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.

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.

Generating Catalytic Sites in UiO-66 through Defect Engineering.

UiO-66 is regarded as an epitome of metal-organic frameworks (MOFs) because of its stability. Defect engineering has been used as a toolbox to alter the performance of MOFs. UiO-66 is among the most widely explored MOFs because of its capability to bear a high number of defects without undergoing structural collapse. Several representative works in the field of MOF-based defect engineering are available based on UiO-66. In this review, more emphasis is given toward the construction of catalytic sites by engineering defects in UiO-66 as a representative including all the detailed synthesis procedures for inducing defects, and the characterization techniques used to analyze these defects in UiO-66 are discussed. Furthermore, a comprehensive review for the defects themselves and the support using defects in catalysis is provided to accentuate the importance of defect engineering.

Creation of Exclusive Artificial Cluster Defects by Selective Metal Removal in the (Zn, Zr) Mixed-Metal UiO-66.

The differentiation between missing linker defects and missing cluster defects in MOFs is difficult, thereby limiting the ability to correlate materials properties to a specific type of defects. Herein, we present a novel and easy synthesis strategy for the creation of solely "missing cluster defects" by preparing mixed-metal (Zn, Zr)-UiO-66 followed by a gentle acid wash to remove the Zn nodes. The resulting material has the reo UiO-66 structure, typical for well-defined missing cluster defects. The missing clusters are thoroughly characterized, including low-pressure Ar-sorption, iDPC-STEM at a low dose (1.5 pA), and XANES/EXAFS analysis. We show that the missing cluster UiO-66 has a negligible number of missing linkers. We show the performance of the missing cluster UiO-66 in CO2 sorption and heterogeneous catalysis.

Flexible luminescent non-lanthanide metal-organic frameworks as small molecules sensors.

Toxic, carcinogenic, and hazardous materials are omnipresent, generally obtained by anthropogenic activities, industrial activities, aerobic and anaerobic degradation of waste materials and are harmful to human health and environment. Thus, sensing, colorimetric detection, and subsequent inclusion of these chemicals are of prime importance for human health and environment. In comparison to other classes of highly porous materials, luminescent metal-organic frameworks (LMOFs) have chromophoric organic ligands, high surface area, high degree of tunability and structural diversity. They have received scientific interest as sensory materials for device fabrication to detect and sense toxic small molecules. Especially, as soft-porous materials exhibiting a degree of flexibility or dynamic behaviour, flexible LMOFs are promising for selective detection and sensing, and for encapsulation of toxic and health hazardous molecules. Such flexible LMOFs offer a potential platform for selective adsorption/separation, molecular recognition, and sensing application. In this perspective, we highlight the advantages of flexibility of LMOFs for selective detection and sensing, and inclusion of toxic small molecules (solvents, anions, halobenzenes, aromatics, aromatic amines, nitro-explosives and acetylacetone). In addition, the principles and strategies guiding the design of these MOF based materials and recent progress in the luminescent detection of toxic small molecules are also discussed. In this perspective we limit our discussion on the 'non-lanthanide' based luminescent MOFs that have flexibility in the framework and show small molecule sensing applications.

Upconverting Er3+-Yb3+ Inorganic/Covalent Organic Framework Core-Shell Nanoplatforms for Simultaneous Catalysis and Nanothermometry.

Lanthanide-based luminescent nanoparticles that are thermally responsive can be used to probe temperature changes at a nanoscale regime. However, materials that can work as both a nanothermometer and a catalyst are limited. Herein, we show that covalent organic frameworks (COFs), which is an emerging class of porous crystalline materials, can be grown around lanthanide nanoparticles to create unique core-shell nanostructures. In this way, the COF (shell) supports copper metal ions as catalytic sites and simultaneously lanthanide nanoparticles (ß-NaLuF4:Gd,Er,Yb-core) locally measure the temperature during the catalytic reaction. Moreover, ß-NaLuF4:Gd,Er,Yb nanoparticles are upconverting materials and hence can be excited at longer wavelengths (975 nm), which do not affect the catalysis substrates or the COF. As a proof-of-principle, a three-component addition reaction of benzaldehyde, indole, and malononitrile was studied. The local temperature was probed using luminescence nanothermometry during the catalytic reaction.

