Cr-MOF composited with facet-engineered bimetallic alloys for inducing photocatalytic conversion of CO to CH.

The design of efficient photocatalysts is crucial for photocatalytic CO reduction. This study developed photocatalysts based on MIL-101(Cr) composited with a facet-engineered Pt/Pd nanoalloy (PPNA). Photocatalytic performance evaluations show that MIL-101(Cr) loaded with PPNA exposing {111} facets, namely M-A(111), exhibits a CO to CH conversion rate of 9.

Metal Center-Tuned Photocatalytic Carbon Dioxide Reduction for Frameworks with the Tetraphenylethene-Imidazole Ligand.

As heterogeneous photocatalysts that can effectively transform CO to CO, two MOFs with different metal centers, namely, [M(tipe)(HO)](ClO)·solvent (M = Ni named as and M = Co referred to as ), were synthesized by reactions of 1,1,2,2-tetrakis(4-(imidazole-1-yl)phenyl)ethene (tipe) with the corresponding metal perchlorate. Both and have 3D structures, in which the metal centers have the same coordination environment with the NO donor set. Driven by visible light, the CO production catalyzed by is 6734.

N, N'-bidentate ligand anchored palladium catalysts on MOFs for efficient Heck reaction.

Metal-organic frameworks (MOFs), recognized as advanced catalyst carriers due to their adjustable porous, diverse structure and highly exposed active sites, have earned increasing attention for their potential to address the longevity of catalytic centers. In this manuscript, we have devised and synthesized a multifunctional amino-pyridine benzoic acid (APBA) ligand to replace the modulator ligand of the MOF-808 and disperse the palladium catalytic centers atomically on the MOF-APBA. The resulting single-site catalytic system, Pd@MOF-APBA, demonstrates preeminent efficiency and stability, as evidenced by a high average turnover number (95000) and a low metal residue (4.

Rh(III)-Catalyzed C(sp)-H Thiolation of 8-Methylquinolines Promoted by Benzoic Anhydride.

Herein, we developed a ligand-promoted Rh(III)-catalyzed C(sp)-H thiolation of 8-methylquinolines. The effect of ligands on improving the activity of the catalytic centers has been studied in detail and proven to be significant. Various substituents are well tolerated under this reaction condition to provide potential precursors for organic synthesis.

Rational design of organic ligands for metal-organic frameworks as electrocatalysts for CO reduction.

Electrocatalytic carbon dioxide (CO) reduction to valuable chemical compounds is a sustainable technology with enormous potential to facilitate carbon neutrality by transforming intermittent energy sources into stable fuels. Among various electrocatalysts, metal-organic frameworks (MOFs) have garnered increasing attention for the electrochemical CO reduction reaction (CORR) owing to their structural diversity, large surface area, high porosity and tunable chemical properties. Ligands play a vital role in MOFs, which can regulate the electronic structure and chemical environment of metal centers of MOFs, thereby influencing the activity and selectivity of products.

Supramolecular assemblies of Cu(II) with a tetraphenylethene-imidazole ligand for tuning photocatalytic CO reduction.

Cu(II) supramolecular assemblies [Cu(tipe)(HO)](NO)·2.5HO (CuN4) and [CuCl(tipe)(CHCN)]·HO (CuN2Cl2) (tipe = 1,1,2,2-tetrakis(4-(imidazole-1-yl)phenyl)ethene) were synthesized and utilized for photocatalytic CO reduction. CuN4 exhibits CO production of up to 891 μmol g with a selectivity of 79.

Silver frameworks based on a tetraphenylethylene-imidazole ligand for electrocatalytic reduction of CO to CO.

Metal-organic frameworks (MOFs) can be used as electrocatalysts for the CO reduction reaction (CORR) because of their well-dispersed metal centers. Silver is a common electrocatalyst for reduction of CO to CO. In this study, two Ag-MOFs with different structures of [AgO(TIPE)](NO) (Ag-MOF1) and [Ag(TIPE)CFSO] (Ag-MOF2) [TIPE = 1,1,2,2-tetrakis(4-(imidazol-1-yl)phenyl)ethene] were synthesized and used for CO electroreduction.

