Deciphering the Radial Ligand Effect of Biomimetic Amino Acid toward Stable Alkaline Oxygen Evolution.

Mismatched electron and proton transport rates impede the manifestation of effective performance of the electrocatalytic oxygen evolution reaction (OER), thereby limiting its industrial applications. Inspired by the natural protein cluster in PS-II, different organic-inorganic hybrid electrocatalysts were synthesized via a hydrothermal method. -Toluidine (PT), benzoic acid (BA), and -aminobenzoic acid (PABA) were successfully intercalated into NiFe-LDH.

Imidazole-Functionalized Zn-MOFs for One-Step CH Purification from CH/CH/CH Ternary Mixture.

The discovery of new structures is very important for metal-organic framework (MOF) adsorbents and their application in gas separation, where the design of ligands and the selection of metal ions play a decisive role. Herein, we synthesized two isoreticular Zn-MOFs, UPC-250 and UPC-251, composed of imidazole-based tricarboxylic acid ligands and binuclear zinc clusters. The pore environment was regulated via modifying fluorine atoms at different positions of ligands, and one-step purification of ethylene from acetylene/ethylene/ethane ternary mixture was realized in UPC-251.

Preprocessed Monomer Interfacial Polymerization for Scalable Fabrication of High-Valent Cluster-Based Metal-Organic Framework Membranes.

Current research on emergent membrane materials with ordered and stable nanoporous structures often overlooks the vital facet of manufacturing scalability. We propose the preprocessed monomer interfacial polymerization (PMIP) strategy for the scalable fabrication of high-valent cluster-based metal-organic framework (MOF) membranes with robust structures. Using a roll-to-roll device on commercial polymer supports, Zr-fum-MOF membranes are continuously processed at room temperature through the PMIP approach.

Two amino-functionalized metal-organic frameworks with different topologies for CH/CH separation.

The rational design of metal-organic framework adsorbents is crucial for target gas separation. Herein, we report two three-dimensional MOFs with different topologies by regulating metal ions with amino-functionalized V-type ligands. Adsorption isotherms and Grand Canonical Monte Carlo simulation reveal that UPC-122 with channel-cavity structure has the potential to separate CH/CH at room temperature with a separation ratio of 2.

Functionalization of Covalent Organic Frameworks with Cyclopentadienyl Cobalt for CH/CO Separation.

Emerging covalent organic frameworks (COFs) have received great attention for their unique features, but the limited building blocks restrict their structural diversity and performance exploration. Reticular chemistry provides guidance for the structural expansion and performance regulation of COFs. Herein, we constructed two novel two-dimensional (2D) COFs functionalized with cyclopentadienyl cobalt, denoted as UPC-COF-1 and UPC-COF-2, via [4+2] imine condensation with diamine building blocks of different length.

Integrated Monomer Synthesis and Framework Assembly: Achieving Isoreticular Modulation of Hydrogen-Bonded Organic Frameworks.

Systematic construction of isoreticular hydrogen-bonded organic frameworks (HOFs) promises tailored material properties crucial for diverse applications, yet is challenging due to the weak, flexible, and non-directional nature of hydrogen bonds. Herein, we develop an "integrated monomer synthesis-framework assembly" (ISA) methodology for constructing a series of isoreticular HOFs. Unlike traditional methods where monomers are first synthesized and then assembled into HOFs, the ISA system employs dicyandiamide rigid hydrogen-bonded hexameric clusters as connecting nodes to covalently react with planarized C-symmetric cyano-precursors (C-CPs) to generate diaminotriazine (DAT) monomers, while simultaneously inducing the directional assembly into isoreticular (6,3)-net hcb topological DAT-C-HOFs.

Asymmetrical Modification of Cyclopentadienyl Cobalt in Eu-MOF for CH/CO Separation.

The development of novel adsorption materials is of significance for the efficient and low-energy purification of acetylene (CH). Emerging metal-organic framework (MOF) adsorbents demonstrate great application prospects in the field of gas adsorption and separation. Herein, we synthesized a Eu-MOF asymmetrically modified with cyclopentadienyl cobalt exhibiting two different types of cages, denoted as UPC-119.

Precise Pore Engineering of Zirconium Metal-Organic Cages for One-Step Ethylene Purification from Ternary Mixtures.

One-step purification of ethylene from ternary mixtures (CH, CH, and CH) can greatly reduce the energy consumption of the separation process, but it is extremely challenging. Herein, we use crystal engineering and reticular chemistry to introduce unsaturated bonds (ethynyl and alkyne) into ligands, and successfully design and synthesized two novel Zr-MOCs (ZrT-1-ethenyl and ZrT-1-alkyne). The introduction of carbon-carbon unsaturated bonds provides abundant adsorption sites within the framework while modulating the pore window size.