Rigid Nanoporous Urea-Based Covalent Triazine Frameworks for C2/C1 and CO2/CH4 Gas Separation.

C2/C1 hydrocarbon separation is an important industrial process that relies on energy-intensive cryogenic distillation methods. The use of porous adsorbents to selectively separate these gases is a viable alternative. Highly stable covalent triazine frameworks (urea-CTFs) have been synthesized using 1,3-bis(4-cyanophenyl)urea. Urea-CTFs exhibited gas uptakes of C2H2 (3.86 mmol/g) and C2H4 (2.92 mmol/g) at 273 K and 1 bar and is selective over CH4. Breakthrough simulations show the potential of urea-CTFs for C2/C1 separation.

Oxygen-rich poly-bisvanillonitrile embedded amorphous zirconium oxide nanoparticles as reusable and porous adsorbent for removal of arsenic species from water.

A new oxygen-rich porous polymer based on bisvanillonitrile was synthesized and characterized. This polymer was employed as support for the anchoring of 14.5 w% amorphous zirconium oxide nanoparticles. The formation of homogeneously dispersed nanoparticles in the poly-bisvanillonitrile (PBVN) host material was confirmed using N2-sorption, XRPD, XPS and electron microscopy. The combination of zirconium oxide nanoparticles having active adsorption sites with the porous supporting material showed excellent adsorption of arsenic species. The resulting adsorption capacities of the hybrid material extend to 245 mg g-1 for arsenite (AsIII) and 115 mg g-1 for arsenate (AsV). Moreover, adsorption kinetics showed a fast removal of both arsenic species with initial adsorption rate h of 0.0646 mg g-1 min-1 for arsenite and 0.0746 mg g-1 min-1 for arsenate. The immobilization was not interfered by the presence of other compounds in solution, indicating the applicability in real working environments. The material could be regenerated in a continuous mode using a 0.1 mol L-1 sodium hydroxide solution at 70 °C to desorb arsenic.

A Visible-Light-Harvesting Covalent Organic Framework Bearing Single Nickel Sites as a Highly Efficient Sulfur-Carbon Cross-Coupling Dual Catalyst.

Covalent Organic Frameworks (COFs) have recently emerged as light-harvesting devices, as well as elegant heterogeneous catalysts. The combination of these two properties into a dual catalyst has not yet been explored. We report a new photosensitive triazine-based COF, decorated with single Ni sites to form a dual catalyst. This crystalline and highly porous catalyst shows excellent catalytic performance in the visible-light-driven catalytic sulfur-carbon cross-coupling reaction. Incorporation of single transition metal sites in a photosensitive COF scaffold with two-component synergistic catalyst in organic transformation is demonstrated for the first time.

Regeneration of Hopcalite used for the adsorption plasma catalytic removal of toluene by non-thermal plasma.

A dielectric barrier discharge reactor packed with both Hopcalite & glass beads has been investigated for the total oxidation of toluene adsorbed on Hopcalite. The catalytic activity and selectivity through the possible formation of by-products during the NTP discharge for the abatement of irreversibly adsorbed toluene have been investigated by FT-IR and mass spectrometer. The regeneration of the used Hopcalite by NTP discharge has been established by (i) determining the amount of toluene adsorbed on NTP regenerated Hopcalite, (ii) investigating the catalytic activity of NTP regenerated Hopcalite and (iii) comparing the bulk and surface properties of the fresh calcined and NTP regenerated Hopcalite. The ratio of amount of irreversibly adsorbed toluene to that of the total amount of adsorbed toluene adsorbed is similar for the fresh calcined and NTP (I) regenerated Hopcalite. The catalytic activity of the NTP (I) regenerated Hopcalite is slightly enhanced when compared to that of the fresh calcined Hopcalite. Although the first NTP treatment induces partial transformation of Hopcalite into Mn3O4 with no detected related CuOx and reduces specific surface area by a factor of 2, the toluene adsorption capacity remains less affected. A plausible reaction scheme for toluene decomposition in Hopcalite PBDBD reactor is proposed.

