Shifting CH/CO Adsorption and Separation in Pillar-Layered Metal-Organic Frameworks Finely-Regulated by Molecular Rotation.

The efficient separation of C₂H₂/CO₂ mixture is crucial for industrial applications.  A promising strategy is proposed herein to fine-tune the C₂H₂/CO adsorption and separation by pillar-layered metal-organic framework (MOF) adsorbents via molecular rotation. Keeping the same ultramicroporous architecture, three Zn-X-TRZ (TRZ = 1,2,4-triazole) adsorbents are prepared with X-pillar rotors varying from 9,10-anthracenedicarboxylic acid (ADC), 1,4-naphthalenedicarboxylic acid (NDC) to 1,4-benzenedicarboxylic acid (BDC).

Controllable Regulation of CO Adsorption Behavior via Precise Charge Donation Modulation for Highly Selective CO Electroreduction to Formic Acid.

The synthesis of value-added products via CO electroreduction (COER) is of great significance, but the development of efficient and versatile strategies for the controllable selectivity tuning is extremely challenging. Herein, the tuning of COER selectivity through the modulation of CO adsorption behavior is proposed. Using the constructed zeolitic MOF (SNNU-339), CO adsorption behavior is controllably changed from *CO to CO* via the precise ligand-to-metal charge donation (LTMCD) regulation.

Modulation of -Block Electron Orbits in Metal-Organic Frameworks for CO Capture and Electrochemical Reduction.

Developing catalysts with excellent CO capture capability and electrochemical CO reduction reaction (CORR) at a wide potential range simultaneously is significant but remains a formidable challenge. Here, two novel InMg defective trinuclear cluster-based MOFs (SNNU-41 and SNNU-42) with abundant -block unsaturated coordinated sites were reported and exhibited good CO capture and CORR performance simultaneously. Due to the suitable micropores, SNNU-41 showed higher CO capture ability at different adsorption pressure conditions.

Extra-High CO Adsorption and Controllable CH/CO Separation Regulated by the Interlayer Stacking in Pillar-Layered Metal-Organic Frameworks.

Pillar-layered metal-organic frameworks (PLMOFs) are promising gas adsorbents due to their high designability. In this work, high CO storage capacity as well as controllable CH/CO separation ability are acquired by rationally manipulating the interlayer stacking in pillar-layered MOF materials. The rational construction of pillar-layered MOFs started from the 2D Ni-BTC-pyridine layer, an isomorphic structure of pioneering MOF-1 reported in 1995.

Spatially Confined π-Complexation within Pore-Space-Partitioned Metal-Organic Frameworks for Enhanced Light Hydrocarbon Separation and Purification.

Ultramicroporous metal-organic frameworks (MOFs) are demonstrated to be advantageous for the separation and purification of light hydrocarbons such as CH, CH, and CH. The introduction of transition metal sites with strong π-complexation affinity into MOFs is more effective than other adsorption sites for the selective adsorption of π-electron-rich unsaturated hydrocarbon gases from their mixtures. However, lower coordination numbers make it challenging to produce robust MOFs directly utilizing metal ions with π-coordination activity, such as Cu, Ag, and Pd.

Maximizing Electrostatic Interaction in Ultramicroporous Metal-Organic Frameworks for the One-Step Purification of Acetylene from Ternary Mixture.

Developing efficient adsorbents for acetylene purification from multicomponent mixtures is of critical significance in the chemical industry, but the trade-off between regenerability and selectivity significantly restricts practical industrial applications. Here, we report ultramicroporous metal-organic frameworks with acetylene-affinity channels to enhance electrostatic interaction between CH and frameworks for the efficient one-step purification of CH from CH/CO/CH mixtures, in which the electrostatic interaction led to high regenerability. The obtained exhibits significantly higher adsorption capacity for CH than that for both CH and CO at 298 K and 0.

High-Valence Metal Doping Induced Lattice Expansion for M-FeNi LDH toward Enhanced Urea Oxidation Electrocatalytic Activities.