In Situ Transformation of an Amorphous Supramolecular Coating to a Hydrogen-Bonded Organic Framework Membrane to Trigger Selective Gas Permeation.

We introduce a "solution-processing-transformation" strategy, deploying solvent vapor as scaffolds, to fabricate high-quality hydrogen-bonded organic framework (HOF) membranes. This strategy can overcome the mismatch in processing conditions and crystal growth thermodynamics faced during the facile solution processing of the membrane. The procedure includes the vapor-trigged in situ transformation of dense amorphous supramolecules to crystalline HOF-16, with HOF-11 as the transient state.

Dual engineering of hetero-interfaces and architecture in MoSe/VSe@NC nanoflower for fast and stable sodium/potassium storage.

Rational structure design is significant for the selenide anodes in the sodium/potassium ion batteries (SIBs/PIBs). Herein, dual engineering of hetero-interfaces and architecture is proposed to design SIB/PIB anodes. Attributed to the coordination binding with MoO and VO, the polydopamine assembly is demonstrated as an ideal template to produce bimetallic selenide of MoSe/VSe anchoring on the in-situ N-doped carbon matrix (MoSe/VSe@NC).

Thiadiazole-Functionalized Th/Zr-UiO-66 for Efficient CH/CO Separation.

Adsorptive separation technology provides an effective approach for separating gases with similar physicochemical properties, such as the purification of acetylene (CH) from carbon dioxide (CO). The high designability and tunability of metal-organic framework (MOF) adsorbents make them ideal design platforms for this challenging separation. Herein, we employ an isoreticular functionalization strategy to fine-tune the pore environment of Zr- and Th-based UiO-66 by the immobilization of the benzothiadiazole group via bottom-up synthesis.

Solution processing of crystalline porous material based membranes for CO separation.

The carbon emission problem is a significant challenge in today's society, which has led to severe global climate issues. Membrane-based separation technology has gained considerable interest in CO separation due to its simplicity, environmental friendliness, and energy efficiency. Crystalline porous materials (CPMs), such as zeolites, metal-organic frameworks, covalent organic frameworks, hydrogen-bonded organic frameworks, and porous organic cages, hold great promise for advanced CO separation membranes because of their ordered and customizable pore structures.

1D/3D dual carbon-supported Mott-Schottky-type Co-CoP heterojunctions for pH-universal hydrogen evolution.

The rational design of low-cost, efficient, and stable heterojunction catalysts for pH-universal hydrogen evolution is attracting increasing attention towards a sustainable hydrogen economy. Herein, a sequential spatial restriction-pyrolysis route is developed to confine Mott-Schottky-type Co-CoP heterojunctions embedded in the one-dimensional (1D) carbon nanotube-modified three-dimensional (3D) N,P dual-doped carbon matrix (Co-CoP@CNT//CM). The synergistic effect between the abundant Mott-Schottky heterointerfaces and the 1D/3D dual carbon confinement system enables fully exposed active sites and facilitated charge transfer dynamics, thus triggering favorable electronic structures of Co-CoP@CNT//CM.

Bioinspired trimesic acid anchored electrocatalysts with unique static and dynamic compatibility for enhanced water oxidation.

Layered double hydroxides are promising candidates for the electrocatalytic oxygen evolution reaction. Unfortunately, their catalytic kinetics and long-term stabilities are far from satisfactory compared to those of rare metals. Here, we investigate the durability of nickel-iron layered double hydroxides and show that ablation of the lamellar structure due to metal dissolution is the cause of the decreased stability.

Engineering Double Sulfur-Vacancy in CoS@MoS Core-Shell Heterojunctions for Hydrogen Evolution in a Wide pH Range.

Heterostructured nanomaterials have arisen as electrocatalysts with great potential for hydrogen evolution reaction (HER), considering their superiority in integrating different active components but are plagued by their insufficient active site density in a wide pH range. In this report, double sulfur-vacancy-decorated CoS@MoS core-shell heterojunctions are designed, which contain a primary structure of hollow CoS nanocubes and a secondary structure of ultrathin MoS nanosheets. Taking advantage of the core-shell type heterointerfaces and double sulfur-vacancy, the CoS@MoS catalyst exhibits pH-universal HER performance, achieving the overpotentials at 10 mA cm of 190, 139, and 220 mV in 0.

An Ultrastable Bifunctional Electrocatalyst Derived from a Co-Anchored Covalent-Organic Framework for High-Efficiency ORR/OER and Rechargeable Zinc-Air Battery.

It remains a great challenge to develop alternative electrocatalysts with high stability for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Herein, a bifunctional electrocatalyst composed of hollow CoO (CoO/CoO) nanoparticles embedded in lamellar carbon nanofibers is derived from a Co-anchored covalent-organic framework. The as-fabricated electrocatalyst (CoO@NC-800) exhibits a half-wave potential () of 0.

