CoFe bimetallic hydroxides(CoFe BMHs)find wide applications as excellent catalysts in the field of water splitting.However,no study has systematically investigated the influence of the morphologies of CoFe BMHs on cat...CoFe bimetallic hydroxides(CoFe BMHs)find wide applications as excellent catalysts in the field of water splitting.However,no study has systematically investigated the influence of the morphologies of CoFe BMHs on catalyst performance.In this study,CoFe BMH nanoflowers(CoFe BMH NFs),CoFe BMH nanosheets(CoFe BMH NSHs),CoFe BMH nanorods(CoFe BMH NRs),and CoFe BMH nanospheres(CoFe BMH NSPs)were prepared on nickel foam via a hydrothermal method.CoFe BMH NSHs exhibited the most beneficial catalytic activity.At a current density of 100 mA·cm^(-2),its overpotential for oxygen evolution reaction(OER)was 282 mV,and the overall water splitting voltage was 2.05 V.The double-layer charging capacitance(Cdl)value of CoFe BMH NSHs was the largest in CoFe BMHs,which proves that CoFe BMH NSHs have the largest active area.Furthermore,the active site in the OER process was metal oxyhydroxide(MOOH)through in situ Raman characterization,and the generation of the active substance was an irreversible process.This work provides important insights into the design of catalyst morphologies and offers valuable guidelines for the enhancement of the performance of other catalysts.展开更多
Novel and promising chloride ion batteries(CIBs)that can operate at room temperature have attracted great attentions,due to the sustainable chloride-containing resources and high theoretical energy density.To achieve ...Novel and promising chloride ion batteries(CIBs)that can operate at room temperature have attracted great attentions,due to the sustainable chloride-containing resources and high theoretical energy density.To achieve the superior electrochemical properties of CIBs,the structure design of electrode materials is essential.Herein,2D NiAl-layered double hydroxide(NiAl-LDH)nanoarrays derived from Al2O3 are in-situ grafted to graphene(G)by atomic layer deposition(ALD)and hydrothermal method.The achieved NiAl-LDH@G hybrids with 2D NiAl-LDH arrays grown perpendicularly on graphene surface,can efficiently prevent the stacking of LDHs and enlarge specific surface area to provide more active sites.The NiAl-LDH@G cathode exhibits a maximum discharge capacity of 223.3 mA h g^(-1)and an excellent reversible capacity of 107 mA h g^(-1)over 500 cycles at 100 mA g^(-1)with a high coulombic efficiency around 96%,whereas pure NiAl-LDH has a discharge capacity of only 48.8 mA h g^(-1)and a coulombic efficiency(CE)of about 78%.More importantly,the NiAl-LDH@G electrode has a stable voltage at 1.9 V and an outstanding discharge capacity of higher than 72 mA h g^(-1)after 120 days.Additionally,XRD,XPS,and EDS have been employed to unveil the electrochemical reaction and Cl-storage mechanism of the NiAlLDH@G cathode in CIBs.This work opens a facile and reasonable way for improving electrochemical performance at anion-type rechargeable batteries in terms of cathode material design and mechanism interpretation.展开更多
High-entropy materials(HEMs),which are typically composed of five or more elements in near-equimolar ratios with concentrations ranging from 5%to 35%,have distinct elemental compositions and geometric properties that ...High-entropy materials(HEMs),which are typically composed of five or more elements in near-equimolar ratios with concentrations ranging from 5%to 35%,have distinct elemental compositions and geometric properties that allow for the development of advanced electrocatalysts for renewable energy conversion systems.The highentropy effect,crystal dislocations,cocktail effect,and slow diffusion in high-entropy layered double hydroxides(HE-LDHs)and amorphous materials(HE-AMs)have all been shown to boost electrocatalytic water oxidation performance significantly.These materials exhibit remarkable activity and stability in both alkaline and acidic conditions.HE-AMs,in particular,benefit from a variety of defects,including coordinatively unsaturated sites and loosely connected atoms,which are critical to their improved catalytic capabilities.HEMs engineering and precise nanostructure control can address the low intrinsic activity,restricted active sites,and poor conductivity of binary and ternary amorphous and LDH catalysts.This study discusses current advances in HE-LDHs and HE-AMs for water electrolysis,including synthesis methods,structural features,active site identification by DFT calculations,and their applications in water electrocatalysis.The presentation also covers potential problems and future directions for developing these materials in energy conversion device systems.展开更多
Electrically driven water splitting is an efficient method for green hydrogen production;however,its practical application is substantially constrained by the kinetically sluggish anodic oxygen evolution reaction(OER)...Electrically driven water splitting is an efficient method for green hydrogen production;however,its practical application is substantially constrained by the kinetically sluggish anodic oxygen evolution reaction(OER).Ruthenium(Ru)and its oxides are widely recognized as highly active OER catalysts.Although Ru is significantly cheaper than iridium(Ir),further reducing its content remains desirable.Herein,atomically dispersed Ru is doped into iron-nickel layered double hydroxides(Ru-FeNi-LDH)to decrease the Ru usage.We found that the Ru doping limit is roughly 9 wt%,and the Ru doping content significantly alters the OER kinetics-note that the high Ru concentration remarkably damages the Ru-FeNi-LDH structure and leads to agglomeration formation.By optimizing the Ru doping content to 3.3 wt%,the Ru-FeNi-LDH presents a low overpotential of 230 mV to reach a current density of 10 mA cm^(-2) in 1 M KOH,which is far better than the reference FeNi-LDH(280 mV)and RuO_(2)(350 mV).In the overall water splitting test,the current density of 10 mA cm^(-2) can be reached at a low voltage of 1.52 V,with stable operation for 80 h.Interestingly,Ru and Fe form an asymmetric Ru-Fe dipole,which is likely doped together into the LDH because the content of Fe instead of Ni is dependent on Ru content in experimental results.The electron-deficient feature of the Ru-Fe dipole thus facilitates the OER process.This work demonstrates a dual-transition metal synergy,providing a design strategy for OER and related catalysts.展开更多
