Engineering Porosity and Functionality in a Robust Twofold Interpenetrated Bismuth-Based MOF: Toward a Porous, Stable, and Photoactive Material.

Defect engineering in metal-organic frameworks (MOFs) has gained worldwide research traction, as it offers tools to tune the properties of MOFs. Herein, we report a novel 2-fold interpenetrated Bi-based MOF made of a tritopic flexible organic linker, followed by missing-linker defect engineering. This procedure creates a gradually augmented micro- and mesoporosity in the parent (originally nonporous) network. The resulting MOFs can tolerate a remarkable extent of linker vacancy (with absence of up to 60% of linkers per Bi node) created by altering the crystal-growth rate as a function of synthesis temperature and duration. Owing to the enhanced porosity and availability of the uncoordinated Lewis acidic Bi sites, the defect-engineered MOFs manifested improved surface areas, augmented CO2 and water vapor uptake, and catalytic activity. Parallel to this, the impact of defect engineering on the optoelectronic properties of these MOFs has also been studied, offering avenues for new applications.

Analysis of COF-300 synthesis: probing degradation processes and 3D electron diffraction structure.

Although COF-300 is often used as an example to study the synthesis and structure of (3D) covalent organic frameworks (COFs), knowledge of the underlying synthetic processes is still fragmented. Here, an optimized synthetic procedure based on a combination of linker protection and modulation was applied. Using this approach, the influence of time and temperature on the synthesis of COF-300 was studied. Synthesis times that were too short produced materials with limited crystallinity and porosity, lacking the typical pore flexibility associated with COF-300. On the other hand, synthesis times that were too long could be characterized by loss of crystallinity and pore order by degradation of the tetrakis(4-aminophenyl)methane (TAM) linker used. The presence of the degradation product was confirmed by visual inspection, Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). As TAM is by far the most popular linker for the synthesis of 3D COFs, this degradation process might be one of the reasons why the development of 3D COFs is still lagging compared with 2D COFs. However, COF crystals obtained via an optimized procedure could be structurally probed using 3D electron diffraction (3DED). The 3DED analysis resulted in a full structure determination of COF-300 at atomic resolution with satisfying data parameters. Comparison of our 3DED-derived structural model with previously reported single-crystal X-ray diffraction data for this material, as well as parameters derived from the Cambridge Structural Database, demonstrates the high accuracy of the 3DED method for structure determination. This validation might accelerate the exploitation of 3DED as a structure determination technique for COFs and other porous materials.

Decoding Excimer Formation in Covalent-Organic Frameworks Induced by Morphology and Ring Torsion.

A thorough and quantitative understanding of the fate of excitons in covalent-organic frameworks (COFs) after photoexcitation is essential for their augmented optoelectronic and photocatalytic applications via precise structure tuning. The synthesis of a library of COFs having identical chemical backbone with impeded conjugation, but varied morphology and surface topography to study the effect of these physical properties on the photophysics of the materials is herein reported. The variation of crystallite size and surface topography substantified different aggregation pattern in the COFs, which leads to disparities in their photoexcitation and relaxation properties. Depending on aggregation, an inverse correlation between bulk luminescence decay time and exciton binding energy of the materials is perceived. Further transient absorption spectroscopic analysis confirms the presence of highly localized, immobile, Frenkel excitons (of diameter 0.3-0.5 nm) via an absence of annihilation at high density, most likely induced by structural torsion of the COF skeletons, which in turn preferentially relaxes via long-lived (nanosecond to microsecond) excimer formation (in femtosecond scale) over direct emission. These insights underpin the importance of structural and topological design of COFs for their targeted use in photocatalysis.

Computational Protocol for the Spectral Assignment of NMR Resonances in Covalent Organic Frameworks.

Solid-state nuclear magnetic resonance spectroscopy is routinely used in the field of covalent organic frameworks to elucidate or confirm the structure of the synthesized samples and to understand dynamic phenomena. Typically this involves the interpretation and simulation of the spectra through the assumption of symmetry elements of the building units, hinging on the correct assignment of each line shape. To avoid misinterpretation resulting from library-based assignment without a theoretical basis incorporating the impact of the framework, this work proposes a first-principles computational protocol for the assignment of experimental spectra, which exploits the symmetry of the underlying building blocks for computational feasibility. In this way, this protocol accommodates the validation of previous experimental assignments and can serve to complement new NMR measurements.

Ratiometric dual-emitting thermometers based on rhodamine B dye-incorporated (nano) curcumin periodic mesoporous organosilicas for bioapplications.

