Ba/Ti MOF: A Versatile Heterogeneous Photoredox Catalyst for Visible-Light Metallaphotocatalysis.

The field of sustainable heterogeneous catalysis is evolving rapidly, with a strong emphasis on developing catalysts that enhance efficiency. Among various heterogeneous photocatalysts, metal-organic frameworks (MOFs) have gained significant attention for their exceptional performance in photocatalytic reactions. In this context, contrary to the conventional homogeneous iridium or ruthenium-based photocatalysts, which face significant challenges in terms of availability, cost, scalability, and recyclability, a new Ba/Ti MOF (ACM-4) is developed as a heterogeneous catalyst that can mimic/outperform the conventional photocatalysts, offering a more sustainable solution for efficient chemical processes.

The Paradoxical Influence of Hydrothermally Treated Zeolites on the Hydrocarbon Pool Mechanism.

Understanding the mechanistic intricacies of hydrothermally treated zeolite is crucial for valorizing any oxygen-containing renewable feedstocks (e. g., methanol, carbon dioxide, biomass).

Zeolite Synthesis in the Presence of Metallosiloxanes for the Quantitative Encapsulation of Metal Species for the Selective Catalytic Reduction (SCR) of NO.

Metal encapsulation in zeolitic materials through one-pot hydrothermal synthesis (HTS) is an attractive technique to prepare zeolites with a high metal dispersion. Due to its simplicity and the excellent catalytic performance observed for several catalytic systems, this method has gained a great deal of attention over the last few years. While most studies apply synthetic methods involving different organic ligands to stabilize the metal under synthesis conditions, here we report the use of metallosiloxanes as an alternative metal precursor.

Calcium Looping: On the Positive Influence of SO and the Negative Influence of HO on CO Capture by Metamorphosed Limestone-Derived Sorbents.

The CO capture performance of sorbents derived from three distinct limestones, including a metamorphosed limestone, is studied under conditions relevant for calcium looping CO capture from power plant flue gas. The combined and individual influence of flue gas HO and SO content, the influence of textural changes caused by sequential calcination/carbonation cycles, and the impact of CaSO accumulation on the sorbents' capture performance were examined using bubbling fluidized bed reactor systems. The metamorphosed limestone-derived sorbents exhibit atypical capture behavior: flue gas HO negatively influences CO capture performance, while limited sulfation can positively influence CO capture, with space time significantly impacting CO and SO co-capture performance.

Triphenylphosphine-Based Covalent Organic Frameworks and Heterogeneous Rh-P-COFs Catalysts.

The synthesis of phosphine-based functional covalent organic frameworks (COFs) has attracted great attention recently. Herein, we present two examples of triphenylphosphine-based COFs (termed P-COFs) with well-defined crystalline structures, high specific surface areas, and good thermal stability. Furthermore, rhodium catalysts with these P-COFs as support material show high turnover frequency for the hydroformylation of olefins, as well as excellent recycling performance.

Shaping of ZSM-5-Based Catalysts via Spray Drying: Effect on Methanol-to-Olefins Performance.

Shaping and optimal compositional formulation are major challenges in the successful industrial application of heterogeneous catalysts. The choice of components during formulation plays a vital role in endowing the final catalyst's mechanical strength, durability, and lifetime and may even affect activity and selectivity. Herein, we evaluate the application of spray drying to manufacture spherical ZSM-5-based catalysts and their applicability in the methanol-to-olefins process.

Nanosheets of Nonlayered Aluminum Metal-Organic Frameworks through a Surfactant-Assisted Method.

During the last decade, the synthesis and application of metal-organic framework (MOF) nanosheets has received growing interest, showing unique performances for different technological applications. Despite the potential of this type of nanolamellar materials, the synthetic routes developed so far are restricted to MOFs possessing layered structures, limiting further development in this field. Here, a bottom-up surfactant-assisted synthetic approach is presented for the fabrication of nanosheets of various nonlayered MOFs, broadening the scope of MOF nanosheets application.

Synthesis, characterization and properties of a glycol-coordinated ε-Keggin-type Al chloride.

Herein we present the first example of a glycol-coordinated ε-Keggin Al13 chloride (gl-ε-Al13), which is the first chelated version since discovery of Al13 in 1960. The molecular structure consists of [AlO4Al12(OH)12(OC2H4OH)12]Cl7·H2O units with chelating mono-anionic ethylene glycol units replacing one bridging and one terminal oxygen site.

Azine-Linked Covalent Organic Framework (COF)-Based Mixed-Matrix Membranes for CO2 /CH4 Separation.

Mixed-matrix membranes (MMMs) comprising Matrimid and a microporous azine-linked covalent organic frameworks (ACOF-1) were prepared and tested in the separation of CO2 from an equimolar CO2 /CH4 mixture. The COF-based MMMs show a more than doubling of the CO2 permeability upon 16 wt % ACOF-1 loading together with a slight increase in selectivity compared to the bare polymer. These results show the potential of COFs in the preparation of MMMs.

