Engineering the size of amine-functionalized dendritic mesoporous silica nanospheres for enhanced formic acid dehydrogenation

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials Pub Date : 2025-05-16 DOI:10.1016/j.micromeso.2025.113699

Youcheng Feng , Chunhui Zhou , Nan Zhang , Hao Chai , Rongmei Zhang , Jinsong Hu , Zhentao Liu , Xilong Wang

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引用次数: 0

Abstract

In this paper, by regulating the molar ratios of cetyltrimethylammonium bromide (CTAB)/sodium salicylate (NaSal) (0.25, 0.5, 1.0, 2.0, 3.0), a series of dendritic mesoporous silica nanospheres (DMSNs) supports with different particle sizes (denoted as DMSNs-x, and x means the different molar ratios of CTAB/NaSal) could be prepared accordingly. Then, Pd nanoparticles (NPs) supported on the amine-functionalized DMSNs-x (Pd/DMSNs-x-NH₂) have been assembled by the surface amine-functionalization and chemical co-reduction strategy successfully. The different particle sizes of the supports for the resulting Pd/DMSNs-x-NH₂ catalysts greatly influence the formic acid dehydrogenation (FAD) activities since they could affect active Pd particle size and mass transfer of the corresponding catalytic reactions. The optimized Pd/DMSNs-1.0-NH₂ catalyst reveals a remarkable catalytic activity of hydrogen (H₂) generation over FAD, giving an initial turnover frequency (TOF) value of 473.8 h⁻¹, and 100 % FA conversion and H₂ selectivity with the additive of sodium formate (SF) at 303 K. The distinct catalytic performance of Pd/DMSNs-1.0-NH₂ could be attributed to the dendritic center-radial 3D pore channels with the high surface area, the notable pore volume, and the relatively concentrative pore size distribution for the modulated mass transfer, ultrasmall size (1.6 nm) with high dispersion of Pd NPs as the catalytically active sites, and the suitable metal-support interaction (MSI) between the introduced Pd NPs and DMSNs-1.0-NH₂ support. This work offers new insight into the regulation of the supports over silica-supported Pd-based catalysts for enhanced FAD application.

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设计胺功能化枝状介孔二氧化硅纳米球的尺寸以增强甲酸脱氢

本文通过调节十六烷基三甲基溴化铵(CTAB)/水杨酸钠（NaSal）的摩尔比（0.25、0.5、1.0、2.0、3.0），可以制备出一系列不同粒径的枝状介孔二氧化硅纳米球（DMSNs）载体（用dmsn -x表示，x表示CTAB/NaSal的不同摩尔比）。然后，通过表面胺化和化学共还原策略，成功地组装了胺功能化dmsn -x （Pd/ dmsn -x- nh2）上的Pd纳米粒子。不同粒径的Pd/ dmsn -x- nh2催化剂载体对甲酸脱氢（FAD）活性的影响很大，因为它们会影响相应催化反应的活性Pd粒径和传质。优化后的Pd/ dmsn -1.0- nh2催化剂在FAD上具有显著的氢（H2）生成活性，初始转换频率（TOF）为473.8 h−1，添加甲酸钠（SF）时，在303 K下FA转化率和H2选择性为100%。Pd/ dmsn -1.0- nh2具有明显的催化性能，这主要归功于其树突状中心-径向三维孔道具有较高的比表面积、显著的孔体积和相对集中的孔径分布，具有超小尺寸（1.6 nm）和高分散的Pd NPs作为催化活性位点，以及引入的Pd NPs与dmsn -1.0- nh2载体之间合适的金属-载体相互作用（MSI）。这项工作为二氧化硅负载的pd基催化剂的支持调节提供了新的见解，以增强FAD的应用。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Microporous and Mesoporous Materials 化学-材料科学：综合

CiteScore

10.70

自引率

5.80%

发文量

649

审稿时长

26 days

期刊介绍： Microporous and Mesoporous Materials covers novel and significant aspects of porous solids classified as either microporous (pore size up to 2 nm) or mesoporous (pore size 2 to 50 nm). The porosity should have a specific impact on the material properties or application. Typical examples are zeolites and zeolite-like materials, pillared materials, clathrasils and clathrates, carbon molecular sieves, ordered mesoporous materials, organic/inorganic porous hybrid materials, or porous metal oxides. Both natural and synthetic porous materials are within the scope of the journal. Topics which are particularly of interest include: All aspects of natural microporous and mesoporous solids The synthesis of crystalline or amorphous porous materials The physico-chemical characterization of microporous and mesoporous solids, especially spectroscopic and microscopic The modification of microporous and mesoporous solids, for example by ion exchange or solid-state reactions All topics related to diffusion of mobile species in the pores of microporous and mesoporous materials Adsorption (and other separation techniques) using microporous or mesoporous adsorbents Catalysis by microporous and mesoporous materials Host/guest interactions Theoretical chemistry and modelling of host/guest interactions All topics related to the application of microporous and mesoporous materials in industrial catalysis, separation technology, environmental protection, electrochemistry, membranes, sensors, optical devices, etc.