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Systematic Tuning and Multifunctionalization of Covalent Organic Polymers for Enhanced Carbon Capture
Porous covalent polymers are attracting increasing interest in the fields of gas adsorption, gas separation, and catalysis due to their fertile synthetic polymer chemistry, large internal surface areas, and ultrahigh hydrothermal stabilities. While precisely manipulating the porosities of porous organic materials for targeted applications remains challenging, we show how a large degree of diversity can be achieved in covalent organic polymers by incorporating multiple functionalities into a single framework, as is done for crystalline porous materials. In this work, we synthesized 17 novel porous covalent organic polymers (COPs) with finely tuned porosities, a wide range of Brunauer–Emmett–Teller (BET) specific surface areas of 430–3624 m 2 g –1 , and a broad range of pore volumes of 0.24–3.50 cm 3 g –1 , all achieved by tailoring the length and geometry of building blocks. Furthermore, we are the first to successfully incorporate more than three distinct functional groups into one phase for porous organic materials, which has been previously demonstrated in crystalline metal–organic frameworks (MOFs). COPs decorated with multiple functional groups in one phase can lead to enhanced properties that are not simply linear combinations of the pure component properties. For instance, in the dibromobenzene-lined frameworks, the bi- and multifunctionalized COPs exhibit selectivities for carbon dioxide over nitrogen twice as large as any of the singly functionalized COPs. These multifunctionalized frameworks also exhibit a lower parasitic energy cost for carbon capture at typical flue gas conditions than any of the singly functionalized frameworks. Despite the significant improvement, these frameworks do not yet outperform the current state-of-art technology for carbon capture. Nonetheless, the tuning strategy presented here opens up avenues for the design of novel catalysts, the synthesis of functional sensors from these materials, and the improvement in the performance of existing covalent organic polymers by multifunctionalization.
Cyclodextrin-Derived Porous Liquids Enabled by In Situ Solvation Shell Formation
Porous liquids (PLs) represent a unique platform for molecular separations by combining permanent porosity with liquid-phase mobility. However, it remains a formidable challenge to construct and stabilize PLs with sub-5 Å pores using readily available porous host and liquid media. Here, we report the construction of cyclodextrin (CD)-derived PLs enabled by in situ solvation shell formation. The acid–base neutralization reaction between CD and an organic base was leveraged to generate a thin ionic solvation shell around the CD host, effectively liquefying CD and preventing its segregation in the liquid base medium while preserving accessible molecular-scale cavities. Spectroscopic analysis, neutron scattering, density functional theory calculations, and molecular dynamics simulations collectively confirm the structural evolution and existence of abundant internal porosity in PLs. The unique architectures of CD-derived PLs enable highly selective encapsulation of fluorinated alkanes and significantly enhanced uptake of inert gases. This facile and generalizable strategy enables construction of high-quality PLs with engineered ultramicroporosity to facilitate molecular separations.
Viscous Behavior of Clay‐Rich Rocks and Its Role in Focused Fluid Flow
Abstract Focused fluid flow is common in sedimentary basins worldwide, where flow structures often penetrate through sandy reservoir rocks, and clay‐rich caprocks. To better understand the mechanisms forming such structures, the impacts of the viscoelastic deformation and strongly nonlinear porosity‐dependent permeability of clay‐rich materials are assessed from an experimental and numerical modeling perspective. The experimental methods to measure the poroviscoelastic and transport properties of intact and remolded shale have been developed, and the experimental data is used to constrain the numerical simulations. It is demonstrated that viscoelastic deformation combined with nonlinear porosity‐dependent permeability triggers the development of localized flow channels, often imaged as seismic chimneys. The permeability inside a channel increases by several orders of magnitude compared to the background values. In addition, the propagation time scale and the channel size strongly depend on the material properties of the fluid and the rock. The time‐dependent behavior of the clay‐rich rock may play a key role in the long‐term integrity of the subsurface formations.