Layered double hydroxides(LDHs)are potential cathode materials for aqueous magnesium-ion batteries(AMIBs).However,the low capacity and sluggish kinetics significantly limit their electrochemical performance in AMIBs.H...Layered double hydroxides(LDHs)are potential cathode materials for aqueous magnesium-ion batteries(AMIBs).However,the low capacity and sluggish kinetics significantly limit their electrochemical performance in AMIBs.Herein,we find that oxygen vacancies can significantly boost the capacity,electrochemical kinetics,and structure stability of LDHs.The corresponding structure-performance relationship and energy storage mechanism are elaborated through exhaustive in/ex-situ experimental characterizations and density functional theory(DFT)calculations.Specially,in-situ Raman and DFT calculations reveal that oxygen vacancies elevate orbital energy of O 2p and electron density of O atoms,thereby enhancing the orbital hybridization of O 2p with Ni/Co 3d.This facilitates electron transfer between O and adjacent Ni/Co atoms and improves the covalency of Ni–O and Co–O bonds,which activates Ni/Co atoms to release more capacity and stabilizes the Ov-NiCo-LDH structure.Moreover,the distribution of relaxation times(DRT)and molecular dynamics(MD)simulations disclose that the enhanced d-p orbital hybridization optimizes the electronic structure of Ov-NiCo-LDH,which distinctly reduces the diffusion energy barriers of Mg^(2+)and improves the charge transfer kinetics of Ov-NiCo-LDH.Consequently,the assembled Ov-NiCo-LDH//active carbon(AC)and Ov-NiCo-LDH//perylenediimide(PTCDI)AMIBs can both deliver high specific discharge capacity(182.7 and 59.4 mAh g^(−1)at 0.5 A g^(−1),respectively)and long-term cycling stability(85.4%and 89.0%of capacity retentions after 2500 and 2400 cycles at 1.0 A g^(−1),respectively).In addition,the practical prospects for Ov-NiCo-LDH-based AMIBs have been demonstrated in different application scenarios.This work not only provides an effective strategy for obtaining high-performance cathodes of AMIBs,but also fundamentally elucidates the inherent mechanisms.展开更多
Noble metal-loaded layered hydroxides exhibit high efficiency in electrocatalyzing water splitting.However,their widespread use as bifunctional electrocatalysts is hindered by low metal loading,inefficient yield,and c...Noble metal-loaded layered hydroxides exhibit high efficiency in electrocatalyzing water splitting.However,their widespread use as bifunctional electrocatalysts is hindered by low metal loading,inefficient yield,and complex synthesis processes.In this work,platinum atoms were anchored onto nickel-iron layered double hydroxide/carbon nanotube(LDH/CNT)hybrid electrocatalysts by using a straightforward milling technique with K_(2)Pt Cl_(6)·6H_(2)O as the Pt source.By adjusting the Pt-to-Fe ratio to 1/2 and 1/10,excellent electrocatalysts—Pt_(1/6)-Ni_(2/3)Fe_(1/3)-LDH/CNT and Pt_(1/30)-Ni_(2/3)Fe_(1/3)-LDH/CNT—were achieved with superior performance in hydrogen evolution reaction(HER)and oxygen evolution reaction(OER),outperforming the corresponding commercial Pt/C(20 wt%)and Ru O_(2)electrocatalysts.The enhanced electrochemical performance is attributed to the modification of Pt's electronic structure,which exhibits electron-rich states for HER and electrondeficient states for OER,significantly boosting Pt's electrochemical activity.Furthermore,the simple milling technology for controlling Pt loading offers a promising approach for scaling up the production of electrocatalysts.展开更多
ZnO/NiO/ZnAl2O4 mixed-metal oxides were successfully synthesized through a hydrotalcite-like precursor route, in which appropriate amounts of metal salts solutions were mixed to obtain a new series of ZnNiAl layered d...ZnO/NiO/ZnAl2O4 mixed-metal oxides were successfully synthesized through a hydrotalcite-like precursor route, in which appropriate amounts of metal salts solutions were mixed to obtain a new series of ZnNiAl layered double hydroxides（LDHs） as precursors, followed by calcination under different temperatures. The as-obtained samples were characterized by SEM, HRTEM, TEM, XRD, BET, TG-DTA, and UV-Vis spectra techniques. The photocatalytic activities of the samples were evaluated by degradation of methyl orange（MO） under the simulated sunlight irradiation. The effects of Zn/Ni/Al mole ratio and calcination temperature on the composition, morphology and photocatalytic activity of the samples were investigated in detail. The results indicated that compared with ZnNiAl-LDHs, the mixed-metal oxide showed superior photocatalytic performance for the degradation of MO. A maximum of 97.3% photocatalytic decoloration rate within 60 min was achieved from the LDH with the Zn/Ni/Al mole ratio of 2：1：1 and the calcination temperature of 500 ℃, which much exceeded that of Degussa P25 under the same conditions. The possible mechanism of photocatalytic degradation over ZnO/NiO/ZnAl2O4 was discussed.展开更多