This study explores the potential of combining periodic mesoporous organosilicas (PMOs) with a fluorescent dye to develop a ratiometric thermometry system with enhanced stability, sensitivity, and biocompatibility. PMOs, ordered porous materials known for their stability and versatility, serve as an ideal platform. Curcumin, a natural polyphenol and fluorescent dye, is incorporated into PMOs to develop curcumin-functionalized PMOs (C-PMO) and curcumin-pyrazole-functionalized PMOs (CP-PMO) via hydrolysis and co-condensation. These PMOs exhibit temperature-dependent fluorescence properties. The next step involves encapsulating rhodamine B (RhB) dye within the PMO pores to create dual-emitting PMO@dye nanocomposites, followed by a lipid bilayer (LB) coating to enhance biocompatibility and dye retention. Remarkably, within the physiological temperature range, C-PMO@RhB@LB and CP-PMO@RhB@LB demonstrate noteworthy maximum relative sensitivity (Sr) values of up to 1.69 and 2.60% K-1, respectively. This approach offers versatile means to create various ratiometric thermometers by incorporating different fluorescent dyes, holding promise for future temperature sensing applications.

The Application of Porous Organic Polymers as Metal Free Photocatalysts in Organic Synthesis.

Concerns about increasing greenhouse gas emissions and their effect on our environment highlight the urgent need for new sustainable technologies. Visible light photocatalysis allows the clean and selective generation of reactive intermediates under mild conditions. The more widespread adoption of the current generation of photocatalysts, particularly those using precious metals, is hampered by drawbacks such as their cost, toxicity, difficult separation, and limited recyclability. This is driving the search for alternatives, such as porous organic polymers (POPs). This new class of materials is made entirely from organic building blocks, can possess high surface area and stability, and has a controllable composition and functionality. This review focuses on the application of POPs as photocatalysts in organic synthesis. For each reaction type, a representative material is discussed, with special attention to the mechanism of the reaction. Additionally, an overview is given, comparing POPs with other classes of photocatalysts, and critical conclusions and future perspectives are provided on this important field.

Super-Oxidizing Covalent Triazine Framework Electrocatalyst for Two-Electron Water Oxidation to H2 O2.

Electrochemical two-electron water oxidation (2e WOR) is gaining surging research traction for sustainable hydrogen peroxide production. However, the strong oxidizing environment and thermodynamically competitive side-reaction (4e WOR) posit as thresholds for the 2e WOR. We herein report a custom-crafted covalent triazine network possessing strong oxidizing properties as a proof-of-concept metal-free functional organic network electrocatalyst for catalyzing 2e WOR. As the first-of-its-kind, the material shows a maximum of 89.9 % Faradaic Efficiency and 1428 µmol/h/cm2 H2 O2 production rate at 3.0 V bias potential (vs reversible hydrogen electrode, RHE), which are either better or comparable to the state-of-the-art electrocatalysts. We have experimentally confirmed a stepwise 2e WOR mechanism which was further computationally endorsed by density functional theory studies.

Lanthanide-grafted hollow bipyridine-based periodic mesoporous organosilicas as chemical sensors.

We have synthesized a co-condensed hollow ethane-bipyridine periodic mesoporous organosilica (HEt-bpy-PMO) as a host material to anchor lanthanides for the purpose of developing a multifunctional chemical sensor. The host material was grafted with lanthanide chloride salts or complexes. The luminescence properties of the developed series of hybrid materials were studied in detail in the solid-state and after dispersing in water. The Eu3+ or Tb3+ singly incorporated materials were investigated for their use as ion sensors, showing ions selectivity towards Cu2+, Co2+ and Fe3+. Additionally, the Eu3+ or Tb3+ incorporated materials showed obvious luminescence quenching behavior towards acetone compared to other organic solvents, indicating excellent acetone sensing selectivity.

Exploring the Charge Storage Dynamics in Donor-Acceptor Covalent Organic Frameworks Based Supercapacitors by Employing Ionic Liquid Electrolyte.

Two donor-acceptor type tetrathiafulvalene (TTF)-based covalent organic frameworks (COFs) are investigated as electrodes for symmetric supercapacitors in different electrolytes, to understand the charge storage and dynamics in 2D COFs. Till-date, most COFs are investigated as Faradic redox pseudocapacitors in aqueous electrolytes. For the first time, it is tried to enhance the electrochemical performance and stability of pristine COF-based supercapacitors by operating them in the non-Faradaic electrochemically double layer capacitance region. It is found that the charge storage mechanism of ionic liquid (IL) electrolyte based supercapacitors is dependent on the micropore size and surface charge density of the donor-acceptor COFs. The surface charge density alters due to the different electron acceptor building blocks, which in turn influences the dense packing of the IL near its pore. The micropores induce pore confinement of IL in the COFs by partial breaking of coulomb ordering and rearranging it. The combination of these two factors enhance the charge storage in the highly microporous COFs. The density functional theory calculations support the same. At 1 A g-1 , TTF-porphyrin COF provides capacitance of 42, 70, and 130 F g-1 in aqueous, organic, and IL electrolyte respectively. TTF-diamine COF shows a similar trend with 100 F g-1 capacitance in IL.

