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Metal-support interaction engineering is considered an efficient strategy for optimizing the catalytic activity. Nevertheless, the fine regulation of metal-support interactions as well as understanding the corresponding catalytic mechanisms (particularly those of non-carbon support-based counterparts) remains challenging. Herein, a controllable adsorption-impregnation strategy was proposed for the preparation of a porous nonlayered 2D NiO nanoflake support anchored with different forms of Pt nanoarchitectures, i.e. single atoms, clusters and nanoparticles. Benefiting from the unique porous architecture of NiO nanosheets, abundant active defect sites facilitated the immobilization of Pt single atoms onto the NiO crystal, resulting in NiO lattice distortion and thus changing the valence state of Pt, chemical bonding, and the coordination environment of the metal center. The synergy of the porous NiO support and the unexpected Pt single atom-NiO interactions effectively accelerated mass transfer and reduced the reaction kinetic barriers, contributing to a significantly enhanced mass activity of 5.59 A mgPt -1 at an overpotential of 0.274 V toward the electrocatalytic oxygen evolution reaction (OER) while 0.42 A mgPt -1 at a potential of 0.7 V vs. RHE for the methanol oxidation reaction (MOR) in an alkaline system, respectively. This work may offer fundamental guidance for developing metal-loaded/dispersed support nanomaterials toward electrocatalysis through the fine regulation of metal-support interactions.
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There is a synergy between coordination chemistry and supramolecular chemistry that has led to the development of innovative hierarchical composites with diverse functionalities. Here, we present a novel approach for the synthesis and characterization of a metal-organic framework on fullerene (MOFOF) composites, achieved through the integration of coordination chemistry and supramolecular chemistry principles. The hierarchical nature of the MOFOF harnesses the inherent properties of metal-organic frameworks and fullerenes. The two-step synthesis procedure involves controlled assembly of fullerenes as tube-like nanostructures (fullerene nanotube: FNT), their surface functionalization, and the on-surface growth of the MOF (in this case, ZIF-67). The method permits the precise tuning of morphology, effective distribution of MOF-on-FNT, and tight compositional control. The materials were comprehensively structurally characterized using electron microscopy, spectroscopic techniques, and other methods to elucidate the unique features and interactions within the MOFOF composites. The main findings reveal that the novel synthesis and characterization of MOFOF composites demonstrate the successful integration of coordination chemistry and supramolecular chemistry for the designing and fabricating of advanced hierarchical composites with tailored properties, including micro- and mesopore channels, interfacial facets, and defect sites. These properties are expected to lead to numerous potential applications such as gas storage and separation, catalysis, sensing, energy storage, and environmental remediation. However, only the capability of acid vapor sensing was tested and is described here.
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Assembling graphene sheets into macroscopic fibers with graphitic layers uniaxially aligned along the fiber axis is of both fundamental and technological importance. However, the optimal performance of graphene-based fibers has been far lower than what is expected based on the properties of individual graphene. Here we show that both mechanical properties and electrical conductivity of graphene-based fibers can be significantly improved if bridges are created between graphene edges through covalent conjugating aromatic amide bonds. The improved electrical conductivity is likely due to extended electron conjugation over the aromatic amide bridged graphene sheets. The larger sheets also result in improved π-π stacking, which, along with the robust aromatic amide linkage, provides high mechanical strength. In our experiments, graphene edges were bridged using the established wet-spinning technique in the presence of an aromatic amine linker, which selectively reacts to carboxyl groups at the graphene edge sites. This technique is already industrial and can be easily upscaled. Our methodology thus paves the way to the fabrication of high-performance macroscopic graphene fibers under optimal techno-economic and ecological conditions.
