Water‐Plasma‐Enabled Exfoliation of Ultrathin Layered Double Hydroxide Nanosheets with Multivacancies for Water Oxidation

An earth‐abundant and highly efficient electrocatalyst is essential for oxygen evolution reaction (OER) due to its poor kinetics. Layered double hydroxide (LDH)‐based nanomaterials are considered as promising electrocatalysts for OER. However, the stacking structure of LDHs limits the exposure of the active sites. Therefore, the exfoliation is necessary to expose more active sites. In addition, the defect engineering is proved to be an efficient strategy to enhance the performance of OER electrocatalysts. For the first time, this study prepares ultrathin CoFe LDHs nanosheets with multivacancies as OER electrocatalysts by water‐plasma‐enabled exfoliation. The water plasma can destroy the electrostatic interactions between the host metal layers and the interlayer cations, resulting in the fast exfoliation. On the other hand, the etching effect of plasma can simultaneously and effectively produce multivacancies in the as‐exfoliated ultrathin LDHs nanosheets. The increased active sites and the multivacancies significantly contribute to the enhanced electrocatalytic activity for OER. Compared to pristine CoFe LDHs, the as‐exfoliated ultrathin CoFe LDHs nanosheets exhibit excellent catalytic activity for OER with a ultralow overpotential of only 232 mV at 10 mA cm^?2 and possesses outstanding kinetics (the Tafel slope of 36 mV dec^?1). This work provides a novel strategy to exfoliate LDHs and to produce multivacancies simultaneously as highly efficient electrocatalysts for OER.     

Tuning Surface Electronic Configuration of NiFe LDHs Nanosheets by Introducing Cation Vacancies (Fe or Ni) as Highly Efficient Electrocatalysts for Oxygen Evolution Reaction

Intrinsically inferior electrocatalytic activity of NiFe layered double hydroxides (LDHs) nanosheets is considered as a limiting factor to inhibit the electrocatalytic properties for oxygen evolution reaction (OER). Proper defect engineering to tune the surface electronic configuration of electrocatalysts may significantly improve the intrinsic activity. In this work, the selective formation of cation vacancies in NiFe LDHs nanosheets is successfully realized. The as‐synthesized NiFe LDHs‐V_Fe and NiFe LDHs‐V_Ni electrocatalysts show excellent activity for OER, mainly attributed to the introduction of rich iron or nickel vacancies in NiFe LDHs nanosheets, which efficiently tune the surface electronic structure increasing the adsorbing capacity of OER intermediates. Density functional theory (DFT) computational results also further indicate that the OER catalytic performance of NiFe LDHs can be pronouncedly improved by introducing Fe or Ni vacancies.     

A General Method to Ultrathin Bimetal‐MOF Nanosheets Arrays via In Situ Transformation of Layered Double Hydroxides Arrays

Structure engineering of ultrathin metal–organic framework (MOF) nanosheets to self‐supporting and well‐aligned MOF superstructures is highly desired for diverse applications, especially important for electrocatalysis. In this work, a facile layered double hydroxides in situ transformation strategy is developed to synthesize ultrathin bimetal‐MOF nanosheets (BMNSs) arrays on conductive substrates. This approach is versatile, and applicable to obtain various BMNSs or even trimetal‐MOF nanosheets arrays on different substrates. As a proof of concept application, the obtained ultrathin NiCo‐BDC BMNSs array exhibits an excellent catalytic activity toward the oxygen evolution reaction with an overpotential of only 230 mV to reach a current density of 10 mA cm^?2 in 1 m KOH. The present work demonstrates a strategy to prepare ultrathin bimetal‐MOF nanosheets arrays, which might open an avenue for various promising applications of MOF materials.     