Enabling hydrate-based methane storage under mild operating conditions by periodic mesoporous organosilica nanotubes.

Biomethane is a renewable natural gas substitute produced from biogas. Storage of this sustainable energy vector in confined clathrate hydrates, encapsulated in the pores of a host material, is a highly promising avenue to improve storage capacity and energy efficiency. Herein, a new type of periodic mesoporous organosilica (PMO) nanotubes, referred to as hollow ring PMO (HR-PMO), capable of promoting methane clathrate hydrate formation under mild working conditions (273 K, 3.5 MPa) and at high water loading (5.1 g water/g HR-PMO) is reported. Gravimetric uptake measurements reveal a steep single-stepped isotherm and a noticeably high methane storage capacity (0.55 g methane/g HR-PMO; 0.11 g methane/g water at 3.5 MPa). The large working capacity throughout consecutive pressure-induced clathrate hydrate formation-dissociation cycles demonstrates the material's excellent recyclability (97% preservation of capacity). Supported by ex situ cryo-electron tomography and x-ray diffraction, HR-PMO nanotubes are hypothesized to promote clathrate hydrate nucleation and growth by distribution and confinement of water in the mesopores of their outer wall, along the central channels of the nanotubes and on the external nanotube surface. These findings showcase the potential for application of organosilica materials with hierarchical and interconnected pore systems for pressure-based storage of biomethane in confined clathrate hydrates.

Engineering of Phenylpyridine- and Bipyridine-Based Covalent Organic Frameworks for Photocatalytic Tandem Aerobic Oxidation/Povarov Cyclization.

Covalent organic frameworks (COFs) are emerging as a new class of photoactive organic semiconductors, which possess crystalline ordered structures and high surface areas. COFs can be tailor-made toward specific (photocatalytic) applications, and the size and position of their band gaps can be tuned by the choice of building blocks and linkages. However, many types of building blocks are still unexplored as photocatalytic moieties and the scope of reactions photocatalyzed by COFs remains quite limited. In this work, we report the synthesis and application of two bipyridine- or phenylpyridine-based COFs: TpBpyCOF and TpPpyCOF. Due to their good photocatalytic properties, both materials were applied as metal-free photocatalysts for the tandem aerobic oxidation/Povarov cyclization and α-oxidation of N-aryl glycine derivatives, with the bipyridine-based TpBpyCOF exhibiting the highest activity. By expanding the range of reactions that can be photocatalyzed by COFs, this work paves the way toward the more widespread application of COFs as metal-free heterogeneous photocatalysts as a convenient alternative for commonly used homogeneous (metal-based) photocatalysts.

Turning 3D Covalent Organic Frameworks into Luminescent Ratiometric Temperature Sensors.

In this study, we report hybrid crystalline lanthanide-containing 3D covalent organic framework (Ln@3D COF) materials that are suitable for temperature sensing applications. Different routes to obtain these hybrid materials were tested and compared for material quality and thermometric properties. In the first approach, a bipyridine-containing 3D COF (Bipy COF) was grafted with a range of visible emitting lanthanide (Eu3+, Tb3+, Dy3+, and Eu3+/Tb3+) ß-diketonate complexes. In the second approach, a novel nanocomposite material was prepared by embedding NaYF4:Er,Yb nanoparticles on the surface of a nonfunctionalized 3D COF (COF-300). To the best of our knowledge, the luminescent materials developed here are the first 3D COFs to be tested as ratiometric temperature sensors. In fact, for the Bipy COF, two different types of thermometers were tested (the Eu3+/Tb3+ system and a rare Dy3+ system), with both showing excellent temperature sensing properties. The reported NaYF4:Er,Yb/COF-300 nanocomposite material combines upconverting nanoparticles with 3D COFs, similar to previously reported metal organic framework (MOF) nanocomposite materials; however, this type of hybrid material has not yet been explored for COFs. As such, our findings open a new pathway toward potential multifunctional materials that can combine thermometry with other modalities, such as catalysis or drug delivery, in just one nanocomposite material.

Pyrene-Based Covalent Organic Frameworks for Photocatalytic Hydrogen Peroxide Production.

