CO-Free Aminocarbonylation of Terminal Alkynes Catalyzed by Synergistic Effect From Metal-Organic Frameworks.

Incorporation of CO into substrates to construct high-value carbonyl compounds is an intensive industrial carbonylation procedure, however, high toxicity and wide explosion limits (12.5-74.0 vol% in air) of CO limit its application in industrial production.

Multi-Emission Carbon Dots Combining Turn-On Sensing and Fluorescence Quenching Exhibit Ultrahigh Selectivity for Mercury in Real Water Samples.

Mercury is a ubiquitous heavy-metal pollutant and poses serious ecological and human-health risks. There is an ever-growing demand for rapid, sensitive, and selective detection of mercury in natural waters, particularly for regions lacking infrastructure specialized for mercury analysis. Here, we show that a sensor based on multi-emission carbon dots (M-CDs) exhibits ultrahigh sensing selectivity toward Hg(II) in complex environmental matrices, tested in the presence of a range of environmentally relevant metal/metalloid ions as well as natural and artificial ligands, using various real water samples.

Portably and Visually Sensing Cytisine through Smartphone Scanning Based on a Post-Modified Luminescence Center Strategy in Zinc-Organic Frameworks.

Cytisine (CTS) is a useful medicine for treating nervous disorders and smoking addiction, and exploring a convenient method to detect CTS is of great significance for long-term/home medication to avoid the risk of poisoning, but it is full of challenges. Here, a modified metal-organic framework sensor Tb@Zn-TDA-80 with dual emission centers was prepared using a post-modified luminescence center strategy. The obtained Tb@Zn-TDA-80 can serve as a CTS sensor with high sensitivity and selectivity.

Thermocatalytic Conversion of CO to Valuable Products Activated by Noble-Metal-Free Metal-Organic Frameworks.

Thermocatalysis of CO into high valuable products is an efficient and green method for mitigating global warming and other environmental problems, of which Noble-metal-free metal-organic frameworks (MOFs) are one of the most promising heterogeneous catalysts for CO thermocatalysis, and many excellent researches have been published. Hence, this review focuses on the valuable products obtained from various CO conversion reactions catalyzed by noble-metal-free MOFs, such as cyclic carbonates, oxazolidinones, carboxylic acids, N-phenylformamide, methanol, ethanol, and methane. We classified these published references according to the types of products, and analyzed the methods for improving the catalytic efficiency of MOFs in CO reaction.

A Strong-Acid-Resistant [Th ] Cluster-Based Framework for Effectively and Size-Selectively Catalyzing Reductive Amination of Aldehydes with N,N-Dimethylformamide.

Utilization of N,N-dimethylformamide (DMF) as an amine source and reductant for synthesizing tertiary amines is a promising way to replace the substrates formaldehyde and dimethylamine, and it is desirable to seek porous acid-resistant catalysts for heterogeneous catalysis of this reaction. Herein, a robust metal-organic framework (MOF) {[Th O (OH) (H O) (BCP) ]⋅10 DMF} (1) containing stacked nanocages with a diameter of 1.55 nm was constructed.

Luminescent Sensor with High Sensitivity and Selectivity for Amikacin Detection in a Serum using a Unique Gallium-Organic Framework.

Amikacin is a widely used antibiotic in the treatment of Gram-negative bacteria, but high concentrations of amikacin can cause cochlear nerve damage. Therefore, accurate and quick detection of the concentration of amikacin is desired and important. In this work, we have synthesized a new gallium-organic framework {[(CH)(NH)Ga(PPTA)]·0.

Recyclable Luminescent Sensor for Detecting Creatinine Based on a Lanthanide-Organic Framework.

Creatinine is an important clinical marker for human health, but detecting it by a luminescent sensor based on metal-organic frameworks is rarely investigated. In this work, we synthesized a new lanthanide-organic framework {[Tb(L)(CHCOO)(HO)]·0.5DMF} () (HL = 3,5-bis(4'-carboxy-phenyl)1,2,4-triazole) with good solvent and acid/alkaline stabilities.

Selectively Regulating Lewis Acid-Base Sites in Metal-Organic Frameworks for Achieving Turn-On/Off of the Catalytic Activity in Different CO Reactions.

Regulating Lewis acid-base sites in catalysts to investigate their influence in the chemical fixation of CO is significant but challenging. A metal-organic framework (MOF) with open metal Co sites, {(NH Me )[Co (μ -OH)(BTB) (H O)]⋅9 H O⋅5 DMF} (1), was obtained and the results of the catalytic investigation show that 1 can catalyze cycloaddition of CO and aziridines to give 99 % yield. The efficiency of the cyclization of CO with propargyl amines is only 32 %.

