性位点的良好分散性、与载体界面结合的稳定性以及颗粒尺寸的调控对催化性能的影响一直是催化领域中的核心问题。现阶段制备金属负载型催化剂所采用的浸渍或煅烧等方法不仅过程繁琐、不易调控、产率低，而且有效的金属负载量往往十分有限。因此开发一种过程简单的大规模制备高金属负载量催化剂的方法是相关领域亟待解决的问题。
溶液浸渍法作为合成金属负载型催化剂的传统方法，其思路是将金属前驱体与载体材料均匀分散后将还原的金属纳米结构负载在基底上。实验结果表明，这一方法可以得到金属负载型催化剂，但存在的问题是金属纳米结构由于其自由能较高，在载体上的分散性以及稳定性还有待提升。本发明提出了一种通过湿化学研磨法制备贵金属团簇或者单原子催化剂的制备方法，选用载体的介孔结构或缺陷作为附着位点，通过液相研磨使金属团簇负载在载体上，通过调节搅拌吸附的时间以及后期的退火处理来控制颗粒尺寸的大小，实现了室温环境下高负载量、高分散度的贵金属负载型纳米催化剂的大规模合成。
(4)发明内容
1、本发明的目标
本发明提出了一种高负载量、高分散度的介孔金属氧化物、氮掺杂介孔碳、导电炭黑 XC72R等载体负载贵金属团簇或者单原子催化剂的制备方法。通过湿化学研磨将贵金属前驱体溶液还原成纳米级团簇，并使其均匀且牢固地分散在载体上，从而简单有效地制备负载型催化剂，并通过退火将纳米级团簇分散为单原子。这一方法可显著提高催化剂的性能，促进其大规模商业化应用进程。
2、本技术的发明要点
本发明要点如下：
(1)选取合适的溶剂配置质量-体积浓度为3.0-5.0mg/mL的载体分散液A，所述前驱体为可溶解或分散性良好的介孔金属氧化物氮掺杂介孔碳、导电炭黑XC72R等；所述的溶剂为乙醇；
(2)所述的贵金属前驱体溶液B为0.1mol/L的氯铂酸、氯铱酸、酞菁铂、四氨合硝酸铂的水溶液；
(3)在室温下，将上述步骤(1)制备的载体分散液A超声处理约20min，使其分散均匀，将(2)中所述的贵金属前驱体溶液B分别加入超声处理后的溶液，再充分搅拌约1h；
(4)将搅拌后成分均匀的溶液倒入玛瑙研钵中用力研磨约2h至溶剂完全挥发且剩余固态物质颜色均一，得到样品C；
(5)将部分种类的样品C在空气或者惰性气体中进行退火处理，得到贵金属状态为单原子的催化剂D。
本发明提出的湿化学研磨法制备贵金属团簇或单原子催化剂的方法，其优点在于具有步骤简单易操作、产率较高、化学性质稳定的特点。可以将化学还原得到的纳米级贵金属团簇稳定分散在载体中，并通过简单处理即可得到均匀分散的贵金属单原子催化剂，显著提升了载体材料的电化学性能。
(5)本发明的附图
图1是本发明方法制备的贵金属Pt/Ir团簇负载的介孔氧化钴(Co3O4)催化剂的透射电子显微镜图。
图2是本发明方法制备的贵金属Pt/Ir单原子负载的介孔氧化钴(Co3O4)催化剂的透射电子显微镜图。
图3是本发明方法制备的贵金属Pt/Ir团簇负载的介孔氧化钴(Co3O4)催化剂的氧析出(OER) 电催化活性与稳定性测试性能图。(a),(b),(c),(d)依次为1M KOH电解液中的极化曲线、稳定性曲线、Tafel动力学曲线以及计时电流曲线。
(6)本发明实施例
以下介绍本发明方法的实施例：
实施例1
贵金属Pt/Ir团簇负载的介孔Co3O4催化剂的制备。
首先，配置载体分散溶液A：20mL 5.0mg/mL介孔Co3O4溶液，溶剂为乙醇；贵金属前驱体溶液B：0.1mol/L的氯铂酸和氯铱酸溶液，溶剂为水；将载体分散液A超声处理约20min，使载体在溶剂中分散均匀。取125uL的0.1mol/L氯铂酸溶液和125uL的0.1mol/L氯铱酸溶液加入载体Co3O4分散溶液中，并使用磁力搅拌器搅拌1h。将搅拌后成分均匀的溶液倒入玛瑙研钵，中用力研磨约2h至溶剂完全挥发且剩余固态物质颜色均一，经自然干燥后即得到Pt/Ir 团簇负载的介孔Co3O4催化剂。