The precise design of low-cost, efficient, and definite electrocatalysts is the key to sustainable renewable energy. The urea oxidation reaction (UOR) offers a promising alternative to the oxygen evolution reaction for energy-saving hydrogen generation. In this study, by tuning the lattice expansion, a series of M-FeNi layered double hydroxides (M-FeNi LDHs, M: Mo, Mn, V) with excellent UOR performance are synthesized.

Development of a Mixed Multinuclear Cluster Strategy in Metal-Organic Frameworks for Methane Purification and Storage.

Metal-organic frameworks (MOFs) have attracted extensive attention in methane (CH) purification and storage. Specially, multinuclear cluster-based MOFs usually have prominent performance because of large cluster size and abundant open metal sites. However, compared to diverse combinations of organic linkers, one MOF with two or more multinuclear clusters is difficult to achieve.

Pore Environmental Modification by Alkoxy Groups in Pore-Space-Partitioned Metal-Organic Frameworks to Achieve Gas Uptake-Selectivity Balance.

Due to the trade-off barrier between high storage capacity and high selectivity, the controllable and systematic design of metal-organic frameworks (MOFs) aiming at performance optimization is still challenging. Herein, considering the effectiveness of alkoxy group functionalization and a pore-space partition strategy, a series of rigid Mg-pacs-MOFs (, = ) with flexible side chains are built for the first time, realizing systematic pore environmental modification. The steric hindrance effects, electron-donating ability, and the flexibility of alkoxy groups are considered as key factors, which lead to a regular change of gas adsorption capacity and selectivity.

Radical-Bridged Heterometallic Single-Molecule Magnets Incorporating Four Lanthanoceniums.

The syntheses and magnetic properties of organometallic heterometallic compounds [K(THF) ]{Co [(μ -HAN)RE Cp* ] } (1-RE) and [K(Crypt)] {Co [(μ -HAN)RE Cp* ] } (2-RE) containing hexaazatrinaphthylene radicals (HAN⋅ ) and four rare earth (RE) ions are reported. 1-RE shows isolable species with ligand-based mixed valency as revealed by cyclic voltammetry (CV) thus leading to the isolation of 2-RE via one-electron chemical reduction. Strong electronic communication in mixed-valency supports stronger overall ferromagnetic behaviors in 2-RE than 1-RE containing Gd and Dy ions.

De-Linker-Enabled Exceptional Volumetric Acetylene Storage Capacity and Benchmark C H /C H and C H /CO Separations in Metal-Organic Frameworks.

An ideal adsorbent for separation requires optimizing both storage capacity and selectivity, but maximizing both or achieving a desired balance remain challenging. Herein, a de-linker strategy is proposed to address this issue for metal-organic frameworks (MOFs). Broadly speaking, the de-linker idea targets a class of materials that may be viewed as being intermediate between zeolites and MOFs.

High-Performance Turn-On Fluorescent Metal-Organic Framework for Detecting Trace Water in Organic Solvents Based on the Excited-State Intramolecular Proton Transfer Mechanism.

Simple, fast, and sensitive detection of trace water in organic solvents is an urgent requirement for chemical industries. Herein, combining the unusual excited-state intramolecular proton transfer (ESIPT) mechanism with the effective strategy of pore space partition, for the first time, we construct a powerful fluorescent metal-organic framework (SNNU-301) probe with excellent water stability. The SNNU-301 probe shows a remarkable performance for turn-on ESIPT-based fluorescence response to water in nine common organic solvents, exhibiting wide linear ranges, low limit of detection values, and ultrafast response, especially in dimethyl sulfoxide (0-5.

Rational regulation of acetylene adsorption and separation for ultra-microporous copper-1,2,4-triazolate frameworks by halogen hydrogen bonds.

It is well known that the introduction of exposed fluorine (F) sites into metal-organic frameworks (MOFs) can effectively promote acetylene (CH) adsorption C-H⋯F hydrogen bonds. However, such super strong hydrogen bonding interactions usually lead to very high acetylene adsorption enthalpy and thus require more energy during the adsorbent regeneration process. As the same group elements, chlorine (Cl), bromine (Br) and iodine (I) also can act as hydrogen bond acceptors but with relatively weak forces.

Precise Introduction of Single Vanadium Site into Indium-Organic Framework for CO Capture and Photocatalytic Fixation.