Characteristics of ultra low-k nanoporous and fluorinated silica based films prepared by plasma enhanced chemical vapor deposition
Low dielectric constant (low-k) silica based films were deposited on p-type silicon and polycarbonate substrates by radio frequency (RF) plasma enhanced chemical vapor deposition method at low temperature. A mixture of tetraethoxysilane vapor, oxygen, and tetrafluoromethane (CF{sub 4}) was used for the deposition of the films in forms of two structures called as SiO{sub x}C{sub y} and SiO{sub x}C{sub y}F{sub z}. Properties of the films were controlled by amount of porosity and fluorine content in the film matrix. The influence of RF power and CF{sub 4} flow on the elemental composition, deposition rate, surface roughness, leakage current, refractive index, and dielectric constant of the films were characterized. Moreover, optical emission spectroscopy was applied to monitor the plasma process at the different parameters. Electrical characteristics of SiO{sub x}C{sub y} and SiO{sub x}C{sub y}F{sub z} films with metal-oxide-semiconductor structure were investigated using current-voltage analysis to measure the leakage current and breakdown field, as well as capacitance-voltage analysis to obtain the film's dielectric constant. The results revealed that SiO{sub x}C{sub y} films, which are deposited at lower RF power produce more leakage current, meanwhile the dielectric constant and refractive index of these films decreased mainly due to the more porosity in the film structure. By adding CF{sub 4} in the deposition process, fluorine, the most electronegative and the least polarized atom, doped into the silica film and led to decrease in the refractive index and the dielectric constant. In addition, no breakdown field was observed in the electrical characteristics of SiO{sub x}C{sub y}F{sub z} films and the leakage current of these films reduced by increment of the CF{sub 4} flow.
Computational modeling and analysis of thermoelectric properties of nanoporous silicon
In this paper, thermoelectric properties of nanoporous silicon are modeled and studied by using a computational approach. The computational approach combines a quantum non-equilibrium Green's function (NEGF) coupled with the Poisson equation for electrical transport analysis, a phonon Boltzmann transport equation (BTE) for phonon thermal transport analysis and the Wiedemann-Franz law for calculating the electronic thermal conductivity. By solving the NEGF/Poisson equations self-consistently using a finite difference method, the electrical conductivity σ and Seebeck coefficient S of the material are numerically computed. The BTE is solved by using a finite volume method to obtain the phonon thermal conductivity k{sub p} and the Wiedemann-Franz law is used to obtain the electronic thermal conductivity k{sub e}. The figure of merit of nanoporous silicon is calculated by ZT=S{sup 2}σT/(k{sub p}+k{sub e}). The effects of doping density, porosity, temperature, and nanopore size on thermoelectric properties of nanoporous silicon are investigated. It is confirmed that nanoporous silicon has significantly higher thermoelectric energy conversion efficiency than its nonporous counterpart. Specifically, this study shows that, with a n-type doping density of 10{sup 20} cm{sup –3}, a porosity of 36% and nanopore size of 3 nm × 3 nm, the figure of merit ZT can reach 0.32 at 600 K. The results also show that the degradation of electrical conductivity of nanoporous Si due to the inclusion of nanopores is compensated by the large reduction in the phonon thermal conductivity and increase of absolute value of the Seebeck coefficient, resulting in a significantly improved ZT.
Determination of elastic properties of a MnO{sub 2} coating by surface acoustic wave velocity dispersion analysis
MnO{sub 2} is a material of interest in the development of high energy-density batteries, specifically as a coating material for internal 3D structures, thus ensuring rapid energy deployment. Its electrochemical properties have been mapped extensively, but there are, to the best of the authors' knowledge, no records of the elastic properties of thin film MnO{sub 2}. Impulsive stimulated thermal scattering (ISTS), also known as the heterodyne diffraction or transient grating technique, was used to determine the Young's modulus (E) and porosity (ψ) of a 500 nm thick MnO{sub 2} coating on a Si(001) substrate. ISTS is an all optical method that is able to excite and detect surface acoustic waves (SAWs) on opaque samples. From the measured SAW velocity dispersion, the Young's modulus and porosity were determined to be E = 25 ± 1 GPa and ψ=42±1%, respectively. These values were confirmed by independent techniques and determined by a most-squares analysis of the carefully fitted SAW velocity dispersion. This study demonstrates the ability of the presented technique to determine the elastic parameters of a thin, porous film on an anisotropic substrate.
Resolution dependence of petrophysical parameters derived from X-ray tomography of chalk
X-ray computed tomography data from chalk drill cuttings were taken over a series of voxel dimensions, ranging from 320 to 25 nm. From these data sets, standard petrophysical parameters (porosity, surface area, and permeability) were derived and we examined the effect of the voxel dimension (i.e., image resolution) on these properties. We found that for the higher voxel dimensions, they are severely over or underestimated, whereas for 50 and 25 nm voxel dimension, the resulting values (5%–30% porosity, 0.2–2 m{sup 2}/g specific surface area, and 0.06–0.34 mD permeability) are within the expected range for this type of rock. We compared our results to macroscopic measurements and in the case of surface area, also to measurements using the Brunauer-Emmett-Teller (BET) method and found that independent of the degree of compaction, the results from tomography amount to about 30% of the BET method. Finally, we concluded that at 25 nm voxel dimension, the essential features of the nanoscopic pore network in chalk are captured but better resolution is still needed to derive surface area.
