Solution–TiO<sub>2</sub>Interface Probed by Frequency-Modulation Atomic Force Microscopy

Hiasa, Takumi; Kimura, Kenjiro; Ōnishi, Hiroshi; Ohta, Makoto; Watanabe, Kazuyuki; Kokawa, Ryohei; Oyabu, Noriaki; Kobayashi, Kei; Yamada, Hirofumi

doi:10.1143/jjap.48.08jb19

Cited by 18 publications

(12 citation statements)

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“…Investigations of the surfaces of TiO 2 are important for understanding the mechanisms of photocatalytic reactions. Scanning probe microcopy (SPM) techniques such as scanning tunneling microscopy and atomic force microscopy (AFM) enable visualization of the atomic-scale surface structures of various crystals, as previously reported. , Rutile, anatase, and brookite are the major stable polymorphs of TiO 2 crystals. ,− Early SPM studies of TiO 2 were mainly performed on crystals of rutile, which is the most stable TiO 2 crystal phase. − In addition, there have been several reports of atomic-scale investigations of anatase TiO 2 by AFM in vacuum . However, the surface structure of brookite TiO 2 has not yet been experimentally investigated by SPM techniques.…”

Section: Introductionmentioning

confidence: 99%

Direct Imaging of Atomic-Scale Surface Structures of Brookite TiO₂ Nanoparticles by Frequency Modulation Atomic Force Microscopy in Liquid

et al. 2018

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1Direct imaging of atomic-scale surface structures of TiO 2 nanoparticles is a promis-2 ing method for understanding the detailed mechanism of their photocatalytic activities. 3 Atomic force microscopy (AFM) is one of the analytical tools used for direct imaging 4 of surfaces, but atomic-scale AFM studies of TiO 2 nanoparticles in a liquid have not 5 been reported. Here, we report two methods for fixing of TiO 2 nanocrystals: an elec-6 trostatic method and a cross-linking method. Both methods enabled visualization of 7 subnanoscale surface structures of brookite TiO 2 nanoparticles in a liquid by frequency 8 modulation AFM (FM-AFM). The FM-AFM imaging results and density functional 9 theory molecular dynamics calculations suggest that the subnanoscale structures in the 10 FM-AFM images can be explained by the arrangement of the surface topmost atoms 11 or their hydration structures on the brookite TiO 2 (210) surface. Our results open 12 up various possibilities for studying atomic-scale surface structures of nanoparticles in 13 liquids by AFM.14

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Section: Introductionmentioning

confidence: 99%

Direct Imaging of Atomic-Scale Surface Structures of Brookite TiO₂ Nanoparticles by Frequency Modulation Atomic Force Microscopy in Liquid

et al. 2018

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“…The development of the frequency-modulation atomic force microscopy (FM-AFM) technique has progressed recently; it can now be applied to solid-liquid interfaces and demonstrates highresolution imaging of solid surfaces in liquids for mica, 9 CaCO 3 , 10-12 and LiNbO 3 . 13 Regarding simple metal oxides, images of TiO 2 14 and Al 2 O 3 15 surfaces in liquid environments are reported. However, true atomic images were not acquired on metal oxides other than mica, and there have been no detailed observations of their atomistic structures in liquids.…”

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confidence: 99%

True atomic-scale imaging of a spinel Li4Ti5O12(111) surface in aqueous solution by frequency-modulation atomic force microscopy

Kitta

Kohyama

Ōnishi

2014

Applied Physics Letters

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“…For further discussions, relationship between IL layering and the surface morphology will be clarified in detail. Recent progress in Grazing Incidence X-ray Diffraction (GIXD), 54 X-ray Reflection (XRR) 31,33,35 and dynamic force microscopy (DFM) [55][56][57] operated at solid/liquid interfaces may provide further insights into the mechanism of layer formation on the surface, including the surface morphological effect.…”

Section: Resultsmentioning

confidence: 99%

Modulating the immobilization process of Au nanoparticles on TiO2(110) by electrostatic interaction between the surface and ionic liquids

Suzuki¹,

Ohta²,

Kurimoto³

et al. 2011

Phys. Chem. Chem. Phys.

