Adsorption of n-Pentane on Mesoporous Silica and Adsorbent Deformation

Gor, Gennady Y.; Paris, Oskar; Prass, Johannes; Russo, Patrícia A.; Carrott, M.M.L. Ribeiro; Neimark, Alexander V.

doi:10.1021/la401513n

Cited by 73 publications

(104 citation statements)

References 61 publications

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“…Here both strain isotherms show monotonic contraction with decreasing relative pressure exhibiting a local minimum at point B. This behavior is qualitatively in good agreement with the theoretical predictions [24,25,28,29] as well as with previous experimental results [9,12,16,17]. According to these references the strain observed in the plateau region can be attributed to the capillary pressure created in the liquid by the hemispherical meniscus of the liquid-vapor interfaces at the pore ends:…”

Section: Sorption-induced Deformationsupporting

confidence: 91%

“…A different approach was chosen by Schoen and coworkers, who performed Grand-Canonical Monte Carlo simulations of fluid adsorption and condensation for slit-shaped mesopores, including a simple model of the solid surface by harmonically bound surface atoms to a rigid backbone [26,27]. Both groups could describe experimental results qualitatively and to some extent quantitatively [16,28,29], however, the more complex pore structures often found in application related materials and their corresponding deformational behavior are far from being fully understood.…”

Section: Introductionmentioning

confidence: 99%

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Relationship Between Pore Structure and Sorption-Induced Deformation in Hierarchical Silica-Based Monoliths

Balzer

Morak

Erko³

et al. 2015

Zeitschrift Für Physikalische Chemie

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Abstract:Experimental results on sorption-induced deformation during npentane desorption were obtained by in-situ dilatometry and in-situ small angle X-ray scattering (SAXS). The sample investigated was a silica-based monolith with hierarchical pore structure comprising a macroporous network of struts, each strut containing well-defined cylindrical mesopores ordered on a 2D hexagonal lattice. In-situ dilatometry and in-situ SAXS measurements revealed strain isotherms of similar shape, which are qualitatively in good agreement with recent theoretical predictions. From the relative pressure range of the liquid filled mesopores a pore load modulus of 1.5 GPa is determined. The relative pressure region of mono-and multilayer formation, however, reveals differences between the two independent methods. In particular, the net strain at saturation pressure is considerably larger for in-situ dilatometry. We attribute this observation to the different sensitivity of the two methods to anisotropic deformation in the hierarchical solid framework. While in-situ SAXS measures the mesopore lattice strain and is therefore exclusively sensitive to radial deformation of the struts, dilato-*Corresponding authors: Oskar Paris,

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Section: Sorption-induced Deformationsupporting

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Relationship Between Pore Structure and Sorption-Induced Deformation in Hierarchical Silica-Based Monoliths

Balzer

Morak

Erko³

et al. 2015

Zeitschrift Für Physikalische Chemie

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“…The authors used in situ grazing-incidence small-angle X-ray scattering to measure the change of in-plane and out-of-plane lattice parameters as a function of relative humidity. 38 The out of plane strain, similar to previous experiments, 30,65,70 showed a linear expansion in the beginning. The in plane strain is different, clearly showing linear contraction at higher pressures (then higher contraction near capillary condensation and finally expansion).…”

Section: Beyond Measuring One Strainsupporting

confidence: 87%

“…In particular, there are a number of systems where adsorption-induced deformation is observed but the isotherms do not show any hysteresis, for example, carbons 37,127 and mesoporous silica with small pore sizes. 30,70 Another work which predicted adsorption-desorption hysteresis due to the flexibility of the adsorbent was a Monte Carlo model by Shen and Siderius. 128 They pointed out that such a model is relevant only to materials with high adsorption strain, such as MOFs.…”

Section: Coupling Between Thermodynamic and Elastic Aspects Of Adsmentioning

confidence: 99%

Adsorption-induced deformation of nanoporous materials—A review

Gor

Huber

Bernstein

2017

Applied Physics Reviews

201

209

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When a solid surface accommodates guest molecules, they induce noticeable stresses to the surface and cause its strain. Nanoporous materials have high surface area and, therefore, are very sensitive to this effect called adsorption-induced deformation. In recent years, there has been significant progress in both experimental and theoretical studies of this phenomenon, driven by the development of new materials as well as advanced experimental and modeling techniques. Also, adsorption-induced deformation has been found to manifest in numerous natural and engineering processes, e.g., drying of concrete, water-actuated movement of non-living plant tissues, change of permeation of zeolite membranes, swelling of coal and shale, etc. In this review, we summarize the most recent experimental and theoretical findings on adsorption-induced deformation and present the state-of-the-art picture of thermodynamic and mechanical aspects of this phenomenon. We also reflect on the existing challenges related both to the fundamental understanding of this phenomenon and to selected applications, e.g., in sensing and actuation, and in natural gas recovery and geological CO2 sequestration.

