Layered Metal Hydroxides and Their Derivatives: Controllable Synthesis,Chemical Exfoliation,and Electrocatalytic Applications

Layered metal hydroxides (LMHs) are regarded as a novel and important class of inorganic functional materials. They have unique layered structure and variable chemical compositions that can be readily tuned. In this review, summarized are the recent advances of synthetic routes to the LMHs with designed morphology, composition, and function for electrocatalysis. Versatile products can be readily derived by hybridization, anion‐exchange, surface modification, self‐assembly, etc. More importantly, LMHs can be artificially exfoliated into unilamellar nanosheets with a molecular‐level thickness of about 1 nm versus 2D lateral size in submicrometer or micrometer scale. Molecular‐scale assembly can be then applied to fabricate superlattice‐like composites and functional nanofilms with high quality. The hydroxides can be transformed into oxides, nitrides, or other compounds via different preparation procedures, which can further extend their application prospects. In this regard, the most promising electrocatalysis‐related applications of LMHs and their derivatives are reviewed, such as oxygen evolution reaction, oxygen reduction reaction, hydrogen evolution reaction, CO₂ reduction reaction, alcohol or urea electrooxidation, etc. At last, future challenges are also discussed from the aspect of synthesis and application, as well as encouraging advancements are anticipated.     

A Chemical Approach to Raise Cell Voltage and Suppress Phase Transition in O3 Sodium Layered Oxide Electrodes

Sodium ion batteries (NIBs) are one of the versatile technologies for low‐cost rechargeable batteries. O3‐type layered sodium transition metal oxides (NaMO₂, M = transition metal ions) are one of the most promising positive electrode materials considering their capacity. However, the use of O3 phases is limited due to their low redox voltage and associated multiple phase transitions which are detrimental for long cycling. Herein, a simple strategy is proposed to successfully combat these issues. It consists of the introduction of a larger, nontransition metal ion Sn⁴⁺ in NaMO₂ to prepare a series of NaNi_0.5Mn_{0.5? y} Sn _y O₂ (y = 0–0.5) compositions with attractive electrochemical performances, namely for y = 0.5, which shows a single‐phase transition from O3 ? P3 at the very end of the oxidation process. Na‐ion NaNi_0.5Sn_0.5O₂/C coin cells are shown to deliver an average cell voltage of 3.1 V with an excellent capacity retention as compared to an average stepwise voltage of ≈2.8 V and limited capacity retention for the pure NaNi_0.5Mn_0.5O₂ phase_. This study potentially shows the way to manipulate the O3 NaMO₂ for facilitating their practical use in NIBs.     

A Layered Inorganic–Organic Open Framework Material as a 4 V Positive Electrode with High‐Rate Performance for K‐Ion Batteries

K‐ion batteries (KIBs) are promising for large‐scale energy storage owing to various advantages like the high abundance of potassium resources in the Earth's crust, high operational potentials, and high power due to fast diffusion of K⁺ ions. However, to realize the practical application of KIBs, electrode materials are needed with high operational voltage, good capacity, long cycle life, and low‐cost. This work reports a layered open framework material, K₂[(VOHPO₄)₂(C₂O₄)], composited with reduced graphene oxide (rGO) as a 4 V positive electrode material for KIBs. The material is prepared by a simple precipitation reaction at room temperature. The material demonstrates reversible K‐extraction/insertion with conventional carbonate ester KPF₆ solutions; however, with low specific capacity and low Coulombic efficiency. A high discharge capacity of >100 mAh g^?1 with good cycling stability and higher Coulombic efficiency is achieved in a highly concentrated electrolyte, 7 mol kg^?1 of potassium bis(fluorosulfonyl)amide (KFSA) in dimethoxyethane (DME) at 0.1 C rate. Due to the facile migration of K⁺ ions in the framework, the material exhibits excellent rate capability with a discharge capacity of 80 mAh g^?1 at 10 C rate, and a good capacity retention of 67% after 500 cycles at 2 C rate.     

Single Ru Atoms Stabilized by Hybrid Amorphous/Crystalline FeCoNi Layered Double Hydroxide for Ultraefficient Oxygen Evolution

In view of the sluggish kinetics suppressing the oxygen evolution reaction (OER), developing efficient and robust OER catalysts is urgent and essential for developing efficient energy conversion technologies. Herein, hybrid amorphous/crystalline FeCoNi layered double hydroxide (LDH)-supported single Ru atoms (Ru SAs/AC-FeCoNi) are developed for enabling a highly efficient electrocatalytic OER. The amorphous outer layer in Ru SAs/AC-FeCoNi is composed of abundant defect sites and unsaturated coordination sites, which can serve as anchoring sites to stabilize single Ru atoms. The crystalline inner has a highly symmetric rigid structure, thereby strengthening the stability of support for a long-lasting OER. The synergistic effects endow this hybrid catalyst with extremely low overpotential (205 mV at 10 mA cm⁻²). Density functional theory calculation indicates that single Ru atoms stabilized by hybrid amorphous/crystalline FeCoNi LDH facilitate the formation of Ru–O* (rate-determining step), thus accelerating the OER process.     