Colored layered double hydroxides （LDHs） can be synthesized by introducing colored cations such as Fe^3＋ and Cr^3 ＋, which call be used as thermal stabilizers for polyvinyl chloride （PVC）. The yellowish Mg/Fe an...Colored layered double hydroxides （LDHs） can be synthesized by introducing colored cations such as Fe^3＋ and Cr^3 ＋, which call be used as thermal stabilizers for polyvinyl chloride （PVC）. The yellowish Mg/Fe and bluish Mg/Cr LDHs are prepared by the co-precipitation method. The results show that the MgsCr_ CO3 and Mg3Fe_ CO3 colored layered double hydroxides can stabilize PVC for more than 30 min under the thermal aging temperature of 180 ℃. The preparation can use cheap Mg（OH） 2 instead of MgCl2, which produces a much smaller amount of the by-product NH4Cl. It is known that NH4Cl is a cheap fertilizer that is difficult to sell; therefore, the preparation is much greener and more economic than the one using magnesium salt.展开更多
The explore and development of electrocatalysts have gained significant attention due to their indispensable status in energy storage and conversion systems, such as fuel cells, metal–air batteries and solar water sp...The explore and development of electrocatalysts have gained significant attention due to their indispensable status in energy storage and conversion systems, such as fuel cells, metal–air batteries and solar water splitting cells. Layered double hydroxides（LDHs） and their derivatives（e.g., transition metal alloys, oxides, sulfides, nitrides and phosphides） have been adopted as catalysts for various electrochemical reactions, such as oxygen reduction, oxygen evolution, hydrogen evolution, and COreduction, which show excellent activity and remarkable durability in electrocatalytic process. In this review, the synthesis strategies, structural characters and electrochemical performances for the LDHs and their derivatives are described. In addition, we also discussed the effect of electronic and geometry structures to their electrocatalytic activity. The further development of high-performance electrocatalysts based on LDHs and their derivatives is covered by both a short summary and future outlook from the viewpoint of the material design and practical application.展开更多
Catalytic oxidation is regarded as one of the most promising strategies for volatile organic compounds(VOCs)purification.Mixed metal oxides(MMOs),after topological transformation using layered double hydroxides(LDHs)a...Catalytic oxidation is regarded as one of the most promising strategies for volatile organic compounds(VOCs)purification.Mixed metal oxides(MMOs),after topological transformation using layered double hydroxides(LDHs)as precursors,are extensively used as catalysts for VOCs oxidation due to their uniformity advantage.This review summarizes the developments in the LDH-derived VOCs heterogeneous catalytic oxidation over the last 10 years.Particularly,it addresses the VOCs abatement performance over MMO,noble metal/MMO,core-shell structured MMO,and integral MMO film catalysts originating from LDHs.Moreover,it highlights the water vapor effect and oxidation mechanism.This review indicates that LDH-based catalysts are a category of important VOCs oxidation materials.展开更多
Anodic oxidation is a prevalent technique to introduce superior corrosion and wear resistance upon the surface of titanium(Ti)alloys,in which the selection of appropriate electrolytes and defect-sealing strategies is ...Anodic oxidation is a prevalent technique to introduce superior corrosion and wear resistance upon the surface of titanium(Ti)alloys,in which the selection of appropriate electrolytes and defect-sealing strategies is a key.This study aims to address such issues through anodizing Ti-10V-2Fe-3Al alloy in malic acid,followed by a post-sealing treatment with Mg-Al layered double hydroxides(LDHs).The characteristics of the samples were investigated using scanning electron microscopy(SEM),atomic force microscopy(AFM),glow discharge optical emission spectroscopy(GDOES),X-ray diffraction(XRD)and energy-dispersive X-ray spectroscopy(EDS).SEM micrographs reveals that the anodic coating had a surface full of bulges and cracks,and was almost sealed by the following LDHs treatment.XRD pattern indicate that the anodic coating was mainly consisted of amorphous TiO2 with a small fraction of anatase,but its crystallization degree was increased through the post-sealing.Moreover,electrochemical and tribological measurements demonstrate that corrosion current density was 2.8×10-6,2.0×10-7,5.9×10-9A cm-2,and wear rate was 1.45×10-3,1.30×10-4 and 6.90×10-5 mm3 N-1 m-1 for respective bare Ti-10V-2Fe-3Al alloy substrate,anodized specimens without and with the LDHs post treatment.Finally,a plausible wear mechanism was proposed.展开更多
In this study,greatly enhanced Mn(Ⅱ) adsorption was achieved by as-synthesized diethylenetriaminepentaacetate acid intercalated Mg/Al layered double hydroxides (LDHs-DTPA).The adsorption capacity of LDHs-DTPA was 83....In this study,greatly enhanced Mn(Ⅱ) adsorption was achieved by as-synthesized diethylenetriaminepentaacetate acid intercalated Mg/Al layered double hydroxides (LDHs-DTPA).The adsorption capacity of LDHs-DTPA was 83.5 mg/g,which is much higher than that of LDHs-EDTA (44.4 mg/g),LDHs-Oxalate (21.6 mg/g) and LDHs (28.8 mg/g).The adsorption data of aqueous Mn(Ⅱ) using LDHs-DTPA could be well described by the pseudosecond order kinetics and Langrnuir isotherm model.Thermodynamics study results also showed that the adsorption process of Mn(Ⅱ) by LDHs-DTPA was exothermic as indicated by the negative △H value.Furthermore,based on the structural,morphological and thermostable features,as well as FT-IR and XPS characterizations of LDHs-DTPA and the pristine LDHs,the adsorption mechanism of Mn(Ⅱ) was proposed.The carboxyl groups of DTPA were proposed to be the main binding sites for Mn(Ⅱ),and the hydroxyl groups of LDHs also played a minor role in the adsorption process.Among the three common regeneration reagents,0.1 mol/L Na2CO3 was the best for reusing LDHs-DTPA in Mn(Ⅱ) adsorption.Besides,the Mn(Ⅱ) adsorption performance could be hindered in the presence of typical inorganic ions,especially cations.Further specific modifications of LDHs-DTPA are suggested to get more selective adsorption of Mn(ll) in practical applications.展开更多
