Substrate‐Friendly Growth of Large‐Sized Ni(OH)2 Nanosheets for Flexible Electrochromic Films

Large‐area, 2D, anisotropic, direct growth of nanostructures is considered an effective and straightforward way to readily fulfill transparent, flexible technology requirements. In addition, formation of thin hybrid structures by combining with another 2D material brings about dimensional advantages, such as intimate heterostructure functionalities, large specific area, and optical transparency. Here, we demonstrate 2D planar growth of thin Ni(OH)₂ nanosheets on arbitrary rigid and soft supports, by exploiting the growth strategies of oriented attachment induced by interfacial chemistry and the intrinsic driving force of layered structure constitution. Moreover, large‐scale 2D heterohybrids have successfully been prepared by direct conformal growth of Ni(OH)₂ nanosheets overlying MoO₃ nanobelts. Unlike the exfoliation and transfer of 2D materials technique, this approach minimizes multiple process contamination and physical‐handling structural defects. Accordingly, proof‐of‐concept flexible electrochromism is demonstrated in view of its prerequisite to the access of a large homogeneous material coating. The as‐synthesized 2D layered structure affirms its optical and electrochemical superiority through the display of wide optical modulation, high coloration efficiency, good cyclic stability, and flexibility.     

Ultrathin Ni(0)-Embedded Ni(OH)2 Heterostructured Nanosheets with Enhanced Electrochemical Overall Water Splitting

The efficiency of splitting water into hydrogen and oxygen is highly dependent on the catalyst used. Herein, ultrathin Ni(0)-embedded Ni(OH)₂ heterostructured nanosheets, referred to as Ni/Ni(OH)₂ nanosheets, with superior water splitting activity are synthesized by a partial reduction strategy. This synthetic strategy confers the heterostructured Ni/Ni(OH)₂ nanosheets with abundant Ni(0)-Ni(II) active interfaces for hydrogen evolution reaction (HER) and Ni(II) defects as transitional active sites for oxygen evolution reaction (OER). The obtained Ni/Ni(OH)₂ nanosheets exhibit noble metal-like electrocatalytic activities toward overall water splitting in alkaline condition, to offer 10 mA cm⁻² in HER and OER, the required overpotentials are only 77 and 270 mV, respectively. Based on such an outstanding activity, a water splitting electrolysis cell using the Ni/Ni(OH)₂ nanosheets as the cathode and anode electrocatalysts has been successfully built. When the output voltage of the electrolytic cell is 1.59 V, a current density of 10 mA cm⁻² can be obtained. Moreover, the durability of Ni/Ni(OH)₂ nanosheets in the alkaline electrolyte is much better than that of noble metals. No obvious performance decay is observed after 20 h of catalysis. This facile strategy paves the way for designing highly active non-precious-metal catalyst to generate both hydrogen and oxygen by electrolyzing water at room temperature.     

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.     

Fe2+‐Doped Layered Double (Ni,Fe) Hydroxides as Efficient Electrocatalysts for Water Splitting and Self‐Powered Electrochemical Systems

Developing nonprecious electrocatalysts with superior activity and durability for electrochemical water splitting is of great interest but challenging due to the large overpotential required above the thermodynamic standard potential of water splitting (1.23 V). Here, in situ growth of Fe²⁺‐doped layered double (Ni, Fe) hydroxide (NiFe(II,III)‐LDH) on nickel foam with well‐defined hexagonal morphology and high crystallinity by a redox reaction between Fe³⁺ and nickel foam under hydrothermal conditions is reported. Benefiting from tuning the local atomic structure by self‐doping Fe²⁺, the NiFe(II,III)‐LDH catalyst with higher amounts of Fe²⁺ exhibits high activity toward oxygen evolution reaction (OER) as well as hydrogen evolution reaction (HER) activity. Moreover, the optimized NiFe(II,III)‐LDH catalyst for OER (O‐NiFe(II,III)‐LDH) and catalyst for HER (H‐NiFe(II,III)‐LDH) show overpotentials of 140 and 113 mV, respectively, at a current density of 10 mA cm^?2 in 1 m KOH aqueous electrolyte. Using the catalysts for overall water splitting in two‐electrode configuration, a low overpotential of just 1.54 V is required at a benchmark current density of 10 mA cm^?2. Furthermore, it is demonstrated that electrolysis of the water device can be drived by a self‐powered system through integrating a triboelectric nanogenerator and battery, showing a promising way to realize self‐powered electrochemical systems.     

