Design Of Porous Materials Research Articles

Phenothiazine-based covalent organic frameworks with low exciton binding energies for photocatalysis.

Designing delocalized excitons with low binding energy (Eb) in organic semiconductors is urgently required for efficient photochemistry because the excitons in most organic materials are localized with a high Eb of >300 meV. In this work, we report the achievement of a low Eb of ∼50 meV by constructing phenothiazine-based covalent organic frameworks (COFs) with inherent crystallinity, porosity, chemical robustness, and feasibility of bandgap engineering. The low Eb facilitates effective exciton dissociation and thus promotes photocatalysis by using these COFs. As a demonstration, we subject these COFs to photocatalytic polymerization to synthesize polymers with remarkably high molecular weight without any requirement of the metal catalyst. Our results can facilitate the rational design of porous materials with low Eb for efficient photocatalysis.

Targeted design of porous materials without strong, directional interactions.

A porous molecular crystal (TSCl) was found to crystallise from dichloromethane and water during the synthesis of tetrakis(4-sulfophenylmethane). Crystal structure prediction (CSP) rationalises the driving force behind the formation of this porous TSCl phase and the intermolecular interactions that direct its formation. Gas sorption analysis showed that TSCl is permanently porous with selective adsorption of CO2 over N2, H2 and CH4 and a maximum CO2 uptake of 74 cm3 g-1 at 195 K. Calculations revealed that TSCl assembles via a combination of weak hydrogen bonds and strong dispersion interactions. This illustrates that CSP can underpin approaches to crystal engineering that do not involve more intuitive directional interactions, such as hydrogen bonding.

Quantitative Coassembly for Precise Synthesis of Mesoporous Nanospheres with Pore Structure-Dependent Catalytic Performance.

Precise synthesis of porous materials is essential for their applications. Self-assembly is a widely used strategy for synthesizing porous materials, but quantitative control of the assembly process still remains a great challenge. Here, a quantitative coassembly approach is developed for synthesizing resin/silica composite and its derived porous spheres. The assembly behaviors of the carbon and silica precursors are regulated without surfactants and the growth kinetics of the composite spheres are quantitatively controlled. This assembly approach enables the precise control of the size and pore structures of the derived carbon spheres. These carbon spheres provide a good platform to explore the structure-performance relationships of porous materials, and demonstrate their pore structure-dependent performance in catalytic water decontamination. This work provides a simple and robust approach for precise synthesis of porous spheres and brings insights into function-oriented design of porous materials.

Investigation of hierarchically porous zeolitic imidazolate frameworks for highly efficient dye removal

Treatment of textile water containing organic molecules as contaminants still remains a challenge and has become a central issue for environment remediation. Here, a nucleotide incorporated zeolitic imidazolate frameworks (NZIF) featuring hierarchically porous structure served as a potential adsorbent for removal of organic dye molecules. Adsorption isotherms of organic dyes were accurately described by Langmuir adsorption model with correlation coefficients of 0.98 and kinetic data followed the pseudo-second-order model. The maximum adsorption capacity of NZIF for Congo red (CR) and methylene blue (MB) reached 769 and 10 mg/g, respectively, which were 6 and 5 times higher than that of ZIF-8. The adsorption behavior of sunset yellow and crystal violet was examined for mechanism investigation. Analysis of pore size, molecular size, zeta potential and FTIR measurement together revealed that mesopores in NZIF provided more interaction sites and led to enhanced adsorption capacity. Hydrogen bonding and π-π stacking which resulted from the interaction between introduced nucleotide monophosphate and dyes dominated the driving forces for adsorption, where electrostatic interaction was also involved. Moreover, the introduced nucleoside monophosphate enabled NZIF to function under acidic condition whereas ZIF-8 collapsed. This study opens a new avenue for design of porous materials for environment remediation.

Novel synthesis of porous Si-TiO2 composite as a high-capacity anode material for Li secondary batteries

Porous Si materials can be considered as a candidate for and an alternative to commercial graphite anodes for Li-ion batteries. In this study, we propose a modified magnesiothermic method to increase the materials’ yield and a design strategy to improve their electrochemical properties. For magnesiothermic solid-state reactions, Mg2Si was used instead of metallic Mg and amorphous nanoscale SiO2 was adopted. The two starting materials were converted into Si and MgO via a high-temperature solid-state reaction, resulting in a high-yield percentage of Si. Then, amorphous TiO2 layers were formed and the MgO was removed by chemical etching, forming a porous structure. The materials at each step were thoroughly characterized by using various analytical tools. Electrochemical test results demonstrated that the amorphous TiO2 coated porous Si composite electrode exhibited a high reversible capacity of 1965 mA h g−1 after 100 cycles and a greatly improved initial Coulombic efficiency of 90.1%. These results can be attributed to the controlled porous structure of the composite and amorphous TiO2 coating layer. The modified magnesiothermic method and porous material design could attract commercial use of Si-based materials as Li-ion battery anodes.

