Negative gas adsorption transitions and pressure amplification phenomena in porous frameworks.

Nanoporous solids offer a wide range of functionalities for industrial, environmental, and energy applications. However, only a limited number of porous materials are responsive, the nanopore dynamically alters its size and shape in response to external stimuli such as temperature, pressure, light or the presence of specific molecular stimuli adsorbed inside the voids deforming the framework. Adsorption-induced structural deformation of porous solids can result in unique counterintuitive phenomena.

Synthetic Aspects and Characterization Needs in MOF Chemistry - from Discovery to Applications.

Even if MOFs are recently developed for large-scale applications, the road to applications of MOFs is long and rocky. This requires to overcome challenges associated with phase discovery, synthesis optimization, basic and advanced characterization, and computational studies. Lab-scale results need to be transferred to large-scale processes, which is often not trivial, and life-cycle analyses and techno-economic analyses need to be performed to realistically assess their potential for industrial relevance.

Rubbery organic frameworks (ROFs) toward ultrapermeable CO-selective membranes.

The capture of CO is of high interest in our society representing an essential tool to mitigate man-made climate warming. Membrane technology applied for CO capture offers several advantages in terms of energy savings, simple operation, and easy scale-up. Glassy membranes are associated with low gas permeability that negatively affect on their industrial implementation.

Metal-organic frameworks based on pyrazolates for the selective and efficient capture of formaldehyde.

Indoor air pollution is one of the major threads in developed countries, notably due to high concentrations of formaldehyde, a harmful molecule difficult to eliminate. Addressing this purification challenge while adhering to the principles of sustainable development requires the use of innovative, advanced sustainable materials. Here we show that by combining state-of-the-art spectroscopic techniques with density-functional theory molecular simulations, we have developed an advantageous mild chemisorption synergistic mechanism using porous metal (III or IV) pyrazole- di-carboxylate based metal-organic framework (MOF) to trap formaldehyde in a reversible manner, without incurring significant energy penalties for regeneration.

Oriented Titanium-MOF Membrane for Hydrogen Purification.

Precise hydrogen sorting from purge gas (H/N) and coke gas (H/CH), commonly carried out by cryogenic distillation, still suffers from low separation efficiency, high energy consumption, and considerable capital cost. Though still in its infancy, membrane technology offers a potential to achieve more efficient hydrogen purification. In this study, an optimum separation of hydrogen towards both methane and nitrogen via a kinetically-driven mechanism is realized through preferred orientation control of a MOF membrane.

Engineering MOF/carbon nitride heterojunctions for effective dual photocatalytic CO conversion and oxygen evolution reactions.

Photocatalysis appears as one of the most promising avenues to shift towards sustainable sources of energy, owing to its ability to transform solar light into chemical energy, production of chemical fuels oxygen evolution (OER) and CO reduction (CORR) reactions. Ti metal-organic frameworks (MOFs) and graphitic carbon nitride derivatives, poly-heptazine imides (PHI) are appealing CORR and OER photo-catalysts respectively. Engineering of an innovative Z-scheme heterojunction by assembling a Ti-MOF and PHI offers an unparalleled opportunity to mimick an artificial photosynthesis device for dual CORR/OER catalysis.

Tuning MOF/polymer interfacial pore geometry in mixed matrix membrane for upgrading CO separation performance.

The current paradigm considers the control of the MOF/polymer interface mostly for achieving a good compatibility between the two components to ensure the fabrication of continuous mixed-matrix metal-organic framework (MMMOF) membranes. Here, we unravel that the interfacial pore shape nanostructure plays a key role for an optimum molecular transport. The prototypical ultrasmall pore AlFFIVE-1-Ni MOF was assembled with the polymer PIM-1 to design a composite with gradually expanding pore from the MOF entrance to the MOF/polymer interfacial region.

Porous Organic Polymers for Efficient and Selective SO Capture from CO-rich Flue Gas.