实施例2
贵金属Pt/Ir单原子负载的介孔Co3O4催化剂的制备。
首先，配置载体分散溶液A：20mL 5.0mg/mL介孔Co3O4溶液，溶剂为乙醇；贵金属前驱体溶液B：0.1mol/L的氯铂酸和氯铱酸溶液，溶剂为水；将载体分散液A超声处理约20min，使载体在溶剂中分散均匀。取125uL的0.1mol/L氯铂酸溶液和125uL的0.1mol/L氯铱酸溶液加入载体Co3O4分散溶液中，并使用磁力搅拌器搅拌1h。将搅拌后成分均匀的溶液倒入玛瑙研钵，中用力研磨约2h至溶剂完全挥发且剩余固态物质颜色均一。
采用快速升温设备(升温速率30℃/s)将所得的样品在450℃条件下于空气气氛中退火2h，即可得到贵金属Pt/Ir单原子负载的介孔Co3O4催化剂。
实施例3
贵金属Pt/Ir团簇负载的氮掺杂介孔碳催化剂的制备。
首先，配置载体分散溶液A：20mL 2.5mg/mL氮掺杂介孔碳溶液，溶剂为乙醇；贵金属前驱体溶液B：0.1mol/L的氯铂酸和氯铱酸溶液，溶剂为水；将载体分散液A超声处理约20min，使载体在溶剂中分散均匀。取63uL的0.1mol/L氯铂酸溶液和63uL的0.1mol/L氯铱酸溶液加入氮掺杂介孔碳载体分散溶液中，并使用磁力搅拌器搅拌1h。将搅拌后成分均匀的溶液倒入玛瑙研钵，中用力研磨约2h至溶剂完全挥发且剩余固态物质颜色均一，经自然干燥后即得到Pt/Ir团簇负载的氮掺杂介孔碳催化剂。
实施例4
贵金属Pt/Ir团簇负载的XC72R催化剂的制备。
首先，配置载体分散溶液A：20mL 2.5mg/mL导电炭黑XC72R溶液，溶剂为乙醇；贵金属前驱体溶液B：0.1mol/L的氯铂酸和氯铱酸溶液，溶剂为水；将载体分散液A超声处理约20min，使载体在溶剂中分散均匀。取63uL的0.1mol/L氯铂酸溶液和63uL的0.1mol/L氯铱酸溶液加入载体XC72R分散溶液中，并使用磁力搅拌器搅拌1h。将搅拌后成分均匀的溶液倒入玛瑙研钵，中用力研磨约2h至溶剂完全挥发且剩余固态物质颜色均一，经自然干燥后即得到Pt/Ir团簇负载的XC72R催化剂。
实施例5
贵金属Pt/Ir团簇负载的介孔二氧化钛催化剂的制备。
首先，配置载体分散溶液A：20mL 5mg/mL TiO2溶液，溶剂为乙醇；贵金属前驱体溶液 B：0.1mol/L的氯铂酸和氯铱酸溶液，溶剂为水；将载体分散液A超声处理约20min，使载体在溶剂中分散均匀。取125uL的0.1mol/L氯铂酸溶液和125uL的0.1mol/L氯铱酸溶液加入介孔二氧化钛载体分散溶液中，并使用磁力搅拌器搅拌1h。将搅拌后成分均匀的溶液倒入玛瑙研钵，中用力研磨约2h至溶剂完全挥发且剩余固态物质颜色均一，经自然干燥后即得到Pt/Ir 团簇负载的介孔二氧化钛催化剂。
实施例6
贵金属Pt/Ir团簇负载的介孔NiCo2O4催化剂的制备。
首先，配置载体分散溶液A：20mL 5mg/mL NiCo2O4溶液，溶剂为乙醇；贵金属前驱体溶液B：0.1mol/L的氯铂酸和氯铱酸溶液，溶剂为水；将载体分散液A超声处理约20min，使载体在溶剂中分散均匀。取125uL的0.1mol/L氯铂酸溶液和125uL的0.1mol/L氯铱酸溶液加入介孔NiCo2O4载体分散溶液中，并使用磁力搅拌器搅拌1h。将搅拌后成分均匀的溶液倒入玛瑙研钵，中用力研磨约2h至溶剂完全挥发且剩余固态物质颜色均一，经自然干燥后即得到Pt/Ir团簇负载的介孔NiCo2O4催化剂。