Mg–Al–Fe layered double hydroxides（LDHs） were exfoliated and incorporated in polyether sulfone membranes for the removal of phosphate and fluoride for the first time. The exfoliation methods, coagulation bath, LDH...Mg–Al–Fe layered double hydroxides（LDHs） were exfoliated and incorporated in polyether sulfone membranes for the removal of phosphate and fluoride for the first time. The exfoliation methods, coagulation bath, LDH amount, interfering ions, adsorption isotherm,desorption and reuse of the membranes were investigated. It was found that LDHs could be quickly exfoliated in formamide/N,N-dimethylformamide（DMF） solvent mixtures with sodium carboxymethyl cellulose as a stabilizer. The membranes displayed much higher adsorption capacity for phosphate（5.61 mg/g） and faster adsorption rate than the unexfoliated materials. With increased DMF content in the coagulation bath, the static and dynamic adsorption capacity rose. Interference from Cl-and SO4^（2-）（50 mg/L） on adsorption of phosphates was not apparent. The membranes displayed excellent reusability in dynamic adsorption/desorption. The membranes also showed high adsorption capacity for fluorides（1.61 mg/g）.展开更多
Layered double hydroxides(LDHs) with the physical property of high ultraviolet(UV)reflectance were used to enhance the anti-UV aging performance of bitumen. In view of the poor compatibility of LDHs with bitumen, thre...Layered double hydroxides(LDHs) with the physical property of high ultraviolet(UV)reflectance were used to enhance the anti-UV aging performance of bitumen. In view of the poor compatibility of LDHs with bitumen, three organic anions, namely, sodium dodecyl benzenesulfonate(SDBS), sodium dodecyl sulfate(SDS) and sodium dodecyl sulfonate(SDSO), were used as modifiers to prepare organic LDHs(OCLDHs) through regeneration process, and the crystal structure, chemical composition, morphological feature and UV shielding capability of synthesized OCLDHs were analyzed. Then the OCLDHs were added into bitumen to evaluate the storage stability and anti-UV aging property of OCLDHs/bitumen composites.The results show that the organic anions are inserted into the interlayers of LDHs, the intercalation expands the interlayer distance of LDHs, makes the particle shapes become more irregular and complicated, and enhances the absorption ability within the range from 200 to 300 nm while has little influence on the UV reflection ability.Result of high temperature storage stability indicates the organic modification ameliorates the compatibility of LDHs with bitumen. Compared with LDHs, OCLDHs decrease the deteriorations of bitumen’s properties during UV exposure test, exhibiting better effect in enhancing anti-UV aging performance of bitumen. Furthermore,among the three OCLDHs, LDHs intercalated by SDBS exhibit the most effective improvement due to the best compatibility with bitumen and comparatively good UV shielding effect.展开更多
This article presents a detailed structural study of a new spherical Mg Cl2-supported Ti Cl4 Ziegler-Natta catalyst for isotactic propylene polymerization, and researches on the relationship between catalyst structure...This article presents a detailed structural study of a new spherical Mg Cl2-supported Ti Cl4 Ziegler-Natta catalyst for isotactic propylene polymerization, and researches on the relationship between catalyst structure and polymer properties. The spherical support with the chemical composition of CH3CH2 OMg OCH(CH2Cl)2 has been synthesized from a new dispersion system and is used as the supporting material to prepare Ziegler-Natta catalyst. The XRD analysis indicates that the catalyst is fully activated with δ-Mg Cl2 in the active catalyst. The far-IR spectrometric results confirm again the presence of δ-Mg Cl2 in the active catalyst. Textural property of the active catalyst exhibits high surface area coupled with high porosity. The high activity in propylene polymerization is mainly ascribed to the full activation and the porous structure of the catalyst. Scanning electron microscopy/energy dispersive spectrometer mapping results indicate a uniform titanium distribution throughout the catalyst particles. Particle size analysis shows that the catalyst has a narrow particle size distribution. The perfect spherical shape, uniform titanium distribution and narrow particle size distribution of the catalyst confirm the advantage of polymer particles production with less fines. The solid state 13 C NMR and mid-IR spectroscopic analyses indicate that there exists strong complexation between diisobutyl phthalate and Mg Cl2, which leads to the high isotacticity of polypropylene.展开更多
To extract selenium(Ⅵ)from the highly caustic leachate of copper anode slime,the Ca-Al-Cl layered double hydroxides(Ca-Al-Cl-LDHs)with a formula of Ca2 Al(OH)6 Cl·2 H2 O by three co-precipitation methods were sy...To extract selenium(Ⅵ)from the highly caustic leachate of copper anode slime,the Ca-Al-Cl layered double hydroxides(Ca-Al-Cl-LDHs)with a formula of Ca2 Al(OH)6 Cl·2 H2 O by three co-precipitation methods were synthesized.A plate-like morphology and hexagonal crystal structure with typical mineral phases and functional groups were identified by the FESEM,XRD,FTIR,BET and XPS analysis.The forward feeding sample exhibits the best adsorption capacity of Se(Ⅵ).The factor experiments then reveal a favorable adsorption process with low temperature,low NaOH concentration and high adsorbent dosage.Furthermore,the adsorption kinetics and isotherm parameters can be well described by the Langmuir isotherm and the pseudo-second-order models,respectively.Accordingly,the maximum adsorption amount of Se(Ⅵ)onto Ca-Al-Cl-LDHs reaches188.6 mg/g at 50 ℃.展开更多
One of the fundamental driving forces in the materials science community is the hunt for new materials with specific properties that meet the requirements of rapidly evolving technology.