Luminescent Ratiometric Thermometers Based on a 4f-3d Grafted Covalent Organic Framework to Locally Measure Temperature Gradients During Catalytic Reactions.

Covalent Organic Frameworks (COFs), an emerging class of crystalline porous materials, are a new type of support for grafting lanthanide ions (Ln3+ ), which can be employed as ratiometric luminescent thermometers. In this work we have shown that COFs co-grafted with lanthanide ions (Eu3+ , Tb3+ ) and Cu2+ (or potentially other d-metals) can synchronously be employed both as a nanothermometer and catalyst during a chemical reaction. The performance of the thermometer could be tuned by changing the grafted d-metal and solvent environment. As a proof of principle, the Glaser coupling reaction was investigated. We show that temperature can be precisely measured during the course of the catalytic reaction using luminescence thermometry. This concept could be potentially easily extended to other catalytic reactions by grafting other d-metal ions on the Ln@COF platform.

Strongly Reducing (Diarylamino)benzene-Based Covalent Organic Framework for Metal-Free Visible Light Photocatalytic H2O2 Generation.

Photocatalytic reduction of molecular oxygen is a promising route toward sustainable production of hydrogen peroxide (H2O2). This challenging process requires photoactive semiconductors enabling solar energy driven generation and separation of electrons and holes with high charge transfer kinetics. Covalent organic frameworks (COFs) are an emerging class of photoactive semiconductors, tunable at a molecular level for high charge carrier generation and transfer. Herein, we report two newly designed two-dimensional COFs based on a (diarylamino)benzene linker that form a Kagome (kgm) lattice and show strong visible light absorption. Their high crystallinity and large surface areas (up to 1165 m2·g-1) allow efficient charge transfer and diffusion. The diarylamine (donor) unit promotes strong reduction properties, enabling these COFs to efficiently reduce oxygen to form H2O2. Overall, the use of a metal-free, recyclable photocatalytic system allows efficient photocatalytic solar transformations.

Illustrating the Role of Quaternary-N of BINOL Covalent Triazine-Based Frameworks in Oxygen Reduction and Hydrogen Evolution Reactions.

Defective nitrogen-doped carbon materials have shown a promising application as metal-free electrocatalysts in the oxygen reduction reaction (ORR) and the hydrogen evolution reaction (HER). However, there are still some challenges in the tuning of metal-free electrocatalysts and in understanding the roles of various nitrogen species in their electrocatalytic performance. Herein, we design a covalent triazine framework (CTF)-based material as an effective metal-free bifunctional electrocatalyst. We chose BINOL-CN (2,2'-dihydroxy-[1,1'-binaphthalene]-6,6'-dicarbonitrile) as both a carbon and a nitrogen source for the fabrication of N-containing CTF-based materials. Four BINOL-CTFs with varying N-functionalities (pyridinic-N/triazine-N, pyrrolic-N, quaternary-N, and pyridine-N-oxide) were successfully obtained. These materials were evaluated in the ORR and the HER in basic and acidic conditions, respectively. The best material has an onset potential of 0.793 V and a half-wave potential of 0.737 V, and it follows first-order kinetics in a 4e- pathway in the ORR reaction. The same material shows an impressive HER activity with an overpotential of 0.31 V to achieve 10 mA/cm2 and a small Tafel slope of 41 mV/dec, which is comparable to 31 mV/dec for Pt/C, making it a potential bifunctional electrocatalyst. We showed that the ORR and HER reactivity of CTF-based materials depends exclusively on the amount of quaternary-N species and on the available surface area and pore volume. This work highlights the engineering of CTF materials with varying amounts of N species as high-performance bifunctional electrocatalysts.

Effect of Building Block Transformation in Covalent Triazine-Based Frameworks for Enhanced CO2 Uptake and Metal-Free Heterogeneous Catalysis.