实施例7
贵金属Pt/Ir团簇负载的少层MoS2催化剂的制备。
首先，配置载体分散溶液A：20mL 2.5mg/mL少层MoS2溶液，溶剂为乙醇；贵金属前驱体溶液B：0.1mol/L的氯铂酸和氯铱酸溶液，溶剂为水；将载体分散液A超声处理约40min，使载体在溶剂中分散均匀。取63uL的0.1mol/L氯铂酸溶液和63uL的0.1mol/L氯铱酸溶液加入少层MoS2载体分散溶液中，并使用磁力搅拌器搅拌1h。将搅拌后成分均匀的溶液倒入玛瑙研钵，中用力研磨约2h至溶剂完全挥发且剩余固态物质颜色均一，经自然干燥后即得到Pt/Ir 团簇负载的少层MoS2催化剂。
实施例8
贵金属Pt团簇负载的介孔Al2O3催化剂的制备。
首先，配置载体分散溶液A：20mL 5mg/mL NiCo2O4溶液，溶剂为乙醇；贵金属前驱体溶液B：0.1mol/L的氯铂酸，溶剂为水；将载体分散液A超声处理约20min，使载体在溶剂中分散均匀。取250uL的0.1mol/L氯铂酸溶液加入介孔Al2O3载体分散溶液中，并使用磁力搅拌器搅拌1h。将搅拌后成分均匀的溶液倒入玛瑙研钵，中用力研磨约2h至溶剂完全挥发且剩余固态物质颜色均一，经自然干燥后即得到Pt团簇负载的介孔Al2O3催化剂。
实施例9
贵金属Pt/Ir团簇负载的介孔MnO2催化剂的制备。
首先，配置载体分散溶液A：20mL 5mg/mL介孔MnO2溶液，溶剂为乙醇；贵金属前驱体溶液B：0.1mol/L的氯铂酸和氯铱酸溶液，溶剂为水；将载体分散液A超声处理约20min，使载体在溶剂中分散均匀。取125uL的0.1mol/L氯铂酸溶液和125uL的0.1mol/L氯铱酸溶液加入介孔MnO2载体分散溶液中，并使用磁力搅拌器搅拌1h。将搅拌后成分均匀的溶液倒入玛瑙研钵，中用力研磨约2h至溶剂完全挥发且剩余固态物质颜色均一，经自然干燥后即得到Pt/Ir团簇负载的介孔MnO2催化剂。
实施例10
贵金属Pt/Ir团簇负载的Mxene催化剂的制备。
首先，配置载体分散溶液A：20mL 5mg/mL Mxene溶液，溶剂为乙醇；贵金属前驱体溶液B：0.1mol/L的氯铂酸和氯铱酸溶液，溶剂为水；将载体分散液A超声处理约40min，使载体在溶剂中分散均匀。取125uL的0.1mol/L氯铂酸溶液和125uL的0.1mol/L氯铱酸溶液加入Mxene载体分散溶液中，并使用磁力搅拌器搅拌1h。将搅拌后成分均匀的溶液倒入玛瑙研钵，中用力研磨约2h至溶剂完全挥发且剩余固态物质颜色均一，经自然干燥后即得到Pt/Ir团簇负载的Mxene催化剂。
Claims (1)
1.一种湿化学研磨法制备贵金属团簇的方法，其特征在于该方法包括以下步骤：
（1）选取合适的溶剂配置质量-体积浓度为3.0-5.0 mg/mL的载体分散液A，所述载体为可溶解或分散性良好的介孔金属氧化物、氮掺杂介孔碳、导电炭黑XC72R；所述的溶剂为乙醇；
（2）配置物质的量浓度为0.1 mol/L的贵金属前驱体溶液B，所述贵金属前驱体为氯铂酸、氯铱酸、酞菁铂、四氨合硝酸铂，所述溶剂为水；
（3）在室温下，将上述步骤（1）制备的载体分散液A超声处理20min，使其分散均匀，将(2)中所述的贵金属前驱体溶液B分别加入超声处理后的溶液，再充分搅拌1h；
（4）将搅拌后成分均匀的溶液倒入玛瑙研钵中用力研磨2h至溶剂完全挥发且剩余固态物质颜色均一，得到的产物结构为贵金属团簇负载于载体之上，所述载体为介孔金属氧化物、氮掺杂介孔碳、导电炭黑XC72R材料。
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