Fabrication of pore window in ordered mesoporous silica by spatial control of functional groups

Park, Man; Kim, Jun Hyung; Shim, In-Keun

doi:10.1016/j.cej.2014.05.029

Cited by 4 publications

(4 citation statements)

References 26 publications

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“…After water washing by filtration, as-synthesized SBA-11 was dried at room temperature. Attachment of pore window was conducted without removal of the template by the step-wise functionalization [17,18]. As-synthesized SBA-11 (100 mg) was washed with anhydrous ethanol (50 ml) four times for 4 h and directly treated with 100 ml of tert-butylphenethyltrichlorosilaneethanol solution (volume ratio of 1:1) for 6 h at room temperature.…”

Section: Methodsmentioning

confidence: 99%

“…OMMs could be topographically multi-functionalized by the stepwise functionalization introduced by Park and Komarneni [17,18]. Based on gradual removal of the templates packed in the inner pores of as-synthesized OMMs, the stepwise functionalization makes possible to topographically graft different kinds of functional groups over the surfaces of an OMM crystal.…”

Section: Introductionmentioning

confidence: 99%

“…However, most surface modifications of OMMs have been confined to nonspecific functionalization that resulted in fully monofunctionalized or mixed bifunctionalized OMMs. There are only a few attempts [17][18][19][20][21] to manipulate the pore shape of OMM or the distribution of grafted organic groups on a singular OMM crystal. Topographical control of organic functional groups could lead to the construction of 3-dimensionalized OMM with functional pore window.…”

Section: Introductionmentioning

confidence: 99%

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Adsorbate-dependent uptake behavior of topographically bi-functionalized ordered mesoporous silica materials

Kim¹,

Park

Kim

et al. 2015

J Porous Mater

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Novel behaviors such as adsorbate-dependent pore opening and functionality-controlled uptake have been accomplished by the bifunctionalized ordered mesoporous silica developed here. SBA-11 was topographically functionalized with two different functional groups by step-wise functionalization. Bulky and flexible tert-butylphenethyl (BP) groups were topographically grafted around the pore entrance and on the external surface, while small dimethyl (DM) groups were attached on the inner pore surface. The resulting bifunctionalized SBA-11 exhibited the selective malathion scavenger, which was not observed by the corresponding mono-functionalized SBA-11s. The uptake behaviors of the functionalized SBA-11s for malathion and toluene strongly suggest that the bulky and flexible BP groups are locally grafted around the pore entrance to act as a functional pore window. The interaction among the adsorbate, BP and DM groups induces a specific rearrangement of functional pore window which leads to the discriminative uptake. Therefore, the functionalized OMMs equipped with the pore window, the nanosized functional vessels, could be developed into the adsorbate-discriminating adsorbents for highly selective removal/recovery of specific organic molecules.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Adsorbate-dependent uptake behavior of topographically bi-functionalized ordered mesoporous silica materials

Kim¹,

Park

Kim

et al. 2015

J Porous Mater

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“…There are many recent citations of heterogeneous tandem and cascade catalysis in the literature that follow this third approach, many involving acid–base combined chemistry. ,− These report different and interesting synthetic methodologies for the addition of the several desired functionalities to a porous solid, but they do not yet offer a universal protocol for doing this. In addition, only a handful of them address the issue of the spatial distribution of the different added groups, − an important consideration when dealing with cascade processes involving unstable intermediates. It is desirable to expand the library of synthetic routes by which such multifunctional catalysts can be made.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Solid Catalysts with Spatially Resolved Acidic and Basic Molecular Functionalities

Weng

Zaera

2018

ACS Catal.

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A synthetic procedure was developed to prepare dual acid–base catalysts on a single platform. Mesoporous SBA-15 was derivatized using known grafting chemistry via the following steps: (1) addition of Boc-protected 3-aminopropyltriethoxysilane; (2) controlled use of UV/ozonolysis to selectively remove the exterior groups; (3) decoration of the exterior sites freed in Step 2 with 3-mercaptopropyltriethoxysilane; (4) selective oxidation of the mercaptan groups to sulfonic acid; and (5) pyrolytic deprotection of the amine. The resulting catalysts contain sulfonic acid functionality on the external surfaces and entrance of the pores and amino groups deep inside those pores, at coverage ratios that can be controlled by tuning the exposure time during the UV/ozonolysis step. The samples were fully characterized by 29Si and 13C solid-state NMR, infrared absorption spectroscopy, acid–base titrations, and N2 adsorption isotherms measurements, and they were successfully tested for the promotion of a cascade Henry reaction. Optimum performance was seen with the catalyst having an overall 1:2 acid:base molar ratio.

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Selective Modification of Hierarchical Pores and Surfaces in Nanoporous Materials

Tiemann

Weinberger

2020

Adv Materials Inter

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Tailor‐made ordered mesoporous materials bear great potential in numerous fields of application where large interfaces are required. However, the inherent surfacechemical properties of conventional materials, such as silica, carbon or organosilica, poses some limitations with respect to their application. Surface manipulation by functionalization with chemically more reactive groups is one way to improve materials for their desired purpose. Another approach is the design of high surface‐area composite materials. The surface manipulation, either by functionalization or by introducing guest species, can be performed selectively. This means that when several distinct, i.e. , hierarchical, types of surfaces or pore systems exist in a material, each of them may be chosen for manipulation. Several strategies can be identified to achieve this goal. Molecules or molecule assemblies can be utilized to temporarily protect pores or surfaces (soft protection), while manipulation occurs at the accessible sites. This approach is a recurring motive in this review and can also be applied to rigid template matrices (hard protection). Furthermore, the size of functionalization agents (size protection) and their reactivity/diffusion (kinetic protection) into the pores can also be utilized to achieve selectivity. In addition, challenges in the synthesis and characterization of selectively manipulated ordered mesoporous materials are discussed.

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Fabrication of pore window in ordered mesoporous silica by spatial control of functional groups

Cited by 4 publications

References 26 publications

Adsorbate-dependent uptake behavior of topographically bi-functionalized ordered mesoporous silica materials

Adsorbate-dependent uptake behavior of topographically bi-functionalized ordered mesoporous silica materials

Synthesis of Solid Catalysts with Spatially Resolved Acidic and Basic Molecular Functionalities

Selective Modification of Hierarchical Pores and Surfaces in Nanoporous Materials

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