Construction of Covalent Organic Frameworks via a Visible-Light-Activated Photocatalytic Multicomponent Reaction.

Multicomponent reactions (MCRs), as a powerful one-pot combinatorial synthesis tool, have been recently applied to the synthesis of covalent organic frameworks (COFs). Compared with the thermally driven MCRs, the photocatalytic MCR-based COF synthesis has not yet been investigated. Herein, we first report the construction of COFs by a photocatalytic multicomponent reaction. Upon visible-light irradiation, a series of COFs with excellent crystallinity, stability, and permanent porosity are successfully synthesized via photoredox-catalyzed multicomponent Petasis reaction under ambient conditions. Additionally, the obtained Cy-N3-COF exhibits excellent photoactivity and recyclability for the visible-light-driven oxidative hydroxylation of arylboronic acids. The concept of photocatalytic multicomponent polymerization not only enriches the methodology for COF synthesis but also opens a new avenue for the construction of COFs that might not be possible with the existing synthetic methods based on thermally driven MCRs.

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.

Source identification of soil elements and risk assessment of trace elements under different land uses on the Loess Plateau, China.

To investigate the source identification of soil elements and risk assessment of trace elements under different land-use types, 32 pairs of topsoil samples (0-20 cm) were collected from two subcatchments in the Liudaogou watershed. The areas of the two subcatchments were 0.343 and 0.045 km2, respectively, and the two subcatchments were divided into four land-use types, including bare land, forestland (FL), grassland (GL) and check-dam land (CDL). The results showed that the coefficients of variations of all soil elements indicated moderate spatial variation. The mean concentrations of Cu, K, Mn, Na and Zn under different land-use types exceeded the soil background values. The results of correlation analysis and principal component analysis illustrated that high homology existed between Cu and Mn in subcatchment 1, and the main source was from coal mines and smelters. Consistent sources of Zn and K in subcatchment 1 were mainly fertilizers and sewage sludge. Cu, K, Mg, Mn, Na and Zn in subcatchment 2 had similar sources, mainly mining and smelting plants, fertilizers and sewage. In addition, Ca had high homology with Fe in two subcatchments, mainly from natural weathering. The enrichment factor values indicated that there was a certain degree of trace element pollution. The values of the pollution index and Nemerow integrated pollution index revealed that moderate pollution was mainly concentrated in FL, GL and CDL. The trace element pollution of GL and CDL may induce contamination of the food chain and threaten human health safety.

Engineering a Highly Defective Stable UiO-66 with Tunable Lewis- Brønsted Acidity: The Role of the Hemilabile Linker.

The stability of metal-organic frameworks (MOFs) typically decreases with an increasing number of defects, limiting the number of defects that can be created and limiting catalytic and other applications. Herein, we use a hemilabile (Hl) linker to create up to a maximum of six defects per cluster in UiO-66. We synthesized hemilabile UiO-66 (Hl-UiO-66) using benzene dicarboxylate (BDC) as linker and 4-sulfonatobenzoate (PSBA) as the hemilabile linker. The PSBA acts not only as a modulator to create defects but also as a coligand that enhances the stability of the resulting defective framework. Furthermore, upon a postsynthetic treatment in H2SO4, the average number of defects increases to the optimum of six missing BDC linkers per cluster (three per formula unit), leaving the Zr-nodes on average sixfold coordinated. Remarkably, the thermal stability of the materials further increases upon this treatment. Periodic density functional theory calculations confirm that the hemilabile ligands strengthen this highly defective structure by several stabilizing interactions. Finally, the catalytic activity of the obtained materials is evaluated in the acid-catalyzed isomerization of α-pinene oxide. This reaction is particularly sensitive to the Brønsted or Lewis acid sites in the catalyst. In comparison to the pristine UiO-66, which mainly possesses Brønsted acid sites, the Hl-UiO-66 and the postsynthetically treated Hl-UiO-66 structures exhibited a higher Lewis acidity and an enhanced activity and selectivity. This is further explored by CD3CN spectroscopic sorption experiments. We have shown that by tuning the number of defects in UiO-66 using PSBA as the hemilabile linker, one can achieve highly defective and stable MOFs and easily control the Brønsted to Lewis acid ratio in the materials and thus their catalytic activity and selectivity.

Metal Organic Frameworks Based Materials for Heterogeneous Photocatalysis.