A Highly Solvent‐Stable Metal–Organic Framework Nanosheet: Morphology Control,Exfoliation, and Luminescent Property

Compared to bulk metal–organic framework (MOF), 2D MOF nanosheets have gained intensive research attention due to their ultrathin thickness and large surface area with highly accessible active sites. However, structural deterioration and morphological damage have impeded producing high‐quality MOF nanosheets during exfoliation. Here, first a new layered bulk MOF ZSB‐1 is synthesized and several solvents such as isopropanol, methanol, n‐hexyl alcohol, and N,N‐dimethylformamide are surveyed to examine their performance for the exfoliation of layered ZSB‐1. As a result, a highly solvent‐stable metal–organic framework rectangular nanosheet retaining undamaged morphology is obtained by the soft‐physical method in n‐hexyl alcohol. Theoretical simulations reveal that the strong interaction energy between n‐hexyl alcohol and MOF layers is responsible for the best exfoliation performance of making the bulk MOF into nanosheets. In addition, ZSB‐1 shows a tunable fluorescence peak position, fluorescent lifetime, and quantum yield by simply changing the solvent and morphology. Besides, the ZSB‐1 was selected as a fluorescence sensor to detect metal ions, and ZSB‐1 nanosheet exhibits excellent sensing ability for Fe³⁺. It is worth noting that the ZSB‐1 nanosheet has better detection limit performance of 0.054 × 10^?6 m than that of its bulk counterpart.     

A Cost‐Efficient Bifunctional Ultrathin Nanosheets Array for Electrochemical Overall Water Splitting

The design of cost‐efficient earth‐abundant catalysts with superior performance for the electrochemical water splitting is highly desirable. Herein, a general strategy for fabricating superior bifunctional water splitting electrodes is reported, where cost‐efficient earth‐abundant ultrathin Ni‐based nanosheets arrays are directly grown on nickel foam (NF). The newly created Ni‐based nanosheets@NF exhibit unique features of ultrathin building block, 3D hierarchical structure, and alloy effect with the optimized Ni₅Fe layered double hydroxide@NF (Ni₅Fe LDH@NF) exhibiting low overpotentials of 210 and 133 mV toward both oxygen evolution reaction and hydrogen evolution reaction at 10 mA cm^?2 in alkaline condition, respectively. More significantly, when applying as the bifunctional overall water splitting electrocatalyst, the Ni₅Fe LDH@NF shows an appealing potential of 1.59 V at 10 mA cm^?2 and also superior durability at the very high current density of 50 mA cm^?2.     

Economizing Production of Diverse 2D Layered Metal Hydroxides for Efficient Overall Water Splitting

2D layered metal hydroxides (LMH) are promising materials for electrochemical energy conversion and storage. Compared with exfoliation of bulk layered materials, wet chemistry synthesis of 2D LMH materials under mild conditions still remains a big challenge. Here, an “MgO‐mediated strategy” for mass production of various 2D LMH nanosheets is presented by hydrolyzing MgO in metal salt aqueous solutions at room temperature. Benefiting from this economical and scalable strategy, ultrathin LMH nanosheets (M = Ni, Fe, Co, NiFe, and NiCo) and their derivatives (e.g., metal oxides and sulfides) can be synthesized in high yields. More importantly, this strategy opens up opportunities to fabricate hierarchically structured LMH nanosheets, resulting in high‐performance electrocatalysts for the oxygen‐ and hydrogen‐evolution reactions to realize stable overall water splitting with a low cell voltage of 1.55 V at 10 mA cm⁻². This work provides a powerful platform for the synthesis and applications of 2D materials.     

Ultrathin 2D Zirconium Metal–Organic Framework Nanosheets: Preparation and Application in Photocatalysis

Synthesizing ultrathin 2D metal–organic framework nanosheets in high yields has received increasing research interest but remains a great challenge. In this work, ultrathin zirconium‐porphyrinic metal–organic framework (MOF) nanosheets with thickness down to ≈1.5 nm are synthesized through a pseudoassembly–disassembly strategy. Owing to the their unique properties originating from their ultrathin thickness and highly exposed active sites, the as‐prepared ultrathin nanosheets exhibit far superior photocatalysis performance compared to the corresponding bulk MOF. This work highlights new opportunities in designing ultrathin MOF nanosheets and paves the way to expand the potential applications of MOFs.     

