Stable Microporous Metal-Organic Framework Based on Tritopic Pyrazolate Ligand for Xe/Kr Separation.

Pyrazolate ligands, renowned for their potent electron-donating capabilities, have emerged as promising building blocks for the construction of stable metal-organic frameworks (MOFs) particularly when paired with late transition metals. While a plethora of diverse MOFs have been meticulously crafted using ditopic pyrazolate ligands, the realm of multidentate pyrazolate-based MOF structures remains relatively unexplored. This research unveils a notable achievement in the synthesis of a novel three-dimensional microporous MOF, characterized by its single-crystal form, meticulously assembled from a tritopic pyrazole ligand and cobalt ions.

Engineering the Local Atomic Environments of Te-Modulated Fe Single-Atom Catalysts for High-Efficiency O Reduction.

Atomically dispersed metal-nitrogen-carbon materials (AD-MNCs) are considered the most promising non-precious catalysts for the oxygen reduction reaction (ORR), but it remains a major challenge for simultaneously achieving high intrinsic activity, fast mass transport, and effective utilization of the active sites within a single catalyst. Here, an AD-MNCs consisting of defect-rich Fe-N sites dispersed with axially coordinated Te atoms on porous carbon frameworks (FeTe-900) is designed. The local charge densities and energy band structures of the neighboring Fe and Te atoms in FeN-Te are rearranged to facilitate the catalytic conversion of the O-intermediates.

Enhancing Near-Infrared Photothermal Performance by Molecular Aggregation Optimization in Semiconductive Coordination Polymers.

Near-infrared (NIR) photothermal conversion materials have recently received widespread attention due to their potential in diverse applications. However, highly efficient organic-based NIR photothermal agents remain limited. Developing strategies to enhance the efficiency of NIR photothermal materials and elucidating the relationship between the NIR photothermal performance and molecular aggregation are highly desired.

One ligand, two roles: novel pillar-layered metal-organic frameworks built with a 3D ligand and asymmetric inorganic nodes.

Herein, we show two cases of pillar-layered MOFs which are built solely with one kind of three-dimensional (3D) ditopic ligand. The ligand in both structures functions not only as an intralayer linker in the layer but also as a "pillar" between adjacent layers. Such multi-functionality of the linker is accompanied by uncommon asymmetric 10- metal hexamer or 7- tetramer nodes, which have never been reported in previous 3D MOF structures.

Construction of Pd-Te Intermetallic Compounds to Achieve Ultrastable Oxygen Reduction Activity.

Palladium (Pd)-transition metal alloys have the potential to regulate the intermediate surface adsorption strength in oxygen reduction reactions (ORR), making them a promising substitute for platinum-based catalysts. Nonetheless, prolonged electrochemical cycling can lead to the depletion of transition metals, resulting in structural degradation and poor durability. Herein, the synthesis of alloy catalysts (PdTe) containing Pd and the metalloid tellurium (Te) through a one-step reduction method is reported.

Phenanthroline-Mediated Photoelectrical Enhancement in Calix[4]arene-Functionalized Titanium-Oxo Clusters.

Incorporating two organic ligands with different functionalities into a titanium-oxo cluster entity simultaneously can endow the material with their respective properties and provide synergistic performance enhancement, which is of great significance for enriching the structure and properties of titanium-oxo clusters (TOCs). However, the synthesis of such TOCs is highly challenging. In this work, we successfully synthesized a TBC4A-functionalized TOC, [Ti(TBC4A)(MeO)] (; MeOH = methanol, TBC4A = tert-butylcalix[4]arene).

Tuning Na-Ion Diffusion in MXene/Graphene Oxide Heterostructures: An Ab Initio Molecular Dynamics Study.

The development of heterostructured anode materials provides an effective approach for enhancing the electrochemical performance of sodium-ion batteries (SIBs). In this work, ab initio molecular dynamics simulations and first-principles calculations are employed to investigate the Na-ion intercalation and diffusion in MXene/graphene oxide heterostructures. The influence of graphene oxidation on interlayer spacing, Na-ion diffusion kinetics, and transport mechanisms is examined at an atomic scale.

Highly bifunctional RhP on N,P-codoped carbon for hydrazine oxidation assisted energy-saving hydrogen production.

Highly pure RhP nanoparticles on N,P-codoped carbon were synthesized by a simple "mix-and-pyrolyze" method using one kind of low-cost nucleotide as the carbon, nitrogen and phosphorus source, which exhibits excellent bifunctional activity for the hydrogen reduction and hydrazine oxidation reactions, achieving energy-efficient hydrogen production.

Accurate assembly of thiophene-bridged titanium-oxo clusters with photocatalytic amine oxidation activity.

