Location-Specific Microenvironment Modulation Around Single-Atom Metal Sites in Metal-Organic Frameworks for Boosting Catalysis.

Despite coordination environment of catalytic metal sites has been recognized to be of great importance in single-atom catalysts (SACs), a significant challenge remains in the understanding how the location-specific microenvironment in the higher coordination sphere influences their catalysis. Herein, a series of Cu-based SACs, namely Cu/UiO-66-X (X=-NO, -H, and -NH), are successfully constructed by anchoring single Cu atoms onto the Zr-oxo clusters of metal-organic frameworks (MOFs), i.e.

Single-Atom Pt Loaded on MOF-Derived Porous TiO with Maxim-Ized Pt Atom Utilization for Selective Hydrogenation of Halonitro-benzene.

The location control of single atoms relative to supports is challenging for single-atom catalysts, leading to a large proportion of inaccessible single atoms buried under supports. Herein, a "sequential thermal transition" strategy is developed to afford single-atom Pt preferentially dispersed on the outer surface of TiO. Specifically, a Ti-MOF confining Pt nanoparticles is converted to Pt and TiO composite coated by carbon (Pt&TiO@C-800) at 800 °C in N.

Introducing Hydrogen-Bonding Microenvironment in Close Proximity to Single-Atom Sites for Boosting Photocatalytic Hydrogen Production.

Inspired by enzymatic catalysis, it is crucial to construct hydrogen-bonding-rich microenvironment around catalytic sites; unfortunately, its precise construction and understanding how the distance between such microenvironment and catalytic sites affects the catalysis remain significantly challenging. In this work, a series of metal-organic framework (MOF)-based single-atom Ru catalysts, namely, Ru/UiO-67-X (X = -H, --(NH), --(NH)), have been synthesized, where the distance between the hydrogen-bonding microenvironment and Ru sites is modulated by altering the location of amino groups. The -NH group can form hydrogen bonds with HO, constituting a unique microenvironment that causes an increased water concentration around the Ru sites.

Tailoring Catalysis of Encapsulated Platinum Nanoparticles by Pore Wall Engineering of Covalent Organic Frameworks.

While supported metal nanoparticles (NPs) have shown significant promise in heterogeneous catalysis, precise control over their interaction with the support, which profoundly impacts their catalytic performance, remains a significant challenge. In this study, Pt NPs are incorporated into thioether-functionalized covalent organic frameworks (denoted COF-S), enabling precise control over the size and electronic state of Pt NPs by adjusting the thioether density dangling on the COF pore walls. Notably, the resulting Pt@COF-S demonstrate exceptional selectivity (> 99 %) in catalytic hydrogenation of p-chloronitrobenzene to p-chloroaniline, in sharp contrast to the poor selectivity of Pt NPs embedded in thioether-free COFs.

Superhydrophobic MOF/polymer composite with hierarchical porosity for boosting catalytic performance in an humid environment.

The poor hydrostability of most reported metal-organic frameworks (MOFs) has become a daunting challenge in their practical applications. Recently, MOFs combined with multifunctional polymers can act as a functional platform and exhibit unique catalytic performance; they can not only inherit the outstanding properties of the two components but also offer unique synergistic effects. Herein, an original porous polymer-confined strategy has been developed to prepare a superhydrophobic MOF composite to significantly enhance its moisture or water resistance.

Superhydrophobic MOFs with enhanced catalytic activity for chemical fixation of CO.

A general approach to prepare superhydrophobic MOFs (denoted as MOFs-CF) through a post-decorating strategy for highly efficient chemical fixation of CO was demonstrated. The enhanced catalytic activity of MOFs-CF is attributed to a synergistic effect between the Lewis acid sites of MOFs and modification of the electron-withdrawing trifluoromethyl group, which resulted in a high CO enrichment capacity. The possible mechanism of cycloaddition catalyzed by the MOFs-CF catalyst was also proposed.