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We found that the adsorption states of Au nanoparticles (NPs) on TiO(2)(110) varied with the ionic liquids (ILs) that encapsulate the NPs during the entire process from synthesis of NPs to immobilization of the NPs on the surface at 323 K. Five kinds of ILs, including three 1-butyl-3-methylimidazolium ([C(4)MIm]) cation-based ILs of tetrafluoroborate ([C(4)MIm][BF(4)]), hexafluorophosphate ([C(4)MIm][PF(6)]) and bis(trifluoromethylsulfonyl)amide ([C(4)MIm][NTf(2)]), and two [BF(4)] anion-based ILs of 1-(methoxymethyl)-1-methylpyrrolidinium ([PY1,1O1][BF(4)]) and N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium ([N122,1O2][BF(4)]), were used. They provided different adsorption states of the Au NPs on the surface. We considered the determinant factor for the adsorption states of NPs on the surface from the viewpoint of electrostatic interactions between IL and IL and between IL and the surface. We deduced the influence of these interactions from the increments of NP's diameter and the amount of NPs after the immobilization, and obtained the order of anions as [BF(4)] ≈ [NTf(2)] > [PF(6)] for the three [C(4)MIm] based ILs and the order of cations as [PY1,1O1] > [C(4)MIm] > [N122,1O2] for the three [BF(4)] based ILs. Interestingly, the above orders were no match with the conventional physicochemical and chemical parameters but β of Kamlet-Taft solvent descriptors and Lewis basicity of anions in the case of anions of ILs. The results of anions indicate that the chemical natures of ILs might affect the immobilization of NPs through hydrogen bonding or coordination bonding with the surface. We suggested that such a trend in anions was 'local viscosity' of ILs in the vicinity of surface. Besides, layer formation of IL on the surface might be also an influential factor to control the size of NPs and the surface density of NPs. Our results show that the combination of a charged surface and charged molecules has the potential for controlling locations of the NPs on the surface preferentially with tuning the electrostatic interaction.

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Solution–TiO₂Interface Probed by Frequency-Modulation Atomic Force Microscopy

Cited by 18 publications

References 18 publications

Direct Imaging of Atomic-Scale Surface Structures of Brookite TiO₂ Nanoparticles by Frequency Modulation Atomic Force Microscopy in Liquid

Direct Imaging of Atomic-Scale Surface Structures of Brookite TiO₂ Nanoparticles by Frequency Modulation Atomic Force Microscopy in Liquid

True atomic-scale imaging of a spinel Li4Ti5O12(111) surface in aqueous solution by frequency-modulation atomic force microscopy

Modulating the immobilization process of Au nanoparticles on TiO2(110) by electrostatic interaction between the surface and ionic liquids

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Solution–TiO2Interface Probed by Frequency-Modulation Atomic Force Microscopy

Cited by 18 publications

References 18 publications

Direct Imaging of Atomic-Scale Surface Structures of Brookite TiO2 Nanoparticles by Frequency Modulation Atomic Force Microscopy in Liquid

Direct Imaging of Atomic-Scale Surface Structures of Brookite TiO2 Nanoparticles by Frequency Modulation Atomic Force Microscopy in Liquid

True atomic-scale imaging of a spinel Li4Ti5O12(111) surface in aqueous solution by frequency-modulation atomic force microscopy

Modulating the immobilization process of Au nanoparticles on TiO2(110) by electrostatic interaction between the surface and ionic liquids

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Solution–TiO₂Interface Probed by Frequency-Modulation Atomic Force Microscopy

Direct Imaging of Atomic-Scale Surface Structures of Brookite TiO₂ Nanoparticles by Frequency Modulation Atomic Force Microscopy in Liquid

Direct Imaging of Atomic-Scale Surface Structures of Brookite TiO₂ Nanoparticles by Frequency Modulation Atomic Force Microscopy in Liquid