Porous Crystals Research Articles

Programmed Pore‐Shape Fixing in a Soft Porous Molecular Crystal—Navigating the Phase Interconversion Landscape

AbstractPore‐shape fixing effects (PSFEs) in soft porous crystals are a relatively unexplored area of materials chemistry. We report the PSFE in the prototypical dynamic van der Waals solid p‐tert‐butylcalix[4]arene (TBC4). Starting with the high‐density guest‐free phase, two porous shape‐fixed phases were programmed using the stimuli of CO2 pressure and temperature. A suite of complementary in situ techniques, including variable‐pressure (VP) single‐crystal X‐ray diffraction, VP powder X‐ray diffraction, VP differential scanning calorimetry, volumetric sorption analysis, and attenuated total reflectance Fourier‐transform infrared spectroscopy was used to track dynamic guest‐induced transformations, providing molecular‐level insight into the PSFE. The interconversion between the two metastable phases is particle size dependent, making this the second example of the PSFE by crystal downsizing, and the first example involving a porous molecular crystal: larger particles undergo reversible transitions while smaller particles remain fixed in the metastable phase. A complete phase interconversion scheme was constructed for the material, thus allowing navigation of the phase interconversion landscape of TBC4 using the easily applied stimuli of CO2 pressure and thermal treatment.

Thickness and porosity characterization in porous silicon photonic crystals: The etch-stop effect

One-dimensional photonic crystals and microcavities were fabricated using porous silicon via anodization. The study investigated the effect of an etch-stop layer, which is included between two adjacent porous layers to resolve the issue of HF diffusion during pore formation. Although proposed as a solution, no systematic investigation had been conducted on this parameter until now. Our study found that the etch-stop layer induces a redshift in the photonic bandgap, regardless of the electrolyte solution used. The fitting analysis of both single and multilayer structures revealed that the redshift resulted from an increase in the silicon etch rate and a decrease in porosity due to the enhancement of HF diffusion through the porous structure. Furthermore, an analysis of oxidation as a function of temperature demonstrated that the inclusion of the etch-stop layer led to the formation of porous layers with varying microstructures. This effect was particularly pronounced in devices where the first upper layer had high porosity. The thermal treatment caused a photonic bandgap inhibition, which was linked to the contraction-expansion phenomena of the low and high porosity layers, respectively. This resulted in the partial violation of Bragg's law. Overall, our study provides insights into the influence of etch-stop layers on the optical properties of porous silicon-based photonic structures.

Inorganic Chemistry in Dalian University of Technology: Fundamental Science and Solution for Renewable Energy, Environment, Health, and Materials

Inorganic Chemistry in Dalian University of Technology: Fundamental Science and Solution for Renewable Energy, Environment, Health, and Materials

Synthesis and Characterization of Metal-Organic Framework as Battery Electrodes

Metal organic framework-derived carbons (MOFDCs) are materials with great potential and can be used as electrochemical energy storage because these have a large surface area and pore structure that can be adapted to needs. MOFs have porous crystals in which metal ions or clusters are linked by organic ligands. The purpose of this study was to determine the physical and electrochemical properties of MOF5 synthesized at different temperatures. The MOFs synthesis method which is classified as complicated can be simplified and the use of hazardous solvents can be reduced by means of partial substitution using water solvents. To prepare MOFs can be done in several ways, such as liquid phase epitaxy, supersonic cold spraying, direct gas phase preparation, and interface-assisted synthesis. MOFs have applications in optics, sensing, catalysis, adsorption, and modeling, as well as electrochemical energy storage. Potential application as an interesting electrode material to be studied through the synthesis method. In this study, MOF5 was synthesized at temperatures between 200°C-600°C. To prepare MOF5, zinc nitrate tetrahydrate and acetic acid were dissolved in DMF (N, N-dimethyl formamide). The remaining precipitate (MOF) was immersed three times in DMF and three times in chloroform for 24 hours for each immersion. In general, different MOF5 synthesis affects the microstructure, elemental content, optical properties (transmittance and absorbance), electrical properties, and electrochemical properties

Green synthesis of stable hybrid biocatalyst using a hydrogen-bonded, π-π-stacking supramolecular assembly for electrochemical immunosensor

