Molecular Heterogeneous Photocatalysts for Visible-Light-Driven CO Reduction.

Photoreduction of CO to high-value chemical fuels presents an effective strategy to reduce reliance on fossil fuels and mitigate climate change. The development of a photocatalyst characterized by superior activity, high selectivity, and good stability is a critical issue for PCR. Molecular heterogeneous photocatalytic systems integrate the advantages of both homogeneous and heterogeneous catalysts, creating a synergistic enhancement effect that increases photocatalytic performance.

Recent Advances of Photocatalytic CO Reduction Based on Hybrid Molecular Catalyst/Semiconductor Photocatalysts: A Review.

Molecular catalysts often exhibit superior activity and selectivity in the process of photocatalytic reduction of CO (PCR). However, the practical application of molecular catalysts is restricted by the unsatisfied charge separation, low stability, and recycling difficulty. Fortunately, constructing organic-inorganic hybrids of molecular catalysts and semiconductors can tackle the above problems, which can improve the efficiency of charge separation and keep beneficial active sites simultaneously.

Precisely Tuning Band Gaps of Hexabenzocoronene-Based MOFs Toward Enhanced Photocatalysis.

Precise adjusting the band gaps in metal-organic frameworks (MOFs) is crucial for improving their visible-light absorption capacity during photocatalysis, presenting both a formidable challenge and a charming opportunity. This present study employed a symmetry-reduction strategy to pre-design six novel 4-connected ligands with systematic substituents (-NO, -H, -Bu, -OCH, -OH and -NH) and synthesized the corresponding pillared-layer Zr-MOFs (NKM-668) retaining the hexaphenylbenzene fragment. Subsequently, the NKM-668 MOFs were transformed into large-π-conjugated hexabenzocoronene-based MOFs (pNKM-668) via the Scholl reaction.

A Review of Metal-Organic Frameworks Derived Hollow-Structured Photocatalysts: Synthesis and Applications.

Photocatalysis is a most important approach to addressing global energy shortages and environmental issues due to its environmentally friendly and sustainable properties. The key to realizing efficient photocatalysis relies on developing appropriate catalysts with high efficiency and chemical stability. Among various photocatalysts, Metal-organic frameworks (MOFs)-derived hollow-structured materials have drawn increased attention in photocatalysis based on advantages like more active sites, strong light absorption, efficient transfer of pho-induced charges, excellent stability, high electrical conductivity, and better biocompatibility.

Molecular Engineering of Porous Fe-N-C Catalyst with Sulfur Incorporation for Boosting CO Reduction and Zn-CO Battery.

Transition metal-nitrogen-carbon (M-N-C) catalysts have emerged as promising candidates for electrocatalytic CO reduction reaction (CORR) due to their uniform active sites and high atomic utilization rate. However, poor efficiency at low overpotentials and unclear reaction mechanisms limit the application of M-N-C catalysts. In this study, Fe-N-C catalysts are developed by incorporating S atoms onto ordered hierarchical porous carbon substrates with a molecular iron thiophenoporphyrin.

Ionic Liquid Modified Fe-Porphyrinic Metal-Organic Frameworks as Efficient and Selective Photocatalysts for CO Reduction.

Porphyrin-based metal-organic frameworks (MOFs) are ideal platforms for heterogeneous photocatalysts toward CO reduction. To further explore photocatalytic MOF systems, it is also necessary to consider their ability to fine-tune the microenvironments of the active sites, which affects their overall catalytic operation. Herein, a kind of ionic liquid (IL, here is 3-butyric acid-1-methyl imidazolium bromide, BAMeImBr) was anchored to iron-porphyrinic Zr-MOFs with different amounts to obtain IL@MOF-526 (MOF-526 = ZrO(OH)(FeTCBPP), FeTCBPP = iron 5,10,15,20-tetra[4-(4'-carboxyphenyl)phenyl]-porphyrin, = 100, 200, and 400).

Working-Together Normative Appeals to Promote Pro-Environmental Donations.

Investigating the role of social norms in fostering pro-environmental behaviors is crucial for advancing human efforts toward environmental protection. This study employed a one-way, two-level, between-participants experimental design, focusing on the type of social norm as the independent variable and pro-environmental donations as the dependent variable. This study aimed to explore the impact of working-together normative appeals on pro-environmental donations and to understand the underlying mediating mechanism.

Photocatalytic antibacterial agents based on inorganic semiconductor nanomaterials: a review.

Microbial contamination and antibiotic pollution have threatened public health and it is important to develop a rapid and safe sterilization strategy. Among various disinfection strategies, photocatalytic antibacterial methods have drawn increasing attention due to their efficient disinfection performances and environment-friendly properties. Although there are some reviews about bacterial disinfection, specific reviews on photocatalysis focused on inorganic semiconductor nanomaterials are rarely reported.

