Microporous Organic Network Hollow Spheres: Useful Templates for Nanoparticulate Co<sub>3</sub>O<sub>4</sub> Hollow Oxidation Catalysts

Kang, Narae; Park, Ji Hoon; Jin, Mingshi; Park, Nojin; Lee, Sang Moon; Kim, Hae Jin; Kim, Ji Man; Son, Seung Uk

doi:10.1021/ja411263h

Cited by 200 publications

(126 citation statements)

References 62 publications

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“…To reduce the diffusion pathway of guest molecules, our research group has studied the hollow structure engineering of MON materials based on nontemplate 15 or template methods. 16 Quartz crystal microbalance is a very useful device for gas sensing. 17 Various inorganic and organic polymeric materials have been used as sensing materials in QCM devices.…”

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confidence: 99%

Hollow and Microporous Zn–Porphyrin Networks: Outer Shape Dependent Ammonia Sensing by Quartz Crystal Microbalance

Park

Hong

et al. 2015

Chem. Mater.

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S Supporting Information R ecently, various microporous organic networks (MONs) have been prepared by coupling reactions of organic building blocks. 1−4 For example, the Cooper research group and others have shown that the Sonogashira coupling of rigid organic building blocks results in the formation of various MON materials. 1−3,5 These materials have shown unique physical properties such as high surface area and microporosity (pore size <2 nm). 1−5 On the basis of these properties, the MON materials have been applied as gas adsorbents 1−7 and sensing materials 1,8,9 for small guests. By using tailored building blocks, various sensing moieties can be introduced into MON materials. For example, metallo-porphyrins with vacant axial coordination sites have been incorporated into MON materials to interact with guest molecules. 10−14 In these applications, the small molecules diffuse into MON materials to interact with inner active moieties. To reduce the diffusion pathway of guest molecules, our research group has studied the hollow structure engineering of MON materials based on nontemplate 15 or template methods. 16 Quartz crystal microbalance is a very useful device for gas sensing. 17 Various inorganic and organic polymeric materials have been used as sensing materials in QCM devices. 17 The porous sensing materials can enhance efficiency because the inner active species can be utilized in the sensing. 18 Although MON materials have promising potential as sensing materials, as far as we are aware, their application to QCM devices has not been reported. MON materials prepared without templates usually have irregular shape and size. In our preliminary studies on the application of nonhollow and irregular MON granules bearing metallo-porphyrins to QCM devices, the materials showed very poor performance as sensing materials. In this work, we report the synthesis of hollow and microporous Zn−porphyrin networks (HMZnP) with controlled outer shapes and their shape dependent ammonia sensing performance in QCM devices. Figure 1 shows a synthetic route for the shape controlled HMZnP materials. For preparation of polyhedral HMZnP (P-HMZnP), polyhedral ZIF-8 nanocrystals were prepared by procedures in the literature. 19,20 Microporous (metal-free) porphyrin network (MP) was formed on the surface of ZIF-8 via the Sonogashira coupling of tetrakis(4-ethynylphenyl)porphyrin with 1,4-diiodobenzene (See Experimental Sections in the Supporting Information, SI). The inner ZIF-8 in ZIF-8@MP was completely etched by treatment of hydrochloric acid to form hollow and microporous porphyrin networks with a polyhedral shape (P-HMP). The reaction of P-HMP with zinc acetate resulted in the P-HMZnP. When Zn−porphyrin building blocks with four terminal alkynes were used instead of metal-free porphyrins, the Zn in porphyrin was decoordinated during the acidic etching process. Thus, the Zn was introduced to P-HMP by post-synthetic modification. Spherical HMZnP (S-HMZnP) was prepared using silica nanospheres as templates, instead of ZIF-8 nanocr...

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Hollow and Microporous Zn–Porphyrin Networks: Outer Shape Dependent Ammonia Sensing by Quartz Crystal Microbalance

Park

Hong

et al. 2015

Chem. Mater.