Colloids of Holey Gd2O3 Nanosheets Converted from Exfoliated Gadolinium Hydroxide Layers

This paper proposes a confined solid‐state conversion approach using layered metal‐hydroxides for the production of a colloidal suspension of porous 2D crystalline metal oxide layers with superior electrochemical H₂O₂ sensing performance. This study investigates the conversion chemistry of delaminated layers of gadolinium hydroxide (LGdH), [Gd₂(OH)₅]⁺, encapsulated in a silica nanoshell that provides an antistacking and antisintering environment during the phase‐transition at high temperature. Thermal treatment of the LGdH layers within the protected environment results in a dimensionally confined phase‐transition into crystalline Gd₂O₃ nanosheets with an isomorphic 2D structure. Furthermore, annealing at higher temperatures leads to the evolution of in‐plane mesoporous structure on the Gd₂O₃ nanosheet. Based on insight acquired from in‐depth investigation, the evolution of in‐plane porosity proceeds through the in‐plane dominant silicate‐formation reaction at the interface with the surrounding silica shell. Their 2D‐anisotropic and mesoporous morphological features are preserved, producing a colloidal suspension of holey nanosheets that can be used to fabricate a thin and porous film through wet‐coating deposition. This study also demonstrates the superior electrochemical H₂O₂ sensing ability of the resultant porous Gd₂O₃ film, which represents a ≈1000‐ and 10‐fold enhancement of the detection limit and sensitivity, respectively, in comparison to previously reported Gd₂O₃ films.     

Layered‐Double‐Hydroxide Nanosheets as Efficient Visible‐Light‐Driven Photocatalysts for Dinitrogen Fixation

Semiconductor photocatalysis attracts widespread interest in water splitting, CO₂ reduction, and N₂ fixation. N₂ reduction to NH₃ is essential to the chemical industry and to the Earth's nitrogen cycle. Industrially, NH₃ is synthesized by the Haber–Bosch process under extreme conditions (400–500 °C, 200–250 bar), stimulating research into the development of sustainable technologies for NH₃ production. Herein, this study demonstrates that ultrathin layered‐double‐hydroxide (LDH) photocatalysts, in particular CuCr‐LDH nanosheets, possess remarkable photocatalytic activity for the photoreduction of N₂ to NH₃ in water at 25 °C under visible‐light irradiation. The excellent activity can be attributed to the severely distorted structure and compressive strain in the LDH nanosheets, which significantly enhances N₂ chemisorption and thereby promotes NH₃ formation.     

Polyhedral‐Like NiMn‐Layered Double Hydroxide/Porous Carbon as Electrode for Enhanced Electrochemical Performance Supercapacitors

Polyhedral‐like NiMn‐layered double hydroxide/porous carbon (NiMn‐LDH/PC‐x ) composites are successfully synthesized by hydrothermal method (x = 1, 2 means different mass percent of porous carbon (PC) in composites). The NiMn‐LDH/PC‐1 composites possess specific capacitance 1634 F g⁻¹ at a current density of 1 A g⁻¹, and it is much better than that of pure LDH (1095 F g⁻¹ at 1 A g⁻¹). Besides, the sample can retain 84.58% of original capacitance after 3000 cycles at 15 A g⁻¹. An asymmetric supercapacitor with NiMn‐LDH/PC‐1 as anode and activated carbon as cathode is fabricated, and the supercapacitor can achieve an energy density of 18.60 Wh kg⁻¹ at a power density of 225.03 W kg⁻¹. The enhanced electrochemical performance attributes to the high faradaic pseudocapacitance of NiMn‐LDH, the introduction of PC, and the 3D porous structure of LDH/PC‐1 composites. The introduction of PC hinders serious agglomeration of LDH and further accelerates ions transport. The encouraging results indicate that these materials are one of the most potential candidates for energy storage devices.     

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.     

α‐Ni(OH)2 Originated from Electro‐Oxidation of NiSe2 Supported by Carbon Nanoarray on Carbon Cloth for Efficient Water Oxidation

Development of effective oxygen evolution reaction (OER) electrocatalysts has been intensively studied to improve water splitting efficiency and cost effectiveness in the last ten years. However, it is a big challenge to obtain highly efficient and durable OER electrocatalysts with overpotentials below 200 mV at 10 mA cm^?2 despite the efforts made to date. In this work, the successful synthesis of supersmall α‐Ni(OH)₂ is reported through electro‐oxidation of NiSe₂ loaded onto carbon nanoarrays. The obtained α‐Ni(OH)₂ shows excellent activity and long‐term stability for OER, with an overpotential of only 190 mV at the current density of 10 mA cm^?2, which represents a highly efficient OER electrocatalyst. The excellent activity could be ascribed to the large electrochemical surface area provided by the carbon nanoarray, as well as the supersmall size (≈10 nm) of α‐Ni(OH)₂ which possess a large number of active sites for the reaction. In addition, the phase evolution of α‐Ni(OH)₂ from NiSe₂ during the electro‐oxidation process was monitored with in situ X‐ray absorption fine structure (XAFS) analysis.     