Self‐Sacrificial Template‐Directed Vapor‐Phase Growth of MOF Assemblies and Surface Vulcanization for Efficient Water Splitting

Direct use of metal–organic frameworks (MOFs) with robust pore structures, large surface areas, and high density of coordinatively unsaturated metal sites as electrochemical active materials is highly desirable (rather than using as templates and/or precursors for high‐temperature calcination), but this is practically hindered by the poor conductivity and low accessibility of active sites in the bulk form. Herein, a universal vapor‐phase method is reported to grow well‐aligned MOFs on conductive carbon cloth (CC) by using metal hydroxyl fluorides with diverse morphologies as self‐sacrificial templates. Specifically, by further partially on‐site generating active Co₃S₄ species from Co ions in the echinops‐like Co‐based MOF (EC‐MOF) through a controlled vulcanization approach, the resulting Co₃S₄/EC‐MOF hybrid exhibits much enhanced electrocatalytic performance toward the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), with overpotentials of 84 and 226 mV required to reach a current density of 10 mA cm^?2, respectively. Density functional theory (DFT) calculations and experimental results reveal that the electron transfer between Co₃S₄ species and EC‐MOF can decrease the electron density of the Co d‐orbital, resulting in more electrocatalytically optimized adsorption properties for Co. This study will open up a new avenue for designing highly ordered MOF‐based surface active materials for various electrochemical energy applications.     

Metal Atom-Doped Co3O4 Hierarchical Nanoplates for Electrocatalytic Oxygen Evolution

Electrocatalysts based on hierarchically structured and heteroatom-doped non-noble metal oxide materials are of great importance for efficient and low-cost electrochemical water splitting systems. Herein, the synthesis of a series of hierarchical hollow nanoplates (NPs) composed of ultrathin Co₃O₄ nanosheets doped with 13 different metal atoms is reported. The synthesis involves a cooperative etching−coordination−reorganization approach starting from zeolitic imidazolate framework-67 (ZIF-67) NPs. First, metal atom decorated ZIF-67 NPs with unique cross-channels are formed through a Lewis acid etching and metal species coordination process. Afterward, the composite NPs are converted to hollow Co₃O₄ hierarchical NPs composed of ultrathin nanosheets through a solvothermal reaction, during which the guest metal species is doped into the octahedral sites of Co₃O₄. Density functional theory calculations suggest that doping of small amount of Fe atoms near the surface of Co₃O₄ can greatly enhance the electrocatalytic activity toward the oxygen evolution reaction (OER). Benefiting from the structural and compositional advantages, the obtained Fe-doped Co₃O₄ hierarchical NPs manifest superior electrocatalytic performance for OER with an overpotential of 262 mV at 10 mA cm⁻², a Tafel slope of 43 mV dec⁻¹, and excellent stability even at a high current density of 100 mA cm⁻² for 50 h.     

Metal‐Layer Assisted Growth of Ultralong Quasi‐2D MOF Nanoarrays on Arbitrary Substrates for Accelerated Oxygen Evolution

Controlled growth of metal–organic frameworks (MOFs) nanocrystals on requisite surfaces is highly desired for myriad applications related to catalysis, energy, and electronics. Here, this challenge is addressed by overlaying arbitrary surfaces with a thermally evaporated metal layer to enable the well‐aligned growth of ultralong quasi‐2D MOF nanoarrays comprising cobalt ions and thiophenedicarboxylate acids. This interfacial engineering approach allows preferred chelation of carboxyl groups in the ligands with the metal interlayers, thereby making possible the fabrication and patterning of MOF nanoarrays on substrates of any materials or morphologies. The MOF nanoarrays grown on porous metal scaffolds demonstrate high electrocatalytic capability for water oxidation, exhibiting a small overpotential of 270 mV at 10 mA cm^?2, or 317 mV at 50 mA cm^?2 as well as negligible decay of performance within 30 h. The enhanced performance stems from the improved electron and ion transport in the hierarchical porous nanoarrays consisting of in situ formed oxyhydroxide nanosheets in the electrochemical processes. This approach for mediating the growth of MOF nanoarrays can serve as a promising platform for diverse applications.     