High-Yielding Green Hydrothermal Synthesis of Ruthenium Nanoparticles and Their Characterization.

Using hydrothermal techniques, a novel synthetic approach to prepare ruthenium nanoparticles has been developed. At 180 degrees C and under autogenous pressure, starting from an aqueous solution of ruthenium trichloride, the method yielded nanoparticles whose form and size both depended on the reducing agent: sodium citrate (hexagonal shaped nanocrystals, 1-20 nm), ascorbic acid (spherical nanoparticles, 3-5 nm) and succinic acid (spherical nanoparticles, 1-120 nm). Depending on the reaction variables, the nature and concentration of partially reduced species determines the characteristics of the final products.

Tris(bipyridine)Metal(II)-Templated Assemblies of 3D Alkali-Ruthenium Oxalate Coordination Frameworks: Crystal Structures, Characterization and Photocatalytic Activity in Water Reduction.

A series of 3D oxalate-bridged ruthenium-based coordination polymers with the formula of {[Z(bpy)₃][MRu(C₂O₄)₃]} (Z = Zn (), Cu (, ), Ru (, ), Os (, ); M = Li⁺, Na⁺; bpy = 2,2'-bipyridine) and {[Zn(bpy)₃](H₂O)[LiRu(C₂O₄)₃]} () has been synthesized at room temperature through a self-assembly reaction in aqueous media and characterized by single-crystal and powder X-ray diffraction, elemental analysis, infrared and diffuse reflectance UV⁻Vis spectroscopy and thermogravimetric analysis. The crystal structures of all compounds comprise chiral 3D honeycomb-like polymeric nets of the srs-type, which possess triangular anionic cages where [Z(bpy)₃] cationic templates are selectively embedded. Structural analysis reveals that the electronic configuration of the cationic guests is affected by electrostatic interaction with the anionic framework.

Structural Effects in Visible-Light-Responsive Metal-Organic Frameworks Incorporating ortho-Fluoroazobenzenes.

The ability to control the interplay of materials with low-energy photons is important as visible light offers several appealing features compared to ultraviolet radiation (less damaging, more selective, predominant in the solar spectrum, possibility to increase the penetration depth). Two different metal-organic frameworks (MOFs) were synthesized from the same linker bearing all-visible ortho-fluoroazobenzene photoswitches as pendant groups. The MOFs exhibit different architectures that strongly influence the ability of the azobenzenes to isomerize inside the voids.

Experimental Evidence of Negative Linear Compressibility in the MIL-53 Metal-Organic Framework Family.

We report a series of powder X-ray diffraction experiments performed on the soft porous crystals MIL-53(Al) and NH-MIL-53(Al) in a diamond anvil cell under different pressurization media. Systematic refinements of the obtained powder patterns demonstrate that these materials expand along a specific direction while undergoing total volume reduction under an increase in hydrostatic pressure. The results confirm for the first time the Negative Linear Compressibility behaviour of this family of materials recently predicted from quantum chemical calculations.

Electronic metal-support interactions in single-atom catalysts.

The synthesis of single-atom catalysts and the control of the electronic properties of catalytic sites to arrive at superior catalysts is a major challenge in heterogeneous catalysis. A stable supported single-atom silver catalyst with a controllable electronic state was obtained by anti-Ostwald ripening. An electronic perturbation of the catalytic sites that is induced by a subtle change in the structure of the support has a strong influence on the intrinsic reactivity.

Series of 2D heterometallic coordination polymers based on ruthenium(III) oxalate building units: synthesis, structure, and catalytic and magnetic properties.

A series of 2D ruthenium-based coordination polymers with hcb-hexagonal topology, {[K(18-crown-6)]3[M(II)3(H2O)4{Ru(ox)3}3]}n (M(II) = Mn (1), Fe (2), Co (3), Cu (4), Zn (5)), has been synthesized through self-assembly reaction. All compounds are isostructural frameworks that crystallize in the monoclinic space group C2/c. The crystal packing consists of a 2D honeycomb-like anionic mixed-metal framework intercalated by [K(18-crown-6)](+) cationic template.

Bis(2,2'-bipyridyl-κ(2)N,N')dichlorido-rhodium(III) perchlorate.

The asymmetric unit of the title compound, [RhCl(2)(C(10)H(8)N(2))(2)]ClO(4), consists of one unit of the cationic complex [RhCl(2)(bipy)(2)](+) and one uncoordinated perchlorate anion. The Rh(III) atom is coordinated by four N atoms from two bipyridyl ligands and two Cl atoms, forming a distorted octa-hedral environment. The Cl ligands are cis.