Flexible thin-film supercapacitors with high specific capacitance are highly desirable for modern wearable or micro-sized electrical and electronic applications. In this contribution, Ni-Co hydroxides（NCH）nanosheets...Flexible thin-film supercapacitors with high specific capacitance are highly desirable for modern wearable or micro-sized electrical and electronic applications. In this contribution, Ni-Co hydroxides（NCH）nanosheets were deposited on top of Ni-Cu alloy（NCA）nanowire arrays forming a freestanding thin-film composite electrode with hierarchical structure for supercapacitors.During electrochemical cycling, the dissolution of Cu into Cu ions will create more active sites on NCA, and the redeposited copper oxide can be coated onto NCH, giving rise to substantial increase in specific capacitance with cycling. Meanwhile, NCA and NCH have excellent conductivity, thus leading to excellent rate performance. This flexible thin-film electrode delivers an ultrahigh initial specific capacitance of 0.63 F·cm^（-2）（or 781.3 F·cm^（-3））.During charge-discharge cycles, the specific capacitance can increase up to 1.18 F·cm^（-2）（or 1475 F·cm^（-3）） along with the“self-etching”process. The electrode presents a better specific capacitance and rate capability compared with previously reported flexible thin-film electrode, and this novel design of etching technique may expand to other binary or ternary materials.展开更多
Oxygen evolution reaction(OER) is a bottle-neck process in many sustainable energy conversion systems due to its sluggish kinetics.The development of cost-effective yet efficient electrocatalysts towards OER is highly...Oxygen evolution reaction(OER) is a bottle-neck process in many sustainable energy conversion systems due to its sluggish kinetics.The development of cost-effective yet efficient electrocatalysts towards OER is highly desirable but still a great challenge at current stage.Herein,a new type of hybrid nanostructure,consisting of two-dimensional(2D) Cerium-doped NiFe-layered double hydroxide nanoflakes directly grown on the 2D Ti3C2Tx MXene surface(denoted as NiFeCe-LDH/MXene),is designed using a facile insitu coprecipitation method.The resultant NiFeCe-LDH/MXene hybrid presents a hierarchical nanoporous structure,high electrical conductivity and strong interfacial junction because of the synergistic effect of Ce doping and MXene coupling.As a result,the hybrid catalyst exhibits an excellent catalytic activity for OER,delivering a low onset overpotential of 197 mV and an overpotential of 260 mV at a current density of 10 mA·cm-2 in the alkaline medium,much lower than its pure LDH counterparts and IrO2 catalyst.Besides,the hybrid catalyst also displays a fast reaction kinetics and a remarkable stable durability.Further theoretic studies using density function theory(DFT) methods reveal that Ce doping could effectively narrow the bandgap of NiFe-LDH and reduce the overpotential in OER process.This work may shed light on the exploration of advanced electrocatalysts for renewable energy conversion and storage systems.展开更多
Exploring highly efficient electrochemical water splitting catalysts has recently attracted extensive research interest from both fundamental researches and practical applications.Transition metal‐based layered doubl...Exploring highly efficient electrochemical water splitting catalysts has recently attracted extensive research interest from both fundamental researches and practical applications.Transition metal‐based layered double hydroxides(LDHs)have been proved to be one of the most efficient materials for oxygen evolution reaction(OER),however,still suffered from low conductivity and sluggish kinetics for hydrogen evolution reaction(HER),which largely inhibited the overall water splitting efficiency.To address this dilemma,enormous approaches including doping regulation,intercalation tuning and defect engineering are therefore rationally designed and developed.Herein,we focus on the recent exciting progress of LDHs hybridization with other two‐dimensional(2D)materials for water splitting reactions,not barely for enhancing OER efficiency but also for boosting HER activity.Particularly,the structural features,morphologies,charge transfer and synergistic effects for the heterostructure/heterointerface that influence the electrocatalytic performance are discussed in details.The hybrid 2D building blocks not only serve as additional conductivity and structural supported but also promote electron transfer at the interfaces and further enhance the electrocatalytic performance.The construction and application of the nanohybrid materials will guide a new direction in developing multifunctional materials based on LDHs,which will contribute to energy conversion and storage.展开更多
基金supported by the National Science Fund for Distinguished Young Scholars(No.52025041)the National Natural Science Foundation of China(Nos.52474319,52250091,U2341267,and 52450003)+1 种基金the Fundamental Research Funds for the Central Universities(No.FRF-TP-20-02C2)supported by the Interdisciplinary Research Project for Young Teachers of USTB,China(Fundamental Research Funds for the Central Universities)(No.FRF-IDRY-GD23-003).
文摘CoFe bimetallic hydroxides(CoFe BMHs)find wide applications as excellent catalysts in the field of water splitting.However,no study has systematically investigated the influence of the morphologies of CoFe BMHs on catalyst performance.In this study,CoFe BMH nanoflowers(CoFe BMH NFs),CoFe BMH nanosheets(CoFe BMH NSHs),CoFe BMH nanorods(CoFe BMH NRs),and CoFe BMH nanospheres(CoFe BMH NSPs)were prepared on nickel foam via a hydrothermal method.CoFe BMH NSHs exhibited the most beneficial catalytic activity.At a current density of 100 mA·cm^(-2),its overpotential for oxygen evolution reaction(OER)was 282 mV,and the overall water splitting voltage was 2.05 V.The double-layer charging capacitance(Cdl)value of CoFe BMH NSHs was the largest in CoFe BMHs,which proves that CoFe BMH NSHs have the largest active area.Furthermore,the active site in the OER process was metal oxyhydroxide(MOOH)through in situ Raman characterization,and the generation of the active substance was an irreversible process.This work provides important insights into the design of catalyst morphologies and offers valuable guidelines for the enhancement of the performance of other catalysts.
基金supported by the National Natural Science Foundation of China(Grant Nos.22278101,22068010,22168016,and 52365044)the Natural Science Foundation of Hainan Province(Grant Nos.2019RC142 and 519QN176)the Finance Science and Technology Project of Hainan Province(Grant No.ZDYF2020009).