Selectivity Control in the Direct CO Esterification over Pd@UiO-66: The Pd Location Matters.

The selectivity control of Pd nanoparticles (NPs) in the direct CO esterification with methyl nitrite toward dimethyl oxalate (DMO) or dimethyl carbonate (DMC) remains a grand challenge. Herein, Pd NPs are incorporated into isoreticular metal-organic frameworks (MOFs), namely UiO-66-X (X=-H, -NO , -NH ), affording Pd@UiO-66-X, which unexpectedly exhibit high selectivity (up to 99 %) to DMC and regulated activity in the direct CO esterification. In sharp contrast, the Pd NPs supported on the MOF, yielding Pd/UiO-66, displays high selectivity (89 %) to DMO as always reported with Pd NPs.

Bioinspired microenvironment modulation of metal-organic framework-based catalysts for selective methane oxidation.

Inspiration from natural enzymes enabling creationary catalyst design is appealing yet remains extremely challenging for selective methane (CH) oxidation. This study presents the construction of a biomimetic catalyst platform for CH oxidation, which is constructed by incorporating Fe-porphyrin into a robust metal-organic framework, UiO-66, furnished with saturated monocarboxylic fatty acid bearing different long alkyl chains. The catalysts demonstrate the high efficiency in the CH to methanol (CHOH) conversion at 50 °C.

Dual Microenvironment Modulation of Pd Nanoparticles in Covalent Organic Frameworks for Semihydrogenation of Alkynes.

The chemical microenvironment modulation of metal nanoparticles (NPs) holds promise for tackling the long-lasting challenge of the trade-off effect between activity and selectivity in catalysis. Herein, ultrafine PdCu NPs incorporated into covalent organic frameworks (COFs) with diverse groups on their pore walls have been fabricated for the semihydrogenation of alkynes. The Cu species, as the primary microenvironment of Pd active sites, greatly improves the selectivity.

Facet Engineering of a Metal-Organic Framework Support Modulates the Microenvironment of Palladium Nanoparticles for Selective Hydrogenation.

The exposed facets of supported catalysts play a crucial role in catalysis; however, they are usually ignored and related studies remain rare. Herein, we have fabricated a series of sandwich-structured metal-organic framework composites, denoted ZIF-8 @Pd@ZIF-8 (x represents the morphology of ZIF-8 core, i.e.

Optimizing Pt Electronic States through Formation of a Schottky Junction on Non-reducible Metal-Organic Frameworks for Enhanced Photocatalysis.

Charge transfer between metal sites and supports is crucial for catalysis. Redox-inert supports are usually unfavorable due to their less electronic interaction with metal sites, which, we demonstrate, is not always correct. Herein, three metal-organic frameworks (MOFs) are chosen to mimic inert or active supports for Pt nanoparticles (NPs) and the photocatalysis is studied.

Trifunctional Metal-Organic Framework Catalyst for CO Conversion into Cyclic Carbonates.

Herein, we reported a facile strategy for the preparation of trifunctional ionic metal-organic frameworks (MOFs) incorporating imidazolium cation functionalities. This strategy exploits the Debus-Radziszewski reaction to create the cationic imidazole ring by postsynthetic modification, meanwhile introducing exchangeable counteranions. On the basis of this strategy, MIL-101-IMOH-Br has been synthesized, which combines Lewis acidic sites, Brønsted acidic sites, and nucleophilic centers to achieve catalysis for the carbon dioxide-epoxide cycloaddition into cyclocarbonate without any cocatalyst and solvent.

An exceptionally stable core-shell MOF/COF bifunctional catalyst for a highly efficient cascade deacetalization-Knoevenagel condensation reaction.

A novel strategy has been developed to construct a highly stable core-shell MOF@COF (PCN-222-Co@TpPa-1) bifunctional catalyst through strong π-π stacking interaction. This hybrid material with spatially isolated antagonistic acid-base sites can effectively catalyze the deacetalization-Knoevenagel condensation cascade reaction.