Efficient Visible-Light-Driven Carbon Dioxide Reduction using a Bioinspired Nickel Molecular Catalyst.

Inspired by natural enzymes, this study presents a nickel-based molecular catalyst, [Ni(NS)]Cl (NiNS, NS=2,11-dithia[3,3](2,6)pyridinophane), for the photochemical catalytic reduction of CO under visible light. The catalyst was synthesized and characterized using various techniques, including liquid chromatography-high resolution mass spectrometry (LC-HRMS), UV-Visible spectroscopy, and X-ray crystallography. The crystallographic analysis revealed a slightly distorted octahedral coordination geometry with a mononuclear Ni cation, two nitrogen atoms and two sulfur atoms.

Dynamic Bond-Directed Synthesis of Stable Mesoporous Metal-Organic Frameworks under Room Temperature.

Stable metal-organic frameworks (MOFs) with mesopores (2-50 nm) are promising platforms for immobilizing nanosized functional compounds, such as metal-oxo clusters, metal-sulfide quantum dots, and coordination complexes. However, these species easily decompose under acidic conditions or high temperatures, hindering their encapsulation in stable MOFs, which are usually synthesized under harsh conditions involving excess acid modulators and high temperatures. Herein, we report a route for the room-temperature and acid-modulator-free synthesis of stable mesoporous MOFs and MOF catalysts with acid-sensitive species encapsulated: (1) we initially construct a MOF template by connecting stable Zr clusters with labile Cu-bipyridyl moieties; (2) Cu-bipyridyl moieties are subsequently exchanged by organic linkers to afford a stable version of Zr-MOFs; (3) acid-sensitive species, including polyoxometalates (POMs), CdSeS/ZnS quantum dots, and Cu-coordination cages, can be encapsulated into the MOFs during step 1.

Monitoring the Activation of Open Metal Sites in [FeM(μ-O)] Cluster-Based Metal-Organic Frameworks by Single-Crystal X-ray Diffraction.

While trinuclear [FeM(μ-O)] cluster-based metal-organic frameworks (MOFs) have found wide applications in gas storage and catalysis, it is still challenging to identify the structure of open metal sites obtained through proper activations and understand their influence on the adsorption and catalytic properties. Herein, we use in situ variable-temperature single-crystal X-ray diffraction to monitor the structural evolution of [FeM(μ-O)]-based MOFs (PCN-250, M = Ni, Co, Zn, Mg) upon thermal activation and provide the snapshots of metal sites at different temperatures. The exposure of open Fe sites was observed along with the transformation of Fe coordination geometries from octahedron to square pyramid.

Dual-Functional Photocatalysis for Cooperative Hydrogen Evolution and Benzylamine Oxidation Coupling over Sandwiched-Like Pd@TiO @ZnIn S Nanobox.

Photocatalytic hydrogen evolution (PHE) over semiconductor photocatalysts is usually constrained by the limited light-harvesting and separation of photogenerated electron-hole pairs. Most of the reported systems focusing on PHE are facilitated by consuming the photoinduced holes with organic sacrificial electron donors (SEDs). The introduction of the SEDs not only causes the environmental problem, but also increases the cost of the reaction.

Perovskite Quantum Dots Encapsulated in a Mesoporous Metal-Organic Framework as Synergistic Photocathode Materials.

Metal halide perovskite quantum dots, with high light-absorption coefficients and tunable electronic properties, have been widely studied as optoelectronic materials, but their applications in photocatalysis are hindered by their insufficient stability because of the oxidation and agglomeration under light, heat, and atmospheric conditions. To address this challenge, herein, we encapsulated CsPbBr nanocrystals into a stable iron-based metal-organic framework (MOF) with mesoporous cages (∼5.5 and 4.

Metal-Organic Frameworks Based on Group 3 and 4 Metals.

Metal-organic frameworks (MOFs) based on group 3 and 4 metals are considered as the most promising MOFs for varying practical applications including water adsorption, carbon conversion, and biomedical applications. The relatively strong coordination bonds and versatile coordination modes within these MOFs endow the framework with high chemical stability, diverse structures and topologies, and interesting properties and functions. Herein, the significant progress made on this series of MOFs since 2018 is summarized and an update on the current status and future trends on the structural design of robust MOFs with high connectivity is provided.

Precisely Embedding Active Sites into a Mesoporous Zr-Framework through Linker Installation for High-Efficiency Photocatalysis.

The pore engineering of microporous metal-organic frameworks (MOFs) has been extensively investigated in the past two decades, and an expansive library of functional groups has been introduced into various frameworks. However, the reliable procurement of MOFs possessing both a targeted pore size and preferred functionality together is less common. This is especially important since the applicability of many elaborately designed materials is often restricted by the small pore sizes of microporous frameworks.