文摘Novel and promising chloride ion batteries(CIBs)that can operate at room temperature have attracted great attentions,due to the sustainable chloride-containing resources and high theoretical energy density.To achieve the superior electrochemical properties of CIBs,the structure design of electrode materials is essential.Herein,2D NiAl-layered double hydroxide(NiAl-LDH)nanoarrays derived from Al2O3 are in-situ grafted to graphene(G)by atomic layer deposition(ALD)and hydrothermal method.The achieved NiAl-LDH@G hybrids with 2D NiAl-LDH arrays grown perpendicularly on graphene surface,can efficiently prevent the stacking of LDHs and enlarge specific surface area to provide more active sites.The NiAl-LDH@G cathode exhibits a maximum discharge capacity of 223.3 mA h g^(-1)and an excellent reversible capacity of 107 mA h g^(-1)over 500 cycles at 100 mA g^(-1)with a high coulombic efficiency around 96%,whereas pure NiAl-LDH has a discharge capacity of only 48.8 mA h g^(-1)and a coulombic efficiency(CE)of about 78%.More importantly,the NiAl-LDH@G electrode has a stable voltage at 1.9 V and an outstanding discharge capacity of higher than 72 mA h g^(-1)after 120 days.Additionally,XRD,XPS,and EDS have been employed to unveil the electrochemical reaction and Cl-storage mechanism of the NiAlLDH@G cathode in CIBs.This work opens a facile and reasonable way for improving electrochemical performance at anion-type rechargeable batteries in terms of cathode material design and mechanism interpretation.
基金supported by the Innovative Research Group Project of the National Natural Science Foundation of China(No.52021004)the Funds for Chongqing Talents Plan(No.CQYC2021059563)+1 种基金the Fundamental Research Funds for the Central Universities(No.2021CDJQY-027)the National Natural Science Foundation of China(No.52206089).
文摘High-entropy materials(HEMs),which are typically composed of five or more elements in near-equimolar ratios with concentrations ranging from 5%to 35%,have distinct elemental compositions and geometric properties that allow for the development of advanced electrocatalysts for renewable energy conversion systems.The highentropy effect,crystal dislocations,cocktail effect,and slow diffusion in high-entropy layered double hydroxides(HE-LDHs)and amorphous materials(HE-AMs)have all been shown to boost electrocatalytic water oxidation performance significantly.These materials exhibit remarkable activity and stability in both alkaline and acidic conditions.HE-AMs,in particular,benefit from a variety of defects,including coordinatively unsaturated sites and loosely connected atoms,which are critical to their improved catalytic capabilities.HEMs engineering and precise nanostructure control can address the low intrinsic activity,restricted active sites,and poor conductivity of binary and ternary amorphous and LDH catalysts.This study discusses current advances in HE-LDHs and HE-AMs for water electrolysis,including synthesis methods,structural features,active site identification by DFT calculations,and their applications in water electrocatalysis.The presentation also covers potential problems and future directions for developing these materials in energy conversion device systems.
基金supported by Guangdong Basic and Applied Basic Research Foundation(2022B1515120079)Tertiary Education Scientific research project of Guangzhou Municipal Education Bureau(2024312194)+1 种基金the Science and Technology Projects in Guangzhou(2024A03J0308)the Outstanding Youth Project of Natural Science Foundation of Guangdong Province(2022B1515020020).
文摘Electrically driven water splitting is an efficient method for green hydrogen production;however,its practical application is substantially constrained by the kinetically sluggish anodic oxygen evolution reaction(OER).Ruthenium(Ru)and its oxides are widely recognized as highly active OER catalysts.Although Ru is significantly cheaper than iridium(Ir),further reducing its content remains desirable.Herein,atomically dispersed Ru is doped into iron-nickel layered double hydroxides(Ru-FeNi-LDH)to decrease the Ru usage.We found that the Ru doping limit is roughly 9 wt%,and the Ru doping content significantly alters the OER kinetics-note that the high Ru concentration remarkably damages the Ru-FeNi-LDH structure and leads to agglomeration formation.By optimizing the Ru doping content to 3.3 wt%,the Ru-FeNi-LDH presents a low overpotential of 230 mV to reach a current density of 10 mA cm^(-2) in 1 M KOH,which is far better than the reference FeNi-LDH(280 mV)and RuO_(2)(350 mV).In the overall water splitting test,the current density of 10 mA cm^(-2) can be reached at a low voltage of 1.52 V,with stable operation for 80 h.Interestingly,Ru and Fe form an asymmetric Ru-Fe dipole,which is likely doped together into the LDH because the content of Fe instead of Ni is dependent on Ru content in experimental results.The electron-deficient feature of the Ru-Fe dipole thus facilitates the OER process.This work demonstrates a dual-transition metal synergy,providing a design strategy for OER and related catalysts.
基金financial support of the National Natural Science Foundation of China (22379063)
文摘Layered double hydroxides(LDHs)are potential cathode materials for aqueous magnesium-ion batteries(AMIBs).However,the low capacity and sluggish kinetics significantly limit their electrochemical performance in AMIBs.Herein,we find that oxygen vacancies can significantly boost the capacity,electrochemical kinetics,and structure stability of LDHs.The corresponding structure-performance relationship and energy storage mechanism are elaborated through exhaustive in/ex-situ experimental characterizations and density functional theory(DFT)calculations.Specially,in-situ Raman and DFT calculations reveal that oxygen vacancies elevate orbital energy of O 2p and electron density of O atoms,thereby enhancing the orbital hybridization of O 2p with Ni/Co 3d.This facilitates electron transfer between O and adjacent Ni/Co atoms and improves the covalency of Ni–O and Co–O bonds,which activates Ni/Co atoms to release more capacity and stabilizes the Ov-NiCo-LDH structure.Moreover,the distribution of relaxation times(DRT)and molecular dynamics(MD)simulations disclose that the enhanced d-p orbital hybridization optimizes the electronic structure of Ov-NiCo-LDH,which distinctly reduces the diffusion energy barriers of Mg^(2+)and improves the charge transfer kinetics of Ov-NiCo-LDH.Consequently,the assembled Ov-NiCo-LDH//active carbon(AC)and Ov-NiCo-LDH//perylenediimide(PTCDI)AMIBs can both deliver high specific discharge capacity(182.7 and 59.4 mAh g^(−1)at 0.5 A g^(−1),respectively)and long-term cycling stability(85.4%and 89.0%of capacity retentions after 2500 and 2400 cycles at 1.0 A g^(−1),respectively).In addition,the practical prospects for Ov-NiCo-LDH-based AMIBs have been demonstrated in different application scenarios.This work not only provides an effective strategy for obtaining high-performance cathodes of AMIBs,but also fundamentally elucidates the inherent mechanisms.
