An iron-containing POM-based hybrid compound as a heterogeneous catalyst for one-step hydroxylation of benzene to phenol.

It is a major challenge to perform one-pot hydroxylation of benzene to phenol under mild conditions, which replaces the environmentally harmful cumene method. Thus, finding highly efficient heterogeneous catalysts that can be recycled is extremely significant. Herein, a (POM)-based hybrid compound {[Fe(pyim)(CHO)][Fe(pyim)(HO)][PMoV2MoVI9VIV3O]}·HO (pyim = 2-(2-pyridyl)benzimidazole) (Fe2-PMo11V3) was successfully prepared by hydrothermal synthesis using typical Keggin POMs, iron ions and pyim ligands.

A molecular sieve with ultrafast adsorption kinetics for propylene separation.

The design of molecular sieves is vital for gas separation, but it suffers from a long-standing issue of slow adsorption kinetics due to the intrinsic contradiction between molecular sieving and diffusion within restricted nanopores. We report a molecular sieve ZU-609 with local sieving channels that feature molecular sieving gates and rapid diffusion channels. The precise cross-sectional cutoff of molecular sieving gates enables the exclusion of propane from propylene.

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.

Mechanism and synergistic effect of sulfadiazine (SDZ) and cadmium toxicity in spinach (Spinacia oleracea L.) and its alleviation through zinc fortification.

Cadmium (Cd) and antibiotic's tendency to accumulate in edible plant parts and fertile land is a worldwide issue. The combined effect of antibiotics and heavy metals on crops was analyzed, but not mitigation of their toxicity. This study investigated the potential of zinc oxide nanoparticles (ZnO NPs) to alleviate the SDZ and Cd toxicity (alone/combined) to promote spinach growth.

Atomic Diffusion Rate Dominated Fabrication of High Entropy Phosphide with Heterogeneous Aggregation for Oxygen Evolution Reaction.

The synthesis of high-entropy phosphide (HEP) remains a great challenge owing to the different migration rates of different metallic atoms. Herein, a new metal organic gel (MOG) precursor strategy is proposed for HEP synthesis by controlling the migration rate of different atoms in an organic gel. The MOG precursor with five kinds of metal and phosphor species homogeneously dispersing is formed through a facile solvothermal method, which is calcined at 900 °C to obtain carbon-supported HEP FeCoNiMnCdP (MPC-5).

Au Cd (SC H ) : A Glance at Structure-Property Relationship.

Doping Cd atom(s) into gold clusters is very promising in both theoretical study and practical applications. However, it has long been a challenge to synthesize heavily Cd-doped AuCd bimetallic clusters and thereby reveal their structure-property correlations. Herein a novel AuCd bimetallic cluster: Au Cd (SC H ) (SC H denotes deprotonated cyclohexanethiol) with a Cd to Au atomic ratio of 1:1 is reported.

Octahedral lanthanide clusters containing a central PO anion: structural, luminescent, magnetic and relaxometric properties.

Lanthanide clusters with good stability and intriguing physical properties are attractive in many fields. By reacting 9-anthracenylphosphonic acid (AnPOH) and lanthanide nitrates under solvothermal conditions, we obtained a series of hexanuclear lanthanide phosphonate cages [HO][Ln(PO)(AnPO)(DMF)]·2DMF·HO (Ln6, Ln = Nd, Eu, Gd, Dy, Ho, Er, Yb). Within the cluster, the six Ln atoms form an octahedron and its eight faces are covered by phosphonate groups.

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.

Manipulating the Subcellular Localization and Anticancer Effects of Benzophenothiaziniums by Minor Alterations of N-Alkylation.

Cationic, water-soluble benzophenothiaziniums have been recognized as effective type I photosensitizers (PSs) against hypoxic tumor cells. However, the study of the structure-property relationship of this type of PS is still worth further exploration to achieve optimized photodynamic effects and minimize the potential side effects. Herein, we synthesized a series of benzophenothiazine derivatives with minor N-alkyl alteration to study the effects on the structure-property relationships.

From amorphous to crystalline: a universal strategy for structure regulation of high-entropy transition metal oxides.

High-entropy materials (HEMs) exhibit extensive application potential owing to their unique structural characteristics. Structure regulation is an effective strategy for enhancing material performance. However, the fabrication of HEMs by integrating five metal elements into a single crystalline phase remains a grand challenge, not to mention their structure regulation.

BOINPYs: facile synthesis and photothermal properties triggered by photoinduced nonadiabatic decay.

Photothermal agents (PTAs) represent a core component of photothermal therapy (PTT). However, the current photothermal dyes are almost derived from well-known chromophores such as porphyrins, cyanine, and BODIPYs, and the design of new chromophores as versatile building blocks for PTA is considerably challenging because of the complexity of the modulation of excited-states. Herein, we adopted the concept of photoinduced nonadiabatic decay (PIND) to develop a photothermal boron-containing indoline-3-one-pyridyl chromophore (.