Efficient Cycloaddition of CO and Aziridines Activated by a Quadruple-Interpenetrated Indium-Organic Framework as a Recyclable Catalyst.

On the basis of the global warming effect, it is of great significance to convert CO into the high value-added products oxazolidinones, but investigations on main-group-based metal-organic frameworks (MOFs) as heterogeneous catalysts still have not been reported so far. In this work, a quadruple-interpenetrated porous indium-based MOF, {[NH(CH)][In(CPT)]·3CHCN·3DMA} (), is constructed from the organic ligand 3,5-bis(4'-carboxyphenyl)-1,2,4-triazole through solvothermal reactions, and N adsorption proves that the framework has a high Brunauer-Emmett-Teller surface areas with 2024 m/g. The catalytic research on CO conversion reveals that compound has high reactivity for the cycloaddition of CO with aziridines, and the product 3-ethyl-5-phenyloxazolidin-2-one can be obtained with a yield of 99% under mild conditions.

Anchoring Ag(I) into Nitro-Functionalized Metal-Organic Frameworks: Effectively Catalyzing Cycloaddition of CO with Propargylic Alcohols under Mild Conditions.

Carboxylative cyclization of propargylic alcohols with CO is significant in synthetic chemistry, but harsh conditions are often needed according to reported results. Herein, a new stable nitro-functionalized metal-organic framework (MOF) of {[Co(L)(bpy)(HO)]·DMF·HO·bpy} () was fabricated through the solvothermal reaction, which exhibited excellent stability in acid and basic solutions. Owing to the porous structure, unsaturated metal sites, and uncoordinated 4,4'-bpy ligands, can serve as an excellent platform for catalytic applications.

A Facile Strategy for Constructing a Carbon-Particle-Modified Metal-Organic Framework for Enhancing the Efficiency of CO Electroreduction into Formate.

Electrocatalytic reduction of CO by metal-organic frameworks (MOFs) has been widely investigated, but insufficient conductivity limits application. Herein, a porous 3D In-MOF {(Me NH )[In(BCP)]⋅2 DMF} (V11) with good stability was constructed with two types of channels (1.6 and 1.

Green Conversion of CO and Propargylamines Triggered by Triply Synergistic Catalytic Effects in Metal-Organic Frameworks.

Cyclization of propargylamines with CO to obtain 2-oxazolidone heterocyclic compounds is an essential reaction in industry but it is usually catalyzed by noble-metal catalysts with organic bases as co-catalysts under harsh conditions. We have synthesized a unique Cu /Cu mixed valence copper-based framework {[(Cu I )Cu L (DMA) ](NO )⋅9DMA} (1) with good solvent and thermal stability, as well as a high density of uncoordinated amino groups evenly distributed in the large nanoscopic channels. Catalytic experiments show that 1 can effectively catalyze the reaction of propargylamines with CO , and the yield can reach 99 %.

Dual-Selective Catalysis in Dephosphorylation Tuned by Hf-Containing Metal-Organic Frameworks Mimicking Phosphatase.

Selective dephosphorylation is full of great challenges in the field of biomimetic catalysis. To mimic the active sites of protein phosphatase, Hf-OH-Hf motif-containing metal-organic frameworks (MOFs) were obtained and structurally characterized, which are assembled from [HfNi] cubic nanocages and exhibit good stability in various solvents and acid/base solutions. Catalytic investigations suggest as-synthesized and display accurate type-selectivity (selectively catalyzed P-O rather than S-O or C-O bonds) and position-selectivity (selectively catalyzed phosphomonoesters over phosphodiesters) for the hydrolysis of phosphoesters.

Recyclable Luminescence Sensor for Dinotefuran in Water by Stable Cadmium-Organic Framework.

Due to the widespread use of dinotefuran around the world, its impact on food and environmental safety has aroused great concern, and the establishment of a rapid and convenient approach for dinotefuran detection is necessary but challenging. Herein, we synthesized a unique three-dimensional framework {[(CH)NH][Cd(BCP)]·10HO·3.5DMF} ().

Photocatalytic Hydrogen Evolution Based on Cobalt-Organic Framework with High Water Vapor Adsorption.

Photocatalytic hydrogen evolution is desired to effectively alleviate the serious crisis of energy and the environment, and the utilization of low-cost photocatalysts, especially cobalt-based MOF catalysts, is meaningful, but rarely investigated. Herein, through a self-assembly strategy, we synthesized a Co clusters-based MOF () by the ligand ,'-bicyclo[2.2.