Analysis of Capillary Flow in a Parallel Microchannel-Based Wick Structure with Circular and Noncircular Geometries.

Capillary flow in porous media is of great significance to many different applications including microfluidics, chromatography, and passive thermal management. For example, heat pipe has been widely used in the thermal management of electronic system due to its high flexibility and low thermal resistance. However, the critical heat flux of heat pipe is often limited by the maximum capillary-driven liquid transport rate through the wicking material. A significant number of novel porous material with complex structures have been proposed in past studies to provide enhanced capillary-driven flow without substantial reduction in pore size and porosity. However, the increasing level of structural complexity often leads to a more tortuous flow path, which deprives the merits of enhanced capillarity. In this study, we examined the capillary performance of a porous material with simple geometric structures both analytically and numerically. Specifically, the capillary rate of rise of water in parallel hollow microchannels with different cross-sectional shapes is derived by solving the momentum transport equation. The relationships between the capillary flow rate and wicking height are further validated by two-phase flow simulation based on the conservative level-set method. The results demonstrate that parallel microchannel configuration, despite its geometric simplicity, provides superior capillary performance than most existing porous media in terms of both capillary flow rate and ultimate wicking height. In addition, design of noncircular cross section reduces the viscous drag and increases the packing density of the microchannels in the bulk solid without affecting the capillary pumping pressure. These features contribute to a further enhancement in the capillary performance by up to 32%. These results provide important guidance to the rational design of porous material with enhanced fluid transport property in a variety of microfluidic systems.

Reticular Chemistry in the Construction of Porous Organic Cages.

Reticular chemistry offers the possibility of systematic design of porous materials with different pores by varying the building blocks, while the emerging porous organic cage (POC) system remains generally unexplored. A series of new POCs with dimeric cages with odd-even behaviors, unprecedented trimeric triangular prisms, and the largest recorded hexameric octahedra have been prepared. These POCs are all constructed from the same tetratopic tetraformylresorcin[4]arene cavitand by simply varying the diamine ligands through Schiff-base reactions and are fully characterized by X-ray crystallography, gas sorption measurements, NMR spectroscopy, and mass spectrometry. The odd-even effects in the POC conformation changes of the [2 + 4] dimeric cages have been confirmed by density functional theory calculations, which are the first examples of odd-even effects reported in the cavitand-based cage system. Moreover, the "V" shape phenylenediamine linkers are responsible for the novel [3 + 6] triangular prisms. The window size and environment can be easily functionalized by different groups, providing a promising platform for the construction of multivariate POCs. Use of linear phenylenediamines led to record-breakingly large [6 + 12] truncated octahedral cages, the maximum inner cavity diameters and volumes of which could be readily modulated by increasing the spacer length of the phenylenediamine linkers. This work can lead to an understanding of the self-assembly behaviors of POCs and also sheds light on the rational design of POC materials for practical applications.

Porous Materials Applied in Nonaqueous Li-O2 Batteries: Status and Perspectives.

Porous materials possessing high surface area, large pore volume, tunable pore structure, superior tailorability, and dimensional effect have been widely applied as components of lithium-oxygen (Li-O2 ) batteries. Herein, the theoretical foundation of the porous materials applied in Li-O2 batteries is provided, based on the present understanding of the battery mechanism and the challenges and advantageous qualities of porous materials. Furthermore, recent progress in porous materials applied as the cathode, anode, separator, and electrolyte in Li-O2 batteries is summarized, together with corresponding approaches to address the critical issues that remain at present. Particular emphasis is placed on the importance of the correlation between the function-orientated design of porous materials and key challenges of Li-O2 batteries in accelerating oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) kinetics, improving the electrode stability, controlling lithium deposition, suppressing the shuttle effect of the dissolved redox mediators, and alleviating electrolyte decomposition. Finally, the rational design and innovative directions of porous materials are provided for their development and application in Li-O2 battery systems.

