Geometrical Supercooling of Liquids in Porous Glass

Warnock, J.; Awschalom, D. D.; Shafer, M. W.

doi:10.1103/physrevlett.57.1753

Cited by 196 publications

(140 citation statements)

References 10 publications

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“…The pore size in zeolites (between 0.2 and 1 nm) is close to the sizes of small molecules like CH 4 or CO 2 , and can be tuned by ion exchange in the zeolite matrix. Because of this similarity in size, it is no surprise that the diffusion coefficient of methane can vary by as much as 6-10 orders of magnitude, depending on the pore topology.…”

Section: Transport In Nanochannelsmentioning

confidence: 99%

“…As an example of phase transition shifts in confinement, in work in which time-resolved optical experiments were used to study the dynamics of liquid oxygen in pores with diameters of between 2.2 and 18.7 nm [4], it was experimentally found that a supercooling of almost 20% below the bulk freezing point is obtained in the smallest pores. The freezing-point depression follows the relationship:…”

Section: Phase Equilibria In Nanochannelsmentioning

confidence: 99%

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Chemistry in nanochannel confinement

Gardeniers

2009

Anal Bioanal Chem

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This review addresses the questions of whether it makes sense to use lithographically defined nanochannels for chemistry in liquids, and what it is possible to learn from experiments on that topic. The behavior of liquids in different classes of pores (categorized according to their size) is reviewed, with a focus on chemical reactions and protein dynamics. A number of interesting phenomena are discussed for nanochannels with feature sizes that are manufacturable with modern photolithography-based fabrication technology. The use of spectroscopic methods to investigate chemistry in nanochannels, where both spectroscopic method and nanochannels are integrated into a single device, will be evaluated.

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Section: Transport In Nanochannelsmentioning

confidence: 99%

Section: Phase Equilibria In Nanochannelsmentioning

confidence: 99%

Chemistry in nanochannel confinement

Gardeniers

2009

Anal Bioanal Chem

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“…13,14 According to a study combining Dielectric Relaxation Spectroscopy and Differential Scanning Calorimetry experiments with Grand Canonical Monte Carlo simulations, 15 uids conned in cylindrical nanopores (e.g. MCM41) should freeze into a single crystalline structure for average pore diameters larger than 20s (s being the diameter of the guest molecule).…”

Section: 12mentioning

confidence: 99%

“…The 1 H spectra, on the other hand, showed that there is always a certain amount of water molecules present inside the porous network, which it is difficult to completely remove. Finally, the 13 C spectra showed evidence of isotropic rotational diffusion of the solvated SNP complexes inside the matrix pores. Therefore, the H 2 O present in the pores could not be reasonably modelled by the PDF analysis.…”

mentioning

confidence: 99%

“…These results were further conrmed by a multinuclear NMR study. NMR is especially suited, due to its local character and its sensitivity towards the 23 Na, 13 C, 1 H and 29 Si isotopes present in the studied material. From the 29 Si spectra, we could infer that the host matrix was not changed by the incorporation of the guest, while the 23 Na spectra conrmed the absence of a crystalline SNP phase.…”

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Structure determination of molecular nanocomposites by combining pair distribution function analysis and solid-state NMR

et al. 2015

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Transparent mesoporous silica monoliths of well-controlled porosity and a narrow pore size distribution around 6 nm have been used to prepare sodium nitroprusside (SNP) nanocomposites. The obtained nanomaterials could be characterised using X-ray total scattering coupled to atomic pair distribution function analysis (PDF) and solid-state NMR spectroscopy. The PDF analysis allows for a structural description of the confined species, as well as for the identification of the various coexisting phases: SNP isolated molecules and SNP crystalline nanoparticles. The model obtained suggests that the nanocrystals have the same molecular structure as the bulk crystalline material and measure about 6 nm in diameter.This result is quite exceptional because the space available inside the pores is only about ten times the size of the molecules. The multi-nuclei solid state NMR investigation confirms the structural model proposed by the PDF analysis and assigns the isolated molecules to the dynamic disorder of a solvated phase. The latter approach additionally provides quantitative information on the relative ratio between the dynamic molecules and the rigid nanocrystals. This result is exploited to study the evolution of the two confined SNP phases with respect to solvating water molecules. We show that the confined SNP nanocrystals can be easily dissolved when storing the nanocomposites at increasing atmospheric relative humidity.

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Condensation‐Controlled Toposelective Vapor Deposition in Nano‐ and Microcavities: Theory, Methods, Applications, and Related Technologies

Lovikka¹

2022

Adv Materials Inter

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fabricable while we are facing increasing complexity in, for example, microelectronics. [6,7] For these reasons, challenges such as bad pattern alignment, [8,9] or pinch-off of pores and void formation [10][11][12][13] in top-down fabrication need to be addressed. On the other hand, a continuous film causes tradeoffs in desirable properties in many nanotechnological applications, such as losing mesoporosity while increasing the mechanical properties of an aerogel [14] or reducing catalytic activity while increasing catalyst stability against sintering. [15] To counter these problems, even atomic layer deposition (ALD), a method known for its superior conformality, has been expanded into area-selective fabrication by the addition of etching and functionalization steps in the workflow. [16][17][18][19] However, additional steps make the workflow increasingly slow, complex, and dependent on surface chemistries. There is also a growing interest in area-selectivity based on properties of precursors and substrates in ALD, [20] but new requirements on precursors would narrow down potential reagents. Furthermore, even conformal methods would leave voids inside ink-bottle-shaped pores and under composite undercuts [21] because conformal methods would clog the pore mouths before filling the internal parts. These problems have very recently revoked calls for profound changes and even a paradigm shift toward selective functionalization in the nanoscale. [18,20,[22][23][24][25] Special attention should be paid to inherently non-conformal methods, especially if they are surface-selective towards cavities. This includes both surface-selective subconformal coatings, those that coat only extremities and protrusions of a substrate, and surface-selective superconformal coatings, those that fill or coat cavities.Bottom-up approaches could eliminate the aforementioned problems while reducing the needed steps for surface-selective treatments-instead of breaking or carving things smaller and using miniaturized techniques (top-down), coatings could be grown self-aligning (bottom-up). One bottom-up category is surface-shape-selective deposition. Currently, this category has limited approaches, which are often based on either anisotropic processes such as directional plasma etching [26] or reagent flux, force fields, [27] competitive adsorption, [28] or reagents and additives with specific properties. [22] Truly bottom-up gap-filling technologies, especially those free of line-of-sight limitations, Nanotechnology drives technological progress in many frontiers, from electronics to medicine, from tougher composites to adaptive surfaces. As the feature sizes are made smaller, the importance of surfaces is increased. Many of the most powerful methods for surface manipulation are variants of vapor deposition (VD). However, VD is typically not surface-selective and, therefore, extra work steps are needed to integrate the methods into nanofabrication routines. Furthermore, many fields are moving toward 3D nanostructures, which unavoidably means...

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Geometrical Supercooling of Liquids in Porous Glass

Cited by 196 publications

References 10 publications

Chemistry in nanochannel confinement

Chemistry in nanochannel confinement

Structure determination of molecular nanocomposites by combining pair distribution function analysis and solid-state NMR

Condensation‐Controlled Toposelective Vapor Deposition in Nano‐ and Microcavities: Theory, Methods, Applications, and Related Technologies

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