Rational integration of native enzymes and nanoscaffold is an efficient means to access robust biocatalyst, yet remains on-going challenges due to the trade-off between fragile enzymes and harsh assembling conditions. Here, we report a supramolecular strategy enabling the in situ fusion of fragile enzymes into a robust porous crystal. A c2-symmetric pyrene tecton with four formic acid arms is utilized as the building block to engineer this hybrid biocatalyst. The decorated formic acid arms afford the pyrene tectons high dispersibility in minute amount of organic solvent, and permit the hydrogen-bonded linkage of discrete pyrene tectons to an extended supramolecular network around an enzyme in almost organic solvent-free aqueous solution. This hybrid biocatalyst is covered by long-range ordered pore channels, which can serve as the gating to sieve the catalytic substrate and thus enhance the biocatalytic selectivity. Given the structural integration, a supramolecular biocatalyst-based electrochemical immunosensor is developed, enabling the pg/mL detection of cancer biomarker.

Efficient and reliable detection of rhodamine B using SERS from silver-decorated photonic crystal silicon nanoscale pores

Porous silicon photonic crystal (PSi PhC) decorated with silver nanoparticles (AgNPs) is shown to provide a new substrate for the improvement of SERS. AgNPs are obtained through immersion of PSi PhC samples in AgNO3 solutions and successive thermal annealing. The nanocomposite material generated by adding AgNPs inside the silicon nanoscale pores, integrates the ability of metal surfaces to amplify Raman scattering signals and an enlarged surface area. Besides, PhC structure formed by multilayer PSi increases interaction time of light and matter of the multilayer structure. The experimental results show that the AgNPs-decorated PSi PhC has the largest Raman intensity in comparison with other SERS substrates based on Si. The enhancement of Raman signals also reduces the threshold of the detection down to below 10-10 M. The analytical enhancement factor of AgNPs/PSi PhC SERS substrate for the detection of Rhodamine B (RhB) reaches 1010. This proposed AgNPs/PSi PhC SERS substrate could serve as a potential candidate for detecting RhB in foodstuffs at very low concentrations.

Air/liquid interfacial formation process of conductive metal–organic framework nanosheets

The air/liquid interface is a superior platform to create nanosheets of materials by promoting spontaneous two-dimensional growth of components. Metal–organic frameworks (MOFs)—intrinsically porous crystals—with π-conjugated triphenylene-based ligands show high electrical conductivities. Forming nanosheets of such conductive MOFs should enable their use in electronic devices. Although highly conductive MOF nanosheets have been created at the air/liquid interface, direct control of their continuity, morphology, thickness, crystallinity, and orientation directly influencing device performance remains as an issue to be addressed. Here, we present detailed insights into the formation process of electrically conductive MOF nanosheets composed of 2,3,6,7,10,11-hexaiminotriphenylene (HITP) and Ni2+ ions (HITP-Ni-NS) at the air/liquid interface. The morphological and structural features of HITP-Ni-NS strongly depend on the standing time—the time without any external actions involved, but leaving the interface undisturbed after setting the ligand solution onto the metal-ion solution. We find that the fundamental features of HITP-Ni-NS are determined by the standing time with conductivity sensitively influenced by such pre-determined HITP-Ni-NS characteristics. These findings will lead towards the establishment of a rational strategy for creating MOF nanosheets at the air/liquid interface with desired properties, thereby accelerating their use in diverse potential applications.

Membrane company UniSieve raises funding

The Swiss membrane start-up UniSieve has raised $5.5 million in seed funding. UniSieve membranes are based on a highly ordered network of porous crystals. The company says they can separate chemicals from one another or carbon dioxide from flue gas based on size exclusion—eliminating the need for energy-intensive processes such as distillation and reducing the energy required for separations by up to 90%. UniSieve claims that separation and purification consume 10–15% of the world’s energy.

Cross-Linked Crystals of Dirhodium Tetraacetate/RNase A Adduct Can Be Used as Heterogeneous Catalysts.

