| 1. |
- Aramburo, Luis R., et al.
(författare)
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The Porosity, Acidity, and Reactivity of Dealuminated Zeolite ZSM-5 at the Single Particle Level : The Influence of the Zeolite Architecture
- 2011
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Ingår i: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 17:49, s. 13773-13781
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Tidskriftsartikel (refereegranskat)abstract
- A combination of atomic force microscopy (AFM), high-resolution scanning electron microscopy (HR-SEM), focused-ion-beam scanning electron microscopy (FIB-SEM), X-ray photoelectron spectroscopy (XPS), confocal fluorescence microscopy (CFM), and UV/Vis and synchrotron-based IR microspectroscopy was used to investigate the dealumination processes of zeolite ZSM-5 at the individual crystal level. It was shown that steaming has a significant impact on the porosity, acidity, and reactivity of the zeolite materials. The catalytic performance, tested by the styrene oligomerization and methanol-to-olefin reactions, led to the conclusion that mild steaming conditions resulted in greatly enhanced acidity and reactivity of dealuminated zeolite ZSM-5. Interestingly, only residual surface mesoporosity was generated in the mildly steamed ZSM-5 zeolite, leading to rapid crystal coloration and coking upon catalytic testing and indicating an enhanced deactivation of the zeolites. In contrast, harsh steaming conditions generated 550 nm mesopores, extensively improving the accessibility of the zeolites. However, severe dealumination decreased the strength of the Bronsted acid sites, causing a depletion of the overall acidity, which resulted in a major drop in catalytic activity.
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| 2. |
- Asahina, Shunsuke, et al.
(författare)
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A new HRSEM approach to observe fine structures of novel nanostructured materials
- 2011
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Ingår i: Microporous and Mesoporous Materials. - : Elsevier BV. - 1387-1811 .- 1873-3093. ; 146:1-3, s. 11-17
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Tidskriftsartikel (refereegranskat)abstract
- A new approach for observing fine structures of novel thin, nanostructured materials called through the employed to observe interesting features on a variety of new, catalyticallyimportant hierarchically porous rattlespheres.
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| 3. |
- Asahina, Shunsuke, et al.
(författare)
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Direct observation and analysis of york-shell materials using low-voltage high-resolution scanning electron microscopy : Nanometal-particles encapsulated in metal-oxide, carbon, and polymer
- 2014
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Ingår i: APL Materials. - : AIP Publishing. - 2166-532X. ; 2:11, s. 113317-
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Tidskriftsartikel (refereegranskat)abstract
- Nanometal particles show characteristic features in chemical and physical properties depending on their sizes and shapes. For keeping and further enhancing their features, the particles should be protected from coalescence or degradation. One approach is to encapsulate the nanometal particles inside pores with chemically inert or functional materials, such as carbon, polymer, and metal oxides, which contain mesopores to allow permeation of only chemicals not the nanometal particles. Recently developed low-voltage high-resolution scanning electron microscopy was applied to the study of structural, chemical, and electron state of both nanometal particles and encapsulating materials in york-shell materials of Au@C, Ru/Pt@C, Au@TiO2, and Pt@Polymer. Progresses in the following categories were shown for the york-shell materials: (i) resolution of topographic image contrast by secondary electrons, of atomic-number contrast by back-scattered electrons, and of elemental mapping by X-ray energy dispersive spectroscopy; (ii) sample preparation for observing internal structures; and (iii) X-ray spectroscopy such as soft X-ray emission spectroscopy. Transmission electron microscopy was also used for characterization of Au@C. (C) 2014 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.
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| 4. |
- Asahina, Shunsuke, et al.