High-nuclearity Luminescent Lanthanide Nanocages for Tumor Drug Delivery.

There is an unmet need for easy-to-visualize drug carriers that can deliver therapeutic cargoes deep into solid tumors. Herein, we report the preparation of ultrasmall luminescent imine-based lanthanide nanocages, Eu and Tb (collectively Ln ), designed to encapsulate anticancer chemotherapeutics for tumor therapy. The as-prepared nanocages possess large cavities suitable for the encapsulation of doxorubicin (DOX), yielding DOX@Ln nanocages with diameters around 5 nm.

A Green Environmental Protection Photocatalytic Molecular Reactor for Aerobic Oxidation of Sulfide to Sulfoxide.

The design and synthesis of metal-organic frameworks (MOFs) as photocatalytic molecular reactors for varied reactions have drawn great attention. In this work, we designed a novel photoactive perylenediimides-based (PDI) carboxylate ligand N,N'-di(3',3",5',5"-tetrakis(4-carboxyphenyl))-1,2,6,7-tetrachloroperylene-3,4,9,10-tetracarboxylic acid diimide (Cl-PDI-TA) and use it to successfully synthesize a novel Zr(IV)-based MOF 1 constructed from [Zr O (H O) ] clusters bridged by Cl-PDI-TA ligands. Structural analysis revealed that Zr-MOF 1 manifests a 3D framework with (4,8)-connected csq topology and possesses triangular channels of ~17 Å and mesoporous hexagonal channels of ~26 Å along c-axis.

Construction of Benzoxazinones from Anilines and Their Derivatives.

Herein we report a strategy concerning Rh(III)-catalyzed direct -C-H bond carbonylation to construct benzoxazinones from anilines and their derivatives with high atom economy. Interestingly, the corresponding amides were generated from anilines when excess AcO was added and directed the following C-H bond carbonylation to form benzoxazinones. Extensive functional group tolerance can be achieved when the alkyl amide directing groups were installed.

Designing Heteroatom-Codoped Iron Metal-Organic Framework for Promotional Photoreduction of Carbon Dioxide to Ethylene.

Rational engineering active sites and vantage defects of catalysts are promising but grand challenging task to enhance photoreduction CO to high value-added C2 products. In this study, we designed an N,S-codoped Fe-based MIL-88B catalyst with well-defined bipyramidal hexagonal prism morphology via a facile and effective process, which was synthesized by addition of appropriate 1,2-benzisothiazolin-3-one (BIT) and acetic acid to the reaction solution. Under simulated solar irradiation, the designed catalyst exhibits high C H evolution yield of 17.

Facet-Dependent Photocatalytic Behavior of Fe-soc-MOF for Carbon Dioxide Reduction.

Exposing different facets on metal-organic frameworks (MOFs) is an efficient approach to regulate their photocatalytic performance for CO reduction. Herein, Fe-soc-MOFs exposed with different facets were successfully synthesized, and the morphologies of Fe-soc-MOF exposed with eight {111} facets (Fe-soc-O) and that exposed with eight {111} and six {100} crystal facets (Fe-soc-M) are first reported. Fe-soc-MOFs have facet-dependent active sites on their surface and correspondingly different catalytic performance for photocatalytic CO reduction.

Metal-organic frameworks incorporating azobenzene-based ligands as a heterogeneous Lewis-acid catalyst for cyanosilylation of imines.

In this work, two novel metal-organic frameworks (MOFs) were synthesized by the reaction of azobenzene-based ligands and Zn(NO)/CdCO under solvothermal conditions with the formula of {[Zn(abtc)(azpy)(HO)]·4HO} (1) and {[Cd(abtc)(azpy)(HO)]·3HO} (2) (Habtc = 3,3',5,5'-azobenzene tetracarboxylic acid, azpy = 4,4'-azobipyridine). According to the single-crystal X-ray diffraction (SC-XRD) analysis, complexes 1 and 2 possessed quite similar structures except for the coordination modes of the central metal nodes attributed to the difference between the cationic radius of Zn(ii) and Cd(ii). The Zn(ii) cations in 1 adopted a distorted seesaw coordination geometry and the coordination between Zn(ii) and organic linkers gave two-dimensional (2D) coordination networks, while the Cd(ii) cations in 2 could also bind with the carboxylate groups from neighboring coordination networks to form a three-dimensional (3D) coordination framework.