Four highly porous covalent organic frameworks (COFs) containing pyrene units were prepared and explored for photocatalytic H2 O2 production. The experimental studies are complemented by density functional theory calculations, proving that the pyrene unit is more active for H2 O2 production than the bipyridine and (diarylamino)benzene units reported previously. H2 O2 decomposition experiments verified that the distribution of pyrene units over a large surface area of COFs plays an important role in catalytic performance. The Py-Py-COF though contains more pyrene units than other COFs which induces a high H2 O2 decomposition due to a dense concentration of pyrene in close proximity over a limited surface area. Therefore, a two-phase reaction system (water-benzyl alcohol) was employed to inhibit H2 O2 decomposition. This is the first report on applying pyrene-based COFs in a two-phase system for photocatalytic H2 O2 generation.

Metal-organic frameworks in photocatalytic Z-scheme heterojunctions: an emerging technology.

There is an urgent need for cleaner production processes for chemicals. An efficient and promising alternative for such reactions is heterogeneous photocatalysis, which works on the principle of converting (visible) light, including solar energy, into chemical energy. To that end, properly designed semiconductor based photocatalysts are necessary to trigger the photocatalytic reactions. Many commonly used photocatalysts have too large bandgaps (3-3.4 eV) to use visible light and a too low surface area for efficient production. Metal-organic frameworks (MOFs) have emerged as an encouraging class of materials for photocatalytic applications due to their (i) large surface area and porosity that facilitate adsorption towards chemicals, (ii) tunable crystallinity and optical and electronic properties for efficient light absorption in the visible region, (iii) tunable composition and functionality that make them versatile photocatalysts for a wide range of reactions, and (iv) facile development of composites with other semiconductors to produce Z-scheme heterojunctions that can effectively suppress the recombination of photogenerated charges. Ongoing research has started focusing on the judicious construction of Z-scheme heterojunctions in MOFs, to mimic natural photosynthesis, such that the MOF photocatalysts have higher light harvesting capacity, spatially separated reductive and oxidative active sites, and well-preserved redox ability. This review provides a concise compilation of the recent progress in the development and applications of MOF-based Z-scheme photocatalysts, their advanced characterization, and future perspectives for further advancements.

Exploring the phase stability in interpenetrated diamondoid covalent organic frameworks.

Soft porous crystals, which are responsive to external stimuli such as temperature, pressure, or gas adsorption, are being extensively investigated for various technological applications. However, while substantial research has been devoted to stimuli-responsive metal-organic frameworks, structural flexibility in 3D covalent organic frameworks (COFs) remains ill-understood, and is almost exclusively found in COFs exhibiting the diamondoid (dia) topology. Herein, we systemically investigate how the structural decoration of these 3D dia COFs-their specific building blocks and degree of interpenetration-as well as external triggers such as temperature and guest adsorption may promote or suppress their phase transformations, as captured by a collection of 2D free energy landscapes. Together, these provide a comprehensive understanding of the necessary conditions to design flexible diamondoid COFs. This study reveals how their flexibility originates from the balance between steric hindrance and dispersive interactions of the structural decoration, thereby providing insight into how new flexible 3D COFs can be designed.

Linker Engineering of 2D Imine Covalent Organic Frameworks for the Heterogeneous Palladium-Catalyzed Suzuki Coupling Reaction.

Covalent organic frameworks (COFs) are an emerging class of porous organic polymers that have been utilized as scaffolds for anchoring metal active species to act as heterogeneous catalysts. Though several examples of such COFs exist, a thorough experimental and computational analysis on such catalysts is limited. In this work, a series of two-dimensional (2D) imine COFs (TTA-DFB COF (N), TTA-TBD COF (N∧O), and TTA-DFP COF(N∧N)) were synthesized by using suitable building units to obtain three different coordination sites (N, N∧O, and N∧N). These were post-modified with Pd(II) to catalyze the Suzuki-Miyaura coupling reaction. Pd@TTA-DFB COF, where Pd(II) was coordinated to N sites, showed the fastest reactivity and lower stability. Pd@TTA-DFP COF showed highest stability but slowest reactivity. Pd@TTA-TBD COF was the best among the three with both high stability and fast reactivity. By combining both experimental and computational results, we conclude that the Pd(II) to Pd(0) reduction is a key step in the difference between the catalytic reactivities of the three COFs. This study demonstrates the importance of the building block approach to design COFs for efficient heterogeneous catalysis and to understand the fate of the reaction profile.

Comprehensive Model for the Synthesis of γ-Al2O3 Microsphere-Supported Bimetallic Iron- and Copper Oxide Materials.