(författare)
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Exploitation of Surface-Sensitive Electrons in Scanning Electron Microscopy Reveals the Formation Mechanism of New Cubic and Truncated Octahedral CeO(2) Nanoparticles
- 2011
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Ingår i: ChemCatChem. - : Wiley. - 1867-3880 .- 1867-3899. ; 3:6, s. 1038-1044
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Tidskriftsartikel (refereegranskat)abstract
- Development of new analytical tools for nanostructures directly contributes to the study of catalysts. By using scanning electron microscopy (SEM) with a newly designed signal enhancer, we study cubic and truncated octahedral cerium oxide (CeO(2)) nanoparticles, which are composed of smaller primary octahedral CeO(2) and are formed through bond formation with hexanedioic acid. The signal enhancer is designed to efficiently collect secondary electrons of kinetic energy less than 10 eV; thus, it greatly improves the S/N ratio. On the basis of the observed SEM images and electron backscattered diffraction patterns of the cross section of the nanoparticles, we discuss the formation mechanism of the nanoparticles and speculate that the primary CeO(2) nanocrystals share their edges in the cubic nanoparticles and truncated octahedral nanoparticles. These results will contribute to the preparation of nanostructured metal oxide surfaces with controlled morphologies that could enhance catalytic activity.
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| 5. |
- Cho, Kanghee, et al.
(författare)
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Mesopore generation by organosilane surfactant during LTA zeolite crystallization investigated by high-resolution SEM and Monte Carlo simulation
- 2011
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Ingår i: Solid State Sciences. - : Elsevier BV. - 1293-2558 .- 1873-3085. ; 13:4, s. 750-756
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Tidskriftsartikel (refereegranskat)abstract
- The crystallization of LTA zeolite under a hydrothermal synthesis condition that contained a quaternary ammonium-type organosilane surfactant was studied with X-ray powder diffraction (XRD), high-resolution scanning electron microscopy (HRSEM) and Monte Carlo simulation of the crystal growth. The hydrothermal reaction products were collected at various crystallization times, and investigated with XRD and HRSEM. The HRSEM images of the final zeolite products were taken as synthesized and also after cross-sectioning with an argon ion beam. The HRSEM investigation revealed presence of a disordered network of mesoporous channels that penetrated the microporous zeolite crystal. Unless the loading of the surfactant was exceedingly high, the microporous zeolite particles exhibited truncated cubic morphologies that were almost like single crystals, despite penetration by the mesopores. The outline of the zeolite particle became progressively rounded as the mesoporosity was increased according to the surfactant loading. The mesoporosity in the zeolite crystals was well maintained against crystal-ripening processes for 6 d. This result supports the fact that the organosilane surfactant micelles became incorporated inside the zeolite crystal as a mesopore generator during the crystallization process. Data from Monte Carlo simulation agreed with these experimental results.
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| 6. |
- Deng, Hexiang, et al.
(författare)
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Large pore apertures in a series of metal organic frameworks
- 2012
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Ingår i: Science. - : American Association for the Advancement of Science (AAAS). - 0036-8075 .- 1095-9203. ; 336:6084, s. 1018-1023
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Tidskriftsartikel (refereegranskat)abstract
- We report a strategy to expand the pore aperture of metal-organic frameworks (MOFs) into a previously unattained size regime (>32 angstroms). Specifically, the systematic expansion of a well-known MOF structure, MOF-74, from its original link of one phenylene ring (I) to two, three, four, five, six, seven, nine, and eleven (II to XI, respectively), afforded an isoreticular series of MOF-74 structures (termed IRMOF-74-I to XI) with pore apertures ranging from 14 to 98 angstroms. All members of this series have non-interpenetrating structures and exhibit robust architectures, as evidenced by their permanent porosity and high thermal stability (up to 300 degrees C). The pore apertures of an oligoethylene glycol-functionalized IRMOF-74-VII and IRMOF-74-IX are large enough for natural proteins to enter the pores.
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| 7. |
- Gu, Dong, et al.