Due to their unique coordination structure, dirhodium paddlewheel complexes are of interest in several research fields, like medicinal chemistry, catalysis, etc. Previously, these complexes were conjugated to proteins and peptides for developing artificial metalloenzymes as homogeneous catalysts. Fixation of dirhodium complexes into protein crystals is interesting to develop heterogeneous catalysts. Porous solvent channels present in protein crystals can benefit the activity by increasing the probability of substrate collisions at the catalytic Rh binding sites. Toward this goal, the present work describes the use of bovine pancreatic ribonuclease (RNase A) crystals with a pore size of 4 nm (P3221 space group) for fixing [Rh2(OAc)4] and developing a heterogeneous catalyst to perform reactions in an aqueous medium. The structure of the [Rh2(OAc)4]/RNase A adduct was investigated by X-ray crystallography: the metal complex structure remains unperturbed upon protein binding. Using a number of crystal structures, metal complex accumulation over time, within the RNase A crystals, and structures at variable temperatures were evaluated. We also report the large-scale preparation of microcrystals (∼10-20 μm) of the [Rh2(OAc)4]/RNase A adduct and cross-linking reaction with glutaraldehyde. The catalytic olefin cyclopropanation reaction and self-coupling of diazo compounds by these cross-linked [Rh2(OAc)4]/RNase A crystals were demonstrated. The results of this work reveal that these systems can be used as heterogeneous catalysts to promote reactions in aqueous solution. Overall, our findings demonstrate that the dirhodium paddlewheel complexes can be fixed in porous biomolecule crystals, like those of RNase A, to prepare biohybrid materials for catalytic applications.

Shape‐ and Size‐Tunable Synthesis of Covalent Organic Cages through Rh‐Catalyzed Regioselective [2+2+2] Cycloaddition

AbstractCovalent organic cages have potential applications in molecular inclusion/recognition and porous organic crystals. Bridging arene units with sp3 atoms enables facile construction of rigid isolated internal vacancies, and various prismatic arene cages have been synthesized by kinetically controlled covalent bond formation. However, the synthesis of a tetrahedral one, which requires twice as much bond formation as prismatic ones, has been limited to a thermodynamically controlled dynamic SNAr reaction, and this reversible covalent bond formation made the resulting cage product chemically unstable. Here we report the Rh‐catalyzed high‐yielding and highly 1,3,5‐selective room temperature [2+2+2] cycloaddition of push‐pull alkynes and its application to the synthesis of chemically stable aryl ether cages of various shapes and sizes, including prismatic and tetrahedral forms. These aryl ether cages are highly crystalline and intertwine with each other to form regular packing structures. Some aryl ether cages encapsulated isolated water molecules in their hydrophobic cavity by hydrogen bonding with the multiple ester moieties.

Shape- and Size-Tunable Synthesis of Covalent Organic Cages through Rh-Catalyzed Regioselective [2+2+2] Cycloaddition.

Covalent organic cages have potential applications in molecular inclusion/recognition and porous organic crystals. Bridging arene units with sp3 atoms enables facile construction of rigid isolated internal vacancies, and various prismatic arene cages have been synthesized by kinetically controlled covalent bond formation. However, the synthesis of a tetrahedral one, which requires twice as much bond formation as prismatic ones, has been limited to a thermodynamically controlled dynamic SN Ar reaction, and this reversible covalent bond formation made the resulting cage product chemically unstable. Here we report the Rh-catalyzed high-yielding and highly 1,3,5-selective room temperature [2+2+2] cycloaddition of push-pull alkynes and its application to the synthesis of chemically stable aryl ether cages of various shapes and sizes, including prismatic and tetrahedral forms. These aryl ether cages are highly crystalline and intertwine with each other to form regular packing structures. Some aryl ether cages encapsulated isolated water molecules in their hydrophobic cavity by hydrogen bonding with the multiple ester moieties.

Experimental Confirmation of a Predicted Porous Hydrogen‐Bonded Organic Framework

AbstractHydrogen‐bonded organic frameworks (HOFs) with low densities and high porosities are rare and challenging to design because most molecules have a strong energetic preference for close packing. Crystal structure prediction (CSP) can rank the crystal packings available to an organic molecule based on their relative lattice energies. This has become a powerful tool for the a priori design of porous molecular crystals. Previously, we combined CSP with structure‐property predictions to generate energy‐structure‐function (ESF) maps for a series of triptycene‐based molecules with quinoxaline groups. From these ESF maps, triptycene trisquinoxalinedione (TH5) was predicted to form a previously unknown low‐energy HOF (TH5‐A) with a remarkably low density of 0.374 g cm−3 and three‐dimensional (3D) pores. Here, we demonstrate the reliability of those ESF maps by discovering this TH5‐A polymorph experimentally. This material has a high accessible surface area of 3,284 m2 g−1, as measured by nitrogen adsorption, making it one of the most porous HOFs reported to date.

Experimental Confirmation of a Predicted Porous Hydrogen-Bonded Organic Framework.

