Themed collection Functional Framework Materials

This themed issue covers functional framework materials and their related applications.

Metal–organic frameworks (MOFs) are potentially promising materials for a variety of applications in several fields owing to their distinctive structural properties, such as ultrahigh surface area, tailorable porosity and structural diversity.

Recent advances on functional framework materials, including PCFs and IOFs, are summarized to regulate interfacial chemistry in metal batteries, which facilitate cation desolvation and metal nucleation for improved electrochemical performance.

Defective MOFs: unique properties and electrochemical sensor applications. Overview of construction principles, mechanisms, and applications.

Type III COFs are constructed using sub-stoichiometric synthesis and result in unconventional topologies and active functional groups with a variety of applications.

This review summarizes the advances in rational design and synthesis of 3D COFs guided by reticular chemistry and briefly discusses recent progress in gas storage and separation, catalysis, fluorescence, batteries, conductivity, and drug delivery.

A novel electrically conducting cubic mesoporous metal–organic framework (MOF), consisting of hexahydroxy-cata-hexabenzocoronene (c-HBC) and Fe^III ions is presented.

An efficient adsorptive molecular sieving strategy to separate aromatic and cyclic aliphatic hydrocarbons via an intrinsic/extrinsic approach.

We present an approach to improve the electrochemical performance of an anthraquinone-based covalent organic framework (COF) cathode material in metal anode (Li, Mg) batteries through proper selection of the electrolyte and binder.

Aerogels of two imine-based COFs showed fast adsorption uptakes of Fe²⁺ from contaminated waters. COF-aerogel@Polysulfone composite beads are easily incorporated into water treatment, they are excellent candidates for large-scale preparation.

Copper(I)–organic frameworks (CuX–bpy) loaded on Cu₂O enable efficient CO₂ photoreduction to formate, leveraging halogens (X = Cl, Br, I) and rapid electron transfer, achieving 1520 μmol g⁻¹ in 12 hours without sacrificial agents or photosensitizers.

In essence, the utilization of renewable energy in the carbon dioxide reduction reaction (CO₂RR) holds the potential to transform carbon emissions into valuable chemicals, encompassing a range of hydrocarbons and alcohols.

The conductivity of ionogels, made by embedding an ionic liquid into lithium alkoxide-grafted MOFs from the UiO-66 family, can be improved by 6 orders of magnitude.

PCN-224 metal–organic framework family is particularly suitable for the electroreduction of molecular nitrogen for the formation of ammonia. The introduction of Ni²⁺ and fluor sites improves both the activity and stability.

The influence of Ni(II) coordinatively unsaturated metal sites and coordinated water on the SO₂ adsorption performance of NiBDP were investigated.

A highly reversible bifunctional electrocatalyst for flexible Zn air batteries was fabricated featuring pyridinic-N exclusively enriched CNT encased NiFe interfacial alloy nanoparticles derived from an LDH template on knitted carbon fiber cloth.

Polar substituents decorating the pore walls of covalent organic frameworks can be used to control the electrostatic potential within the pores and to tune the alignment of the electronic states in guest molecules and the COF scaffold.

The dehydroaromatization of methane is a promising process to produce aromatics and ultra-pure hydrogen. Increased yields and stability of Mo/HZSM-5 against irreversible deactivation were achieved via a redox interaction by doping with otherwise inert Nb.

An in situ proton filter covalent organic framework (COF) is developed to integrate the chlorine evolution reaction (CER) with the oxygen-depolarized cathode and an excellent CER faradaic efficiency of 92% is achieved.

A series of Cu–Zn@CNx catalysts incorporated with platinum group metal (PGM) elements, such as Ru, Pd, Pt, and Ir were synthesised via the hard template approach, where a metal–organic framework (MOF) is utilised as a hard template.

Selective chemoresistive gas sensors using a monolithic membrane-sensing layer architecture.

A high-efficiency photocatalyst with a strong built-in electric field was fabricated by anchoring π-conjugated molecules on the surface of crystalline nitride carbon via π–π stacking interactions with efficient photocatalytic CO₂ reduction into CO and CH₄.

This work investigates a Mo–Tp 2D MOF screened from a number of different transition-metal-based 2D MOFs. After exfoliation, the Mo–Tp 2D MOF produces ammonia via the distal pathway at a very low limiting potential of −0.38 V.

A new composite with two-dimensional graphene oxide decoration is designed through microwave sintering for efficient microwave attenuation.