(författare)
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Surface-Casting Synthesis of Mesoporous Zirconia with a CMK-5-Like Structure and High Surface Area
- 2017
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Ingår i: Angewandte Chemie International Edition. - : Wiley. - 1433-7851 .- 1521-3773. ; 56:37, s. 11222-11225
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Tidskriftsartikel (refereegranskat)abstract
- About 15 years ago, the Ryoo group described the synthesis of CMK-5, a material consisting of a hexagonal arrangement of carbon nanotubes. Extension of the surface casting synthesis to oxide compositions, however, was not possible so far, in spite of many attempts. Here it is demonstrated, that crystalline mesoporous hollow zirconia materials with very high surface areas up to 400 m(2) g(-1), and in selected cases in the form of CMK-5-like, are indeed accessible via such a surface casting process. The key for the successful synthesis is an increased interaction between the silica hard template surface and the zirconia precursor species by using silanol group-rich mesoporous silica as a hard template. The surface areas of the obtained zirconias exceed those of conventionally hard-templated ones by a factor of two to three. The surface casting process seems to be applicable also to other oxide materials.
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| 8. |
- Han, Lu, et al.
(författare)
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Silica-Based Nanoporous Materials
- 2014
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Ingår i: Zeitschrift für Anorganische und Allgemeines Chemie. - : Wiley. - 0044-2313 .- 1521-3749. ; 640:3-4, s. 521-536
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Forskningsöversikt (refereegranskat)abstract
- Ordered nanoporous structures are among the most fascinating and industrially important materials currently in use. The archetypal zeolite material has now been joined by an eclectic array of new structures that exhibit porosity over a wide range of length scales and with order/disorder expressed in a multitude of ways. This raises the bar in terms of characterization and extends a real challenge to the scientific community to fully understand the properties and potential future applications of such materials. In this review we discuss the importance of modern microscopy tools combined with diffraction in this endeavour and show how the details of even the most complex quasi-crystalline nanoporous architectures can be elucidated. We show by using the appropriate spherical aberration (C-s) corrections in scanning transmission electron microscopy it is possible to decipher all the individual silicon and aluminum atoms in a zeolite structure. Automated routines for using large electron diffraction datasets for crystal structure determination of nanocrystals is described making the need for large single crystal synthesis less-and-less important. The power of complementary combinations of surface tools such as atomic force microscopy and high-resolution scanning electron microscopy is discussed to elucidate crystal growth mechanisms. For mesoporous materials synthesized from self-organized organic mesophases electron microscopy reveals the details of the complex hierarchy of porosity so crucial for the functional performance of the structure.
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| 9. |
- Kjellman, Tomas, et al.
(författare)
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Direct Observation of Plugs and Intrawall Pores in SBA-15 Using Low Voltage High Resolution Scanning Electron Microscopy and the Influence of Solvent Properties on Plug-Formation
- 2013
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 25:20, s. 4105-4112
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Tidskriftsartikel (refereegranskat)abstract
- Through the use of low voltage high resolution scanning electron microscopy (LV-HRSEM) we have studied the fine details of the intricate pore structure of SBA-15. Intrawall pores and deviations from the ideal and uniform cylindrical pores are clearly observed, and we report for the first time the direct observation of plugs in the pores. N-2-sorption measurements confirm their existence. LV-HRSEM provides an opportunity to quantify the frequency of occurrence of plugs within the pore structure. The rate of mesophase formation, followed with in situ small angle X-ray scattering (SAXS) under different solvent conditions, is shown to have a significant influence on the development of plugs and how frequently they occur. We suggest a mechanism explaining the existence of the plugs, providing means for a better understanding and control over material properties.
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| 10. |
- Li, Yanbo, et al.