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“…Hollow spheres have been applied in many applications such as catalysis, energy storage, biosensors, and environmental remediation [28][29][30][31][32]. We have expected that the hollow spheres reveal the relationship between the catalytic activity and geometrical structure because their geometrical structure can be controlled such as shell thickness, particle size, and the size of pores in the shell.…”

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Influence of morphology of hollow silica–alumina composite spheres on their activity for hydrolytic dehydrogenation of ammonia borane

et al. 2017

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Hollow silica-alumina composite spheres were prepared by a polystyrene (PS) template method using various amounts of PS suspension. Homogeneous hollow spheres prepared using 40 g were found to be with a diameter of about 300 nm in scanning electron microscopy, and transmission electron microscopy demonstrated their hollow sphere morphology. From the nitrogen adsorption isotherm results, the homogeneous hollow spheres prepared using 40 g of the PS suspension were found to be an ordered pore structure. The activities of the hollow spheres prepared using various amounts of the PS suspension for hydrolytic dehydrogenation of ammonia borane were compared. The results showed that 10, 7, and 6 mL of hydrogen were evolved from the aqueous ammonia borane solution in about 40 min in the presence of the hollow spheres prepared using 40, 80, and 120 g of PS suspension, respectively. The homogeneous hollow spheres with an ordered pore structure showed the highest activity among all the hollow spheres. The amount of acid sites and the coordination number of aluminum active species were characterized using neutralization titration and solid-state 27 Al magic angle spinning nuclear magnetic resonance spectroscopy. The homogeneous hollow spheres with an ordered pore structure had high amount of acid sites and 4-coordinated aluminum species. The relative proportion of 4-coordinated aluminum species was related to the dispersion of aluminum species. These results indicate that the homogeneous hollow spheres with an ordered pore structure showed the high activity because of high amount of acid sites induced by the highly dispersed aluminum species.

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“…In brief, the target precursors are filled in a template with a desirable pore structure, and then porous structures are generated by template removal [40]. Organic templates, compared to other various templates, are an ideal one in that it could be removed easily through heat-treatment under air [41]. The decomposition of organic species produces the hollow structure and then the release of CO 2 gas results in porous surface.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of hollow porous ZnCo2O4 microspheres as high-performance oxygen reduction reaction electrocatalyst

Wang

Song

Wang

et al. 2016

International Journal of Hydrogen Energy

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Microporous Organic Network Hollow Spheres: Useful Templates for Nanoparticulate Co₃O₄ Hollow Oxidation Catalysts

Cited by 200 publications

References 62 publications

Hollow and Microporous Zn–Porphyrin Networks: Outer Shape Dependent Ammonia Sensing by Quartz Crystal Microbalance

Hollow and Microporous Zn–Porphyrin Networks: Outer Shape Dependent Ammonia Sensing by Quartz Crystal Microbalance

Influence of morphology of hollow silica–alumina composite spheres on their activity for hydrolytic dehydrogenation of ammonia borane

Synthesis of hollow porous ZnCo2O4 microspheres as high-performance oxygen reduction reaction electrocatalyst

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Microporous Organic Network Hollow Spheres: Useful Templates for Nanoparticulate Co3O4 Hollow Oxidation Catalysts

Cited by 200 publications

References 62 publications

Hollow and Microporous Zn–Porphyrin Networks: Outer Shape Dependent Ammonia Sensing by Quartz Crystal Microbalance

Hollow and Microporous Zn–Porphyrin Networks: Outer Shape Dependent Ammonia Sensing by Quartz Crystal Microbalance

Influence of morphology of hollow silica–alumina composite spheres on their activity for hydrolytic dehydrogenation of ammonia borane

Synthesis of hollow porous ZnCo2O4 microspheres as high-performance oxygen reduction reaction electrocatalyst

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Microporous Organic Network Hollow Spheres: Useful Templates for Nanoparticulate Co₃O₄ Hollow Oxidation Catalysts