Photocatalytic CO Reduction to Multi-Carbon Products.

Photocatalytic CO reduction represents a sustainable pathway for mitigating carbon emissions and producing renewable chemicals by utilizing solar energy. While extensive research has been dedicated to single-carbon (C) products, the selective formation of multi-carbon (C) compounds, such as ethylene, ethane, ethanol and acetic acid, has garnered increasing attention due to their higher energy density and broader industrial relevance. However, achieving efficient C─C coupling under mild photocatalytic conditions remains a formidable challenge, hindered by complex reaction pathways, sluggish kinetics and competitive side reactions.

Ce(III)-Doped Mixed-Valence Metal-Organic Frameworks Boosting Ligand-To-Metal Charge Transfer for Photooxidation of a Mustard-Gas Simulant.

Due to the high toxicity and potential threats to society, extensive efforts are devoted to developing catalysts for efficient photodegradation of mustard gas. Metal-organic frameworks (MOFs) are considered as promising candidates for photooxidation, but the limited charge separation efficiency of the pristine MOFs restricts their further applications. Herein, through a one-pot synthesis strategy, Ce(III) ions are incorporated in a Ti-based porphyrin MOF (DGIST-1), leading to a mixed-valence MOF with enhanced charge transfer efficiency.

Synergistic Catalysis by Cu Single Atoms and Atomically Cu-Doped Au Nanoparticles in a Metal-Organic Framework for Photocatalytic CO Reduction to CH.

Photocatalytic CO reduction to C hydrocarbons is considered more valuable and yet highly challenging due to the multielectron process and sluggish kinetics of C-C coupling, which requires multiple active sites to work synergistically. In this work, through a photodeposition method, Cu single-atom sites and atomically Cu-doped Au nanoparticles were simultaneously anchored on a photoactive metal-organic framework (MOF) with mesoporous channels, closely integrating distinct sites within a confined environment. Thanks to the electron accumulation of plasmonic metal nanoparticles and the synergy among different active sites, this MOF composite can achieve efficient photocatalytic reduction of CO to CH with a production rate as high as 69.

Rational Design of a Quasi-Metal-Organic Framework by Ligand Engineering for Efficient Biomass Upgrading.

The electrooxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), a monomer for degradable bioplastic, is a promising strategy for biomass upgrade and yet requires well-designed catalysts with high efficiency and selectivity. Taking advantage of the open metal sites of metal-organic frameworks (MOFs), quasi-MOFs represent viable catalysts, but the poor designability and unpredictable structures hinder their development. In this work, a Ni-based quasi-MOF was rationally designed and synthesized by controlled ligand engineering.

Electronic regulation of single-atomic Ti sites on metal hydroxide for boosting photocatalytic CO reduction.

Photocatalytic CO reduction is considered a sustainable method to address energy and environmental issues by converting CO into fuels and chemicals, yet the performance is still unsatisfactory. Single atom catalysts hold promising potential in photocatalysis, but the selection of metal species is still limited, especially in early transition metals. Herein, inspired by the structure of anatase TiO, single Ti sites were successfully incorporated into a metal hydroxide support for the first time cationic defects, significantly enhancing the photocatalytic performance by more than 30 times (from 0.

Integration of Plasmonic Ag(I) Clusters and Fe(II) Porphyrinates into Metal-Organic Frameworks for Efficient Photocatalytic CO Reduction Coupling with Photosynthesis of Pure HO.

Efficient photocatalytic CO reduction coupled with the photosynthesis of pure HO is a challenging and significant task. Herein, using classical CO photoreduction site iron porphyrinate as the linker, Ag(I) clusters were spatially separated and evenly distributed within a new metal-organic framework (MOF), namely AgTPyP-Fe. With water as electron donors, AgTPyP-Fe exhibited remarkable performances in artificial photosynthetic overall reaction with CO yield of 36.

High-Pressure Molecular Sieving of High-Humidity CH/CH Mixture by a Hydrophobic Flexible Metal-Organic Framework.

Molecular sieving is an ideal separation mechanism, but controlling pore size, restricting framework flexibility, and avoiding strong adsorption are all very challenging. Here, we report a flexible adsorbent showing molecular sieving at ambient temperature and high pressure, even under high humidity. While typical guest-induced transformations are observed, a high transition pressure of 16.