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“…The behavior observed is typical of adsorption-induced deformations of mesoporous materials and is due to the change of the pressure P of the confined fluid (adsorption stress) in the mesopores [17]. The shape of the strain at low pressures (before the hysteresis loop related to capillary condensation) may differ and depends on the strength of the solid-fluid interactions [35]. At higher pressures, when the pores are filled with capillary condensate, the strain changes linearly with ln(p/p 0 ).…”

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confidence: 97%

Elastic response of mesoporous silicon to capillary pressures in the pores

Gor

Bertinetti

Bernstein

et al. 2015

Applied Physics Letters

112

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We study water adsorption-induced deformation of a monolithic, mesoporous silicon membrane traversed by independent channels of ∼8 nm diameter. We focus on the elastic constant associated with the Laplace pressure-induced deformation of the membrane upon capillary condensation, i.e. the pore-load modulus. We perform finite-element method (FEM) simulations of the adsorption-induced deformation of hexagonal and square lattices of cylindrical pores representing the membrane. We find that the pore-load modulus weakly depends on the geometrical arrangement of pores, and can be expressed as a function of porosity. We propose an analytical model which relates the pore-load modulus to the porosity and to the elastic properties of bulk silicon (Young's modulus and Poisson's ratio), and provides an excellent agreement with FEM results. We find good agreement between our experimental data and the predictions of the analytical model, with the Young's modulus of the pore walls slightly lower than the bulk value. This model is applicable to a large class of materials with morphologies similar to mesoporous silicon. Moreover, our findings suggest that liquid condensation experiments allow one to elegantly access the elastic constants of a mesoporous medium.Mesoporous silicon (pSi) prepared by electrochemical etching of bulk silicon has been attracting much attention from both fundamental and applied sciences owing to its unique optical, electrical and thermal properties [1][2][3][4][5][6]. While control over mechanical properties of pSi is necessary for its applications, the understanding of its response to mechanical loads is mainly limited to measuring Young's modulus of porous samples [7,8].Since pSi can be prepared as a bulk (monolithic) mesoporous system with parallel, channel-like independent pores, it has been of a particular interest for studies of fluid adsorption [4]. On the one hand, this matrix allows one to study the influence of spatial confinement on the physics and chemistry of liquids [9][10][11][12][13][14][15]. On the other hand, it is possible to synthesize composite materials with finely tuned optical and electrical properties by liquid adsorption or infiltration [4,16]. Therefore, exploration of the mechanical properties of silicon relevant to interactions with liquids, the topic of this Letter, is also of high importance.When a fluid is adsorbed in a mesopore, it exerts a pressure on the pore walls, which is typically of the order of 10 7 Pa [17]. This pressure causes deformation of the pore, and as a result deformation of the porous material as a whole. This effect, known as adsorption-induced deformation has been experimentally observed for various mesoporous materials: Vycor glass [18,19], templated silica [20][21][22], low-k films [23,24], aerogels [25,26], porous gold [27] and pSi [28]. There are two ways to * ggor@princeton.edu measure the adsorption strains experimentally: for materials which can be prepared as macroscopic samples, the dilatometric technique can be used, and the reported strain is...

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Adsorption of n-Pentane on Mesoporous Silica and Adsorbent Deformation

Cited by 73 publications

References 61 publications

Relationship Between Pore Structure and Sorption-Induced Deformation in Hierarchical Silica-Based Monoliths

Relationship Between Pore Structure and Sorption-Induced Deformation in Hierarchical Silica-Based Monoliths

Adsorption-induced deformation of nanoporous materials—A review

Elastic response of mesoporous silicon to capillary pressures in the pores

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