[Gd(MeCOO)(PhCOO)₂], a 2D MOF is reported and characterized, the material shows a magnetocaloric effect both in bulk and chemisorbed on a Silicon substrate. This opens up the possibilities for on-surface cooling devices.

We developed a strategy for synthesizing single-crystal Zr-phosphonate MOFs, retaining parent topology via post-synthesis. SALE and post-synthetic oxidation enable linker modification, enhancing hydrophilicity and Brønsted acidity.

Photocatalytic CO₂ reduction over metal organic frameworks is investigated by constructing a database from published articles and analyzed using machine learning tools to predict the total gas product yield and predominant product types under various conditions.

Single-site Co-embedded CTF-TPE exhibits high photocatalytic CO₂ conversion to CO with a production rate of 945 μmol g⁻¹ h⁻¹.

Integration of mesoporous thin films and metal–organic frameworks as stacked bilayers, towards hierarchical porous 1D photonic crystals.

The microscopic mechanism of ZIF-4 amorphization and ZIF-zni melting are elucidated via a combination of data science and computer simulation approaches. Gradual density changes and the breaking and formation of Zn–N bonds are key to both processes.

An extensive electrochemical investigation of PEDOT has been carried out with a particular focus on understanding the structural electrochemistry during its faradaic process, a topic that has not been previously explored in such detail.

Two of the main factors controlling the activity and selectivity of metal sites within MOF-like copper metalloenzymes are: (i) their coordination environments, and (ii) the number and connectivity of metal ions at the active site (i.e., nuclearity).

A two dimensional CuCN-based semiconducting MOF with nitrogen rich ligand has been synthesized which shows supercapattery behaviour. The energy storage device formed by CuCN-MOF exhibits excellent energy density, power density and cyclic stability.

Employing a functionality scissoring approach, a hydrogen-bonded MOF shows selective and regenerable uranium extraction alongside exceptionally improved electrochemical oxygen evolution via post-metalation.

Alcohol adsorption using hydrophobic MOFs is a promising strategy for heating and cooling applications. Finding optimal conditions for each adsorbent-working fluid pair is key to maximize the performance of the devices.

Nitrate, a water-pollutant, is converted to valuable product ammonia electrochemically using Fe(TCNQ)₂/CF nanorod arrays with yield rate 11351.6 μg h^–1 cm^–2 and faradaic efficiency 85.2% under ambient conditions.

A carboxylic acid functionalized sp³ N-rich imine bonded COF shows a humidity-dependent visible color change. This COF is easily exfoliated to nanosheets, which are explored as a potential humidity sensor that detects trace water in organic solvents.

MOFs can achieve atom-precision in the design of single-atom catalysts (SACs). We elucidated the PROX-reaction mechanism on a well-defined Cu-SAC supported by UiO-66 framework using a multitude of experimental methods and detailed DFT computations.

In this study, 2 to 4 nm ruthenium nanoparticles were loaded by decomposition of Ru₃(CO)₁₂ through microwave heating on thiophene containing CTFs to assess the influence of thiophene on the electrocatalytic properties in the hydrogen evolution reaction.

Efficient pH-universal electrocatalysts composed of highly dispersive tiny Fe nanoparticle units in a carbon nanofiber network is reported. The as-assembled zinc–air batteries in alkaline and neutral electrolytes exhibit excellent overall performance.

A novel solid polymer electrolyte based on chemically stable vinylene-linked covalent organic framework was developed, demonstrating enhanced Li⁺ conductivity and improved battery performance.

We have studied the formation of core–shell hybrid metal–organic framework@activated carbon sphere (MOF@AC) adsorbents, by means of a layer-by-layer (LBL) growth method of MOFs on shaped AC materials.

Here we show the improvement in solar driven H₂ production due to the synergy between a novel BOPHY based COF and TiO₂.

The pyrolysis of ZIF-67 is followed in situ, and the conditions are correlated with the structural evolution and electrocatalytic performance.

Two steps must be satisfied to achieve high activity enzyme@MOFs: proper enzyme folding and low MOF crystallinity.

This study reports moisture-triggered proton-conductivity switching behavior in Zn₅FDC MOFs, [Zn₅(μ₃-OH)₂(FDC)₄(solvent)₂] (FDC = 9H-fluorene-2,7-dicarboxylate), induced by the presence and absence of coordinating solvents.

Through regulated and less toxic MIL-101(Cr) synthesis and superabsorbent polymeric binders, this work reports MIL-101(Cr)-coated heat exchangers with twice the water uptake of the silica gel-coated control towards energy-efficient cooling.