Predicting transport characteristics of hyperuniform porous media via rigorous microstructure-property relations

This paper is concerned with the estimation of the effective transport characteristics of fluid-saturated porous media via rigorous microstructure-property relations. We are particularly interested in predicting the formation factor F, mean survival time τ, principal NMR (diffusion) relaxation time T1, principal viscous relaxation time Θ1, and fluid permeability k. To do so, we employ rigorous methods to estimate the fluid permeability and these other transport properties of “hyperuniform” and nonhyperuniform models of porous media from microstructural information. Disordered hyperuniform materials are exotic amorphous states of matter that have attracted great attention in the physical, mathematical and biological science but little is known about their fluid transport characteristics. In carrying out this investigation, we not only draw from ideas and results of the emerging field of hyperuniformity, but from homogenization theory, statistical geometry, differential equations (spectrum of Laplace and Stokes operators), and the covering and quantizer problems of discrete geometry. Among other results, we derive a Fourier representation of a classic rigorous upper bound on the fluid permeability that depends on the spectral density to infer how the permeabilities of hyperuniform porous media perform relative to those of nonhyperuniform ones. We find that the velocity fields in nonhyperuniform porous media are generally much more localized over the pore space compared to those in their hyperuniform counterparts, which has implications for their permeabilities. Rigorous bounds on transport properties suggest a new approximate formula for the fluid permeability that provides reasonably accurate permeability predictions of a certain class of hyperuniform and nonhyperuniform porous media. These comparative studies shed new light on the microstructural characteristics that determine the transport properties of general porous media. Our findings also have implications for the design of porous materials with desirable transport properties.

Anilate Tethered Neutral Tetrahedral Pd(II) Cages Exhibiting Selective Encapsulation of Xylenes and Mesitylene

The design of porous materials for the recognition of multiple hydrocarbons is highly desirable for the energy-efficient separation and recognition of chemical feedstock. Here, we report three new iso-structural porous discrete metal-organic cages of formula {[Pd 3 (N i Pr) 3 PO] 4 (R-AN) 6 } (R-AN = Anilate linkers) for the selective recognition of substituted aromatic hydrocarbons. The tetrahedral cages 1 , 2 and 3 containing anilate, chloranilate and bromanilate linkers exhibited selective encapsulation of mesitylene, o - xylene and p - xylene, respectively, over other analogous aromatic hydrocarbons. These selective encapsulations were driven by the variations in the portal diameters present at each of these cages and their interactions with the hydrocarbon guests. These observations are supported by mass-spectrometry, NMR studies and theoretical binding energy calculations.

Inverse design of porous materials using artificial neural networks.

Generating optimal nanomaterials using artificial neural networks can potentially lead to a notable revolution in future materials design. Although progress has been made in creating small and simple molecules, complex materials such as crystalline porous materials have yet to be generated using any of the neural networks. Here, we have implemented a generative adversarial network that uses a training set of 31,713 known zeolites to produce 121 crystalline porous materials. Our neural network takes in inputs in the form of energy and material dimensions, and we show that zeolites with a user-desired range of 4 kJ/mol methane heat of adsorption can be reliably produced using our neural network. The fine-tuning of user-desired capability can potentially accelerate materials development as it demonstrates a successful case of inverse design of porous materials.

Effect of SiC layer on microwave absorption properties of novel three-dimensional interconnected SiC foam with double-layer hollow skeleton

To design a lightweight and high-performance absorber, this work introduced a novel three-dimensional interconnected SiC foam with double-layer hollow skeleton (3D-ISF), which was prepared by depositing SiC, pyrolytic carbon, and SiC layer on interconnected carbon foam, followed by oxidation of carbon. SEM results showed the interconnected hollow structure had been successfully synthesized, which was beneficial for microwave absorbing efficiency, and numerous columnar SiC defects were observed and played a critical role in the microwave absorption properties. The electromagnetic performances of 3D-ISF-I and 3D-ISF-II were investigated in depth. With the increase of thickness of SiC layer, 3D-ISF-II exhibited a better microwave absorption property, which could be ascribed to the higher impedance matching ratio (Zr) and attenuation constant (α). The optimum reflection loss value of 3D-ISF-II could reach −45.649 dB while that of 3D-ISF-I was just −32.070 dB. There is no doubt that the prepared materials have tunable microwave absorbing properties, which can promote the development of SiC-based absorbing materials to a certain extent. Finally, it was confirmed that the Zr played a dominant role in 3D-ISF, which provided practical guidance for the design of porous materials.

