结构化学最新文献

The escalating emissions of greenhouse gases into atmosphere have precipitated a host of ecology and environmental concerns. Electrochemical reduction of CO₂ (CO₂RR) is emerging as a sustainable solution for effectively addressing these issues. Leveraging the cost-effectiveness and eco-friendly attributes, Bi-based catalysts have been extensively studied with the purpose of enhancing activity and stability. This minireview majorly overviews the research advancements in Bi-based catalysts for CO₂ electrocatalysis towards formic acid/formate production. Initially, we offer a concise overview of the reaction pathways involved in electrochemical CO₂ reduction. Subsequently, we summarize the progress in various types of electrolysis cells and associated influencing factors. Specifically, the electronic structure modulation strategies of Bi-based catalysts including oxide-derived bismuth, bismuth-based chalcogenides, bimetallic and high-entropy compounds, etc. have been highlighted. Future research endeavors are poised to delve deeper into comprehending system dynamics during the reaction process to achieve exemplary stability high energy efficiency under industrial conditions.

As an emerging class of inorganic hybrid materials, salt-inclusion chalcogenides (SICs) have garnered significant attention in the past decade owing to their distinct host-guest structural characteristics and outstanding performance in the field of optoelectronics. In this study, a novel quaternary SIC [Cs₁₄Cl][Tm₇₁Se₁₁₀] has been discovered using an appropriate flux method. The structure comprises two distinct parts within the lattice: the host [Tm₇₁Se₁₁₀]¹³⁻ framework and the guest [Cs₁₄Cl]¹³⁺ polycation. Notably, this structure reveals the presence of mixed-valent Tm²⁺/Tm³⁺ and different types of closed cavities for the first time. Additionally, thermal transport performance testing shows that it has ultralow thermal conductivity, ranging from 0.29 to 0.24 W/m⋅K within the temperature range of 323–673 K, which is one of the lowest reported values among polycrystalline chalcogenides. This research not only advances the coordination chemistry of rare-earth-based compounds but also reaffirms that SIC semiconductors are promising systems for achieving ultralow thermal conductivity.

Low-dimensional hybrid lead halides with responsive emissions have attracted considerable attention due to their potential applications in sensing. Herein, a new one-dimensional hybrid lead bromide CyPbBr₃ (Cy = cytosine cation) was synthesized to explore its emission evolution in response to temperature and pressure. The compound possesses an edge-sharing 1D double-chain structure and emits warm white light across nearly the entire visible spectrum upon ultraviolet excitation. This emission arises from the self-trapped excitons and its broadband feature is attributed to the strong electron-phonon coupling as revealed by the variable-temperature photoluminescence experiments. Moreover, a 4.5-fold pressure-induced emission enhancement was observed at 2.7 GPa which is caused by the pressure suppressed non-radiative energy loss. Furthermore, in-situ powder X-ray diffraction and Raman experiments reveal the maxima of the emission enhancement is associated with a phase transition at the same pressure. Our work demonstrates that low-dimensional metal halides are a promising class of stimuli-responsive materials which could have potential applications in temperature and pressure sensing.

The identical molecular size and similar physical properties of carbon dioxide (CO₂) and acetylene (C₂H₂) make their adsorptive separation extremely challenging to achieve with most adsorbents. Reports on the separation of CO₂ and C₂H₂ mixtures by zeolites are even rarer with the mechanism of adsorptive separation requiring further exploration. In this paper, we report that ion modulation of zeolite 5A promotes the difference in kinetic diffusion of CO₂ and C₂H₂, realizing the inverse separation of zeolite from selective adsorption of C₂H₂ to selective adsorption of CO₂. Creating a compact pore space restricting the orientation of gas molecules enables charge recognition. The positive electrostatic potential at the pore openings was utilized to hinder the diffusion of C₂H₂ between the cages while ensuring the transfer of CO₂, increasing their diffusion differences in pore channels and leading to the CO₂/C₂H₂ kinetic selectivity of 31.97. Grand canonical Monte Carlo (GCMC) simulation demonstrates that the CO₂ distribution in K-5A-β is significantly higher than that of C₂H₂. Dynamic breakthrough experiments verify the excellent performance of material in practical CO₂/C₂H₂ separation, for CO₂/C₂H₂ (50/50 and 1/99, V/V) mixtures can be separated in one step, thus directly generating high purity C₂H₂ (> 99.95%), which provides a promising thought for the zeolite-based separation of CO₂ and C₂H₂.

Thermo-responsive microcrystals exhibiting obvious emission intensity or color changes have great potentials in sensing, information encryption, and microelectronics. We report herein the binary assembly of a blue-emissive iridium complex and a red-emissive ruthenium complex into homogeneously-doped or optically-heterostructured microcrystals with thermo-responsive properties. Depending on the assembly conditions, lateral or longitudinal triblock heterostructures with a microplate shape are obtained, which display distinct emission pattern changes upon heating as a result of the decreased efficiency of energy transfer. In addition, branched heterostructures are prepared by a stepwise assembly. The luminescence polarization of the homogeneously-doped binary crystals and the waveguiding property of the longitudinal triblock heterostructure are further examined. This work evidences the versatility of transition metal complexes in the assembly into various luminescent nano/micro structures with potential applications in thermo-sensing and nanophotonics.

Interface is a necessary channel of carrier permeation in sulfide-based all-solid-state lithium battery (ASSLB). Homogeneous and fast lithium-ion (Li⁺) interfacial transport of cathode is the overriding premise for high capability of ASSLBs. However, the inherent transport heterogeneity of crystalline materials in cathode and the cathode active material (CAM)/sulfide solid electrolyte (SSE) interfacial issues result in high interfacial impedance, decreasing the Li⁺ transfer kinetics. In this review, we outline the Li⁺ transport properties of CAMs and SSEs, followed by a discussion of their interfacial electro-chemo-mechanical issues. Commentary is also provided on the solutions to the multiple-scale interfacial Li⁺ transport failure. Furthermore, the underlying interdependent mechanisms between electrodes are summarized and overviewed. Finally, we suggest future paths to better comprehend and promote the interfacial Li⁺ transport in ASSLBs. This review provides an in-depth understanding of cathodal interfacial issues and the proposed improvement strategies will provide guidance for further advancement of high-performance ASSLBs.