The increase in environmental pollution due to the excessive use of fossil fuels has prompted the development of alternative and sustainable energy sources. As an abundant and sustainable energy, solar energy represents the most attractive and promising clean energy source for replacing fossil fuels. Metal organic frameworks (MOFs) are easily constructed and can be tailored towards favorable photocatalytic properties in pollution degradation, organic transformations, CO2 reduction and water splitting. In this review, we first summarize the different roles of MOF materials in the photoredox chemical systems. Then, the typical applications of MOF materials in heterogeneous photocatalysis are discussed in detail. Finally, the challenges and opportunities in this promising field are evaluated.

In situ utilization of photogenerated hydrogen for hydrogenation reaction over a covalent organic framework.

A fully sp2-carbon conjugated COF (Py-FTP-COF) was designed and synthesized, exhibiting excellent hydrogen evolution rate of 5.22 mmol g-1 h-1. More importantly, in situ hydrogenation of nitroarenes under visible-light irradiation without any additional hydrogen source was successfully accomplished for the first time over COF-based materials.

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.

Rational design of benzodifuran-functionalized donor-acceptor covalent organic frameworks for photocatalytic hydrogen evolution from water.

A benzodifuran-based donor-acceptor covalent organic framework was synthesized and employed for efficient simulated sunlight-driven photocatalytic hydrogen evolution from water, which exhibited a superior and steady hydrogen evolution rate of 1390 µmol g-1 h-1 and an outstanding apparent quantum yield (AQY) of 7.8% was obtained at 420 nm.

Nanoscale covalent organic frameworks as theranostic platforms for oncotherapy: synthesis, functionalization, and applications.

Cancer nanomedicine is one of the most promising domains that has emerged in the continuing search for cancer diagnosis and treatment. The rapid development of nanomaterials and nanotechnology provide a vast array of materials for use in cancer nanomedicine. Among the various nanomaterials, covalent organic frameworks (COFs) are becoming an attractive class of upstarts owing to their high crystallinity, structural regularity, inherent porosity, extensive functionality, design flexibility, and good biocompatibility. In this comprehensive review, recent developments and key achievements of COFs are provided, including their structural design, synthesis methods, nanocrystallization, and functionalization strategies. Subsequently, a systematic overview of the potential oncotherapy applications achieved till date in the fast-growing field of COFs is provided with the aim to inspire further contributions and developments to this nascent but promising field. Finally, development opportunities, critical challenges, and some personal perspectives for COF-based cancer therapeutics are presented.

A benzothiadiazole-based covalent organic framework for highly efficient visible-light driven hydrogen evolution.

We demonstrate herein a newly designed benzothiadiazole-based covalent organic framework through an imine linkage with high crystallinity, excellent chemical stability and significant light absorption ability, which was further applied as a high-performance platform for efficient visible-light driven hydrogen evolution.

1,2-Dibenzoyl-hydrazine-dimethyl-formamide (3/1).

The title compound, 3C(14)H(12)N(2)O(2)·C(3)H(7)NO, was synthesized by reaction of benzoyl chloride with hydrazine hydrate under microwave irradition. The asymmetric unit comprises three 1,2-dibenzoyl-hydrazine mol-ecules and one dimethyl-formamide mol-ecule. The 1,2-dibenzoyl-hydrazine mol-ecules are linked by pairs of N-H⋯O hydrogen bonds into chains propagating along [010].

Straightforward preparation of fluorinated covalent triazine frameworks with significantly enhanced carbon dioxide and hydrogen adsorption capacities.

The development of advanced functional porous materials for efficient carbon capture and separation is of prime importance with respect to energy and environmental sustainability and employing covalent triazine frameworks as the adsorbents for carbon capture is deemed to be one of the most promising means to alleviate this issue. Herein, we report the construction of a set of partially fluorinated microporous covalent triazine frameworks (FCTFs) with appropriate CO2-philic functionalities (N and F) and high porosities (up to 2060 m2 g-1) for effective gas adsorption and separation. Markedly, the CO2 adsorption capacity of the FCTF materials prepared at a ZnCl2/monomer ratio of 20 and 400 °C reaches up to 4.70 mmol g-1 at 273 K and 1 bar, which is among the top level of all the reported CTFs. In addition, the studied FCTFs also exhibit a significantly high H2 uptake of 1.88 wt% at 77 K and 1 bar, outperforming most of the reported CTF materials under identical conditions. Apart from this, the obtained FCTF materials also display moderate CO2 selectivities over N2 (28) and CH4 (5.6) at room temperature.

Newly Designed Covalent Triazine Framework Based on Novel N-Heteroaromatic Building Blocks for Efficient CO2 and H2 Capture and Storage.

