Main Group Analogs of Dichalcogeniranes

Main Group Analogs of Dichalcogeniranes

The Front Cover shows main group dichalcogeniranes bearing three-membered rings composed of one main group atom and two group 16 atoms. Such three-membered-ring compounds appear to be unstable because of their highly strained structures and the electronic repulsion between the lone-pair electrons of two group 16 atoms incorporated into the rigid structures. However, very recently, stable compounds were characterized by X-ray diffraction analysis on many occasions, revealing unique molecular structures with very long chalcogen−chalcogen single-bonds in some cases. Accordingly, it is time to highlight recent advances in the preparation and reactivity of main group analogs of dichalcogeniranes. More information can be found in the Review by M. Saito and co-workers.


Synthesis and Oxygen Evolution Reaction Application of a Co−Cd Based Bimetallic Metal‐Organic Framework

Synthesis and Oxygen Evolution Reaction Application of a Co−Cd Based Bimetallic Metal-Organic Framework

This research focuses on synthesizing a novel bimetallic metal-organic framework with a distinctive structure with distorted octahedral chains of CoO and CdO, linked by benzene tricarboxylic acid (BTC). Electrochemical testing revealed that bimetallic MOF/NF begins water oxidation at an onset potential of 1.62 V versus RHE, demonstrating high activity with a lower overpotential.


Abstract

In the realm of renewable energy technologies, the development of efficient and durable electrocatalysts is paramount, especially for applications like electrochemical water splitting. This research focuses on synthesizing a novel bimetallic metal-organic framework (BMMOF11) using earth-abundant elements, cobalt (Co) and cadmium (Cd). BMMOF11 showcases a distinctive structure with distorted octahedral chains of CoO and CdO, linked by benzene tricarboxylic acid (BTC). Our study primarily investigates the electrocatalytic efficiency of BMMOF11, particularly in water oxidation reactions. For practical analysis, BMMOF11 was anchored onto nickel foam, forming BMMOF11/NF, to evaluate its electrocatalytic properties. Electrochemical testing revealed that BMMOF11/NF begins water oxidation at an onset potential of 1.62 V versus RHE, demonstrating high activity with a lower overpotential of 0.4 V to achieve a current density of 10 mA/cm2. Moreover, BMMOF11/NF maintained stable water splitting performance, sustaining a current density of approximately 70 mA/cm2 under a voltage of 1.9 V relative to RHE. These findings indicate that BMMOF11/NF is a promising candidate for large-scale electrochemical water splitting, offering a blend of high activity and stability.

Highly Ordered Hierarchical Macro–Mesoporous Carbon‐Supported Cobalt Electrocatalyst for Efficient Oxygen Evolution Reaction

Highly Ordered Hierarchical Macro–Mesoporous Carbon-Supported Cobalt Electrocatalyst for Efficient Oxygen Evolution Reaction

Drawing inspiration from hierarchical structures allowing for the transport and exchange of substances in the biological world, a three-dimensional ordered layered porous nitrogen-doped carbon-coated magnetic cobalt catalyst was successfully constructed and achieved outstanding OER performance. The existence of biomimetic grade pore structure can effectively reduce the mass transfer resistance, improve the material exchange efficiency, and accelerate the reaction kinetics.


Abstract

Metal-organic frameworks (MOFs) and their derivatives have been extensively employed in Oxygen Evolution Reaction (OER) catalysts due to their significantly larger specific surface areas, distinct metal centers, and well-organized porous structures. However, the microporous structure of MOFs and their derivatives presents mass transfer resistance, limiting their further development. Drawing inspiration from hierarchical structures allowing for the transport and exchange of substances in the biological world, we designed and fabricated biomimetic layered porous structures within ZIF-67 and its derivatives. Based on this, we achieved a three-dimensional ordered layered porous nitrogen-doped carbon-coated magnetic cobalt catalyst (3DOLP Co@NDC) with a biomimetic pore structure. It is found that the 3DOLP Co@NDC (352 mV @10 mA cm−1) was better than Co@NDC (391 mV @10 mA cm−1). The introduction of a three-dimensional ordered layered porous structure is conducive to increasing the specific surface area of the material, increasing the electrochemical active area, and improving the catalytic performance of the material. The introduction of a three-dimensional ordered layered porous structure would help to build a bionic grade pore structure. The existence of biomimetic grade pore structure can effectively reduce the mass transfer resistance, improve the material exchange efficiency, and accelerate the reaction kinetics.

Alkoxylated Fluoranthene‐Fused [3.3.3]Propellanes: Facile Film Formation against High π‐Core Content

Alkoxylated Fluoranthene-Fused [3.3.3]Propellanes: Facile Film Formation against High π-Core Content

Structural, thermal, and optical properties reveal that amorphous assembling is easily attained in a series of fluoranthene-fused [3.3.3]propellanes with a rigid 3D skeleton bearing n-butoxy or longer alkoxy groups. Drop-cast films can be obtained despite the high D 3h molecular symmetry and high ratios of π-core atoms to peripheral rotatable ones.