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The CoSn(OH)6 perovskite hydroxide is a structure stable and inexpensive electrocatalyst for the oxygen evolution reaction (OER). However, the OER activity of CoSn(OH)6 is still unfavorable due to its limited active sites. In this work, an Fe3+ doping strategy is used to optimize the d-band state of the CoSn(OH)6 perovskite hydroxide. The CoSn(OH)6 catalyst with slightly Fe3+ doped nanocubes is synthesized by a facile hydrothermal method. Structure characterization shows that Fe3+ ions are incorporated into the crystal structure of CoSn(OH)6. Owing to the regulation of the electronic structure, CoSn(OH)6-Fe1.8% exhibits an OER overpotential of 289 mV at a current density of 10 mA cm-2 in OER electrochemical tests. In situ Raman spectroscopy shows that no obvious re-construction occurred during the OER for both CoSn(OH)6 and CoSn(OH)6-Fe1.8%. DFT calculations show that the introduction of Fe3+ into CoSn(OH)6 can shift the d-band center to a relatively high position, thus promoting the OER intermediates' adsorption ability. Further DFT calculations suggest that incorporation of an appropriate amount of Fe3+ into CoSn(OH)6 significantly reduces the rate-determining Gibbs free energy during the OER. This work offers valuable insights into tuning the d-band center of perovskite hydroxide materials for efficient OER applications.
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Most nonoxide catalysts based on transition metal elements will inevitably change their primitive phases under anodic oxidation conditions in alkaline media. Establishing a relationship between the bulk phase and surface evolution is imperative to reveal the intrinsic catalytic active sites. In this work, it is demonstrated that the introduction of Fe facilitates the phase transition of orthorhombic CoSe2 into its cubic counterpart and then accelerates the Co-Fe hydroxide layer generation on the surface during electrocatalytic oxygen evolution reaction (OER). As a result, the Fe-doped cubic CoSe2 catalyst exhibits a significantly enhanced activity with a considerable overpotential decrease of 79.9 and 66.9 mV to deliver 10 mA·cm-2 accompanied by a Tafel slope of 48.0 mV·dec-1 toward OER when compared to orthorhombic CoSe2 and Fe-doped orthorhombic CoSe2, respectively. Density functional theory (DFT) calculations reveal that the introduction of Fe on the surface hydroxide layers will tune electron density around Co atoms and raise the d-band center. These findings will provide deep insights into the surface reconstitution of the OER electrocatalysts based on transition metal elements.
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A series of porous organic polymers based on a singlet oxygen generating oxoporphyinogen ('OxP') has been successfully prepared from a pseudotetrahedral OxP-tetraamine precursor (OxP(4-NH2Bn)4) by its reaction with tetracarboxylic acid dianhydrides under suitable conditions. Of the compounds studied, those containing naphthalene (OxP-N) and perylene (OxP-P) spacers, respectively, have large surface areas (~530 m2 g-1). On the other hand, the derivative with a simple benzene spacer (OxP-B) exhibits the best 1O2 generating capability. Although the starting OxP-tetraamine precursor is a poor 1O2 generator, its incorporation into OxP POPs leads to a significant enhancement of 1O2 productivity, which is largely due to the transformation of NH2 groups to electron-withdrawing diimides. Overall 1O2 production efficacy of OxP-POPs under irradiation by visible light is significantly improved over the common reference material PCN-222. All the materials OxP-B, OxP-N and OxP-P promote oxidation of thioanisole involving conversion of ambient triplet state oxygen to singlet oxygen under visible light irradiation and its reaction with the sulfide. Although the reaction rate of the oxidation promoted by OxP POPs is generally lower than for conventional materials (such as PCN-222) or previously studied OxP derivatives, undesired overoxidation of the substrate to methyl phenyl sulfone is suppressed. For organic sulfides, selectivity of oxidation is especially important for detoxification of mustard gas (bis(2-chloroethyl)sulfide) or similarly toxic compounds since controlled oxidation leads to the low toxicity bis(2-chloroethyl)sulfoxide while overoxidation leads to intoxification (since bis(2-chloroethyl)sulfone presents greater toxicity to humans than the sulfide substrate). Therefore, OxP POPs capable of promoting selective oxidation of sulfides to sulfoxides have excellent potential to be used as mild and selective detoxification agents.
Oxoporphyrinogen (OxP) is a unique chromophore compound in that it is intrinsically de-aggregated allowing large quantum yields of singlet oxygen generation. Due to its structure, OxP is also an ideal building block for porous systems. In this work, we describe the first incorporation of OxP in highly stable microporous polymers strongly enhanced singlet oxygen generation for selective oxidation of organic sulfides to sulfoxides (as a model reaction) under heterogeneous conditions. The novelty of this work lies in the high stability and easy recovery of the materials, the synergetic enhancement of singlet oxygen generation in the polymers over the starting OxP, and the excellent selectivity for the oxidation reaction.