Bimetallic Lanthanide-Organic Framework Membranes as a Self-Calibrating Luminescent Sensor for Rapidly Detecting Antibiotics in Water.

Rapid, facile, and reliable recognition of different antibiotics by self-calibrating luminescent sensors are important for practical requirements. Herein, we design and synthesize a series of EuTb-MOF using a flexible ligand HL (5,5'-(propane-1,3-diylbis(oxy))di-isophthalic acid). With changing reactant time, submicrometer bimetallic with homogeneous morphology was achieved and further fabricated MOF-based membrane combining with polymer materials.

Highly Sensitive and Selective Luminescence Sensor Based on Two-Fold Interpenetrated MOFs for Detecting Glutamate in Serum.

Glutamate is a biomarker for many nervous system diseases, and sensitively detecting glutamate is meaningful in the clinic. Therefore, a unique 3D framework of Cd-MOF () is synthesized and characterized. A single-crystal X-ray study reveals that it is a two-fold interpenetration (4,4)-connected framework with a topology, where a large 1D rhombic channel with a size of 8 × 14 Å exists and the total potential void volume can reach 62%.

MOFs-Based Catalysts Supported Chemical Conversion of CO.

The dramatic increase in atmospheric carbon dioxide (CO) concentrations has attracted human attention and many strategies about converting CO into high-value chemicals have been put forward. Metal-organic frameworks (MOFs), as a class of versatile materials, have been widely used in CO capture and chemical conversion, due to their unique porosity, multiple active centers and good stability and recyclability. Herein, we focused on the processes of chemical conversion of CO by MOFs-based catalysts, including the coupling reactions of epoxides, aziridines or alkyne molecules, CO hydrogenation, and other CO conversion reactions.

Luminescent Detection of Colchicine by a Unique Indium-Organic Framework in Water with High Sensitivity.

Colchicine is highly toxic to creatures, and sensitively detecting colchicines is of profound significance in the pharmaceutical, clinical, food, and breeding industries. We herein designed and constructed a unique luminescent indium-organic framework {[(CH)NH][In(L)]·9DMF} () via an in situ ligand-mediated method, which possesses a 2-fold interpenetrated 3D anionic framework. Due to the large channels that exist in the framework with the size of 12 Å × 14 Å, can rapidly remove harmful cationic dyes from water in a few minutes.

Formation of CX Bonds in CO Chemical Fixation Catalyzed by Metal-Organic Frameworks.

Transformation of CO based on metal-organic framework (MOF) catalysts is becoming a hot research topic, not only because it will help to reduce greenhouse gas emission, but also because it will allow for the production of valuable chemicals. In addition, a large number of impressive products have been synthesized by utilizing CO . In fact, it is the formation of new covalent bonds between CO and substrate molecules that successfully result in CO solidly inserting into the products, and only four types of new CX bonds, including CH, CC, CN, and CO bonds, are observed in this exploration.

Stable Lanthanide-Organic Framework as a Luminescent Probe To Detect Both Histidine and Aspartic Acid in Water.

A three-dimensional metal-organic framework (MOF) {[Eu(L)(HO)]·DMF} (1) (HL = 2'-nitro-3,4',5-biphenyl tricarboxylic acid) was obtained by hydrothermal methods and was characterized in detail. Compound 1 contains [Eu] binuclear units, and [Eu] units are further linked by HL, forming a three-dimensional structure. Stability tests suggest that compound 1 exhibits high solvent, pH, and thermal stability.

Triple-Interpenetrated Lanthanide-Organic Framework as Dual Wave Bands Self-Calibrated pH Luminescent Probe.

pH value is a key parameter in reflecting the health status, reaction process, and water quality. The construction of highly sensitive pH luminescent ratiometric is important but challenging. Herein we designed and synthesized a unique triple-interpenetrated luminescent lanthanide-organic framework {[Eu(PPTA)(NO)(DMF)]·HO} (V104) based on an amphoteric ligand 4,4',4'',4'''-(1,4-phenylenebis(pyridine-4,2,6-triyl))tetrabenzoic acid (HPPTA).

A Noble-Metal-Free Metal-Organic Framework (MOF) Catalyst for the Highly Efficient Conversion of CO with Propargylic Alcohols.

Cyclization of propargylic alcohols with CO is an important reaction in industry, and noble-metal catalysts are often employed to ensure the high product yields under environmentally friendly conditions. Herein a porous noble-metal-free framework 1 with large 1D channels of 1.66 nm diameter was synthesized for this reaction.