The effects of incipient wetness impregnation synthesis conditions on the macro- and microscopic properties of bimetallic iron oxide/copper oxide@γ-Al2O3 microspheres were elucidated. The key steering factors for the macroscopic distribution of the metals throughout the support, and for the metal nanoparticle sizes, were the pH of the impregnation solution, the counterions present in the metal precursor, the amount of negatively charged groups on the alumina, the complexation of iron, the impregnation strategy (simultaneous or sequential) and, in the latter case, the order of impregnation. The interactions taking place during impregnation are identified as competitive adsorption of charged dissolved species (Fe/Cu cations, protons, and additional anions) in the impregnation solution. Adsorption can take place on either charged alumina sites or previously deposited metal (i.e., iron on iron, copper on copper, iron on copper, and copper on iron) and is affected by counterion shielding. Modeling of these interactions via simulation on an in-house-developed python code allowed quantification of the adsorption constants for each of the above-mentioned processes, where iron adsorbs much faster than copper on all surfaces, and adsorption of iron on both alumina surface groups and previously deposited copper contributes majorly to the final iron distribution. The findings in this work will allow for better prediction and control over bimetallic materials synthesized via the simple and scalable impregnation procedure.

Engineering Covalent Organic Frameworks as Heterogeneous Photocatalysts for Organic Transformations.

Covalent organic frameworks (COFs) are an emerging category of organic polymers with highly porous crystalline structures. In the last decade, reports on the use of COFs as heterogeneous photocatalysts for organic transformations have shown significant progress. Still, comprehensive reviews on the mechanisms of the photocatalytic organic transformations using COFs are lacking. This Review provides a comprehensive and systematic overview of COF-based photocatalysts for organic transformations. Firstly, we discuss the photophysical properties and the characterization methods of COF-based photocatalysts. Then, the general photocatalytic mechanism, the advantages, and the strategies to improve the photocatalytic efficiency of COF-based photocatalysts are summarized. After that, advanced examples of COF-based photocatalysts for organic transformations are analyzed with regard to the underlying mechanisms. The Review ends with a critical perspective on the challenges and prospects.

A Green Alternative for the Direct Aerobic Iodination of Arenes Using Molecular Iodine and a POM@MOF Catalyst.

Iodoarenes are important precursors for fine chemicals and pharmaceuticals. The direct iodination of arenes using molecular iodine (I2) has emerged as an attractive green synthesis method. Most of the direct iodination protocols are still homogeneous systems that require harsh conditions and use or produce toxic products. We report a new heterogeneous catalytic route for the direct aerobic iodination of arenes under mild conditions using a PMoV2 polyoxometalate (POM) embedded in the metal-organic framework (MOF) MIL-101 (PMoV2@MIL-101). The catalyst shows full yield for the conversion of mesitylene to 2-iodomesitylene at a rate that is similar to the homogeneous POM system. Moreover, the catalyst is applicable for a wide range of substrates in an oxygen atmosphere without using any co-catalysts or sacrificial agents. To the best of our knowledge, this is the first report on designing a sustainable and green MOF-based heterogeneous catalytic system for the direct iodination reaction using molecular oxygen and iodine.

Chemical sensors based on periodic mesoporous organosilica @NaYF4:Ln3+ nanocomposites.

Here, three unique organic-inorganic hybrid nanocomposite materials prepared by combining NaYF4:Yb3+,Ln3+ (Ln3+ = Er3+, Tm3+, Ho3+) and periodic mesoporous organosilica (PMO) are proposed for both metal ion sensing and solvent sensing. The luminescence properties of the developed hybrid materials, PMO@NaYF4:Yb3+,Ln3+, were studied in detail in the solid state and after dispersing in water. It is found that PMO@NaYF4:Yb3+,Er3+ showed selective "turn on" luminescence for Hg2+ with the detection limit of 24.4 µM in an aqueous solution. Additionally, the above three materials showed different luminescence emission responses towards water and organic solvents. It is worth noting that all three PMO@NaYF4:Yb3+,Ln3+ materials showed "turn on" luminescence towards alcohols. PMO@NaYF4:Yb3+,Er3+ and PMO@NaYF4:Yb3+,Ho3+ were selected and further developed into sensitive sensors for the detection of water in alcohols by taking advantage of their quenching behavior in water. The detection limit for sensing of water was determined to be 0.21%, 0.18% and 0.29%, corresponding to isopropanol (PMO@NaYF4:Yb3+,Er3+), n-butanol (PMO@NaYF4:Yb3+,Er3+) and ethanol (PMO@NaYF4:Yb3+,Ho3+), respectively. The above results illustrate the potential of these hybrid materials for applications in environmental fields as well as in chemical industries.