Template-free synthesis to micro-meso-macroporous hierarchy in nanostructured MIL-101(Cr)with enhanced catalytic activity  

无模板法合成具有增强催化活性的分级纳米孔结构MIL-101(Cr)

作　　者：Tian Zhao Songhe Li Yu-Xuan Xiao Christoph Janiak Ganggang Chang Ge Tian Xiao-Yu Yang 赵田;李松贺;肖宇轩;Christoph Janiak;常刚刚;田歌;阳晓宇(State Key Laboratory of Advanced Technology for Materials Synthesis and Processing&School of Materials Science and Engineering&School of Chemistry,Chemical Engineering and Life Science,Wuhan University of Technology,Wuhan,430070,China;Southern Marine Science and Engineering Guangdong Laboratory(Zhuhai)&School of Chemical Engineering and Technology,Sun Yat-sen University,Zhuhai,519000,China;School of Engineering and Applied Sciences,Harvard University,Cambridge,Massachusetts,02138,USA;Institut für Anorganische Chemie und Strukturchemie,Universität Düsseldorf,Universitätsstr.1,D-40225,Düsseldorf,Germany;Key Laboratory of Advanced Packaging Materials and Technology of Hunan Province,School of Packaging and Materials Engineering,Hunan University of Technology,Zhuzhou,412007,China)

机构地区：[1]State Key Laboratory of Advanced Technology for Materials Synthesis and Processing&School of Materials Science and Engineering&School of Chemistry,Chemical Engineering and Life Science,Wuhan University of Technology,Wuhan,430070,China [2]Southern Marine Science and Engineering Guangdong Laboratory(Zhuhai)&School of Chemical Engineering and Technology,Sun Yat-sen University,Zhuhai,519000,China [3]School of Engineering and Applied Sciences,Harvard University,Cambridge,Massachusetts,02138,USA [4]Institut für Anorganische Chemie und Strukturchemie,Universität Düsseldorf,Universitätsstr.1,D-40225,Düsseldorf,Germany [5]Key Laboratory of Advanced Packaging Materials and Technology of Hunan Province,School of Packaging and Materials Engineering,Hunan University of Technology,Zhuzhou,412007,China

出　　处：《Science China Materials》2021年第1期252-258,共7页中国科学（材料科学（英文版）

基　　金：supported by the National Key R&D Program of China(2017YFC1103800);a joint National Natural Science Foundation of China-Deutsche Forschungsgemeinschaft(NSFC-DFG)project(NSFC 51861135313,DFG JA466/39-1);Program for Changjiang Scholars and Innovative Research Team in University(IRT_15R52);the National Natural Science Foundation of China(51802094,U1663225,U1662134,21711530705 and 21706199);International Science&Technology Cooperation Program of China(2015DFE52870);Hubei Provincial Natural Science Foundation of China(2016CFA033);Hunan Provincial Natural Science Foundation of China(2018JJ3122);the S&T Program of Hunan Province,China(2018RS3084);the Science Research Project of Hunan Provincial Department of Education(18B294);the Fundamental Research Funds for the Central Universities(19lgzd16)。

摘　　要：Hierarchical porous(HP)materials[1,2],having multimodal pore-size distribution,receive keen attention due to advantages offered by improved diffusion efficiency and mass transport.HP metal-organic frameworks(HPMOFs)is an emerging field focussing on delivering improved performance in catalysis[3,4],adsorption/separation[5,6],sensorics[7]and energy storage[8,9],especially when bulky guest molecules are involved.Micropores usually offer high surface area while mesopores/macropores will significantly enlarge the application as a host material to carry bulky anchoring molecular catalysts,large drug molecules and even nanomaterials.This is indeed an advantage for catalysis reaction or transformation without transportation limitations in a confined space.Some MOFs with the large pore-sizes of over 2 nm diameter are formally micro-/mesoporous in the defectfree crystalline state.Isoreticular expansion[10]allows synthesizing MOF materials with pore sizes of up to 10 nm[11].MIL-101(Cr)是最重要的金属有机框架(MOFs)材料之一,稳定的框架结构和超高的比表面积使其在众多科学领域得到了广泛研究和应用.但是MIL-101(Cr)的合成条件比较苛刻,且稳定性较强,因此,有关于其分级结构的研究报道仍比较少.本文提出了一种简单制备分级纳米孔结构MIL-101(Cr)的方法,即以乙酸作为调节剂,采用水热合成的方法,一步得到具有微孔-介孔-大孔分级结构的MIL-101(Cr)材料.实验结果表明,该分级结构的MIL-101(Cr)与无分级结构的MIL-101(Cr)相比,其大分子染料吸附能力和催化能力均有显著提高.而且分级结构MIL-101(Cr)负载了磷钨酸催化剂之后,表现出了与均相催化剂(纯磷钨酸)相当的催化能力.进一步研究发现,使用其他短碳链的一元羧酸作为调节剂,如丙酸、丁酸等,也可获得类似分级纳米结构MIL-101(Cr).

关 键 词：催化能力 磷钨酸催化剂 分级结构 均相催化剂 一元羧酸 染料吸附 框架结构 水热合成 

分 类 号：TB383.1[一般工业技术—材料科学与工程] O643.36[理学—物理化学]