(författare)
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Cobalt phosphate-modified barium-doped tantalum nitride nanorod photoanode with 1.5% solar energy conversion efficiency
- 2013
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Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 4
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Tidskriftsartikel (refereegranskat)abstract
- Spurred by the decreased availability of fossil fuels and global warming, the idea of converting solar energy into clean fuels has been widely recognized. Hydrogen produced by photoelectrochemical water splitting using sunlight could provide a carbon dioxide lean fuel as an alternative to fossil fuels. A major challenge in photoelectrochemical water splitting is to develop an efficient photoanode that can stably oxidize water into oxygen. Here we report an efficient and stable photoanode that couples an active barium-doped tantalum nitride nanostructure with a stable cobalt phosphate co-catalyst. The effect of barium doping on the photoelectrochemical activity of the photoanode is investigated. The photoanode yields a maximum solar energy conversion efficiency of 1.5%, which is more than three times higher than that of state-of-the-art single-photon photoanodes. Further, stoichiometric oxygen and hydrogen are stably produced on the photoanode and the counter electrode with Faraday efficiency of almost unity for 100 min.
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| 11. |
- Liu, Shaohua, et al.
(författare)
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Synthesis of chiral TiO2 nanofibre with electron transition-based optical activity
- 2012
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Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 3, s. 1215-
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Tidskriftsartikel (refereegranskat)abstract
- The optical chirality induced at the absorption bands due to electronic exciton coupling of the transition dipole moments between chromophores in close proximity is ubiquitous in helical organic materials. However, inorganic materials with optical activity resulting from electronic transitions have not been explored. Here we report the synthesis of chiral TiO2 fibres via transcription of the helical structure of amino acid-derived amphiphile fibres through coordination bonding interactions between the organics and the TiO2 source. Upon calcination, the as-prepared amorphous TiO2 double-helical fibres with a pitch length of ~100 nm were converted to double-helical crystalline fibres with stacks of anatase nanocrystals in an epitaxial helical relationship. Both the amorphous and anatase crystalline helical TiO2 fibres exhibited optical response to circularly polarized light at the absorption edge around ~350 nm. This was attributed to the semiconductor TiO2-based electronic transitions from the valence band to the conduction band under an asymmetric electric field.
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| 12. |
- Liu, Zheng, et al.
(författare)
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A review of fine structures of nanoporous materials as evidenced by microscopic methods
- 2013
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Ingår i: Microscopy. - : Oxford University Press (OUP). - 2050-5698 .- 2050-5701. ; 62:1, s. 109-146
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Forskningsöversikt (refereegranskat)abstract
- This paper reviews diverse capabilities offered by modern electron microscopy techniques in studying fine structures of nanoporous crystals such as zeolites, silica mesoporous crystals, metal organic frameworks and yolk-shell materials. For the case of silica mesoporous crystals, new approaches that have been developed recently to determine the three-dimensionally periodic average structure, e. g., through self-consistent analysis of electron microscope images or through consideration of accidental extinctions, are presented. Various structural deviations in nanoporous materials from their average structures including intergrowth, surface termination, incommensurate modulation, quasicrystal and defects are demonstrated. Ibidem observations of the scanning electron microscope and atomic force microscope give information about the zeolite-crystal-growth mechanism, and an energy for unstitching a building-unit from a crystal surface is directly observed by an anatomic force microscope. It is argued how these observations lead to a deeper understanding of the materials.
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| 13. |
- Suga, Mitsuo, et al.
(författare)
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Recent progress in scanning electron microscopy for the characterization of fine structural details of nano materials
- 2014
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Ingår i: Progress in Solid State Chemistry. - : Elsevier BV. - 0079-6786 .- 1873-1643. ; 42:1-2, s. 1-21
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Forskningsöversikt (refereegranskat)abstract
- Research concerning nano-materials (metal-organic frameworks (MOFs), zeolites, mesoporous silicas, etc.) and the nano-scale, including potential barriers for the particulates to diffusion to/from is of increasing importance to the understanding of the catalytic utility. of porous materials when combined with any potential super structures (such as hierarchically porous materials). However, it is difficult to characterize the structure of for example MOFs via X-ray powder diffraction because of the serious overlapping of reflections caused by their large unit cells, and it is also difficult to directly observe the opening of surface pores using ordinary methods. Electron-microscopic methods including high-resolution scanning electron microscopy (HRSEM) have therefore become imperative for the above challenges. Here, we present the theory and practical application of recent advances such as through-the-lens detection systems, which permit a reduced landing energy and the selection of high-resolution, topographically specific emitted electrons, even from electrically insulating nano-materials.