Designing and synthesizing well-defined crystalline catalysts for the photocatalytic oxidative coupling of amines to imines remains a great challenge. In this work, a crystalline dumbbell-shaped titanium oxo cluster, [TiO(Thdc)(Dmg)(PrO)] (Ti10, Thdc = 2,5-thiophenedicarboxylic acid, Dmg = dimethylglyoxime, PrOH = isopropanol), was constructed through a facile one-pot solvothermal strategy and treated as a catalyst for the photocatalytic oxidative coupling of amines. In this structure, Thdc serves as the horizontal bar, while the {TiDmg} layers on each side act as the weight plates.

All-catecholate-stabilized black titanium-oxo clusters for efficient photothermal conversion.

The controlled synthesis of titanium-oxo clusters (TOCs) completely stabilized by organic dye ligands with high stability and superior light absorption remains a significant challenge. In this study, we report the syntheses of three atomically precise catechol (Cat)-functionalized TOCs, [Ti(Cat)(OEgO)(OEgOH)] (Ti2), [TiO(Cat)(PrO)(PrOH)] (Ti8), and [TiO(OH)(Cat)]·HO·PhMe (Ti16), using a solvent-induced strategy (HOEgOH = ethylene glycol; PrOH = isopropanol; PhMe = toluene). Interestingly, the TiO core of Ti16 is almost entirely enveloped by catechol ligands, making it the first all-catechol-protected high-nuclearity TOC.

Morphology Regulation of Zeolite MWW via Classical/Nonclassical Crystallization Pathways.

The morphology and porosity of zeolites have an important effect on adsorption and catalytic performance. In the work, simple inorganic salts, i.e.

Interfacial oxygen atom modification of a PdSn alloy to boost oxygen reduction in zinc-air batteries.

Modifying the surface of a catalyst with heteroatoms can regulate the interfacial atomic valence state and adjust the charge distribution, which is promising for obtaining desirable platinum carbon catalyst (Pt/C)-matched oxygen reduction reaction (ORR) catalytic performance. Here, we developed an efficient method to access O-rich crystalline interfacial-exposed palladium-tin alloy (111) crystal surfaces [PdSn (111)] for highly efficient ORR via direct reduction of Pd/Sn metal salt species that are well dispersed in a nitrogen, phosphorus-doped carbonaceous (NPC) substrate. In addition to the other materials, preembedded Pd/Sn metal salt species in NPC control the release of metal sources upon reduction in the liquid phase, resulting in the grafting of an as-prepared PdSn alloy with many merits, such as efficient electron conduction, short-range crystallinity and increased crystal interface exposure.

Pillaring Behavior of Organic Molecules on MXene: Insights from Molecular Dynamics Simulations.

Pillaring MXene with organic molecules is an effective approach to expand the interlayer spacing and increase the accessible surface area for enhanced performance in energy storage applications. Herein, molecular dynamics simulations are employed to explore the pillaring effect of six organic molecules on TiCO. The interlayer spacing and structural characteristics of MXene after the insertion of different organic molecules are examined, and the influence of the type and quantity of organic molecules on the pillared MXene structure is systematically investigated.

Multifunctional Crystalline Coordination Polymers Constructed from 4,4'-Bipyridine-,'-dioxide: Photochromism, White-Light Emission, and Photomagnetism.

Multifunctional photochromic coordination polymers (CPs) have shown great potential in many areas, like molecular switches, anticounterfeiting, magnetics, and optoelectronics. Although multifunctional photochromic CPs can be obtained by introducing photoresponsive functional units or by exploiting the synergy effect of each component, relatively limited photochromic ligands hinder the development of various multifunctional photochromic CPs. In this work, we reported two multifunctional coordination polymers {[Zn(bpdo)(fum)(HO)]} () and {[Mn(bpdo)(fum)(HO)]} () based on an easily accessible but underestimated photoactive molecule 4,4'-bipyridine-'-dioxide ().

Highly enhanced hydrazine oxidation on bifunctional Ni tailored by alloying for energy-efficient hydrogen production.

The low-potential hydrazine oxidation reaction (HzOR) can replace the oxygen evolution reaction (OER) and thus assemble with the hydrogen evolution reaction (HER), consequently achieving energy-saving hydrogen (H) production. Notably, developing sophisticated bifunctional electrocatalysts for HER and HzOR is a prerequisite for efficient H production. Alloying noble metals with eligible non-precious ones can increase affordability, catalytic activity, and stability, alongside rendering bifunctionality.

Synthesis and Crystal Structure of a New RTH-Type Precursor and Its Interlayer Expanded Zeolite.

Two dimensional zeolites have drawn a lot of attention due to their structural diversity and chemical composition, which can be used to obtain 3D zeolites, for which there is no direct synthesis. Here, a new layer silicate zeolite L was synthesized using the N, N-dimethyl-(2-methyl)-benzimidazolium as the organic structure-directing agent (OSDA) in the presence of fluoride. Structure determination by single-crystal X-ray diffraction reveals that the pure silica precursor with five-ring pores in the crystalline sheets is composed of the rth layer stacking along the (001) direction in an …AAAA… sequence with SDA cations and F residing within the interlayer spaces.