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Nanoconfinement of cations in layered oxide cathode is an important approach to realize advanced zinc ion storage performance. However, thus far, the conventional hydrothermal/solvothermal route for this nanoconfinement has been restricted to its uncontrollable phase structure and the difficulty on the multiple cation co-confinement simultaneously. Herein, this work reports a general, supramolecular self-assembly of ultrathin V2O5 nanosheets using various unitary cations including Na+, K+, Mg2+, Ca2+, Zn2+, Al3+, NH4 +, and multiple cations (NH4 + + Na+, NH4 + + Na+ + Ca2+, NH4 + + Na+ + Ca2+ +Mg2+). The unitary cation confinement results in a remarkable increase in the specific capacity and Zn-ion diffusion kinetics, and the multiple cation confinement gives rise to superior structural and cycling stability by multiple cation synergetic pillaring effect. The optimized diffusion coefficient of Zn-ion (7.5 × 10-8 cm2 s-1) in this assembly series surpasses most of the V-based cathodes reported up to date. The work develops a novel multiple-cations nanoconfinement strategy toward high-performance cathode for aqueous battery. It also provides new insights into the guest cation regulation of zinc-ion diffusion kinetics through a general, supramolecular assembly pathway.
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Zeolites have been widely applied as versatile catalysts, sorbents, and ion exchangers with unique porous structures showing molecular sieving capability. In these years, it is reported that some layered zeolites can be delaminated into molecularly thin 2-dimensional (2D) nanosheets characterized by inherent porous structures and highly exposed active sites. In the present study, two types of zeolite nanosheets with distinct porous structures with MWW topology (denoted mww) and ferrierite-related structure (denoted bifer) are deposited on a substrate through the solution process via electrostatic self-assembly. Alternate deposition of zeolite nanosheets with polycation under optimized conditions allows the layer-by-layer growth of their multilayer films with a stacking distance of 2-3 nm. Furthermore, various hierarchical structures defined at the unit-cell dimensions can be constructed simply by conducting the deposition of mww and bifer nanosheets in a designed sequence. Adsorption of a dye, Rhodamine B, in these films, is examined to show that adsorption is dependent on constituent zeolite nanosheets and their assembled nanostructures. This work has provided fundamental advancements in the fabrication of artificial zeolite-related hierarchical structures, which may be extended to other zeolite nanosheets, broadening their functionalities, applications, and benefits.
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Electrochemical NO3- reduction reaction (NO3RR) is a promising technique for green NH3 synthesis. Tungsten oxide (WO3) has been regarded as an effective electrocatalyst for electrochemical NH3 synthesis. However, the weak adsorption and the sluggish hydrogenation of oxynitride intermediates (NOx, e.g., *NO3 and *NO2) over WO3 materials hinder the efficiency of converting NO3- to NH3. Herein, we design a heterostructure of tungsten nitride (WN) and WO3 (WN/WO3) nanosheets to optimize *NO3 and *NO2 adsorptions and facilitate *NO2 hydrogenations to achieve a highly efficient electrochemical NO3RR to produce NH3. Theoretical calculations predict that locally introducing WN into WO3 will shorten the distance between adjacent W atoms, resulting in *NO3 and *NO2 being strongly adsorbed on W active sites in the form of bidentate ligands instead of the relatively weak monodentate ligands. Furthermore, WN facilitates H2O dissociation to supply the requisite protons, which is beneficial for *NO2 hydrogenations. Inspired by theoretical prediction, WN/WO3 nanosheets are successfully fabricated through a high-temperature nitridation process. The transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray absorption near-edge spectroscopy investigations confirm that the amorphous WN has been locally introduced in situ into WO3 nanosheets to form a composite heterostructure. The as-prepared WN/WO3 nanosheets exhibit a high Faraday efficiency of 88.9 ± 7.2% and an appreciable yield rate of 8.4 mg h-1 cm-2 toward NH3 production, which is much higher than that of individual WO3 and WN. The enhanced adsorption and hydrogenation behaviors of *NOx over WN/WO3 are characterized by in situ Fourier-transform infrared spectroscopy, consistent with the theoretical predictions. This work develops facile and effective heterostructure nanomaterials to tune the adsorption and hydrogenation of NOx for boosting the efficiency from NO3- to NH3.