Photophysical characterization of methyl viologen ion-exchanged within a zirconium phosphate framework

The photophysical properties of 1,1′-dimethyl-4,4′dipyridinium (methyl viologen, MV²⁺) intercalated within zirconium phosphate (ZrP) were investigated. The intercalation of MV²⁺ within ZrP was achieved by ion-exchange using a hydrated form of ZrP with six water molecules per formula unit and an interlayer distance of 10.3 Å. The intercalation yields a new phase with an interlayer distance up to 10.6 Å. The MV²⁺-exchanged ZrP material was characterized using elemental analysis, XRPD and IR data. The MV²⁺-exchanged ZrP materials show a red shift in the UV-Vis spectra in contrast with solution. The photoexcitation of nitrogen purged, MV²⁺-exchanged ZrP water suspensions with UV light leads to fluorescence emission with a maximum at 337 nm. The photoexcitation of MV²⁺-exchanged ZrP suspensions without nitrogen purging yields two fluorescence emissions with maxima at 337 and 450 nm. The emission in the visible region can be attributed to a photodecomposition product. The fluorescence quantum yields indicate that the emission of MV²⁺-exchanged ZrP is of the same order of magnitude as that of MV²⁺ in water indicating a strong deactivation of the excited state by non-radiative pathways.     

Probing Dopant Redistribution,Phase Propagation,and Local Chemical Changes in the Synthesis of Layered Oxide Battery Cathodes

Achieving the targeted control of layered oxide properties calls for more fundamental studies to mechanistically probe their evolution during their synthesis. Herein, dopant distribution, phase propagation, and local chemical changes as well as their interplay in multielement-doped LiNiO₂ materials are investigated using spectroscopic, imaging, and scattering techniques. It is shown that dopants undergo dynamic redistribution in the Ni(OH)₂ host lattice at the early stage of calcination (below 300 °C). Such redistribution behavior exhibits strong dopant-dependent characteristics, allowing for targeted surface and bulk doping control. The Ni oxidation process exhibits depth-dependent characteristics and the most rapid Ni oxidation takes place between 300 and 700 °C. Using Ni oxidation state as the proxy for the phase transformation, the buildup of heterogenous phase propagation in the early stage of calcination is shown, especially along the radial direction of secondary particles. The radial heterogenous phase distribution gradually decreases upon completing the calcination. However, a high degree of mosaic-like heterogeneity may still be present in the final product, departing from the perfect layered oxide. The present study offers fundamental insights into manipulating multiscale materials properties during calcination for obtaining stable, high-energy layered oxide cathodes.     

纳米材料层状双氢氧化物（LDH）对茄二十八星瓢虫dsECR致死效应的影响

纳米材料被视为重要的RNA干扰增效物质。层状双氢氧化物（LDH）是具有生物相容性的可降解纳米材料，可以显著提高dsRNA防控黄瓜花叶病毒的效果。为明确LDH能否提高昆虫RNA干扰的效果，以期促进RNA生物农药在农业害虫防治中的应用和推广，本研究选择茄二十八星瓢虫Henosepilachna vigintioctopunctata的EcR基因进行RNA干扰介导的致死效应研究。将LDH与dsEcR组装形成复合物LDH-dsEcR，利用琼脂糖凝胶电泳确定LDH-dsEcR的最佳装载比例。通过静置法检测LDH-dsEcR的稳定性，借助透射电子显微镜验证其组装状态。采用浸叶法测定LDH-dsEcR的增效性，使用体视镜观察其对试虫形态的影响。结果表明：LDH与dsEcR可形成稳定的复合物，其最佳装载比为16∶1。LDH对茄二十八星瓢虫无毒性，但经LDH与dsEcR处理，部分试虫虫体呈黑褐色，或无法蜕皮化蛹，或维持在预蛹状态。遗憾的是LDH-dsEcR复合物的增效作用不明显，推测昆虫肠道的酸碱度可能是影响LDH-dsRNA增效的因素之一。本研究首次为利用LDH研究昆虫RNA生物农药提供了可观的理论基础。