The capture and fixation of CO under mild conditions is a cost-effective route to reduce greenhouse gases, but it is challenging because of the low conversion and selectivity issues. Metal-organic frameworks (MOFs) are promising in the fields of adsorption and catalysis because of their structural tunability and variability. However, the precise structural design of MOFs is always pursued and elusive.

Pore-Window Partitions in Metal-Organic Frameworks for Highly Efficient Reversed Ethylene/Ethane Separations.

The development of paraffin-selective adsorbents is desirable but extremely challenging because adsorbents usually prefer olefin over paraffin. Herein, a new pore-window-partition strategy is proposed for the rational design of highly efficient paraffin-preferred metal-organic framework (MOF) adsorbents. The power of this strategy is demonstrated by stepwise installations of linear bidentate N-donor linkers into a prototype MOF (SNNU-201) to produce a series of partitional MOF adsorbents (SNNU-202-204).

Micropore Regulation in Ultrastable [ScO]-Organic Frameworks for Acetylene Storage and Purification.

High storage capacity, high separation selectivity, and high structure stability are essential for an idea gas adsorbent. However, it is not easy to achieve all three at the same time, even for the promising metal-organic framework (MOF) adsorbents. We demonstrate herein that robust [ScO]-organic frameworks could be regulated by a micropore combination strategy for high-performance acetylene adsorption.

Competitive Coordination-Oriented Monodispersed Ruthenium Sites in Conductive MOF/LDH Hetero-Nanotree Catalysts for Efficient Overall Water Splitting in Alkaline Media.

Rational exploration of efficient, inexpensive, and robust electrocatalysts is critical for the efficient water splitting. Conjugated conductive metal-organic frameworks (cMOFs) with multicomponent layered double hydroxides (LDHs) to construct bifunctional heterostructure catalysts are considered as an efficient but complicated strategy. Here, the fabrication of a cMOF/LDH hetero-nanotree array catalyst (CoNiRu-NT) coupled with monodispersed ruthenium (Ru) sites via a controllable grafted-growth strategy is reported.

Amide-Functionalized Metal-Organic Frameworks Coupled with Open Fe/Sc Sites for Efficient Acetylene Purification.

Acetylene (CH) purification is of great importance for many chemical synthesis and processes. Metal-organic frameworks (MOFs) are widely used for gas adsorption and separation due to their variable structure and porosity. However, the exploitation of ideal MOF adsorbents for CH keeps a challenging task.

Enhancement of the fluorescence properties introducing the tetraphenylethylene chromophores into a novel Mn-organic framework with a rare [Mn(μ-OH)] cluster.

By employing a tetraphenylethylene (TPE)-based tetracarboxylate linker, tetrakis(4-carboxyphenyl)ethylene (HTCPE), we herein constructed a novel luminescent Mn-MOF based on a rare [Mn(μ-OH)] cluster (SQNU-55). Interestingly, the TPE-based SQNU-55 not only provides a good material for the blue LED device, but also has a better luminescent molecular thermometer for low-temperature detection.

Recent advancement in BiOI-based nanocomposites for high performance photocatalysts.

BiOI belongs to the family of bismuth oxyhalides (BiOX, X = Cl, Br, I), having a unique layered structure with an internal electrostatic field that promotes the separation and transfer of photo-generated charge carriers. Interestingly, BiOI exhibits higher thermal stability compared to its other BiOX member compounds and absorption spectrum extended to the visible region. BiOI has demonstrated applications in diverse fields such as photocatalytic degradation of various organic pollutants, marine antifouling, etc.

Cobalt phosphide nanorings towards efficient electrocatalytic nitrate reduction to ammonia.

High-quality CoP nanorings (CoP NRs) are easily achieved using a phosphorating treatment of CoOOH nanorings, and reveal high activity towards the hydrogen evolution reaction and the nitrate electrocatalytic reduction reaction due to substantial coordinately unsaturated active sites, a high surface area, and available mass transfer pathways. Consequently, the CoP NRs can achieve a faradaic efficiency of 97.1% towards NO-to-NH conversion and provide an NH yield of 30.