Covalent triazine frameworks (CTFs) have provided a unique platform in functional material design for a wide range of applications. This work reports a series of new CTFs with two new heteroaromatic building blocks (pyrazole and isoxazole groups) through a building-block transformation approach aiming for carbon capture and storage (CCS) and metal-free catalysis. The CTFs were synthesized from their respective building blocks [(4,4'-(1H-pyrazole-3,5-diyl)dibenzonitrile (pyz) and 4,4'-(isoxazole-3,5-diyl)dibenzonitrile (isox))] under ionothermal conditions using ZnCl2 . Both of the building blocks were designed by an organic transformation of an acetylacetone containing dinitrile linker to pyrazole and isoxazole groups, respectively. Due to this organic transformation, (i) linker aromatization, (ii) higher surface areas and nitrogen contents, (iii) higher aromaticity, and (iv) higher surface basicity was achieved. Due to these enhanced properties, CTFs were explored for CO2 uptake and metal-free heterogeneous catalysis. Among all, the isox-CTF, synthesized at 400 °C, showed the highest CO2 uptake (4.92 mmol g-1 at 273 K and 2.98 mmol g-1 at 298 K at 1 bar). Remarkably, these CTFs showed excellent metal-free catalytic activity for the aerobic oxidation of benzylamine at mild reaction conditions. On studying the properties of the CTFs, it was observed that organic transformations and ligand aromatization of the materials are crucial factor to tune the important parameters that influence the CO2 uptake and the catalytic activity. Overall, this work highlights the substantial effect of designing new CTF materials by building-block organic transformations resulting in better properties for CCS applications and heterogeneous catalysis.

Effect of Building Block Transformation in Covalent Triazine-Based Frameworks for Enhanced CO2 Uptake and Metal-Free Heterogeneous Catalysis.

Invited for the cover of this issue is the group of Pascal Van Der Voort at the University of Ghent and colleagues at Technische Universität Berlin. The image depicts the covalent triazine frameworks reported in the manuscript for the sorption of CO2 and also in metal-free catalysis. Read the full text of the article at 10.1002/chem.201903926.

Development of Covalent Triazine Frameworks as Heterogeneous Catalytic Supports.

Covalent triazine frameworks (CTFs) are established as an emerging class of porous organic polymers with remarkable features such as large surface area and permanent porosity, high thermal and chemical stability, and convenient functionalization that promotes great potential in heterogeneous catalysis. In this article, we systematically present the structural design of CTFs as a versatile scaffold to develop heterogeneous catalysts for a variety of chemical reactions. We mainly focus on the functionalization of CTFs, including their use for incorporating and stabilization of nanoparticles and immobilization of molecular complexes onto the frameworks.

Triggering White-Light Emission in a 2D Imine Covalent Organic Framework Through Lanthanide Augmentation.

Recently, covalent organic frameworks (COFs) have emerged as an interesting class of porous materials, featuring tunable porosity and fluorescence properties based on reticular construction principles. Some COFs display highly emissive monocolored luminescence, but attaining white-light emission from COFs is difficult as it must account for a wide wavelength range. White-light emission is highly desired for solid-state lighting applications, and obtaining it usually demands the combination of red-, green-, and blue-light components. Hence, to achieve the targeted white-light emission, we report for the first time grafting of lanthanides (Eu3+/Tb3+) on a two-dimensional imine COF (TTA-DFP-COF). We studied the luminescence properties of the hybrid materials prepared by anchoring Eu3+ (red light) and Tb3+ (green light) ß-diketonate complexes onto the TTA-DFP-COF. Reticular construction is exploited to design strong coordination of Eu3+ and Tb3+ ions into nitrogen-rich pockets of the imine COF. Mixed Eu3+/Tb3+ materials are then prepared to incorporate red and green components along with the inherent blue light from the organic moieties of the COF to produce white-light emission. We show that COFs have the potential for hosting Eu3+ and Tb3+ complexes, which can be tuned to obtain desired excitations for applications in the field of optoelectronics, microscopy, optical sensing, and bioassay.