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We report the facile bottom-up fabrication at ambient temperature of such a perfect preferentially oriented metal–organic frameworks nanofilm on a solid surface, consisting of metalloporphyrin building units

Surface nano-architecture of a metal-organic framework.

Nature materials, no. 7 (2010): 565-571

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摘要

The rational assembly of ultrathin films of metal-organic frameworks (MOFs)--highly ordered microporous materials--with well-controlled growth direction and film thickness is a critical and as yet unrealized issue for enabling the use of MOFs in nanotechnological devices, such as sensors, catalysts and electrodes for fuel cells. Here we r...更多

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  • The rational assembly of ultrathin films of metal–organic frameworks (MOFs)—highly ordered microporous materials1–5 —with well-controlled growth direction and film thickness is a critical and as yet unrealized issue for enabling the use of MOFs in nanotechnological devices, such as sensors, catalysts and electrodes for fuel cells.
  • The 2D CoTCPP-py-Cu sheets were deposited on a Si[100] substrate and stacked by a sequential layer-by-layer growth procedure that included
重点内容
  • The rational assembly of ultrathin films of metal–organic frameworks (MOFs)—highly ordered microporous materials1–5 —with well-controlled growth direction and film thickness is a critical and as yet unrealized issue for enabling the use of MOFs in nanotechnological devices, such as sensors, catalysts and electrodes for fuel cells
  • Metalloporphyrins are very stable π -conjugated macrocyclic molecules forming a diverse class of multifunctional materials, which exhibit interesting and useful catalytic, optical, electronic and biological properties6
  • Metalloporphyrin molecules are excellent candidates to act as components of molecular building blocks for the construction of MOFs because of the huge variety of available derivatives incorporating different centre-coordinated metals and various functional group substituents in the periphery of the molecule, thereby allowing fine control of the linkage motif
  • The basis of the layer-by-layer growth technique is that the reaction components are combined in a sequential manner
  • The rational bottom-up assembly of MOF thin films on substrates, where crystalline order is endowed in both out-of-plane and in-plane orientations, has remained an elusive target
  • Detailed insight into the crystallinity, preferred orientation and homogeneity of the fabricated NAFS-1 films was obtained from synchrotron X-ray diffraction (XRD; λ = 1.554 Å) carried out in two different scattering geometries—out-of-plane mode, which is sensitive to the lattice parameter in the growth direction, and in-plane mode, which is sensitive to the in-plane lattice dimensions
结果
  • NAFS-1 films on a quartz substrate after successive cycles of sheet deposition, rinsing/solvent immersion and drying.
  • Ultraviolet–visible absorption spectroscopy was used to follow the successful layer-by-layer film growth of NAFS-1 on a quartz substrate by monitoring the evolution of the characteristic Soret band of the porphyrin units as a function of the number of sheet deposition and solvent immersion cycles (Fig. 2a).
  • The linear increase of the absorbance with increasing number of cycles as shown in Fig. 2b provides unambiguous evidence that, to a good approximation, each step of the layer stacking protocol leads to deposition of the same amount of material.
  • Detailed insight into the crystallinity, preferred orientation and homogeneity of the fabricated NAFS-1 films was obtained from synchrotron X-ray diffraction (XRD; λ = 1.554 Å) carried out in two different scattering geometries—out-of-plane mode, which is sensitive to the lattice parameter in the growth direction, and in-plane mode, which is sensitive to the in-plane lattice dimensions.
  • To obtain further structural information on the ordering of the individual layers in NAFS-1, the authors carried out rocking curve (θ -scan) and sample direction dependence measurements at the (001) peak position in the out-of-plane orientation.
  • In contrast to the pillaring role played by bpy in linking the layers in the bulk porphyrin MOFs, in the NAFS-1 structural model two monodentate pyridine molecules coordinate axially to both the copper dinuclear block and CoTCPP to complete the coordination sphere and retain two-dimensionality.
结论
  • The authors' results suggest that the π–π interaction plays an important stereoelectronic role in defining the perfect directional control in the growth of NAFS-1 as the metal-coordinated pyridine molecules projected from the 2D sheets allow each further layer to dock in a highly ordered interdigitated manner in the growth of NAFS-1.
  • The results presented here show the first successful construction of a crystalline MOF film on a surface with complete structural growth control in both the out-of-plane and in-plane geometries using an unconventional fabrication protocol at room temperature.
总结
  • The rational assembly of ultrathin films of metal–organic frameworks (MOFs)—highly ordered microporous materials1–5 —with well-controlled growth direction and film thickness is a critical and as yet unrealized issue for enabling the use of MOFs in nanotechnological devices, such as sensors, catalysts and electrodes for fuel cells.
  • The 2D CoTCPP-py-Cu sheets were deposited on a Si[100] substrate and stacked by a sequential layer-by-layer growth procedure that included
  • NAFS-1 films on a quartz substrate after successive cycles of sheet deposition, rinsing/solvent immersion and drying.
  • Ultraviolet–visible absorption spectroscopy was used to follow the successful layer-by-layer film growth of NAFS-1 on a quartz substrate by monitoring the evolution of the characteristic Soret band of the porphyrin units as a function of the number of sheet deposition and solvent immersion cycles (Fig. 2a).
  • The linear increase of the absorbance with increasing number of cycles as shown in Fig. 2b provides unambiguous evidence that, to a good approximation, each step of the layer stacking protocol leads to deposition of the same amount of material.
  • Detailed insight into the crystallinity, preferred orientation and homogeneity of the fabricated NAFS-1 films was obtained from synchrotron X-ray diffraction (XRD; λ = 1.554 Å) carried out in two different scattering geometries—out-of-plane mode, which is sensitive to the lattice parameter in the growth direction, and in-plane mode, which is sensitive to the in-plane lattice dimensions.
  • To obtain further structural information on the ordering of the individual layers in NAFS-1, the authors carried out rocking curve (θ -scan) and sample direction dependence measurements at the (001) peak position in the out-of-plane orientation.
  • In contrast to the pillaring role played by bpy in linking the layers in the bulk porphyrin MOFs, in the NAFS-1 structural model two monodentate pyridine molecules coordinate axially to both the copper dinuclear block and CoTCPP to complete the coordination sphere and retain two-dimensionality.
  • The authors' results suggest that the π–π interaction plays an important stereoelectronic role in defining the perfect directional control in the growth of NAFS-1 as the metal-coordinated pyridine molecules projected from the 2D sheets allow each further layer to dock in a highly ordered interdigitated manner in the growth of NAFS-1.
  • The results presented here show the first successful construction of a crystalline MOF film on a surface with complete structural growth control in both the out-of-plane and in-plane geometries using an unconventional fabrication protocol at room temperature.
基金
  • We thank JST (CREST), NEDO and JSPS (No 20350030 and 20655030) and the Global COE Program ‘Science for Future Molecular Systems’ for financial support, SPring-8 for access to the synchrotron X-ray facilities under the Priority Nanotechnology Support Program administered by JASRI (2008B1801, 2009A1703) and under proposal 2008B2205 and the Center of Advanced Instrumental Analysis, Kyushu University for the use of the FT-IR spectrometer and the ESCA system. Author contributions This work has been carried out mainly by JST-CREST and METI-NEDO projects where H.K. is a project leader and responsible for all
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