Single-atom engineering of hemicyanine and its amphiphilic derivative for optimized near infrared phototheranostics.

Near-infrared (NIR) dyes are widely used in the field of phototheranostics. Hemicyanine dyes (HDs) have recently received tremendous attention due to their easy synthesis and excellent NIR features. However, HDs can easily form non-fluorescent aggregates and their potential for phototherapy still needs further exploration due to their poor ability to generate reactive oxygen species (ROS).

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.

Two Windmill-Shaped Ln Nanoclusters Exhibiting High Magnetocaloric Effect and Luminescence.

The self-assembly of the high-nuclearity Ln-exclusive nanoclusters is challenging but of significance due to its aesthetically pleasing architectures and far-reaching latent applications in magnetic cooling technologies. Herein, two novel high-nuclearity lanthanide nanoclusters were successfully synthesized under solvothermal conditions, formulated as {[Gd(IN)(HCOO)(μ-O)(μ-OH)(HO)]·4HO} and {[Eu(IN)(HCOO)(CHCOO)(μ-O)(μ-OH)(HO)]·5HO} (abbreviated as and , HIN = isonicotinic acid). Both of them possess novel and exquisite windmill-shaped cationic cores in the family of high-nuclearity Ln-exclusive nanoclusters.

One-Step Phase Separation for Core-Shell Carbon@Indium Oxide@Bismuth Microspheres with Enhanced Activity for CO Electroreduction to Formate.

It is a substantial challenge to construct electrocatalysts with high activity, good selectivity, and long-term stability for electrocatalytic reduction of carbon dioxide to formic acid. Herein, bismuth and indium species are innovatively integrated into a uniform heterogeneous spherical structure by a neoteric quasi-microemulsion method, and a novel C@In O @Bi core-shell structure is constructed through a subsequent one-step phase separation strategy due to melting point difference and Kirkendall effect with the nano-limiting effect of the carbon structure. This core-shell C@In O @Bi catalyst can selectively reduce CO to formate with high selectivity (≈90% faradaic efficiency), large partial current density (24.

Crystal Face Dominated Fabrication of Prussian Blue Analogue with Oriented Growth and Naturally Nonpreferred Unsaturated Coordination Center.

Defects, such as unsaturated coordination centers and vacancies, can fundamentally change materials' inherent properties and growth habits. The development of defect engineering has promoted the application of many technologies, but it is still a great challenge to selectively manufacture defect sites in existing material systems. It is shown here that in situ site-directed tailoring of metal sites in Prussian blue analogs (PBA) can be achieved according to the reducibility differences of different metal atoms, forming naturally nonpreferred unsaturated coordination centers.

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.

Efficient Visible-Light-Driven Hydrogen Production over Cu-Modified Polyoxotungstate Hybrids.

Hydrogen energy is a renewable and clean source, which makes a great difference in future sustainable energy systems. Visible-light-driven photocatalysis reaction involves harnessing the abundance of sunlight for hydrogen production among many catalytic technologies. However, the fabrication of photocatalysts that have distinctive performance in visible light is still the primary challenge.

One-Pot Construction of Heteroarylation/Esterification Products of Acrylic Acids via Iridium(III)-Catalyzed C-H Activation.

A carboxylate-assisted iridium(III)-catalyzed regioselective C(sp)-H heteroarylation/esterification reaction of acrylic acid is disclosed herein for the first time. This catalytic protocol tolerates various α-substituted, β-substituted, and α, β-disubstituted acrylic acids as well as heteroaromatic boronates well. The resulting 3,4-dihydro-2-pyran-6-carboxylic acid derivative highlighted the AIE-active luminophore with multiple emission signal properties and a high quantum yield of 28%, exhibiting the potential application of this methodology for the synthesis of nitrogen-containing organic functional materials.

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.

Two-Dimensional Imide-Based Covalent Organic Frameworks with Tailored Pore Functionality as Separators for High-Performance Li-S Batteries.

Modifying the separator of lithium-sulfur batteries (LSBs) is considered to be one of the most effective strategies for relieving the notorious polysulfide shuttle effect. Constructing a stable, lightweight, and effective LSB separator is still a big challenge but highly desirable. Herein, a stable and lightweight imide-based covalent organic framework (COF-TpPa) is facilely fabricated on reduced graphene oxide (rGO) through an oxygen-free solvothermal technique.

Rh-Catalyzed C-H -Heteroarylation and Esterification Cascade of Carboxylic Acid with Organoboron Reagents and 1,2-Dichloroethane in One-Pot Synthesis.

A Rh-catalyzed C(sp)-H -heteroarylation and esterification cascade of aryl carboxylic acids with -heteroaromatic boronates and 1,2-dichloroethane in a one-pot synthesis has been disclosed. The strong coordinating ability of - and -substituted pyridine boronates and pyrazoles as well as unsubstituted pyrimidine allows them to serve as the coupling partners. This protocol allows late-stage modification of the key precursor of roflumilast and compounds of pharmaceutical interest, which highlights the potential application of this synthetic method.

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.