Addressing the synthesis–property relations in the Assembly step of ADOR enabled to design previously unknown IPC-17 zeolite by optimization of the chemical composition and crystallite dimensions in the parent IWR germanosilicate.

Comparison of seven archetype MOFs post-synthetically modified with and possessing Eu³⁺ as connectivity centers illuminates pros and cons of reversible, optical sensing of O₂ based on photoluminescence emission quenching.

The N-atom orientation of imine bonds towards the acceptor in COFs may induce local charge polarization and delocalization, which could fundamentally improve the exciton dissociation and charge separation, thus achieving the promoted photocatalytic H₂ evolution.

This work discloses a new functionalized material comprising a mesoporous matrix and a luminescent tag, both composed of carbon for the detection and removal of specific antibiotics from aqueous solutions with superior performances.

Vapor-phase synthesis of metal–organic frameworks (MOFs) on nanofibrous aerogels provides a hierarchically porous and mechanically robust material platform for use in a multitude of applications, from carbon dioxide capture to heavy metal removal.

In this study we have synthesized a Cd-MOF and explored for TENG performance. MOF-TENG device utilzed for various low powered electronics. Furthermore, device was attached to the finger of a glove to control the mouse movement. This device setup was used for biomechanical energy harvesting.

Ni₃P@Ni/CNP exhibits excellent OER electrocatalytic activity. The current density of 10 mA cm⁻² in 1 M KOH electrolyte only needs an overpotential of 239 mV in the presence of the catalyst, and it showed excellent stability.

Three novel MOF phases based on catecholate porphyrin and M(III) cations are isolated. Their properties are elucidated through comprehensive structural and physical analyses, and a high surface area and reversible redox activity are evidenced.

Two nitrogen-rich porous organic cages (POCs) have been investigated for acetylene (C₂H₂) storage and separation applications, achieving a high C₂H₂ uptake value of up to 146 cm³ g⁻¹ at 298 K and 1 atm and effective separation of C₂H₂/CO₂ mixtures.

A conductive and redox-active COF (Ni-TTF) have been synthesized and applied as an promising anode for KIBs, exhibiting remarkable stability with no capacity loss after 2500 cycles at 2C, making it one of the best organic anode materials for KIBs.

In this study, machine learning has been used to assist the fabrication of high-quality SURMOFs that are then further used as a template to fabricate polymer-based SURGEL membranes for gas separation.

The ultra-fast and green encapsulation of biomolecules in ZIF-90 results in biocomposites with biological activity and a size-sheltering effect. This is achieved through a 10-second, one-pot mechanical synthesis, assisted by a small amount of buffer.

Three zeolitic imidazolate framework-90 derivatives were synthesized via post-synthetic modification method, which exhibited ultrahigh iodine capture capacities.

The synergistic effects of the fabricated CuO/c-UiO-66 catalyst and hydrogen lead to the efficient scission of C–O bonds of the methoxylated β-O-4′ intermediates, transforming hardwood lignins into monophenols.

A series of Fe(III)-thiolate layered MOFs was prepared. These solids present a strong absorption in the visible range, a good chemical stability and an interesting electrochemical activity.

The misuse and improper handling of norfloxacin (NOR) can cause serious harm; therefore, the sensitive and visual detection of NOR is of great significance.

In this work, we studied the encapsulation of a range of proteins in a hydrogen-bonded organic framework (HOF) comprised of a tetraamidinium cation and diazobenzene-based dicarboxylate anion.

The properties of hierarchical solid acid materials have been explored combining experimental catalysis findings, neutron scattering and positron lifetime spectroscopy to understand the multi-porous nature of these materials.

Surfactant-assisted nano-synthesis and post-synthetic modification of three archetype bulk MOFs illuminate the size-dependent morphological and photophysical property changes of nanoMOFs.

A hydrophobic/superoleophilic spongy composite based on alkyne-rich 2D Zr-MOF and polyurethane executes solar-assisted self-cleaning oil/water separation.

A pore engineering optimized strategy by enlarging the core size of rigid monomers is proposed to increase the pore size of benzene cyanide-based HOFs, resulting in the highest performing HOF material for Xe/Kr separation.

The synthesized Ru-Co₃O₄ delivers a high performance towards the OER in alkaline (292 mV) and acidic (365 mV) media. Structural optimization demonstrates the distortion of bond length favours the selective adsorption of OH⁻ which facilitates the OER.

Guest-induced breathing mediated selective alcohol adsorption.