In Situ Growth of Pd Nanosheets on g‐C3N4 Nanosheets with Well‐Contacted Interface and Enhanced Catalytic Performance for 4‐Nitrophenol Reduction

Loading novel metal nanosheets onto nanosheet support can improve their catalytic performance, but the morphological incompatibility makes it difficult to construct a well‐contacted interface, which is of particular interest in supported catalysts. Herein, Pd nanosheets (Pd NSs) are supported onto graphitic carbon nitride nanosheets (CNNSs) with intimate face‐to‐face contact through an in situ growth method. This method overcomes the limitations of the morphological incompatibility and ensures the intimate interfacial contact between Pd NSs and CNNSs. The nitrogen‐rich nature of CNNSs endows Pd NSs with abundant anchoring sites, which optimizes the electronic structure and improves the chemical and morphological stability of Pd NSs. The supported Pd NSs demonstrate high dispersion and exhibit largely enhanced activity toward the reduction of 4‐nitrophenol. The concentration‐normalized rate constant is up to 3052 min^?1 g^?1 L, which is 5.4 times higher than that obtained by unsupported Pd NSs. No obvious deactivation is observed after six runs of the recycling experiments. It is believed that the supported novel metal nanosheets with the intimately contacted interface may show promising applications in catalysis.     

Accelerated Hydrogen Evolution Kinetics on NiFe‐Layered Double Hydroxide Electrocatalysts by Tailoring Water Dissociation Active Sites

Owing to its earth abundance, low kinetic overpotential, and superior stability, NiFe‐layered double hydroxide (NiFe‐LDH) has emerged as a promising electrocatalyst for catalyzing water splitting, especially oxygen evolution reaction (OER), in alkaline solutions. Unfortunately, as a result of extremely sluggish water dissociation kinetics (Volmer step), hydrogen evolution reaction (HER) activity of the NiFe‐LDH is rather poor in alkaline environment. Here a novel strategy is demonstrated for substantially accelerating the hydrogen evolution kinetics of the NiFe‐LDH by partially substituting Fe atoms with Ru. In a 1 m KOH solution, the as‐synthesized Ru‐doped NiFe‐LDH nanosheets (NiFeRu‐LDH) exhibit excellent HER performance with an overpotential of 29 mV at 10 mA cm^?2, which is much lower than those of noble metal Pt/C and reported electrocatalysts. Both experimental and theoretical results reveal that the introduction of Ru atoms into NiFe‐LDH can efficiently reduce energy barrier of the Volmer step, eventually accelerating its HER kinetics. Benefitting from its outstanding HER activity and remained excellent OER activity, the NiFeRu‐LDH steadily drives an alkaline electrolyzer with a current density of 10 mA cm^?2 at a cell voltage of 1.52 V, which is much lower than the values for Pt/C–Ir/C couple and state‐of‐the‐art overall water‐splitting electrocatalysts.     

Porous Hybrid Network of Graphene and Metal Oxide Nanosheets as Useful Matrix for Improving the Electrode Performance of Layered Double Hydroxides

Mesoporous hybrid network of reduced graphene oxide (rG‐O) and layered MnO₂ nanosheets could act as an efficient immobilization matrix for improving the electrochemical activity of layered double hydroxide (LDH). The control of MnO₂/rG‐O ratio is crucial in optimizing the porous structure and electrical conductivity of the resulting hybrid structure. The immobilization of Co‐Al‐LDH on hybrid MnO₂/rG‐O network is more effective in enhancing its electrode activity compared with that of on pure rG‐O network. The Co‐Al‐LDH?rG‐O?MnO₂ nanohybrid deliveres a greater specific capacitance than does MnO₂‐free Co‐Al‐LDH?rG‐O nanohybrid. The beneficial effect of MnO₂ incorporation on the electrode performance of nanohybrid is more prominent for higher current density and faster scan rate, underscoring the significant enhancement of the electron transport of Co‐Al‐LDH?rG‐O. This is supported by electrochemical impedance spectroscopy. The present study clearly demonstrates the usefulness of the porously assembled hybrid network of graphene and metal oxide nanosheets as an effective platform for exploring efficient LDH‐based functional materials.     

A Heterostructure Coupling of Exfoliated Ni–Fe Hydroxide Nanosheet and Defective Graphene as a Bifunctional Electrocatalyst for Overall Water Splitting

Herein, the authors demonstrate a heterostructured NiFe LDH‐NS@DG10 hybrid catalyst by coupling of exfoliated Ni–Fe layered double hydroxide (LDH) nanosheet (NS) and defective graphene (DG). The catalyst has exhibited extremely high electrocatalytic activity for oxygen evolution reaction (OER) in an alkaline solution with an overpotential of 0.21 V at a current density of 10 mA cm^?2, which is comparable to the current record (≈0.20 V in Fe–Co–Ni metal‐oxide‐film system) and superior to all other non‐noble metal catalysts. Also, it possesses outstanding kinetics (Tafel slope of 52 mV dec^?1) for the reaction. Interestingly, the NiFe LDH‐NS@DG10 hybrid has also exhibited the high hydrogen evolution reaction (HER) performance in an alkaline solution (with an overpotential of 115 mV by 2 mg cm^?2 loading at a current density of 20 mA cm^?2) in contrast to barely HER activity for NiFe LDH‐NS itself. As a result, the bifunctional catalyst the authors developed can achieve a current density of 20 mA cm^?2 by a voltage of only 1.5 V, which is also a record for the overall water splitting. Density functional theory calculation reveals that the synergetic effects of highly exposed 3d transition metal atoms and carbon defects are essential for the bifunctional activity for OER and HER.