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Layered gadolinium hydroxide (LGdH) and Ti3C2 monolayers were assembled into a LGdH/Ti3C2 (GTC) hybrid. The hybrid demonstrated enhanced near-infrared (NIR) light absorption properties and superior photothermal performance. Moreover, the GTC hybrid achieved an excellent T1-weighted magnetic resonance imaging (MRI) effect.
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Water electro-splitting driven by renewable energy is significant in energy conversion for the development of hydrogen energy sources. The hydrogen evolution reaction (HER) directly generating hydrogen products occurs in cathode catalysis. Over the years, significant progress has been made to boost the HER efficiency by exploratively designing highly active and economical Pt-based electrocatalysts. However, there are still some urgent problems to be solved for Pt-based HER catalysts in more economical alkaline electrolytes, such as the slow kinetics caused by additional hydrolysis dissociation steps, which greatly hinders the practical application. This review systematically summarizes several strategies for optimizing alkaline HER kinetics and provides direct guidelines for the design of highly active Pt-based electrocatalysts. Specifically, the intrinsic HER activity in alkaline water electrolysis can be boosted by accelerating the water dissociation, optimizing the hydrogen binding energy or modulating the spatial dimensions of the electrocatalyst based on the HER mechanism. Finally, we prospect the challenges for the alkaline HER on novel Pt-based electrocatalysts, including the active site study, the HER mechanism exploration and the extensible catalyst preparation technologies.
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Heterointerface engineering of NiFe (oxy)hydroxides is a prospective way of improving OER activity by the pre-catalysis of metal hydroxides accompanying the modulation of defects, but enhancement of the kinetics is controversial. Herein, in situ phase transformation of NiFe hydroxides was proposed and heterointerface engineering was optimized by sub-nano Au anchoring in simultaneously formed cation vacancies. Controllable size and concentrations of anchored sub-nano Au in the cation vacancies resulted in the modulation of the electronic structure at the heterointerface, and improved water oxidation activity was ascribed to the enhanced intrinsic activity and charge transfer rate. Here, Au/NiFe (oxy)hydroxide/CNTs with an Fe/Au molar ratio of 24 exhibited an overpotential of â¼236.3 mV at 10 mA cm-2 in 1.0 M KOH under simulated solar light irradiation, which is â¼19.8 mV lower than that without the consumption of solar energy. Spectroscopic studies reveal that the photo-responsive FeOOH in these hybrids and modulation of sub-nano Au anchoring in cation vacancies are favorable in improving solar energy conversion and suppressing photo-induced charge recombination.
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The design and development of efficient catalysts for electrochemical nitrogen reduction reaction (ENRR) under ambient conditions are critical for the alternative ammonia (NH3 ) synthesis from N2 and H2 O, wherein iron-based electrocatalysts exhibit outstanding NH3 formation rate and Faradaic efficiency (FE). Here, the synthesis of porous and positively charged iron oxyhydroxide nanosheets by using layered ferrous hydroxide as a starting precursor, which undergoes topochemical oxidation, partial dehydrogenated reaction, and final delamination, is reported. As the electrocatalyst of ENRR, the obtained nanosheets with a monolayer thickness and 10-nm mesopores display exceptional NH3 yield rate (28.5 µg h-1 mgcat. -1 ) and FE (13.2%) at a potential of -0.4 V versus RHE in a phosphate buffered saline (PBS) electrolyte. The values are much higher than those of the undelaminated bulk iron oxyhydroxide. The larger specific surface area and positive charge of the nanosheets are beneficial for providing more exposed reactive sites as well as retarding hydrogen evolution reaction. This study highlights the rational control on the electronic structure and morphology of porous iron oxyhydroxide nanosheets, expanding the scope of developing non-precious iron-based highly efficient ENRR electrocatalysts.