The quest for effective technologies to reduce SO pollution is crucial due to its adverse effects on the environment and human health. Markedly, removing a ppm level of SO from CO-containing waste gas is a persistent challenge, and current technologies suffer from low SO/CO selectivity and energy-intensive regeneration processes. Here using the molecular building blocks approach and theoretical calculation, we constructed two porous organic polymers (POPs) encompassing pocket-like structures with exposed imidazole groups, promoting preferential interactions with SO from CO-containing streams.

Lanthanide MOF-based luminescent sensor arrays for the detection of castration-resistant prostate cancer curing drugs and biomarkers.

In recent years, castration-resistant prostate cancer (CRPC) has profoundly impacted the lives of many men, and early diagnosis of medication and illness is crucial. Therefore, a highly efficient detection method for CRPC biomarkers and curing drugs is required. However, the complex and diverse structures of CRPC drugs pose significant challenges for their detection and differentiation.

Engineered Nanoporous Frameworks for Adsorption Cooling Applications.

The energy demand for traditional vapor-compressed technology for space cooling continues to soar year after year due to global warming and the increasing human population's need to improve living and working conditions. Thus, there is a growing demand for eco-friendly technologies that use sustainable or waste energy resources. This review discusses the properties of various refrigerants used for adsorption cooling applications followed by a brief discussion on the thermodynamic cycle.

Molecular-Level Insight into the Chlorofluorocarbons Adsorption by Defective Covalent Organic Polymers.

Halocarbons have important industrial applications, but because of their contribution to global warming and the fact that they can cause ozone depletion, they are considered highly toxic. Hence, the techniques that can capture and recover the used halocarbons with energy-efficient methods have been recently received greater attention. In this contribution, we report the capture of dichlorodifluoromethane (R12), which has high global warming and ozone depletion potential, using covalent organic polymers (COPs).

Unconventional mechanical and thermal behaviours of MOF CALF-20.

CALF-20 was recently identified as a benchmark sorbent for CO capture at the industrial scale, however comprehensive atomistic insight into its mechanical/thermal properties under working conditions is still lacking. In this study, we developed a general-purpose machine-learned potential (MLP) for the CALF-20 MOF framework that predicts the thermodynamic and mechanical properties of the structure at finite temperatures within first-principles accuracy. Interestingly, CALF-20 was demonstrated to exhibit both negative area compression and negative thermal expansion.

Machine learning potential for modelling H adsorption/diffusion in MOFs with open metal sites.

Metal-organic frameworks (MOFs) incorporating open metal sites (OMS) have been identified as promising sorbents for many societally relevant-adsorption applications including CO capture, natural gas purification and H storage. This has been ascribed to strong specific interactions between OMS and the guest molecules that enable the MOF to achieve an effective capture even under low gas pressure conditions. In particular, the presence of OMS in MOFs was demonstrated to substantially boost the H binding energy for achieving high adsorbed hydrogen densities and large usable hydrogen capacities.

A Scalable Robust Microporous Al-MOF for Post-Combustion Carbon Capture.

Herein, a robust microporous aluminum tetracarboxylate framework, MIL-120(Al)-AP, (MIL, AP: Institute Lavoisier and Ambient Pressure synthesis, respectively) is reported, which exhibits high CO uptake (1.9 mmol g at 0.1 bar, 298 K).

Design of Mixed-Matrix MOF Membranes with Asymmetric Filler Density and Intrinsic MOF/Polymer Compatibility for Enhanced Molecular Sieving.

The separation of high-value-added chemicals from organic solvents is important for many industries. Membrane-based nanofiltration offers a more energy-efficient separation than the conventional thermal processes. Conceivably, mixed-matrix membranes (MMMs), encompassing metal-organic frameworks (MOFs) as fillers, are poised to promote selective separation via molecular sieving, synergistically combining polymers flexibility and fine-tuned porosity of MOFs.

A Microporous Multi-Cage Metal-Organic Framework for an Effective One-Step Separation of Branched Alkanes Feeds.