Atomic Iridium Incorporated in Cobalt Hydroxide for Efficient Oxygen Evolution Catalysis in Neutral Electrolyte

Developing highly efficient catalysts for oxygen evolution reaction (OER) in neutral media is extremely crucial for microbial electrolysis cells and electrochemical CO₂ reduction. Herein, a facile one‐step approach is developed to synthesize a new type of well‐dispersed iridium (Ir) incorporated cobalt‐based hydroxide nanosheets (nominated as CoIr) for OER. The Ir species as clusters and single atoms are incorporated into the defect‐rich hydroxide nanosheets through the formation of rich Co–Ir species, as revealed by systematic synchrotron radiation based X‐ray spectroscopic characterizations combining with high‐angle annular dark‐field scanning transmission electron microscopy measurement. The optimized CoIr with 9.7 wt% Ir content displays highly efficient OER catalytic performance with an overpotential of 373 mV to achieve the current density of 10 mA cm^?2 in 1.0 m phosphate buffer solution, significantly outperforming the commercial IrO₂ catalysts. Further characterizations toward the catalyst after undergoing OER process indicate that unique Co oxyhydroxide and high valence Ir species with low‐coordination structure are formed due to the high oxidation potentials, which authentically contributes to superior OER performance. This work not only provides a state‐of‐the‐art OER catalyst in neutral media but also unravels the root of the excellent performance based on efficient structural identifications.     

Multifunctional Nickel Sulfide Nanosheet Arrays for Solar‐Intensified Oxygen Evolution Reaction

Electrochemical water splitting for hydrogen production is currently hindered by the sluggish kinetic of anodic oxygen evolution reaction (OER). By integrating photothermal materials into electrocatalytic network and thus allowing solar energy to work as additional driving force, the OER is expected to be boosted. However, the rational design of such electrochemical system still remains a challenge due to the spatial inconsistency between photothermal component and electrocatalytic component. Herein, it is reported that multifunctional nickel sulfide (Ni₃S₂) nanosheet arrays show both photothermal and electrocatalytic properties for solar‐intensified electrocatalytic system, which well eliminates the spatial inconsistency between the aforementioned two types of functional components by using one bifunctional material. The deliberate design of nanoarray architecture formed by the interconnected Ni₃S₂ nanosheets endows larger surface area and higher surface roughness, thus enhancing light absorption by suppressing diffuse reflection and facilitating electron transfer in electrocatalytic reactions. Therefore, the OER activity is significantly improved. Under light illumination, the current density of Ni₃S₂ nanosheets could reach 492.2 mA cm^?2 at 1.55 V, about 2.5‐fold that in dark conditions, with a Tafel slope of as low as 60 dec^?1. The solar‐intensified electrochemical system based on multifunctional material presents prospective potential in electrochemical water splitting for efficient hydrogen production.     

Monodispersed Pt Sites Supported on NiFe-LDH from Synchronous Anchoring and Reduction for High Efficiency Overall Water Splitting

Precise design of low-cost, efficient and definite electrocatalysts is the key to sustainable renewable energy. Herein, this work develops a targeted-anchored and subsequent spontaneous-redox strategy to synthesize nickel-iron layered double hydroxide (LDH) nanosheets anchored with monodispersed platinum (Pt) sites (Pt@LDH). Intermediate metal-organic frameworks (MOF)/LDH heterostructure not only provides numerous confine points to guarantee the stability of Pt sites, but also excites the spontaneous reduction for Pt^II. Electronic structure, charge transfer ability and reaction kinetics of Pt@LDH can be effectively facilitated by the monodispersed Pt moieties. As a result, the optimized Pt@LDH that with the 5% ultra-low content Pt exhibits the significant increment in electrochemical water splitting performance in alkaline media, which only afford low overpotentials of 58 mV at 10 mA cm⁻² for hydrogen evolution reaction (HER) and 239 mV at 10 mA cm⁻² for oxygen evolution reaction (OER), respectively. In a real device, Pt@LDH can drive an overall water-splitting at low cell voltage of 1.49 V at 10 mA cm⁻², which can be superior to most reported similar LDH-based catalysts. Moreover, the versatility of the method is extended to other MOF precursors and noble metals for the design of ultrathin LDH supported monodispersed noble metal electrocatalysts promoting research interest in material design.     