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The non-metal NH4 + carrier has attracted tremendous interests for aqueous energy storage owing to its light molar mass and fast diffusion in aqueous electrolytes. Previous study inferred that NH4 + ion storage in layered VOPO4 â 2 H2 O is impossible due to the removal of NH4 + from NH4 VOPO4 leads to a phase change inevitably. Herein, we update this cognition and demonstrated highly reversible intercalation/de-intercalation behavior of NH4 + in layered VOPO4 â 2 H2 O host. Satisfactory specific capacity of 154.6â mAh g-1 at 0.1â A g-1 and very stable discharge potential plateau at 0.4â V based on reference electrode was achieved in VOPO4 â 2 H2 O. A rocking-chair ammonium-ion full cell with the VOPO4 â 2 H2 O//2.0â M NH4 OTf//PTCDI configuration exhibited a specific capacity of 55â mAh g-1 , an average operating voltage of about 1.0â V and excellent long-term cycling stability over 500â cycles with a coulombic efficiency of ≈99 %. Theoretical DFT calculations suggest a unique crystal water substitution process by ammonium ion during the intercalation process. Our results provide new insight into the intercalation/de-intercalation of NH4 + ions in layered hydrated phosphates through crystal water enhancement effect.
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Multiwalled carbon nanotubes (MWCNTs) have shown effectiveness in improving the suitability of MXenes for energy-related applications. However, the ability of individually dispersed MWCNTs to control the structure of MXene-based macrostructures is unclear. Here, the correlation among composition, surface nano- and microstructure, MXenes' stacking order, structural swelling, and Li-ion transport mechanisms and properties in individually dispersed MWCNT-Ti3C2 films was investigated. The compact surface microstructure of MXene film, characterized by prominent wrinkles, is dramatically changed as MWCNTs occupy MXene/MXene edge interfaces. The 2D stacking order is preserved up to 30 wt% MWCNTs despite a significant swelling of â¼400%. Such alignment is completely disrupted at 40 wt%, and a more pronounced surface opening and internal expansion of â¼770% are realized. Both 30 wt% and 40 wt% membranes show stable cycling performance under a significantly higher current density due to faster transport channels. Notably, for the 3D membrane, the overpotential during repeated Li deposition/dissolution reactions is further reduced by â¼50%. Ion-transport mechanisms in the absence and presence of MWCNTs are discussed. Furthermore, ultralight yet continuous hybrid films comprising up to â¼0.027 mg cm-2 Ti3C2 can be prepared using aqueous colloidal dispersions and vacuum filtration for specific applications. The potential application of such ultralight membranes as interlayers for Li-O2 batteries is briefly examined.
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Because of the combined merits of rich physicochemical properties, abundance, low toxicity, etc., hematite (α-Fe2O3), one of the most chemically stable compounds based on the transition metal element iron, is endowed with multifunctionalities and has steadily been a research hotspot for decades. Very recently, advanced α-Fe2O3 materials have also been developed for applications in some cutting-edge fields. To reflect this trend, the latest progress in developing α-Fe2O3 materials for newly emerging applications is reviewed with a particular focus on the relationship between composition/nanostructure-induced electronic structure modulation and practical performance. Moreover, perspectives on the critical challenges as well as opportunities for future development of diverse functionalities are also discussed. We believe that this timely review will not only stimulate further increasing interest in α-Fe2O3 materials but also provide a profound understanding and insight into the rational design of other materials based on transition metal elements for various applications.