In this article, a set of novel covalent triazine frameworks (CTFs) were prepared by trimerization of 4,4',4″,4‴-(1,4-phenylenebis(pyridine-4,2,6-triyl))tetrabenzonitrile in molten ZnCl2 under ionothermal conditions. The influence of several parameters such as the ZnCl2/monomer ratio and reaction temperature on the structure and porosity of the resulting frameworks was systematically examined. After a thorough characterization, their performance in H2 and CO2 adsorption as well as their selectivity of CO2 over N2 was assessed. Notably, the CTF obtained using 20 molar equiv of ZnCl2 at a reaction temperature of 400 °C (CTF-20-400) exhibits an excellent CO2 adsorption capacity of 3.48 mmol/g at 1 bar and 273 K as well as a significantly high H2 uptake of 1.5 wt % at 1 bar and 77 K. These values belong to the top levels for all the CTFs measured under identical conditions to date. In addition, the obtained CTFs also present a relatively high CO2/N2 selectivity (up to 36 at 298 K), making them promising adsorbents for gas sorption and separation.

Luminescent Lanthanide MOFs: A Unique Platform for Chemical Sensing.

In recent years, lanthanide metal-organic frameworks (LnMOFs) have developed to be an interesting subclass of MOFs. The combination of the characteristic luminescent properties of Ln ions with the intriguing topological structures of MOFs opens up promising possibilities for the design of LnMOF-based chemical sensors. In this review, we present the most recent developments of LnMOFs as chemical sensors by briefly introducing the general luminescence features of LnMOFs, followed by a comprehensive investigation of the applications of LnMOF sensors for cations, anions, small molecules, nitroaromatic explosives, gases, vapors, pH, and temperature, as well as biomolecules.

A series of sulfonic acid functionalized mixed-linker DUT-4 analogues: synthesis, gas sorption properties and catalytic performance.

In this work, we present the successful synthesis of a series of sulfonic acid functionalized mixed-linker metal-organic frameworks (MOFs) having the DUT-4 topology by using different ratios of 2,6-naphthalenedicarboxylic acid (H2-NDC) and 4,8-disulfonaphthalene-2,6-dicarboxylic acid (H2-NDC-2SO3H) in one-pot reactions. The obtained materials were fully characterized and their CO2 adsorption properties at low and high pressures were studied and compared with those of the pristine DUT-4 material. Generally, the CO2 adsorption capacities range from 3.28 and 1.36 mmol g-1 for DUT-4 to 1.54 and 0.78 mmol g-1 for DUT-4-SO3H (50) up to 1 bar at 273 K and 303 K, respectively. Computational calculations corroborated the structural changes of the material in function of the loading of sulfonic acid groups. Furthermore, due to the strong Brønsted acid character, the resulting sulfonic acid based MOF material was evaluated as a catalyst for the ring opening of styrene oxide with methanol as a nucleophile under mild conditions, showing almost full conversion (99%) after 5 hours of reaction. A hot filtration experiment demonstrated that the catalysis occurred heterogeneously and the catalyst could be recovered and reused for multiple runs without significant loss in activity and crystallinity.

Microwave induced "egg yolk" structure in Cr/V-MIL-53.

Using a one pot microwave procedure, mixed-metal "egg yolk" MOFs are created, with a core of (Cr/V)-MIL-53 and a shell of Cr-MIL-53. In contrast, the solvothermal method produces homogeneous mixed-metal MOFs. The influence of Cr and V on the flexibility and breathing was studied via T-XRPD and CO2 adsorption measurements.

Enhanced gas sorption and breathing properties of the new sulfone functionalized COMOC-2 metal organic framework.

A new sulfone functionalized vanadium metal-organic framework (MOF), denoted as SO2-COMOC-2, has been synthesized solvothermally. Its structural and gas sorption properties towards CO2 and CH4 have been evaluated and compared to those of the pristine COMOC-2 material. The SO2-COMOC-2 shows a remarkable increase in CO2 capacity at ambient pressure (2.13 mmol g(-1) at 273 K vs. 1.23 mmol g(-1) for the pristine COMOC-2). Additionally, the high pressure CO2 sorption isotherm shows a distinctive two-step sorption behavior with a final capacity of 12.45 mmol g(-1) for SO2-COMOC-2 at 303 K, while for CH4 a typical Type I isotherm was obtained with a capacity of 4.13 mmol g(-1). In situ synchrotron X-ray powder diffraction measurements have been carried out to characterize the structural flexibility of the materials, showing both the presence of large pore and narrow pore form. Furthermore, synchrotron XANES and a variety of spectroscopic techniques have been utilized to verify the presence of hydroxyl groups and the existence of the mixed vanadium oxidation states in the titled MOF structure.