The improvement of the Total Isomerization Process (TIP) for the production of high-quality gasoline with the ultimate goal of reaching a Research Octane Number (RON) higher than 92 requires the use of specific sorbents to separate pentane and hexane isomers into classes of linear, mono- and di-branched isomers. Herein we report the design of a new multi-cage microporous Fe(III)-MOF (referred to as MIP-214, MIP stands for materials of the Institute of Porous Materials of Paris) with a flu-e topology, incorporating an asymmetric heterofunctional ditopic ligand, 4-pyrazolecarboxylic acid, that exhibits an appropriate microporous structure for a thermodynamic-controlled separation of hydrocarbon isomers. This MOF produced via a direct, scalable, and mild synthesis route was proven to encompass a unique separation of C5/C6 isomers by classes of low RON over high RON alkanes with a sorption hierarchy: (n-hexane≫n-pentane≈2-methylpentane>3-methylpentane)≫(2,3-dimethylbutane≈i-pentane≈2,2-dimethylbutane) following the adsorption enthalpy sequence.

Unravelling abnormal in-plane stretchability of two-dimensional metal-organic frameworks by machine learning potential molecular dynamics.

Two-dimensional (2D) metal-organic frameworks (MOFs) hold immense potential for various applications due to their distinctive intrinsic properties compared to their 3D analogues. Herein, we designed a highly stable NiF(pyrazine) 2D MOF with a two-dimensional periodic wine-rack architecture. Extensive first-principles calculations and molecular dynamics (MD) simulations based on a newly developed machine learning potential (MLP) revealed that this 2D MOF exhibits huge in-plane Poisson's ratio anisotropy.

Chiral Reticular Chemistry: A Tailored Approach Crafting Highly Porous and Hydrolytically Robust Metal-Organic Frameworks for Intelligent Humidity Control.

Control of humidity within confined spaces is critical for maintaining air quality and human well-being, with implications for environments ranging from international space stations and pharmacies to granaries and cultural relic preservation sites. However, existing techniques rely on energy-intensive electrically driven equipment or complex temperature and humidity control (THC) systems, resulting in imprecision and inconvenience. The development of innovative techniques and materials capable of simultaneously meeting the stringent requirements of practical applications holds the key to creating intelligent and energy-efficient humidity control devices.

Ultrarapid and Sustainable Synthesis of Trimetallic-Based MOF (CrNiFe-MOF) from Stainless Steel and Disodium Terephthalate-Derived PET Wastes.

Designing easy and sustainable strategies for the synthesis of metal-organic frameworks (MOFs) from organic and inorganic wastes with the efficient removal of phosphate from water remains a challenge. The majority of the reported works have utilized costly precursors and nonsoluble ligands for the synthesis of MOFs. Herein, we have developed a low-cost, simple, and sustainable alternative approach using the coprecipitation method in water at room temperature for the synthesis of a new adsorbent-based trimetallic MOF.

Metal-Organic Frameworks for Phthalate Capture.

Indoor air contamination by phthalate ester (PAE) derivatives has become a significant concern since traces of PAEs can cause endocrine disruption, among other health issues. PAE abatement from the environment is thus mandatory to further ensure a good quality of indoor air. Herein, we explored the physisorption-based capture of volatile PAEs by metal-organic frameworks (MOFs).

A squarate-pillared titanium oxide quantum sieve towards practical hydrogen isotope separation.

Separating deuterium from hydrogen isotope mixtures is of vital importance to develop nuclear energy industry, as well as other isotope-related advanced technologies. As one of the most promising alternatives to conventional techniques for deuterium purification, kinetic quantum sieving using porous materials has shown a great potential to address this challenging objective. From the knowledge gained in this field; it becomes clear that a quantum sieve encompassing a wide range of practical features in addition to its separation performance is highly demanded to approach the industrial level.

MIL-101(Cr)@QCM and MIL-101(Cr)@IDE as Sorbent-Based Humidity Sensors for Indoor Air Monitoring.

MIL-101(Cr) films were deposited on the quartz crystal microbalance and interdigitated electrode transductors as humidity sensors. Both devices combine high sensitivity with fast response/recovery times, good repeatability, long-term stability, favorable selectivity versus toluene alongside a dual mode behavior in the optimal domain of humidity for indoor air.