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| 14. |
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| 15. |
- Wang, Tao, et al.
(författare)
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A Co3O4-embedded porous ZnO rhombic dodecahedron prepared using zeolitic imidazolate frameworks as precursors for CO2 photoreduction
- 2016
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Ingår i: Nanoscale. - : Royal Society of Chemistry (RSC). - 2040-3364 .- 2040-3372. ; 8:12, s. 6712-6720
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Tidskriftsartikel (refereegranskat)abstract
- Metal-organic frameworks (MOFs) are attracting considerable attention for their use as both the precursor and the template to prepare metal oxides or carbon-based materials. For the first time in this paper, the core-shell ZIF-8@ZIF-67 crystals are thermally converted into porous ZnO@Co3O4 composites by combining a seed-mediated growth process with a two-step calcination. The designed porous ZnO@Co3O4 composites exhibited the highest photocatalytic activity with an excellent stability for the reduction of CO2 among the commonly reported composite photocatalysts. Their superior photocatalytic performance is demonstrated to be resulting from the unique porous structure of ZnO@Co3O4 and the co-catalytic function of Co3O4 which can effectively suppress the photocorrosion of ZnO.
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| 16. |
- Zhang, Xueyi, et al.
(författare)
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Synthesis of Self-Pillared Zeolite Nanosheets by Repetitive Branching
- 2012
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Ingår i: Science. - : American Association for the Advancement of Science (AAAS). - 0036-8075 .- 1095-9203. ; 336:6089, s. 1684-1687
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Tidskriftsartikel (refereegranskat)abstract
- Hierarchical zeolites are a class of microporous catalysts and adsorbents that also contain mesopores, which allow for fas transport of bulky molecules and thereby enable improved performance in petrochemical and biomass processing. We used repetitive branching during one-step hydrothermal crystal growth to synthesize a new hierarchical zeolite made of orthogonally connected microporous nanosheets. The nanosheets are 2 nanometers thick and contain a network of 0.5-nanometer micropores. The house-of-cards arrangement of the nanosheets creates a permanent network of 2- to 7-nanometer mesopores, which, along with the high external surface area and reduced micropore diffusion length, account for higher reaction rates for bulky molecules relative to those of other mesoporous and conventional MFI zeolites.
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| 17. |
- Zhao, Yingbo, et al.
(författare)
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Mesoscopic Constructs of Ordered and Oriented Metal-Organic Frameworks on Plasmonic Silver Nanocrystals
- 2015
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 137:6, s. 2199-2202
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Tidskriftsartikel (refereegranskat)abstract
- We enclose octahedral silver nanocrystals (Ag NCs) in metal-organic frameworks (MOFs) to make mesoscopic constructs O-h-nano-Ag MOF in which the interface between the Ag and the MOF is pristine and the MOF is ordered (crystalline) and oriented on the Ag NCs. This is achieved by atomic layer deposition of aluminum oxide on Ag NCs and addition of a tetra-topic porphyrin-based linker, 4,4',4?,4 ''-(porphyrin-5,10,15,20-tetrayl)tetrabenzoic acid (H4TCPP), to react with alumina and make MOF [Al-2(OH)2TCPP] enclosures around Ag NCs. Alumina thickness is precisely controlled from 0.1 to 3 nm, thus allowing control of the MOF thickness from 10 to 50 nm. Electron microscopy and grazing angle X-ray diffraction confirm the order and orientation of the MOF by virtue of the porphyrin units being perpendicular to the planes of the Ag. We use surface-enhanced Raman spectroscopy to directly track the metalation process on the porphyrin and map the distribution of the metalated and unmetalated linkers on a single-nanoparticle level.
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