Hydrogen-bonded organic frameworks (HOFs) with low densities and high porosities are rare and challenging to design because most molecules have a strong energetic preference for close packing. Crystal structure prediction (CSP) can rank the crystal packings available to an organic molecule based on their relative lattice energies. This has become a powerful tool for the a priori design of porous molecular crystals. Previously, we combined CSP with structure-property predictions to generate energy-structure-function (ESF) maps for a series of triptycene-based molecules with quinoxaline groups. From these ESF maps, triptycene trisquinoxalinedione (TH5) was predicted to form a previously unknown low-energy HOF (TH5-A) with a remarkably low density of 0.374 g cm-3 and three-dimensional (3D) pores. Here, we demonstrate the reliability of those ESF maps by discovering this TH5-A polymorph experimentally. This material has a high accessible surface area of 3,284 m2 g-1 , as measured by nitrogen adsorption, making it one of the most porous HOFs reported to date.

Dehydration of a crystal hydrate at subglacial temperatures

Water is one of the most important substances on our planet1. It is ubiquitous in its solid, liquid and vaporous states and all known biological systems depend on its unique chemical and physical properties. Moreover, many materials exist as water adducts, chief among which are crystal hydrates (a specific class of inclusion compound), which usually retain water indefinitely at subambient temperatures2. We describe a porous organic crystal that readily and reversibly adsorbs water into 1-nm-wide channels at more than 55% relative humidity. The water uptake/release is chromogenic, thus providing a convenient visual indication of the hydration state of the crystal over a wide temperature range. The complementary techniques of X-ray diffraction, optical microscopy, differential scanning calorimetry and molecular simulations were used to establish that the nanoconfined water is in a state of flux above −70 °C, thus allowing low-temperature dehydration to occur. We were able to determine the kinetics of dehydration over a wide temperature range, including well below 0 °C which, owing to the presence of atmospheric moisture, is usually challenging to accomplish. This discovery unlocks opportunities for designing materials that capture/release water over a range of temperatures that extend well below the freezing point of bulk water.

Covalent organic framework atropisomers with multiple gas-triggered structural flexibilities.

Covalent organic frameworks (COFs) are emerging crystalline porous polymers, showing great potential for applications but lacking gas-triggered flexibility. Atropisomerism was experimentally discovered in 1922 but has rarely been found in crystals with infinite framework structures. Here we report atropisomerism in COF single crystals. The obtained COF atropisomers, namely COF-320 and COF-320-A, have identical chemical and interpenetrated structures but differ in the spatial arrangement of repeating units. In contrast to the rigid COF-320 structure, its atropisomer (COF-320-A) exhibits unconventional gas sorption behaviours with one or more sorption steps in isotherms at different temperatures. Single-crystal structures determined from continuous rotation electron diffraction and in situ powder X-ray diffraction demonstrate that these adsorption steps originate from internal pore expansion with or without changing the crystal space group. COF-320-A recognizes different gases by expanding its internal pores continuously (crystal-to-amorphous transition) or discontinuously (crystal-to-crystal transition) or having mixed transition styles, distinguishing COF-320-A from existing soft/flexible porous crystals. These findings extend atropisomerism from molecules to crystals and propel COFs into the covalently linked soft porous crystal regime, further advancing applications of soft porous crystals in gas sorption, separation and storage.

Synthesis and Structure of an Aqueous Stable Europium-Based Metal-Organic Framework with Ratiometric Fluorescence Sensing for Phosphate and Luminescence Quenching for Salicylaldehyde.

An aqueous stable europium-based metal-organic framework with properties of ratiometric fluorescence sensing, namely, {[(CH3)2NH2][Eu(TCPB)(H2O)2]·DMF}n (Eu-MOF; H4TCPB = 1,2,4,5-tetrakis(4-carboxyphenyl)-benzene), was synthesized under solvothermal conditions and structurally characterized. Crystal structure analysis shows that Eu-MOF is a three-dimensional porous crystal, in which the EuIII ion is an eight-coordinate square inverse prism with eight oxygen atoms. Fluorescence measurements show that Eu-MOF exhibits characteristic emission of the EuIII ion and ligand. Eu-MOF displays good selectivity and sensitivity as a ratiometric fluorescence sensor for phosphate anions with a low detection limit in Tris-HCl buffer solution. Furthermore, Eu-MOF also has a good ability to identify salicylaldehyde through fluorescence quenching with a detection limit of 0.095 ppm. Therefore, it is an excellent fluorescent sensing material for phosphate and organic salicylaldehyde.