Quasi-periodic Fibonacci and periodic one-dimensional hypersonic phononic crystals of porous silicon: Experiment and simulation
A one-dimensional Fibonacci phononic crystal and a distributed Bragg reflector were constructed from porous silicon. The structures had the same number of layers and similar acoustic impedance mismatch, and were electrochemically etched in highly boron doped silicon wafers. The thickness of the individual layers in the stacks was approximately 2 μm. Both types of hypersonic band gap structure were studied by direct measurement of the transmittance of longitudinal acoustic waves in the 0.1–2.6 GHz range. Acoustic band gaps deeper than 50 dB were detected in both structures. The experimental results were compared with model calculations employing the transfer matrix method. The acoustic properties of periodic and quasi-periodic structures in which half-wave retarding bi-layers do not consist of two quarter-wave retarding layers are discussed. The strong correlation between width and depth of gaps in the transmission spectra is demonstrated. The dominant mechanisms of acoustic losses in porous multilayer structures are discussed. The elastic constants remain proportional over our range of porosity, and hence, the Grüneisen parameter is constant. This simplifies the expression for the porosity dependence of the Akhiezer damping.
The thin section rock physics: Modeling and measurement of seismic wave velocity on the slice of carbonates
This paper discusses a new approach for investigating the seismic wave velocity of rock, specifically carbonates, as affected by their pore structures. While the conventional routine of seismic velocity measurement highly depends on the extensive laboratory experiment, the proposed approach utilizes the digital rock physics view which lies on the numerical experiment. Thus, instead of using core sample, we use the thin section image of carbonate rock to measure the effective seismic wave velocity when travelling on it. In the numerical experiment, thin section images act as the medium on which wave propagation will be simulated. For the modeling, an advanced technique based on artificial neural network was employed for building the velocity and density profile, replacing image's RGB pixel value with the seismic velocity and density of each rock constituent. Then, ultrasonic wave was simulated to propagate in the thin section image by using finite difference time domain method, based on assumption of an acoustic-isotropic medium. Effective velocities were drawn from the recorded signal and being compared to the velocity modeling from Wyllie time average model and Kuster-Toksoz rock physics model. To perform the modeling, image analysis routines were undertaken for quantifying the pore aspect ratio that is assumed to represent the rocks pore structure. In addition, porosity and mineral fraction required for velocity modeling were also quantified by using integrated neural network and image analysis technique. It was found that the Kuster-Toksoz gives the closer prediction to the measured velocity as compared to the Wyllie time average model. We also conclude that Wyllie time average that does not incorporate the pore structure parameter deviates significantly for samples having more than 40% porosity. Utilizing this approach we found a good agreement between numerical experiment and theoretically derived rock physics model for estimating the effective seismic wave velocity of rock.
Controlling morphology, mesoporosity, crystallinity, and photocatalytic activity of ordered mesoporous TiO{sub 2} films prepared at low temperature
Partly ordered mesoporous titania films with anatase crystallites incorporated into the pore walls were prepared at low temperature by spin-coating a microemulsion-based reaction solution. The effect of relative humidity employed during aging of the prepared films was studied using SEM, TEM, and grazing incidence small angle X-ray scattering to evaluate the mesoscopic order, porosity, and crystallinity of the films. The study shows unambiguously that crystal growth occurs mainly during storage of the films and proceeds at room temperature largely depending on relative humidity. Porosity, pore size, mesoscopic order, crystallinity, and photocatalytic activity of the films increased with relative humidity up to an optimum around 75%.