Abstract

Solid-state assembling modes are as crucial as the chemical structures of single molecules for real applications. In this work, solid-state structures and phase-transition temperatures are investigated for a series of fluoranthene-fused [3.3.3]propellanes consisting of a rigid three-dimensional (3D) π-core and varying lengths of alkoxy groups. Compounds in this series with n-butoxy or longer alkoxy groups take an amorphous state at room temperature. In these molecules, rotatable biaryl-type bonds are not incorporated and high D 3h molecular symmetry is retained. Therefore, π-fused [3.3.3]propellanes present a unique platform for amorphous molecular materials with low ratios of flexible alkoxy atoms to rigid π-core ones.

Hard Carbon Derived From Different Precursors for Sodium Storage

Due to the almost unlimited resource and acceptable performance, Sodium-ion batteries (SIBs) have been regarded as a promising alternatives for lithium-ion batteries for grid-scale energy storage. As the key material of SIBs, hard carbon (HC) plays a decisive role in determining the batteries’ performance. Nevertheless, the micro-structure of HCs is quite complex and the random organization of turbostratically stacked graphene layers, closed pores, and defects makes the structure-performance relationship insufficiently revealed. On the other hand, the impending large-scale deployment of SIBs leads to producing HCs with low-cost and abundant precursors actively pursued. In this work, the recent progress of preparing HCs from different precursors including biomass, polymers, and fossil fuels is summarized with close attention to the influences of precursors on the structural evolution of HCs. After a brief introduction of the structural features of HCs, the recent understanding of the structure-performance relationship of HCs for sodium storage is summarized. Then, the main focus is concentrated on the progress of producing HCs from distinct precursors. After that, the pros and cons of HCs derived from different precursors are comprehensively compared to conclude the selection rules of precursors. Finally, the further directions of HCs are deeply discussed to end this review.

Iridium Nanoparticles as Highly Effective Peroxidase Mimics: Synthesis, Characterization, and Application in Biosensing

Peroxidase mimics made of inorganic nanomaterials as alternatives to natural peroxidases have been extensively developed over the past few decades, owing to their superior properties relative to their natural counterparts. Nevertheless, it has been still a challenge to substantially enhance the catalytic efficiency of peroxidase mimics. In this work, we report a type of highly efficient peroxidase mimics that are made of iridium nanoparticles (Ir NPs) with rough surfaces. The Ir NPs possess an ultrahigh catalytic efficiency with a catalytic constant (Kcat) at the regime of 1010 s-1, orders of magnitude higher than the Kcat of horseradish peroxidase as a natural peroxidase. As a proof-of-concept demonstration, the Ir NPs were applied to colorimetric lateral flow assay (CLFA). Using carcinoembryonic antigen as a model disease biomarker, the Ir NPs-based CLFA achieved a low limit of detection (LoD) of 39 pg/mL, which was ~28 times lower than the LoD of conventional gold nanoparticles-based CLFA using the same antibodies.

The Impact of the Ratio Between Stronger and Weaker Acid Sites on the Production of 5‐Hydroxymethylfurfural and Furfural from Monosaccharides

Sulfonated carbons and commercial Amberlyst 15 and 45 served as model catalysts to explore the impact of the ratio between stronger and weaker acid sites (NS/NW) on 5-hydroxymethylfurfural (HMF) and furfural production from fructose and xylose. Catalysts with varying structural and surface properties, and consequently different NS/NW ratios, were prepared from diverse templated mesoporous carbons and distinct sulfonation methods. HMF or furfural yields exhibited an exponential correlation with the NS/NW ratio. However, the catalytic activity per site (TON) displayed a volcano-like plot, reaching a maximum between NS/NW = 2 – 4. Consequently, our findings suggest the involvement of both strong (sulfonic acid) and weak acid (surface carboxylic acid, alcohol, and phenol groups) sites in monosaccharide dehydration mechanisms. These insights may guide the development of novel catalysts.

Two energetic framework materials based on DNM‐TNBI as host molecule: Effectively coordinated by different cations

With the demand to develop outstanding-performance energetic materials, 1-(dinitromethyl)-4,4',5,5'-tetranitro-1H,1'H-2,2'-biimidazole (DNM-TNBI) emerged as a great contender (D: 9102 m·s-1; P: 37.6 GPa). However, the relatively poor thermal stability (Td: 142 ℃) limits its practical application. In this study, DNM-TNBI as a host molecule to synthesize two new energetic open-framework materials by effectively coordinated with different cations. Their supramolecular structures were investigated and indicated that [DNM-TNBI2-][2NH4+] and [DNM-TNBI2-][2K+] can be classified as a new energetic hydrogen-bonded ammonium framework (EHAF) and an energetic metal organic framework (EMOF). Meanwhile, their thermal stabilities are higher than that of DNM-TNBI and have satisfactory detonation performance ([DNM-TNBI2-][2NH4+], D: 8050 m·s-1, P: 26.4 GPa; [DNM-TNBI2-][2K+], D: 8301 m·s-1, P: 30.8 GPa).