Highly Excavated Octahedral Nanostructures Integrated from Ultrathin Mesoporous PtCu3 Nanosheets: Construction of Three‐Dimensional Open Surfaces for Enhanced Electrocatalysis

Developing electrocatalysts with ultrathin nanostructures and high mesoporosity is a relevant high‐priority research direction toward enhancing the performance of noble metals. Herein, mesoporous, highly excavated octahedral PtCu₃ nanostructures are prepared by a facile one‐pot synthesis. The mesoporous, highly excavated octahedral PtCu₃ nanostructures are built with mutually perpendicular interlaced mesoporous nanosheets with a thickness of ≈4.5 nm. Benefiting from its mesoporous features, three‐dimensional (3D) open surfaces, ultrathin nanosheets, and a Cu‐rich surface, PtCu₃ exhibits excellent electrocatalytic performance and high antipoisoning activity toward the methanol oxidation reaction.     

A Self-Templated Design Approach toward Multivariate Metal–Organic Frameworks for Enhanced Oxygen Evolution

Multivariate metal–organic framework (MOF) is an ideal electrocatalytic material due to the synergistic effect of multiple metal active sites. In this study, a series of ternary M-NiMOF (M = Co, Cu) through a simple self-templated strategy that the Co/Cu MOF isomorphically grows in situ on the surface of NiMOF is designed. Owing to the electron rearrange of adjacent metals, the ternary CoCu-NiMOFs demonstrate the improved intrinsic electrocatalytic activity. At optimized conditions, the ternary Co₃Cu-Ni₂MOFs nanosheets give the excellent oxygen evolution reaction (OER) performance of current density of 10 mA cm⁻² at low overpotential of 288 mV with a Tafel slope of 87 mV dec⁻¹, which is superior to that of bimetallic nanosheet and ternary microflowers. The low free energy change of potential-determining step identifies that the OER process is favorable at Cu–Co concerted sites along with strong synergistic effect of Ni nodes. Partially oxidized metal sites also reduce the electron density, thus accelerating the OER catalytic rate. The self-templated strategy provides a universal tool to design multivariate MOF electrocatalysts for highly efficient energy transduction.     

Ultrathin 2D Cerium-Based Metal–Organic Framework Nanosheet That Boosts Selective Oxidation of Inert C(sp3)?H Bond through Multiphoton Excitation (Small 26/2023)

The development of methodologies for inducing and tailoring activities of catalysts is an important issue in various catalysis. The ultrathin 2D monolayer metal–organic framework (MOF) nanosheets with more accessible active sites and faster diffusion obtained by exfoliating 3D layered MOFs are of great potential as heterogeneous catalysts, but the rational design and preparation of 3D layered MOFs remains a grand challenge. Herein, a novel weak electrostatic interaction strategy to construct a 3D layered cerium-bearing MOF by coordinating chlorine-capped cerium nodes and linear photoactive methyl viologen ( MV ⁺) organic linkers is used. Under multiphoton excitation, the MV ⁺ ligands and Ce  Cl chromophores are triggered consecutively to form the high activity chlorine radical (Cl^•) for activation of inert C(sp³)  H bond through a hydrogen atom transfer. Benefiting from framework confinement effects, synergistic effects of two active sites and/or flexibility of the ultrathin framework nanosheets with high surface utilization, the observed activities increase in the order CeCl₃/ MV ⁺ < bulk 3D MOF crystals < 2D MOF nanosheets in photocatalysis. This work not only contributes a new strategy to construct 3D layered MOFs and their ultrathin nanosheets but also paves the way to use nanostructured MOFs to handle synergy of multiple molecular catalysts.     