Use of nanotomographic images for structure analysis of carbonate rocks
Carbonate rocks store more than 50% of world's petroleum. These rocks' structures are highly complex and vary depending on many factors regarding their formation, e.g., lithification and diagenesis. In order to perform an effective extraction of petroleum it is necessary to know petrophysical parameters, such as total porosity, pore size and permeability of the reservoir rocks. Carbonate rocks usually have a range of pore sizes that goes from nanometers to meters or even dozen of meters. The nanopores and micropores might play an important role in the pores connectivity of carbonate rocks. X-ray computed tomography (CT) has been widely used to analyze petrophysical parameters in recent years. This technique has the capability to generate 2D images of the samples' inner structure and also allows the 3D reconstruction of the actual analyzed volume. CT is a powerful technique, but its results depend on the spatial resolution of the generated image. Spatial resolution is a measurement parameter that indicates the smallest object that can be detected. There are great difficulties to generate images with nanoscale resolution (nanotomographic images). In this work three carbonate rocks, one dolomite and two limestones (that will be called limestone A and limestone B) were analyzed by nanotomography. The measurements were performed with the SkyScan2011 nanotomograph, operated at 60 kV and 200 μA to measure the dolomite sample and 40 kV and 200 μA to measure the limestone samples. Each sample was measured with a given spatial resolution (270 nm for the dolomite sample, 360 nm for limestone A and 450 nm for limestone B). The achieved results for total porosity were: 3.09 % for dolomite, 0.65% for limestone A and 3.74% for limestone B. This paper reports the difficulties to acquire nanotomographic images and further analysis about the samples' pore sizes.
Contributed Review: Nuclear magnetic resonance core analysis at 0.3 T
Nuclear magnetic resonance (NMR) provides a powerful toolbox for petrophysical characterization of reservoir core plugs and fluids in the laboratory. Previously, there has been considerable focus on low field magnet technology for well log calibration. Now there is renewed interest in the study of reservoir samples using stronger magnets to complement these standard NMR measurements. Here, the capabilities of an imaging magnet with a field strength of 0.3 T (corresponding to 12.9 MHz for proton) are reviewed in the context of reservoir core analysis. Quantitative estimates of porosity (saturation) and pore size distributions are obtained under favorable conditions (e.g., in carbonates), with the added advantage of multidimensional imaging, detection of lower gyromagnetic ratio nuclei, and short probe recovery times that make the system suitable for shale studies. Intermediate field instruments provide quantitative porosity maps of rock plugs that cannot be obtained using high field medical scanners due to the field-dependent susceptibility contrast in the porous medium. Example data are presented that highlight the potential applications of an intermediate field imaging instrument as a complement to low field instruments in core analysis and for materials science studies in general.
Small angle scattering methods to study porous materials under high uniaxial strain
We developed a high pressure cell for the in situ study of the porosity of solids under high uniaxial strain using neutron small angle scattering. The cell comprises a hydraulically actioned piston and a main body equipped with two single-crystal sapphire windows allowing for the neutron scattering of the sample. The sample cavity is designed to allow for a large volume variation as expected when compressing highly porous materials. We also implemented a loading protocol to adapt an existing diamond anvil cell for the study of porous materials by X-ray small angle scattering under high pressure. The two techniques are complementary as the radiation beam and the applied pressure are in one case perpendicular to each other (neutron cell) and in the other case parallel (X-ray cell). We will illustrate the use of these two techniques in the study of lamellar porous systems up to a maximum pressure of 0.1 GPa and 0.3 GPa for the neutron and X-ray cells, respectively. These devices allow obtaining information on the evolution of porosity with pressure in the pore dimension subdomain defined by the wave-numbers explored in the scattering process. The evolution with the applied load of such parameters as the fractal dimension of the pore-matrix interface or the apparent specific surface in expanded graphite and in expanded vermiculite is used to illustrate the use of the high pressure cells.
Computational stochastic model of ions implantation
Implantation flux ions into crystal leads to phase transition /PT/ 1-st kind. Damaging lattice is associated with processes clustering vacancies and gaseous bubbles as well their brownian motion. System of stochastic differential equations /SDEs/ Ito for evolution stochastic dynamical variables corresponds to the superposition Wiener processes. The kinetic equations in partial derivatives /KE/, Kolmogorov-Feller and Einstein-Smolukhovskii, were formulated for nucleation into lattice of weakly soluble gases. According theory, coefficients of stochastic and kinetic equations uniquely related. Radiation stimulated phase transition are characterized by kinetic distribution functions /DFs/ of implanted clusters versus their sizes and depth of gas penetration into lattice. Macroscopic parameters of kinetics such as the porosity and stress calculated in thin layers metal/dielectric due to Xe{sup ++} irradiation are attracted as example. Predictions of porosity, important for validation accumulation stresses in surfaces, can be applied at restoring of objects the cultural heritage.