Single-Site Metal-Organic Framework and Copper Foil Tandem Catalyst for Highly Selective CO Electroreduction to C H.

Tandem catalysis is a promising way to break the limitation of linear scaling relationship for enhancing efficiency, and the desired tandem catalysts for electrochemical CO reduction reaction (CO RR) are urgent to be developed. Here, a tandem electrocatalyst created by combining Cu foil (CF) with a single-site Cu(II) metal-organic framework (MOF), named as Cu-MOF-CF, to realize improved electrochemical CO RR performance, is reported. The Cu-MOF-CF shows suppression of CH , great increase in C H selectivity (48.

Pillar-Layered Metal-Organic Frameworks for Sensing Specific Amino Acid and Photocatalyzing Rhodamine B Degradation.

Metal-organic frameworks (MOFs) have presented potential for detection of specific species and catalytic application due to their diverse framework structures and functionalities. In this work, two novel pillar-layered MOFs [Cd(DPA)(NTB)(HO)]·n(DPA·5DMA·HO) () and [Cu(DPA)(OBA)]·n(2.5DMF·HO) () [DPA = 2,5-di(pyridin-4-yl)aniline, HNTB = 4,4',4''-nitrilotribenzoic acid, HOBA = 4,4'-oxydibenzoic acid, DMA = N,N-dimethylacetamide, DMF = N,N-dimethylformamide] were successfully synthesized and structurally characterized.

Ti(IV)-MOF with Specific Facet-Ag Nanoparticle Composites for Enhancing the Photocatalytic Activity and Selectivity of CO Reduction.

Metal nanoparticles deposited in the photocatalyst not only can serve as a cocatalyst but also can act as a light harvester to extend the light absorption, resulting from the surface plasmon resonance (SPR). In this study, we deposited silver nanoparticles (Ag NPs) onto NH-MIL-125(Ti) with exposed specific facets and achieved effectively improved activity and selectivity for photocatalytic CO reduction. Loading Ag NPs on the exposed {111} facets of NH-MIL-125(Ti) generates a highly effective composite catalyst for the photoreduction of CO, resulting in the maximal CO and CH yields of 26.

Mild Three-Step Consecutive C-H Activations.

Herein, the Rh-catalyzed consecutive C-H bond olefination/annulation/olefination cascade, tandemly directed by sulfonamide and ester groups, has been developed under mild conditions with the assistance of 1-adamantane carboxylic acid. A seven-membered metallacycle including an ester group was preferred to the five-membered one including a sulfonamide group for the third C-H activation. In this transformation, the Rh catalyst exhibits its high reactivity by catalyzing a triple C-H activation process with a low catalyst loading at 50 °C.

Copper(II) Frameworks with Varied Active Site Distribution for Modulating Selectivity of Carbon Dioxide Electroreduction.

Metal-organic frameworks (MOFs) can be utilized as electrocatalysts for CO reduction reaction (CORR) due to their well dispersed metal centers. However, the influence of metal node distribution on electrochemical CORR was rarely explored. Here, three Cu-MOFs with different copper(II) site distribution were employed for CO electroreduction.

Fluorescent Zn(II) frameworks with multicarboxylate and pyridyl N-donor ligands for sensing specific anions and organic molecules.