Porous single crystalline-like titanium dioxide monolith with enhanced photoelectrochemical performance

Macro-sized porous single crystalline-like (PSC-like) TiO2 is endowed with unique structural advantages due to its structural consistency and porosity in a large area, which would significantly enhance its photoelectrochemical function. However, there are significant technical challenges in the growth of porous single crystalline-like monoliths. The consistency of structure dominates the structure so that the grain boundary is reduced to the minimum, which is in contradiction with the three-dimensional percolation structure. Here we report a lattice reconstruction strategy based on solid-solid transformation to grow porous single crystal-like anatase TiO2 dominated by (200) and (101) facets at 2 cm scale. In comparison with the traditional definition of porous single crystal, it has two different lattice orientations, but still has good photoelectrochemical properties. The band gap engineering introduces Ti3+ gap into the lattice to generate TinO2n−1 with Magneli phase, limiting the created active structure to the lattice with two-dimensional surface, which would open a new avenue to create highly active surfaces to capture photons and transport electrons stably. The PSC-like TinO2n−1 provides enhanced exciton lifetime (3–5 ns) as a photocatalytic catalyst and shows significant visible light absorption. The independent PSC-like TinO2n−1 delivers high photocurrent of 1.8–5.5 mA · cm−2 at room temperature and does not decay for 10 h.

Exploration of urease-mediated biomineralization for defluoridation by Proteus columbae MLN9 with an emphasis on its genomic characterization

Fluoride (F-) contamination of groundwater is a silent killer of human health that has now become a global problem. In the present study, we sought to isolate fluoride-resistant, urease producing bacteria from F- contaminated groundwater to evaluate their potential F- biomineralization. Strain MLN9, isolated from the fluoride-contaminated village of Madhabpur in Birbhum, could resist up to 5600 mg L−1 F- concentration. Taxonomic classification of strain MLN9 based on whole genome sequence identified it as Proteus columbae MLN9. Strain MLN9 showed 88.9% of maximum F- removal efficiency at pH 8.0, 1.0 g L−1 CaCl2, and 10.0 g L−1 urea concentration. Scanning electron micrographs showed dense and porous biological crystal precipitates surrounding the surface of the bacterial cells, and the adherence of F- to the cell surface was confirmed by the energy dispersion spectrum. Moreover, the X-ray diffraction pattern showed that the F- precipitates on the cell surface were biological crystals of Ca5(PO4)3F and CaF2. Genomic analysis of strain MLN9 revealed the presence of crcB gene homologs possibly encoding F- transporters and urease regulatory proteins such as UreA, UreB, UreC, UreD, and UreG suggesting a role in defluoridation. Our findings provide new insights into the urease based MICP technology using a noble bacterium Proteus columbae MLN9 for fluoride removal.

Application of Zn-MOFs in Treating Cancer

Metal-organic frameworks (MOFs) are extremely porous crystals belonging to metallic complexes, made up of metal ions or clusters and organic ligands via coordinative bonding. The construction of tailored MOFs has attracted increasing interest over the past few decades. Particularly, a variety of applications for the delivery of drugs using MOFs are being investigated. MOFs were initially employed to deliver small-molecule medications. In this article, the construction of electrochemical (EC) biosensors based on MOFs that are directed toward certain analytes are mainly introduced. The classification of MOFs for drug-delivery systems (DDSs) based on the types of constitutes is presented in this article as an overview and point of view of MOF-based DDSs, among which, Zn-based MOFs are one of the best choices to be used in cancer treatment. This article demonstrates the advantages of Zn-based MOFs in cancer treatment compared to their counterparts.

Hydrated electrons as nodes in porous clathrate hydrates.

We investigate the structures of hydrated electrons (e- aq) in one of water's solid phases, namely, clathrate hydrates (CHs). Using density functional theory (DFT) calculations, DFT-based ab initio molecular dynamics (AIMD), and path-integral AIMD simulations with periodic boundary conditions, we find that the structure of the e- aq@node model is in good agreement with the experiment, suggesting that an e- aq could form a node in CHs. The node is a H2O defect in CHs that is supposed to be composed of four unsaturated hydrogen bonds. Since CHs are porous crystals that possess cavities that can accommodate small guest molecules, we expect that these guest molecules can be used to tailor the electronic structure of the e- aq@node, and it leads to experimentally observed optical absorption spectra of CHs. Our findings have a general interest and extend the knowledge of e- aq into porous aqueous systems.