Up-scaling transport in porous polymer membranes using asymptotic homogenization

PurposeEfficient numerical assessment of performance is particularly important in digital material design of porous materials. This study aims to present an up-scaled approach to virtually investigate permeation of fluids through a real porous filter membrane with a heterogeneous micro-structure.Design/methodology/approachThe method of asymptotic homogenization is applied. The structural parameters of the micro-structure are directly obtained from structural equation modeling image analysis of a commercial filter membrane without fitting procedures. The simulation results are compared to permeation experiments of gaseous nitrogen and liquid water.FindingsThe authors found that variations in the pressure gradients across the membrane, resulting from the heterogeneity of pore structure, need to be considered. Remarkable agreement between simulations and experiments is observed.Originality/valueDespite some research in the field of filtration, no studies on filter membranes have been published yet, although they represent a large segment of filtration technology.

Realization of equivalent gradience of porous materials with periodic macro void structure

Abstract In this paper, a periodic macro void (PMV) design of porous materials is proposed, through which different acoustic properties can be obtained with uniform porous materials. The proposed PMV structure is an alternative to realize gradient sound absorbers, which experimentally shows the potential to enhance the sound absorption performance of porous materials. Based on the wave finite element (WFE) method and a homogenization procedure, the equivalent density and bulk modulus of PMV porous materials are obtained, which are validated by finite-unit’s simulation and experiment. These equivalent acoustic parameters are between that of uniform porous materials and air, which are controlled by the macro porosity, but independent of void position and shape. The proposed PMV porous material with gradient macro voids is used to optimize the anechoic chamber performance with an optimization procedure provided. For a chamber with size of 9 m × 8 m × 7 m, and cut-off frequency of 100 Hz, the performance of gradient PMV design is compared with the classic wedge design. It is found that the optimized gradient PMV design can achieve better performance than the classic wedge design with the same thickness of 0.8 m. Moreover, the thickness of gradient PMV design can be reduced up to 15% (0.68 m) while keeping better performance than the wedge design.

Structured Porous Material Design for Passive Flow and Noise Control of Cylinders in Uniform Flow.

Cylindrical bodies in uniform flows can be coated with a porous medium as a passive flow and noise control method in an effort to reduce the acoustic effects of vortex shedding. To date, the employed open-cell porous materials typically possess a randomized internal structure. This paper presents the design and validation of a novel 3-D printed structured porous coated cylinder that has significant flexibility, in that the porosity and pores per inch of the porous coating can be modified independently and relatively easily. The performance of the structured porous coating design is compared against porous polyurethane and metal foam with the same coating dimensions and similar pores per inch and porosity via an experimental acoustic investigation, revealing strong similarity in the passive noise control performance of each material type. A numerical comparison illustrates the similarities of the wake structure of the 3-D printed porous coated cylinder to an equivalent Darcy–Forchheimer model simulation that represents a randomized internal porous structure. The performance similarities of these different porous material types indicate that a structured porous geometry can be used to understand the internal flow behavior of the porous medium responsible for reducing the cylinder vortex shedding tone that is otherwise extremely difficult or impossible with typical randomized porous structures. Moreover, significant potential exists for the porous structure to be further optimized or smartly tailored by architectural design for different control purposes, coating geometries and dimensions, and working conditions.

First-Principles Study on Hydrogen Storage Performance of Transition Metal-Doped Zeolite Template Carbon

The hydrogen adsorption characteristics and mechanism of transition metal-doped zeolite template carbon (ZTC) as a novel porous material are studied by theoretical calculations employing first-principle all-electron atomic orbital method based on density functional theory. The stability of transition metal atoms (Sc, Ti, and V) decorated on zeolite template carbon is investigated by calculating the absorption binding energy. The adsorption configurations of the doped metal atom and adsorbed hydrogen are obtained from the energy functional minimization of first-principles calculations. The underlying mechanism for improving hydrogen storage performance of ZTC by doping transition metal atoms are explored through analyzing charge/spin populations of metal atoms in combination with the calculated results of hydrogen adsorption quantity and binding energy. To improve the hydrogen storage capability, the Sc, Ti, and V are individually introduced into the ZTC model according to the triplex axisymmetry. The hydrogen storage properties of ZTC decorated with different metal atoms are characterized by the adsorption energy and structure of several hydrogen atoms. The more energetically stable complex system with higher binding energy and adsorbing distance of hydrogen than lithium-doped ZTC can be achieved by doping Sc, Ti, V atoms in ZTC, which is expected to fulfill the substantial safe hydrogen storage by increasing hydrogen capacity with multi-sites doping of transition metal atoms. The present investigation provides a theoretical basis and predictions for the following experimental research and design of porous materials for hydrogen storage.