基金supported by the Natural Science Foundation of Henan(242300421230)the Young Teacher Fundamental Research Cultivation Program of Zhengzhou University(JC23557030)the National Natural Science Foundation of China(U21A20281 and 22208322)。
文摘Noble metal-loaded layered hydroxides exhibit high efficiency in electrocatalyzing water splitting.However,their widespread use as bifunctional electrocatalysts is hindered by low metal loading,inefficient yield,and complex synthesis processes.In this work,platinum atoms were anchored onto nickel-iron layered double hydroxide/carbon nanotube(LDH/CNT)hybrid electrocatalysts by using a straightforward milling technique with K_(2)Pt Cl_(6)·6H_(2)O as the Pt source.By adjusting the Pt-to-Fe ratio to 1/2 and 1/10,excellent electrocatalysts—Pt_(1/6)-Ni_(2/3)Fe_(1/3)-LDH/CNT and Pt_(1/30)-Ni_(2/3)Fe_(1/3)-LDH/CNT—were achieved with superior performance in hydrogen evolution reaction(HER)and oxygen evolution reaction(OER),outperforming the corresponding commercial Pt/C(20 wt%)and Ru O_(2)electrocatalysts.The enhanced electrochemical performance is attributed to the modification of Pt's electronic structure,which exhibits electron-rich states for HER and electrondeficient states for OER,significantly boosting Pt's electrochemical activity.Furthermore,the simple milling technology for controlling Pt loading offers a promising approach for scaling up the production of electrocatalysts.
基金Project(21306041)supported by the National Natural Science Young Foundation of ChinaProject(21271071)supported by the National Natural Science Foundation of ChinaProject(15A076)supported by the Scientific Research Foundation of Hunan Provincial Education Department of China
文摘ZnO/NiO/ZnAl2O4 mixed-metal oxides were successfully synthesized through a hydrotalcite-like precursor route, in which appropriate amounts of metal salts solutions were mixed to obtain a new series of ZnNiAl layered double hydroxides（LDHs） as precursors, followed by calcination under different temperatures. The as-obtained samples were characterized by SEM, HRTEM, TEM, XRD, BET, TG-DTA, and UV-Vis spectra techniques. The photocatalytic activities of the samples were evaluated by degradation of methyl orange（MO） under the simulated sunlight irradiation. The effects of Zn/Ni/Al mole ratio and calcination temperature on the composition, morphology and photocatalytic activity of the samples were investigated in detail. The results indicated that compared with ZnNiAl-LDHs, the mixed-metal oxide showed superior photocatalytic performance for the degradation of MO. A maximum of 97.3% photocatalytic decoloration rate within 60 min was achieved from the LDH with the Zn/Ni/Al mole ratio of 2：1：1 and the calcination temperature of 500 ℃, which much exceeded that of Degussa P25 under the same conditions. The possible mechanism of photocatalytic degradation over ZnO/NiO/ZnAl2O4 was discussed.
基金The Fundamental Research Funds for the Central Universities,the Scientific Innovation Research of College Graduates in Jiangsu Province(No.CXLX12-0105)the Analysis and Test Fund of Southeast University(No.201226)
文摘Colored layered double hydroxides （LDHs） can be synthesized by introducing colored cations such as Fe^3＋ and Cr^3 ＋, which call be used as thermal stabilizers for polyvinyl chloride （PVC）. The yellowish Mg/Fe and bluish Mg/Cr LDHs are prepared by the co-precipitation method. The results show that the MgsCr_ CO3 and Mg3Fe_ CO3 colored layered double hydroxides can stabilize PVC for more than 30 min under the thermal aging temperature of 180 ℃. The preparation can use cheap Mg（OH） 2 instead of MgCl2, which produces a much smaller amount of the by-product NH4Cl. It is known that NH4Cl is a cheap fertilizer that is difficult to sell; therefore, the preparation is much greener and more economic than the one using magnesium salt.
基金supported by the National Natural Science Foundation of China(Nos.U146211821601011)+2 种基金the 973 Program(Grant No.2014CB932102)the Fundamental Research Funds for the Central Universities(buctrc201506PYCC1704)
文摘The explore and development of electrocatalysts have gained significant attention due to their indispensable status in energy storage and conversion systems, such as fuel cells, metal–air batteries and solar water splitting cells. Layered double hydroxides（LDHs） and their derivatives（e.g., transition metal alloys, oxides, sulfides, nitrides and phosphides） have been adopted as catalysts for various electrochemical reactions, such as oxygen reduction, oxygen evolution, hydrogen evolution, and COreduction, which show excellent activity and remarkable durability in electrocatalytic process. In this review, the synthesis strategies, structural characters and electrochemical performances for the LDHs and their derivatives are described. In addition, we also discussed the effect of electronic and geometry structures to their electrocatalytic activity. The further development of high-performance electrocatalysts based on LDHs and their derivatives is covered by both a short summary and future outlook from the viewpoint of the material design and practical application.
基金supported by the National Key R&D Program of China(2017YFC0211503,2016YFC0207100)the Strategic Priority Research Program(A)of the Chinese Academy of Sciences(XDA23030300)+2 种基金the National Natural Science Foundation of China(21401200,51672273)the Open Research Fund of State Key Laboratory of Multi-phase Complex Systems(MPCS-2017-D-06)the Young Talent Project of the Center for Excellence in Regional Atmospheric Environment,CAS(CERAE201805)~~
文摘Catalytic oxidation is regarded as one of the most promising strategies for volatile organic compounds(VOCs)purification.Mixed metal oxides(MMOs),after topological transformation using layered double hydroxides(LDHs)as precursors,are extensively used as catalysts for VOCs oxidation due to their uniformity advantage.This review summarizes the developments in the LDH-derived VOCs heterogeneous catalytic oxidation over the last 10 years.Particularly,it addresses the VOCs abatement performance over MMO,noble metal/MMO,core-shell structured MMO,and integral MMO film catalysts originating from LDHs.Moreover,it highlights the water vapor effect and oxidation mechanism.This review indicates that LDH-based catalysts are a category of important VOCs oxidation materials.