Transition-Metal-Containing Porphyrin Metal-Organic Frameworks as π-Backbonding Adsorbents for NO Removal.

Mitigating ambient nitrogen dioxide (NO ) pollution via selective adsorption on porous materials is a promising approach to tackle such an increasingly pressing environmental health issue. However, very few porous adsorbents have sufficiently high NO adsorption capacity and good regenerability simultaneously. Here we attempt to address this challenge by developing π-backbonding adsorbents in the transition metal (TM) incorporated porphyrin metal-organic frameworks (PMOFs).

Functionalization of Zirconium-Based Metal-Organic Layers with Tailored Pore Environments for Heterogeneous Catalysis.

Intriguing properties and functions are expected to implant into metal-organic layers (MOLs) to achieve tailored pore environments and multiple functionalities owing to the synergies among multiple components. Herein, we demonstrate a facile one-pot synthetic strategy to incorporate multiple functionalities into stable zirconium MOLs via secondary ligand pillaring. Through the combination of Zr -BTB (BTB=benzene-1,3,5-tribenzoate) layers and diverse secondary ligands (including ditopic and tetratopic linkers), 31 MOFs with multi-functionalities were systematically prepared.

Fluorescence Enhancement in the Solid State by Isolating Perylene Fluorophores in Metal-Organic Frameworks.

Polycyclic aromatic hydrocarbons such as perylene and pyrene and their derivatives are highly emissive fluorophores in solution. However, the practical applications of these materials in the field of molecular electronic and light-emitting devices are often hindered by self-quenching effects because of the formation of nonfluorescent aggregates in concentrated solutions or in the solid state. Herein, we demonstrate that aggregation-caused quenching of perylenes can be minimalized by molecular incorporation into metal-organic frameworks (MOFs).

A Honeycomb-Like Bulk Superstructure of Carbon Nanosheets for Electrocatalysis and Energy Storage.

Superstructures have attracted extensive attention because of their potential applications in materials science and biology. Herein, we fabricate the first centimeter-sized porous superstructure of carbon nanosheets (SCNS) by using metal-organic framework nanoparticles as a template and polyvinylpyrrolidone as an additional carbon source. The SCNS shows a honeycomb-like morphology with wall-sharing carbon cages, in each cavity of which a porous carbon sphere is encapsulated.

Spatially Separated Bifunctional Cocatalysts Decorated on Hollow-Structured TiO for Enhanced Photocatalytic Hydrogen Generation.

Efficient charge separation can promote photocatalysis of semiconductors. Herein, a hollow-structured TiO sphere decorated with spatially separated bifunctional cocatalysts was designed, which exhibited enhanced photocatalytic hydrogen generation. Ultrasmall-sized MO (M = Pd, Co, Ni, or Cu) nanoparticles (NPs) were first introduced into a zeolite via confinement synthesis, and then, hollow TiO was fabricated by using the zeolite as a sacrificial template forming MO@TiO.

Stepwise Assembly of Turn-on Fluorescence Sensors in Multicomponent Metal-Organic Frameworks for in Vitro Cyanide Detection.

The controlled synthesis of multicomponent metal-organic frameworks (MOFs) allows for the precise placement of multiple cooperative functional groups within a framework, leading to emergent synergistic effects. Herein, we demonstrate that turn-on fluorescence sensors can be assembled by combining a fluorophore and a recognition moiety within a complex cavity of a multicomponent MOF. An anthracene-based fluorescent linker and a hemicyanine-containing CN -responsive linker were sequentially installed into the lattice of PCN-700.

Continuous Variation of Lattice Dimensions and Pore Sizes in Metal-Organic Frameworks.

The continuous variation of the lattice metric in metal-organic frameworks (MOFs) allows precise control over their chemical and physical properties. This has been realized herein by a series of mixed-linker and Zr-cluster-based MOFs, namely, continuously variable MOFs (CVMOFs). Similar to the substitutional solid solutions, organic linkers with different lengths and various ratios were homogeneously incorporated into a framework rather than being allowed to form separate phases or domains, which was manifested by single-crystal X-ray diffraction, powder X-ray diffraction, fluorescence quenching experiments, and molecular simulations.

Face-Sharing Archimedean Solids Stacking for the Construction of Mixed-Ligand Metal-Organic Frameworks.

Reticular chemistry has been an important guiding principle for the design of metal-organic frameworks (MOFs). This approach utilizes discrete building units (molecules and clusters) that are connected through strong bonds into extended networks assisted by topological considerations. Although the simple design principle of connecting points and lines has proved successful, new design strategies are still needed to further explore the structures and functions of MOFs.