Analytical model of the elastic behavior of a modified face-centered cubic lattice structure

As result of the advances made in additive manufacturing in recent years, the design of porous materials with controlled mechanical properties has gained importance due to their capability to offer case-specific solutions in multiple applications. In terms of biomaterials, the use of lattice structures provides a considerable variety of mechanical and geometric properties that can enhance osseointegration and reduce stress shielding. In this paper, the elastic response of a modified face-centered cubic (FCC) unit cell was studied, and analytical expressions for macroscopic effective Young's moduli, shear moduli and Poisson's ratios were obtained, thus providing the necessary parameters for the homogenization of the unit cell. The analytical expressions of the homogenization parameters open the possibility for implementation in other research fields, such as topology optimization. Timoshenko beam theory was used to model the struts of the modified FCC unit cell and a finite element analysis using shear flexible beam elements was performed to assess the accuracy of the analytical expressions. In addition to modelling the bending of the beams, axial and torsional displacements were also considered for a more detailed analysis. It can be concluded that the expressions obtained represent the elastic behavior of the modified FCC unit cell with high accuracy. Finally, the elastic response was further analyzed by introducing variability in the aspect ratio in order to enable the design of unit cells with controlled anisotropy.

Study of the dispersion and specific interactions affected by chemical functions of the granular activated carbons

Knowing the surface functional groups and free energy of adsorption are the most important factors affecting the adsorption capacity of granular activated carbon (GAC). The dispersion and specific interactions between hydrocarbon and GAC surface must be verified. This study used the Boehm titration to quantify the surface functional groups for four different GAC samples and the inverse gas chromatography to determine the free energy of adsorption. The result findings verified that the coconut-based GRW2 and TAS surfaces and mineral-based F400 surface can be considered more dominant basic functional group than total acidic functional group while the wood-based PIC surface has a very high acidic functional group. The ΔGoCxH2x value of understanding dispersion interaction may associate with the nature of raw GAC material and its surface chemical properties. The ΔGoπ value of understanding specific interaction depends on the surface physical and chemical properties of the GAC sample. The dispersion and specific interactions between either saturated or unsaturated hydrocarbon and GAC surface are verified to get better understanding of the design of porous material with multilevel energy for the novel technological applications.

Hydrophobic metal-organic frameworks: Potential toward emerging applications

Metal-organic frameworks, popularly known as MOFs, have come of age—thanks to custom-built design principles enabling them to serve a myriad of task-specific applications. In an era where >6000 new MOFs are annually published, driven by academic research, a new generation of MOFs that can find use in niche markets is on the rise. One of the foremost challenges that plague the translation of MOFs into materials suited for commercialization is their water-influenced degradation, largely accountable to hydrolytic instability and the ubiquity of water. Hydrophobic MOFs offer one of the most promising solutions which can enable these porous materials to leverage their functionalization guided properties even under extreme humid conditions, a criterion that application-ready materials should necessarily serve. In this contribution, our discussion focuses on the state-of-the-art hydrophobic MOFs and MOF-derived composites. Outlining a brief overview of the structure-property correlation aspects in each of these promising hydrophobic MOFs with little or no influence exhibited to water and/or humidity, a future outlook is put forward to enable potentially better design strategies leading to futuristic MOFs tolerant to water/moisture. Concise premise of this review allows us to limit our discussion to the design principles in action behind the most hydrophobic MOFs/derived composites reported thus far and to discuss their prime applications viz., oil/water separation inclusive of self-cleaning, hydrocarbon separation, and tackling marine oil spillage. When synergized, such improved porous material design approaches lean toward a greener environment of tomorrow.

Molecular Sieves for the Separation of Hydrogen Isotopes

Stable molecular hydrogen isotopes, D2 and T2, are both scarce and essential in several energy, industrial, and large-scale fundamental research applications. Due to the chemical similarity of these isotopes, their extraction and purification from hydrogen has relied for decades on expensive and energy-demanding processes. However, factoring in the phenomenon of quantum sieving could provide a new route for these separations. In this work, we have explored how to separate hydrogen isotopes by adsorption taking these quantum effects into account. To this end, we have conducted adsorption measurements to test our deuterium model and performed a widespread computational screening over 210 pure-silica zeolites for D2/H2 and T2/H2 separations. Based on low-coverage adsorption properties, a reduced set of zeolites have been singled out and their performance in terms of adsorption capacity, selectivity, and dynamic behavior have been assessed. Overall, the BCT-type zeolite clearly stands out for highly selective separations of both D2 and T2 over H2, achieving the highest reported selectivities at cryogenic temperatures. We also identified other interesting zeolites for the separation of hydrogen isotopes that offer an alternative way to tackle similar isotopic separations by an aimed selection or design of porous materials.