Three novel fluorescent Zn(II) frameworks, namely [Zn(DPA)(NDA)]·2DMF (1), [Zn(DPA)(OBA)]·2DMF·4HO (2) and [Zn(DPA)(HNTB)]·HO (3) (DPA = 2,5-di(pyridin-4-yl)aniline, HNDA = 1,4-naphthalenedicarboxylic acid, HOBA = 4,4'-oxydibenzoic acid, HNTB = 4,4',4''-nitrilotribenzoic acid, DMF = ,-dimethylformamide), were successfully fabricated and structurally characterized. Due to the variety of organic linkers, 1-3 exhibit varied topologies: 1 is a 4-c three-dimensional (3D) framework with {6·8} topology, 2 is a 6-c 3D net with point symbol of {4·6·8}, and 3 is a 4-c two-dimensional network that further stacks into a 3D structure by hydrogen bonding interactions with {4·6} topology. Experiments related to fluorescence show that 1-3 can be utilized to quickly identify specific anions of CrO/CrO, and organic molecules such as 2,4,6-trinitrophenol and benzaldehyde.

Hydroxy-Group-Functionalized Single Crystal of Copper(II)-Porphyrin Complex for Electroreduction CO to CH.

Purposefully developing crystalline materials at molecular level to improve the selectivity of electroreduction CO to CH is still rarely studied. Herein, a single crystal of copper(II) complex with hydroxy groups was designed and synthesized, namely 5,10,15,20-tetrakis(3,4-dihydroxyphenyl)porphyrin copper(II) (Cu-PorOH), which could serve as a highly efficient heterogeneous electrocatalyst for electroreduction of CO toward CH . In 0.

Coordination Polymers with 2,2':6',2″-Terpyridine Earth-Abundant Metal Complex Units for Selective CO Photoreduction.

Combining molecular metal complexes into coordination polymers (CPs) is an effective strategy for developing photocatalysts for CO reduction; however, most such reported catalysts are noble metal-containing CPs. Herein, two novel Zr-containing bimetallic CPs, and , were designed and successfully synthesized by connecting 2,2':6',2″-terpyridine-based molecular earth-abundant metal (Co or Ni) complexes with ZrO nodes. Both CPs were applied as catalysts for CO photoreduction to selectively produce CO.

Effect of the Defect Modulator and Ligand Length of Metal-Organic Frameworks on Carbon Dioxide Photoreduction.

The nature of defects and organic ligands can fine-tune the absorption energy () of metal-organic frameworks (MOFs), which is crucial for photocatalytic reactions; however, the relevant studies are in their infancy. Herein, a series of typical MOFs of the UiO family (UiO-6-NH, = 8, 7, and 6) with ligands of varied lengths and amino-group-modified defects were synthesized and employed to explore their performance for photocatalytic CO reduction. Sample UiO-66-NH-2ABA (2ABA = 3,5-diamino-benzoate) with the shortest dicarboxylate ligand and two amino-group-modified defects exhibits superior photocatalytic activity due to the lowest .

Sensing Properties of NH-MIL-101 Series for Specific Amino Acids via Turn-On Fluorescence.

Metal-organic frameworks (MOFs) have been demonstrated to be desired candidates for sensing definite species owing to their tunable composition, framework structure and functionality. In this work, the NH-MIL-101 series was utilized for sensing specific amino acids. The results show that cysteine (Cys) can significantly enhance the fluorescence emission of NH-MIL-101-Fe suspended in water, while NH-MIL-101-Al exhibits the ability to sense lysine (Lys), arginine (Arg) and histidine (His) in aqueous media via turn-on fluorescence emission.

Metalloporphyrin Encapsulation for Enhanced Conversion of CO to CH.

Electrochemical conversion of CO into valuable products is a promising approach. Efficient electrocatalysts are highly desirable but remain to be developed. Here, we proposed a molecular encapsulation strategy to enrich intermediates for facilitating electrochemical conversion of CO to CH.

Supramolecular Engineering to Improve Electrocatalytic CO Reduction Activity of Cu O.

Electrochemical conversion of CO into value-added fuels and feedstocks attracts worldwide attention to mitigate energy and environmental problems. However, pursuing highly efficient electrocatalyst is still a challenge. In this study, cuprous oxide (Cu O) modified by cucurbit[6]urils (Q[6]), a kind of rigid macromolecule, is found to act as an efficient supramolecular inorganic nanocomposite catalyst for the electrochemical CO reduction reaction (CO RR) to C fuels.