Enrooted-Type Metal-Support Interaction Boosting Oxygen Evolution Reaction in Acidic Media.

Supported metal catalysts with appropriate metal-support interactions (MSIs) hold a great promise for heterogeneous catalysis. However, ensuring tight immobilization of metal clusters/nanoparticles on the support while maximizing the exposure of surface active sites remains a huge challenge. Herein, we report an Ir/WO catalyst with a new enrooted-type MSI in which Ir clusters are, unprecedentedly, atomically enrooted into the WO lattice.

Universal Synthesis of Single-Atom Catalysts by Direct Thermal Decomposition of Molten Salts for Boosting Acidic Water Splitting.

Single-atom catalysts (SACs) are considered prominent materials in the field of catalysis due to their high metal atom utilization and selectivity. However, the wide-ranging applications of SACs remain a significant challenge due to their complex preparation processes. Here, a universal strategy is reported to prepare a series of noble metal single atoms on different non-noble metal oxides through a facile one-step thermal decomposition of molten salts.

Crystal Engineering of MOF-Derived Bimetallic Oxide Solid Solution Anchored with Au Nanoparticles for Photocatalytic CO Reduction to Syngas and C Hydrocarbons.

Considering that CO reduction is mostly a multielectron reaction, it is necessary for the photocatalysts to integrate multiple catalytic sites and cooperate synergistically to achieve efficient photocatalytic CO reduction to various products, such as C hydrocarbons. Herein, through crystal engineering, we designed and constructed a metal-organic framework-derived Zr/Ti bimetallic oxide solid solution support, which was confirmed by X-ray diffraction, electron microscopy and X-ray absorption spectroscopy. After anchoring Au nanoparticles, the composite photocatalyst exhibited excellent performances toward photocatalytic CO reduction to syngas (H and CO production rates of 271.

Reticular framework materials for photocatalytic organic reactions.

Photocatalytic organic reactions, harvesting solar energy to produce high value-added organic chemicals, have attracted increasing attention as a sustainable approach to address the global energy crisis and environmental issues. Reticular framework materials, including metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), are widely considered as promising candidates for photocatalysis owing to their high crystallinity, tailorable pore environment and extensive structural diversity. Although the design and synthesis of MOFs and COFs have been intensively developed in the last 20 years, their applications in photocatalytic organic transformations are still in the preliminary stage, making their systematic summary necessary.

Proteomic and metabolomic approaches elucidate the molecular mechanism of emodin against neuropathic pain through modulating the gamma-aminobutyric acid (GABA)-ergic pathway and PI3K/AKT/NF-κB pathway.

Neuropathic pain (NeP) is a major health concern. Due to the complex pathological mechanisms, management of NeP is challenging. Emodin, a natural anthraquinone derivative, exerts excellent analgesic effects.

Coupling Ruthenium Bipyridyl and Cobalt Imidazolate Units in a Metal-Organic Framework for an Efficient Photosynthetic Overall Reaction in Diluted CO.

Artificial photocatalytic CO reduction, using water as the reductant, is challenging mainly because it is difficult for multiple functional units to cooperate efficiently. Here, we show that the classic photosensitive and HO-oxidizing ruthenium bipyridyl units and CO-reducing cobalt imidazolate units can be incorporated into a metal-organic framework using a classic organic ligand, imidazo[4,5-][1,10]phenanthroline. Under visible light without additional sacrificial agents and photosensitizers, the overall conversion of CO and HO to CO and O was achieved by the multifunctional photocatalyst in the CHCN/HO mixed solvent with a high CO production rate of 11.

The pathogenesis and treatment mechanism of Parkinson's disease from the perspective of traditional Chinese medicine.

Background: Parkinson's disease (PD) is the second most common neurodegenerative disease with no treatment currently available to modify its progression. Traditional Chinese medicine (TCM) has gained attention for its unique theoretical basis and clinical effects. Many studies have reported on the clinical effects and pharmacological mechanisms of Chinese herbs in PD.

A Cu(111)@metal-organic framework as a tandem catalyst for highly selective CO electroreduction to CH.

Here, we report an improved tandem catalytic mechanism for electroreduction of CO to CH. Cu(111) nanoparticles with an average size of 5.5 ± 0.

Electrostatic Attraction-Driven Assembly of a Metal-Organic Framework with a Photosensitizer Boosts Photocatalytic CO Reduction to CO.