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The energy storage performances of supercapacitors are expected to be enhanced by the use of nanostructured hierarchically micro/mesoporous hollow carbon materials based on their ultra-high specific surface areas and rapid diffusion of electrolyte ions through the interconnected channels of their mesoporous structures. In this work, we report the electrochemical supercapacitance properties of hollow carbon spheres prepared by high-temperature carbonization of self-assembled fullerene-ethylenediamine hollow spheres (FE-HS). FE-HS, having an average external diameter of 290 nm, an internal diameter of 65 nm, and a wall thickness of 225 nm, were prepared by using the dynamic liquid-liquid interfacial precipitation (DLLIP) method at ambient conditions of temperature and pressure. High temperature carbonization (at 700, 900, and 1100 °C) of the FE-HS yielded nanoporous (micro/mesoporous) hollow carbon spheres with large surface areas (612 to 1616 m2 g-1) and large pore volumes (0.925 to 1.346 cm3 g-1) dependent on the temperature applied. The sample obtained by carbonization of FE-HS at 900 °C (FE-HS_900) displayed optimum surface area and exhibited remarkable electrochemical electrical double-layer capacitance properties in aq. 1 M sulfuric acid due to its well-developed porosity, interconnected pore structure, and large surface area. For a three-electrode cell setup, a specific capacitance of 293 F g-1 at a 1 A g-1 current density, which is approximately 4 times greater than the specific capacitance of the starting material, FE-HS. The symmetric supercapacitor cell was assembled using FE-HS_900 and attained 164 F g-1 at 1 A g-1 with sustained 50% capacitance at 10 A g-1 accompanied by 96% cycle life and 98% coulombic efficiency after 10,000 consecutive charge/discharge cycles. The results demonstrate the excellent potential of these fullerene assemblies in the fabrication of nanoporous carbon materials with the extensive surface areas required for high-performance energy storage supercapacitor applications.
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ZnS materials exhibit very negative potential of the conduction band, which is promising in photocatalytic reduction reactions. Unfortunately, previously reported ZnS materials for photocatalysis are mainly in the cubic phase, which produce high activity for H2 evolutions and low activity toward CO2 reductions. Herein, a hexagonal phase ZnS photocatalyst is fabricated for highly efficient CO2 reduction reactions. The hexagonal ZnS nanoplates with the pure phase and well crystallization are synthesized via three-step solvothermal methods. In photocatalytic CO2 reduction reactions under an aqueous solution environment, the hexagonal ZnS produces a CO selectivity of 21%, which is distinctly higher than that of 0.2% for commonly used cubic ZnS. The energy band study suggests that hexagonal ZnS possesses a slightly more negative conduction band and wider bandgap than cubic ZnS. Theoretical calculations reveal that the hexagonal ZnS possesses increased electron density around Zn atoms as that of cubic ZnS. Furthermore, hexagonal ZnS exhibits relatively reduced absorption energy of CO2 reduction intermediates and increased absorption energy of H* as cubic ZnS, which result in better selectivity toward CO2 reduction reactions. This study offers deep insights into the synthesis and electronic structure of hexagonal ZnS for CO2 reduction reactions, which inspire the design of highly active photocatalysts for artificial photosynthesis.
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Li metal is the ultimate anode material for next-generation high-energy-density rechargeable batteries. However, the uncontrollable growth of Li dendrites and low Coulombic efficiency (CE) prevent it from practical applications in Li metal batteries (LMBs). Here, a facile and low-cost strategy is developed to decorate a Cu current collector with a self-assembled γ-aminopropyltrimethoxysilane (γ-APS) film. The thin polymer film with nanopores promotes the formation of cobblestone-like Li deposition and suppresses Li-dendrite formation due to its low surface energy. The protecting layer not only increases the lithiophilicity of the Cu current collector but also alleviates the ambient corrosion and galvanic corrosion in practical use. Owing to these advantages, the half cell using γ-APS-Cu collectors exhibits a high average CE value of 99.2% for 100 cycles. The symmetric cell of γ-APS-Cu@Li shows an improved lifespan of 1400 h with a small voltage hysteresis of 12 mV at 0.5 mA cm-2. The full cell assembled with LiFePO4 (LFP) cathodes and γ-APS-Cu@Li anodes delivers a high capacity of 136 mAh g-1 after 600 cycles at 0.5C.
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Transition metal oxides have drawn tremendous interest due to their unique physical and chemical properties. As one of the most promising electrochromic (EC) materials, tungsten trioxide (WO3) has attracted great attention due to its exceptional EC characteristics. This review summarizes the background and general concept of EC devices, and key criteria for evaluation of WO3-based EC materials. Special focus is placed on preparation techniques and performance enhancement of WO3 EC films. Specifically, four methods - nanostructuring, regulating crystallinity, fabricating hybrid films, and preparing multilayer composite structures - have been developed to enhance the EC performance of WO3 films. Finally, we offer some important recommendations and perspectives on potential research directions for further study.