Dense and half-dense NiZnCo ferrite ceramics: Their respective relevance for antenna downsizing, according to their dielectric and magnetic properties at microwave frequencies
Spinel ferrite Ni{sub 0.5}Zn{sub 0.3}Co{sub 0.2}Fe{sub 1.98}O{sub 4−x} nanoparticles were synthesized by co-precipitation method, and samples were realized by moulding and annealing at key temperatures (T{sub M} = 800 °C, 900 °C, 1050 °C, determined beforehand through shrinkage measurements) going with calcining and sintering processes. Annealing at 800 °C and 900 °C led to half-dense ceramics (porosity ∼50 vol. %), whereas bulky ferrite was obtained after annealing at 1050 °C. Elemental analysis, X-ray diffraction and ion chromatography analysis were performed. Complex dielectric permittivity (ε*) and magnetic permeability (μ*) were investigated up to 6 GHz. With increasing T{sub M}, a decreasing amount of Fe{sup 2+} was observed, going with increasing sample density. Coupled effects of the Fe{sup 2+} concentration and of the porosity, both on dielectric and magnetic properties, were chiefly investigated and discussed. The materials show almost constant permittivities (ε′ = 5.0, 6.0, and 14.8 for T{sub M} = 800 °C, 900 °C and 1050 °C, respectively). The bulk value at f = 1 GHz (ε′ = 14.8) can be interpreted well according to Shannon's theory. The permittivities of the half-dense ceramics are discussed on the basis of Bruggeman's Effective Medium Theory. The materials annealed at 800 °C and 900 °C show almost constant magnetic permeabilities in the frequency range from 0.2 to 1 GHz (μ′ = 3.4 and 6.0 for T{sub M} = 800 °C and 900 °C). The observed permeability behavior is typical of monodomain particles, except for the sample annealed at 1050 °C, for which domain wall contribution to μ* is suspected because of non-negligible losses at low frequency (μ″ = 1.3–1.8 at f < 0.3 GHz). This finding is supported by estimations of the upper and lower values for the critical grain size, on the basis of Brown–Van der Zaag's theory. Facing bulk ceramics, and in view of using Ni{sub 0.5}Zn{sub 0.3}Co{sub 0.2}Fe{sub 1.98}O{sub 4−x} ferrite as substrate for antenna miniaturization, the electromagnetic properties of half-dense ceramics materials seem to be very competitive at frequencies beyond 0.2 GHz, and up to 0.7–0.8 GHz.
In-situ ellipsometric characterization of the growth of porous anisotropic nanocrystalline ZnO layers
ZnO films have increasingly been in the spotlight due to their largely varied electro-physical and optical properties. For several applications, porous anisotropic nanocrystalline layers are especially interesting. To study the growth kinetics of such films during different fabrication processes, a powerful non-destructive in-situ technique is required. In this work, both ex-situ and in-situ spectroscopic ellipsometry are used along with advanced modelling techniques that are able to take both the anisotropy and the porosity of the films into account. Scanning electron microscopy, along with nitrogen absorption methods for measuring porosity, validated the ellipsometric data and proposed model. The film, grown by chemical bath deposition, was monitored from around 700 to 1800 nm in thickness. This same principle can now be used to monitor any other porous and/or anisotropic structure in an effective in-situ manner, e.g., growth of porous anodic aluminium oxides, nano-porous silica films, etc.
Three-dimensional analysis by serial sectioning of cubic zirconia sinters
Three-dimensional electron backscatter diffraction technique was used for the characterization of grain boundary geometry and pore morphology in cubic zirconia. A set of three samples composed of cubic yttria stabilized zirconia, sintered under different conditions was investigated. Analysis of grain boundaries and pore structure was carried out in a dual-beam scanning electron microscope. For each sample, a volume of 15·10{sup 3} μm{sup 3} was investigated. The results of three-dimensional microstructure analysis were compared to the results derived from regular, two-dimensional maps of the area of 2500 µm{sup 2}. Based on two-dimensional and three-dimensional data the average grain diameter, number of grains, average number of neighbors and porosity were calculated. The average grain diameter varied in the range from 2.39 µm to 2.91 µm and from 3.00 µm to 3.79 µm, while the level of porosity varied in the range from 1.22% to 1.77% and from 1.30% to 5.61% for two-dimensional and three-dimensional data, respectively. The analysis of grain boundary networks revealed a strong dependence between grain boundary density and sample preparation parameters. The parameters of the sintering process affected also the size and distribution of pores. The comparison of the results of 2D and 3D materials characterization revealed significant differences in the values of calculated microstructure parameters.