Strong Electronic Interaction in Dual‐Cation‐Incorporated NiSe2 Nanosheets with Lattice Distortion for Highly Efficient Overall Water Splitting

Exploring highly efficient and low‐cost electrocatalysts for electrochemical water splitting is of importance for the conversion of intermediate energy. Herein, the synthesis of dual‐cation (Fe, Co)‐incorporated NiSe₂ nanosheets (Fe, Co‐NiSe₂) and systematical investigation of their electrocatalytic performance for water splitting as a function of the composition are reported. The dual‐cation incorporation can distort the lattice and induce stronger electronic interaction, leading to increased active site exposure and optimized adsorption energy of reaction intermediates compared to single‐cation‐doped or pure NiSe₂. As a result, the obtained Fe_0.09Co_0.13‐NiSe₂ porous nanosheet electrode shows an optimized catalytic activity with a low overpotential of 251 mV for oxygen evolution reaction and 92 mV for hydrogen evolution reaction (both at 10 mA cm^?2 in 1 m KOH). When used as bifunctional electrodes for overall water splitting, the current density of 10 mA cm^?2 is achieved at a low cell voltage of 1.52 V. This work highlights the importance of dual‐cation doping in enhancing the electrocatalyst performance of transition metal dichalcogenides.     

Metabolizable Ultrathin Bi2Se3 Nanosheets in Imaging‐Guided Photothermal Therapy

Poly(vinylpyrrolidone)‐encapsulated Bi₂Se₃ nanosheets with a thickness of 1.7 nm and diameter of 31.4 nm are prepared by a solution method. Possessing an extinction coefficient of 11.5 L g^?1 cm^?1 at 808 nm, the ultrathin Bi₂Se₃ nanosheets boast a high photothermal conversion efficiency of 34.6% and excellent photoacoustic performance. After systemic administration, the Bi₂Se₃ nanosheets with the proper size and surface properties accumulate passively in tumors enabling efficient photoacoustic imaging of the entire tumors to facilitate photothermal cancer therapy. In vivo biodistribution studies reveal that they are expelled from the body efficiently after 30 d. The ultrathin Bi₂Se₃ nanosheets have large clinical potential as metabolizable near‐infrared‐triggered theranostic agents.     

Ultrathin Nitrogen‐Doped Carbon Layer Uniformly Supported on Graphene Frameworks as Ultrahigh‐Capacity Anode for Lithium‐Ion Full Battery

The designable structure with 3D structure, ultrathin 2D nanosheets, and heteroatom doping are considered as highly promising routes to improve the electrochemical performance of carbon materials as anodes for lithium‐ion batteries. However, it remains a significant challenge to efficiently integrate 3D interconnected porous frameworks with 2D tunable heteroatom‐doped ultrathin carbon layers to further boost the performance. Herein, a novel nanostructure consisting of a uniform ultrathin N‐doped carbon layer in situ coated on a 3D graphene framework (NC@GF) through solvothermal self‐assembly/polymerization and pyrolysis is reported. The NC@GF with the nanosheets thickness of 4.0 nm and N content of 4.13 at% exhibits an ultrahigh reversible capacity of 2018 mA h g^?1 at 0.5 A g^?1 and an ultrafast charge–discharge feature with a remarkable capacity of 340 mA h g^?1 at an ultrahigh current density of 40 A g^?1 and a superlong cycle life with a capacity retention of 93% after 10 000 cycles at 40 A g^?1. More importantly, when coupled with LiFePO₄ cathode, the fabricated lithium‐ion full cells also exhibit high capacity and excellent rate and cycling performances, highlighting the practicability of this NC@GF.     

Photothermal‐Responsive Microporous Nanosheets Confined Ionic Liquid for Efficient CO2 Separation

2D materials hold promising potential for novel gas separation. However, a lack of in‐plane pores and the randomly stacked interplane channels of these membranes still hinder their separation performance. In this work, ferrocene based‐MOFs (Zr‐Fc MOF) nanosheets, which contain abundant of in‐plane micropores, are synthesized as porous supports to fabricate Zr‐Fc MOF supported ionic liquid membrane (Zr‐Fc‐SILM) for highly efficient CO₂ separation. The micropores of Zr‐Fc MOF nanosheets not only provide extra paths for CO₂ transportation, and thus increase its permeance up to 145.15 GPU, but also endow the Zr‐Fc‐SILM with high selectivity (216.9) of CO₂/N₂ through the nanoconfinement effect, which is almost ten times higher than common porous polymer SILM. Furthermore, based on the photothermal‐responsive properties of Zr‐Fc MOF, the performance is further enhanced (35%) by light irradiation through a photothermal heating process. This provides a brand new way to design light facilitating gas separation membranes.