Understanding the tunable sodium storage performance in pillared MXenes: a first-principles study.

Pillared MXenes with large interlayer spacing have shown great potential as an anode material for sodium-ion batteries (SIBs). To better understand the underlying mechanism of the pillar effect in enhancing the electrochemical performance, first-principles calculations were used to investigate the adsorption and diffusion of Na in MXenes (TiCO and TiCO), as well as the mechanical properties of the system under different MXenes layer spacings. The results showed that when the MXene layer spacing was ∼4 Å, the strongest adsorption of Na on MXenes was achieved due to the interlayer synergy effect.

New crystalline 1D/2D/3D indium selenides directed by piperidine and auxiliary solvents.

The construction of cluster-based crystalline chalcogenide structures through the traditional solvothermal method relies on synergistic control of precursors, template cations and auxiliary solvents. Generally, the combination of metal precursors plays a crucial role in controlling the size of clusters, while organic templates and auxiliary solvents usually contribute to the type of clusters and architecture of the framework. Decades of synthetic efforts have been mainly devoted to expanding organic amine templates for constructing new structures.

Ir nanoclusters/porous N-doped carbon as a bifunctional electrocatalyst for hydrogen evolution and hydrazine oxidation reactions.

One common iridium(III) complex was employed to facilely prepare ultrafine Ir nanoclusters embedded in porous N-doped carbon, which displayed significant bifunctional activity for both hydrogen evolution and hydrazine oxidation under alkaline conditions, enabling energy-efficient hydrogen production.

Porogen-in-Resin-Induced Fe, N-Doped Interconnected Porous Carbon Sheets as Cathode Catalysts for Proton Exchange Membrane Fuel Cells.

The high dependence of cathodic oxygen reduction reaction on precious Pt catalysts hinders the large-scale commercialization of proton exchange membrane (PEM) fuel cells, while the most promising alternative FeNC catalyst cannot achieve satisfying fuel cell performance yet. By considering the different requirements of atomically dispersed FeNC catalyst on the mass-transfer structure from that of nanoparticle Pt-based catalysts, this work develops a "porogen-in-resin" strategy to approach the Fe, N-doped interconnected porous carbon sheet (ip-FeNCS) catalyst. Three-dimensional (3D) interconnected porous structure and two-dimensional (2D) nanosheet morphology are therefore facilely combined in ip-FeNCS to simultaneously achieve the requirements on the transfer of reactants and accessibility of FeN active sites.

The template synthesis of ultrathin metallic Ir nanosheets as a robust electrocatalyst for acidic water splitting.

Ultrathin metallic iridium nanosheets (∼4 nm) were synthesized using MIL-88A as the sacrificing template at room temperature. Ir-NS shows superior and stable water splitting performance in an acidic medium.

Natural DNA-assisted RuP on highly graphitic N,P-codoped carbon for pH-wide hydrogen evolution.

Natural DNA was employed for the first time as a phosphorization agent and carbon source to controllably synthesize a RuP/N,P-codoped carbon composite by a simple "mix-and-pyrolyze" strategy, which displays higher activity for alkaline and acidic HER and neutral activity compared to Pt/C together with outstanding durability.

Electronically interacted CoO/WS as superior oxygen electrode for rechargeable zinc-air batteries.

The electronically interacted Co3O4/WS2 with a maximum power density of 174 mW cm-2, 2.3 fold better than Pt/C-IrO2, shows its superiority as an oxygen electrode for rechargeable zinc-air batteries.

Electrospinning Synthesis of Carbon-Supported PtMn Intermetallic Nanocrystals and Electrocatalytic Performance towards Oxygen Reduction Reaction.

To realize the large-scale application of fuel cells, it is still a great challenge to improve the performance and reduce the cost of cathode catalysts towards oxygen reduction reaction (ORR). In this work, carbon-supported ordered PtMn intermetallic catalysts were prepared by thermal annealing electrospun polyacrylonitrile nanofibers containing Platinum(II) acetylacetonate/ Manganese(III) acetylacetonate. Compared with its counterparts, the ordered PtMn intermetallic obtained at 950 °C exhibits a more positive half-potential and higher kinetic current density during the ORR process.

New insights into O and OH adsorption on the Pt-Co alloy surface: effects of Pt/Co ratios and structures.

In this study, the electronic structure and adsorption properties of O and OH for a series of Pt-Co alloys with different Pt/Co ratios (5 : 1, 2 : 1, 1 : 1, 1 : 2, and 1 : 5) were systematically studied using density functional theory calculations. Our computational results demonstrated that the introduced Co atoms have multiple effects on the surface electronic structure in different atomic layers of the alloy, leading to the discrepancies in the electronic structure between Pt-skin structures and non-Pt-skin structures. Moreover, the influence of the surface electronic structure on the adsorption of O and OH slightly differs.