Enhanced CO capture in partially interpenetrated MOFs: Synergistic effects from functional group, pore size, and steric-hindrance.

Excessive CO emissions have contributed to global environmental issues, driving the development of CO capture adsorbents. Among various candidates, metal-organic frameworks (MOFs) are considered the most promising due to their unique microporous structure. Herein, a series of partially interpenetrated MOFs named UPC-XX were built to investigate the continuous enhancement in CO capture performance via synergistic effects from functional group, pore size, and steric-hindrance using theoretical calculations.

Guest-Stimulated Nonplanar Porphyrins in Flexible Metal-Organic Frameworks.

Nonplanar porphyrins with out-of-plane distortions play crucial roles in many biological functions and chemical applications. The artificial construction of nonplanar porphyrins usually involves organic synthesis and modification, which is a highly comprehensive approach. However, incorporating porphyrins into guest-stimulated flexible systems allows to manipulate the porphyrin distortion through simple ad/desorption of guest molecules.

Ortho Effects of Tricarboxylate Linkers in Regulating Topologies of Rare-Earth Metal-Organic Frameworks.

A linker design strategy is developed to attain novel polynuclear rare-earth (RE) metal-organic frameworks (MOFs) with unprecedented topologies. We uncover the critical role of ortho-functionalized tricarboxylate ligands in directing the construction of highly connected RE MOFs. The acidity and conformation of the tricarboxylate linkers were altered by substituting with diverse functional groups at the ortho position of the carboxyl groups.

Confined Assembly of Hydrated Vanadium Oxide into Hollow Mesoporous Carbon Nanospheres for Fast and Stable K Storage Capability.

The rational structural design of the electrode materials is significant to enhance the electrochemical performance for potassium ion storage, benefiting from the shortened ion diffusion distance, increased conductivity, and pseudo-capacitance promotion. Herein, hydrated vanadium oxide (HVO) nanosheets with enriched oxygen defects are well confined into hollow mesoporous carbon spheres (HMCS), producing O -VOH@C nanospheres through one-step hydrothermal reaction. Attributed to the restricted growth in the HMCS, the HVO nanosheets are loosely packed, generating abundant interfacial boundaries and large specific areas.

Metal-Organic Assembly Strategy for the Synthesis of Layered Metal Chalcogenide Anodes for Na /K -Ion Batteries.

Layered transition metal chalcogenides (MX, M=Mo, W, Sn, V; X=S, Se, Te) have large ion transport channels and high specific capacity, making them promising for large-sized Na /K energy-storage technologies. Nevertheless, slow reaction kinetics and huge volume expansion will induce an undesirable electrochemical performance. Numerous efforts have been devoted to designing MX anodes and enhancing their electrochemical performance.

Fe-MOF with U-Shaped Channels for CH/CO and CH/CH Separation.

The development of high-performance adsorbents is critical for the low-energy separation of acetylene. Herein, we synthesized an Fe-MOF (MOF, metal-organic framework) with U-shaped channels. The adsorption isotherms of CH, CH, and CO show that the adsorption capacity of acetylene is significantly larger than that of the other two gases.

Rare-earth squarate frameworks with topology.

As a typical planar 4-connected ligand that possesses symmetry, the squarate ligand is expected to construct some interesting topologies. Here, we report that the assembly of the squarate ligand with rare-earth ions can produce a series of (4, 8)-connected frameworks with the "smallest" type topology. Among these compounds, the Tb based analogue not only possesses a good proton conductivity, but also exhibits luminescence responses toward MnO and CrO, making it a candidate for multifunctional materials.

Recent advances in metal-organic frameworks for gas adsorption/separation.

The unique structural advantage of metal-organic frameworks (MOFs) determines the great prospect and developability in gas adsorption and separation. Both ligand design and microporous engineering based on crystal structure are significant lever for coping with new application exploration and requirements. Focusing on the designable pore and modifiable frameworks of MOFs, this review discussed the recent advances in the field of gas adsorption and separation, and analyzed the host-guest interaction, structure-performance relations, and the adsorption/separation mechanism from ligand design, skeleton optimization, metal node regulation, and active sites construction.

Self-Assembly of Metal-Organic Frameworks on Graphene Oxide Nanosheets and In Situ Conversion into a Nickel Hydroxide/Graphene Oxide Battery-Type Electrode.

Graphene oxide (GO) has been widely reported as a supercapacitor electrode. Especially, GO is usually utilized to composite with electrochemical active materials, such as transition-metal oxide/hydroxide/sulfide, due to its considerable conductivity and mechanical strength. However, the ideal design and treatment for compositing GO with active materials are still challenging.