Reducing CO into fuels via photochemical reactions relies on highly efficient photocatalytic systems. Herein, we report a new and efficient photocatalytic system for CO reduction. Driven by electrostatic attraction, an anionic metal-organic framework (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) as host and a cationic photosensitizer [Ru(phen)] (phen = 1,10-phenanthroline) as guest were self-assembled into a photocatalytic system , which showed high activity for photocatalytic CO reduction under laboratory light source (CO production rate of 130(5) mmol g h, selectivity of 92.

A Hydrogen-Bonded yet Hydrophobic Porous Molecular Crystal for Molecular-Sieving-like Separation of Butane and Isobutane.

Porous molecular crystals sustained by hydrogen bonds and/or weaker connections are an intriguing type of adsorbents, but they rarely demonstrate efficient adsorptive separation because of poor structural robustness and tailorability. Herein, we report a porous molecular crystal based on hydrogen-bonded cyclic dinuclear Ag complex, which exhibits exceptional hydrophobicity with a water contact angle of 134°, and high chemical stability in water at pH 2-13. The seemingly rigid adsorbent shows a pore-opening or nonporous-to-porous type butane adsorption isotherm and complete exclusion of isobutane, indicating potential molecular sieving.

A metal-organic framework with in situ generated low-coordinate binuclear Cu(i) units as a highly effective catalyst for photodriven hydrogen production.

Herein, we report a metal-organic framework featuring a binuclear copper unit, showing extraordinarily high catalytic activity (102.8 mmol g-1 h-1) for photodriven hydrogen generation, which is attributed to the synergistic catalytic effect between the two copper ions.

An exceptionally stable octacobalt-cluster-based metal-organic framework for enhanced water oxidation catalysis.

Extensive efforts have been devoted to developing efficient and durable catalysts for water oxidation. Herein, we report a highly stable metal-organic framework that shows high catalytic activity and durability for electrically driven (an overpotential of 430 mV at 10 mA cm in neutral aqueous solution) and photodriven (a turnover frequency of 16 s and 12 000 cycles) water oxidation, representing the best catalyst for water oxidation reported to date. Computational simulation and isotope tracing experiments showed that the μ-OH group of the {Co(μ-OH)} unit participates in the water oxidation reaction to offer an oxygen vacancy site with near-optimal OH adsorption energy.

A local hydrophobic environment in a metal-organic framework for boosting photocatalytic CO reduction in the presence of water.

The methylene groups surrounding the metal center in a metal-organic framework provide hydrophobic repulsive forces to H2O, resulting in a high catalytic activity (TOF = 73.8 h-1, selectivity of 96%) for photodriven CO2 reduction into CO.

Selective Aerobic Oxidation of a Metal-Organic Framework Boosts Thermodynamic and Kinetic Propylene/Propane Selectivity.

Efficient adsorptive separation of propylene/propane (C H /C H ) is highly desired and challenging. Known strategies focus on either the thermodynamic or the kinetic mechanism. Here, we report an interesting reactivity of a metal-organic framework that improves thermodynamic and kinetic adsorption selectivity simultaneously.

Hydroxide Ligands Cooperate with Catalytic Centers in Metal-Organic Frameworks for Efficient Photocatalytic CO Reduction.

Converting CO into fuels via photochemical reactions relies on highly efficient and selective catalysts. We demonstrate that the catalytic active metal center can cooperate with neighboring hydroxide ligands to boost the photocatalytic CO reduction. Six cobalt-based metal-organic frameworks (MOFs) with different coordination environments are studied at the same reaction condition (photosensitizer, electron donor, water/organic mixed solvent, and visible light).

Controlling guest conformation for efficient purification of butadiene.

Conventional adsorbents preferentially adsorb the small, high-polarity, and unsaturated 1,3-butadiene molecule over the other C hydrocarbons from which it must be separated. We show from single-crystal x-ray diffraction and computational simulation that a hydrophilic metal-organic framework, [Zn(btm)], where Hbtm is bis(5-methyl-1-1,2,4-triazol-3-yl)methane, has quasi-discrete pores that can induce conformational changes in the flexible guest molecules, weakening 1,3-butadiene adsorption through a large bending energy penalty. In a breakthrough operation at ambient temperature and pressure, this guest conformation-controlling adsorbent eluted 1,3-butadiene first, then butane, butene, and isobutene.