A highly stable nanofibrous Eu-MOF membrane as a convenient fluorescent test paper for rapid and cyclic detection of nitrobenzene.

A stable fluorescent nanofibrous membrane was fabricated by in situ growing Eu-MOF crystals on electrospun polyacrylonitrile nanofibers modified with γ-aminobutyric acid. This nanofibrous membrane can be used as a convenient fluorescent test paper for rapid and cyclic detection of nitrobenzene.

Superhydrophobic/Superoleophilic MOF Composites for Oil-Water Separation.

A universal strategy is developed to construct metal-organic framework (MOF)-based superhydrophobic/superoleophilic materials by the reaction of activated MOFs and octadecylamine. In particular, S-MIL-101(Cr) composite can efficiently separate chloroform, toluene, petroleum ether, and n-hexane from water with excellent oil-water separation performance, with potential application in the environmental field.

Fully Automatic Segmentation and Three-Dimensional Reconstruction of the Liver in CT Images.

Automatic segmentation and three-dimensional reconstruction of the liver is important for liver disease diagnosis and surgical treatment. However, the shape of the imaged 2D liver in each CT image changes dramatically across the slices. In all slices, the imaged 2D liver is connected with other organs, and the connected organs also vary across the slices.

Robust Bifunctional Core-Shell MOF@POP Catalyst for One-Pot Tandem Reaction.

A new bifunctional acid-base catalyst, core-shell UiO-66@SNW-1, with robust chemical and thermal stability, recyclability, and durable catalytic activity is synthesized by a convenient, universal strategy. Interestingly, this hybrid material can effectively catalyze deacetalization-Knoevenagel condensation reaction in the presence of excellent compartmentalization to spatially isolate opposing acid-base sites.

Robust Bifunctional Lanthanide Cluster Based Metal-Organic Frameworks (MOFs) for Tandem Deacetalization-Knoevenagel Reaction.

A series of 12-connected lanthanide cluster based metal-organic frameworks (MOFs) have been constructed by [Ln(μ-OH)(COO-)] secondary building units (SBUs) and 2-aminobenzenedicarboxylate (BDC-NH) ligands. These obtained materials exhibit high chemical stability and generic thermal stability, especially in acidic and basic conditions. They also present commendable CO adsorption capacity, and Yb-BDC-NH was further confirmed by a breakthrough experiment under both dry and wet conditions.

Microporous Hexanuclear Ln(III) Cluster-Based Metal-Organic Frameworks: Color Tunability for Barcode Application and Selective Removal of Methylene Blue.

Two hexanuclear Ln(III) cluster-based metal-organic frameworks (MOFs) (Ln = Tb or Eu) and a series of isomorphic bimetallic Ln(III)-MOFs have been synthesized by changing the ratio of Tb(III) and Eu(III) under solvothermal conditions. The excellent linear color tunability (from green to red) makes them suitable for barcode application. In addition, the anionic Ln(III)-MOFs exhibit superior uptake capacity toward methylene blue (MB) by an ion-exchange process, and its reversible adsorption performance makes 1 suitable for removal of organic dye MB.

Reconstruction of three-dimensional porous media from a single two-dimensional image using three-step sampling.

A random three-dimensional (3D) porous medium can be reconstructed from a two-dimensional (2D) image by reconstructing an image from the original 2D image, and then repeatedly using the result to reconstruct the next 2D image. The reconstructed images are then stacked together to generate the entire reconstructed 3D porous medium. To perform this successfully, a very important issue must be addressed, i.

[Research on the influence of infrared spectral resolution on gas quantitative analysis].

Spectra with different resolution (1, 2, 4 and 8 cm(-1)) of samples with combined CO/CO2/NO were used to build models for quantitative analysis of each component. Using these models, the influence of spectral resolution on gas quantitative analysis was studied. Research data show that for each component there is a best competent resolution for its quantitative analysis.