冷冻干燥浸渍法制备具有高分散铁物种和强金属-载体相互作用的FeZSM-5催化剂

doi:10.1016/S1872-2067(18)63198-5

催化学报 ›› 2019, Vol. 40 ›› Issue (7): 1109-1115.DOI: 10.1016/S1872-2067(18)63198-5

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冷冻干燥浸渍法制备具有高分散铁物种和强金属-载体相互作用的FeZSM-5催化剂

范立耸, 程党国, 陈丰秋, 詹晓力

浙江大学化学工程与生物学院, 浙江省化工高效制造技术重点实验室, 浙江杭州 310027

收稿日期:2018-10-04 修回日期:2018-11-09 出版日期:2019-07-18 发布日期:2019-05-24
通讯作者: 程党国
基金资助:
国家重点研发计划（2016YFA0202900）；国家自然科学基金（21622606）；浙江省自然科学基金（LR18B060001）；中央高校基本科研业务费专项资金.

Preparation of highly dispersed iron species over ZSM-5 with enhanced metal-support interaction through freeze-drying impregnation

Lisong Fan, Dangguo Cheng, Fengqiu Chen, Xiaoli Zhan

Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China

Received:2018-10-04 Revised:2018-11-09 Online:2019-07-18 Published:2019-05-24
Supported by:
This work was supported by the National Key R&D Program of China (2016YFA0202900), the National Natural Science Foundation of China (21622606), Zhejiang Provincial Natural Science Foundation of China (LR18B060001), and the Fundamental Research Funds for the Central Universities.

摘要/Abstract

摘要：

负载型催化剂在现代化工中发挥着重要作用.其中，金属与载体的相互作用是负载型催化剂的重要特性.浸渍法是制备这类催化剂的一种简便方法.然而，传统浸渍法在浸渍达到平衡后采用蒸发干燥时，大量金属前驱体在毛细管力的作用下沿着孔道迁移并堆积在载体表面，焙烧后形成大块的金属团簇，这使得到的催化剂中金属与载体相互作用较弱.有研究者在浸渍溶液中添加高粘度物质来降低毛细管力的影响，或者采用微波干燥来减少团簇的产生，但总体上关于浸渍法中增强金属与载体相互作用的通用性方法研究很少.为此，本文采用冷冻干燥对传统的浸渍法进行改进.冷冻干燥是一种将冰冻样品置于真空条件下使溶剂升华的干燥方式，在化学上主要用于制备纳米金属粉末，很少用来制备金属负载型催化剂.本文以⁵⁷FeZSM-5为例，采用传统蒸发干燥和改进的冷冻干燥方法制备了两种催化剂，采用超导量子干涉仪（SQUID），H₂-TPR和穆斯堡尔谱等表征手段研究了两者在铁物种组成和N₂O分解活性上的区别，并提出了形成机理.
SQUID测试表明，两种催化剂均具有铁磁性和顺磁性特性，这意味着催化剂中可能存在α-Fe₂O₃，以及与骨架相连的二价或三价铁物种.H₂-TPR结果显示，冻干催化剂中含有更少的铁物种数和更多的Fe²⁺含量.进一步的穆斯堡尔谱表征不仅印证了上述结果，而且给出了铁物种的定量结果.相比于传统的蒸干催化剂，冻干催化剂拥有更多与分子筛骨架铝相连的铁物种，说明冷冻干燥可以增强金属与载体的相互作用.在冻干催化剂中，更多的铁物种存在于孔道内，说明冷冻干燥对铁物种有着良好的限域作用.此外，冻干催化剂含有更多纳米级金属氧化物，大块团簇较少，金属物种的平均尺寸小于蒸干催化剂.冻干催化剂在N₂O分解中更高的活性也证明了铁物种结构的变化.
基于上述结果，本文提出了不同干燥方式下铁物种的形成机理.在蒸干催化剂中，由于蒸发过程中毛细管力的存在，原本在载体中均匀分散的铁前驱体被转移到载体表面，形成大量的大块铁团簇.而对于冻干催化剂，溶剂是通过升华的方式去除，铁前驱体不会受干燥的影响而保持均匀分布的状态.由于ZSM-5分子筛拥有丰富的孔隙，大量铁被限制在狭窄的孔道中，所形成的铁物种尺寸更小，同时铁有更多机会与骨架铝发生相互作用，从而达到增强金属与载体相互作用的目的.该方法属于浸渍法的通用性改进，可以在制备其他负载型催化剂时调控金属与载体的相互作用以及金属尺寸大小.

关键词: 铁, ZSM-5分子筛, 冷冻干燥, 浸渍法, 金属与载体相互作用, 金属粒径

Abstract:

Supported metal catalysts play a vital role in the chemical industry, and the metal-support interaction is an important property of the catalyst. However, in the traditional impregnation method, it is difficult to obtain sufficient metal-support interactions owing to the mobility of the metal precursor during evaporation drying. Here, freeze drying is applied during impregnation instead of evaporation drying for enhancing the metal-support interactions. ⁵⁷FeZSM-5 was chosen as a representative catalyst. A quantitative analysis was conducted based on Mössbauer spectroscopy. Compared with traditional evaporation-drying catalyst, freeze-drying catalyst has stronger metal-support interactions. In addition, more iron species are confined in the channel and smaller metal sizes and less diversity are obtained. The compositional change is also proved because of the superior performance of the freeze-drying catalyst during N₂O decomposition. This method can be extended to other supported metal catalysts prepared through an impregnation method, which can be used to tune the metal-support interactions and metal sizes.

Key words: Iron, ZSM-5 zeolite, Freeze drying, Impregnation, Metal-support interaction, Metal size

范立耸, 程党国, 陈丰秋, 詹晓力. 冷冻干燥浸渍法制备具有高分散铁物种和强金属-载体相互作用的FeZSM-5催化剂[J]. 催化学报, 2019, 40(7): 1109-1115.

Lisong Fan, Dangguo Cheng, Fengqiu Chen, Xiaoli Zhan. Preparation of highly dispersed iron species over ZSM-5 with enhanced metal-support interaction through freeze-drying impregnation[J]. Chinese Journal of Catalysis, 2019, 40(7): 1109-1115.

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冷冻干燥浸渍法制备具有高分散铁物种和强金属-载体相互作用的FeZSM-5催化剂

Preparation of highly dispersed iron species over ZSM-5 with enhanced metal-support interaction through freeze-drying impregnation

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