基金supported financially by the National Natural Science Foundation of China(Nos.51971040,51701029 and 51531002)the National Key Research and Development Program of China(No.2016YFB0301100)+3 种基金the Chongqing Research Program of Basic Research and Frontier Technology(No.cstc2016jcyjA0388)the China Postdoctoral Science Foundation Funded Project(Nos.2017M620410 and 2018T110942)the Chongqing Postdoctoral Scientific Research Foundation(No.Xm2017010)the Fundamental Research Funds for the Central Universities(No.2018CDGFCL005).
文摘Anodic oxidation is a prevalent technique to introduce superior corrosion and wear resistance upon the surface of titanium(Ti)alloys,in which the selection of appropriate electrolytes and defect-sealing strategies is a key.This study aims to address such issues through anodizing Ti-10V-2Fe-3Al alloy in malic acid,followed by a post-sealing treatment with Mg-Al layered double hydroxides(LDHs).The characteristics of the samples were investigated using scanning electron microscopy(SEM),atomic force microscopy(AFM),glow discharge optical emission spectroscopy(GDOES),X-ray diffraction(XRD)and energy-dispersive X-ray spectroscopy(EDS).SEM micrographs reveals that the anodic coating had a surface full of bulges and cracks,and was almost sealed by the following LDHs treatment.XRD pattern indicate that the anodic coating was mainly consisted of amorphous TiO2 with a small fraction of anatase,but its crystallization degree was increased through the post-sealing.Moreover,electrochemical and tribological measurements demonstrate that corrosion current density was 2.8×10-6,2.0×10-7,5.9×10-9A cm-2,and wear rate was 1.45×10-3,1.30×10-4 and 6.90×10-5 mm3 N-1 m-1 for respective bare Ti-10V-2Fe-3Al alloy substrate,anodized specimens without and with the LDHs post treatment.Finally,a plausible wear mechanism was proposed.
基金supported by the National Natural Science Foundation of China(Nos.21677055 and 21407052)the Key Project in the National Science&Technology Pillar Program during the Twelfth Five-year Plan Period(No.2015BAB01B04)the Fundamental Research Funds for the Central Universities,HUST(Nos.2017KFXKJC004 and 2016YXMS287)
文摘In this study,greatly enhanced Mn(Ⅱ) adsorption was achieved by as-synthesized diethylenetriaminepentaacetate acid intercalated Mg/Al layered double hydroxides (LDHs-DTPA).The adsorption capacity of LDHs-DTPA was 83.5 mg/g,which is much higher than that of LDHs-EDTA (44.4 mg/g),LDHs-Oxalate (21.6 mg/g) and LDHs (28.8 mg/g).The adsorption data of aqueous Mn(Ⅱ) using LDHs-DTPA could be well described by the pseudosecond order kinetics and Langrnuir isotherm model.Thermodynamics study results also showed that the adsorption process of Mn(Ⅱ) by LDHs-DTPA was exothermic as indicated by the negative △H value.Furthermore,based on the structural,morphological and thermostable features,as well as FT-IR and XPS characterizations of LDHs-DTPA and the pristine LDHs,the adsorption mechanism of Mn(Ⅱ) was proposed.The carboxyl groups of DTPA were proposed to be the main binding sites for Mn(Ⅱ),and the hydroxyl groups of LDHs also played a minor role in the adsorption process.Among the three common regeneration reagents,0.1 mol/L Na2CO3 was the best for reusing LDHs-DTPA in Mn(Ⅱ) adsorption.Besides,the Mn(Ⅱ) adsorption performance could be hindered in the presence of typical inorganic ions,especially cations.Further specific modifications of LDHs-DTPA are suggested to get more selective adsorption of Mn(ll) in practical applications.
基金supported by the National Natural Science Foundation of China and Qinghai Qaidam Saline Lake Chemical Science Research Joint Fund (No. U1607109)
文摘Mg–Al–Fe layered double hydroxides（LDHs） were exfoliated and incorporated in polyether sulfone membranes for the removal of phosphate and fluoride for the first time. The exfoliation methods, coagulation bath, LDH amount, interfering ions, adsorption isotherm,desorption and reuse of the membranes were investigated. It was found that LDHs could be quickly exfoliated in formamide/N,N-dimethylformamide（DMF） solvent mixtures with sodium carboxymethyl cellulose as a stabilizer. The membranes displayed much higher adsorption capacity for phosphate（5.61 mg/g） and faster adsorption rate than the unexfoliated materials. With increased DMF content in the coagulation bath, the static and dynamic adsorption capacity rose. Interference from Cl-and SO4^（2-）（50 mg/L） on adsorption of phosphates was not apparent. The membranes displayed excellent reusability in dynamic adsorption/desorption. The membranes also showed high adsorption capacity for fluorides（1.61 mg/g）.
基金Funded by the National Natural Science Foundation of China(No.51708121)the National Basic Research Program of China(973 Program)(No.2014CB932104)the Educational Research Projects for Young and Middle-Aged Teachers of Education Department of Fujian Province(No.JAT170067)
文摘Layered double hydroxides(LDHs) with the physical property of high ultraviolet(UV)reflectance were used to enhance the anti-UV aging performance of bitumen. In view of the poor compatibility of LDHs with bitumen, three organic anions, namely, sodium dodecyl benzenesulfonate(SDBS), sodium dodecyl sulfate(SDS) and sodium dodecyl sulfonate(SDSO), were used as modifiers to prepare organic LDHs(OCLDHs) through regeneration process, and the crystal structure, chemical composition, morphological feature and UV shielding capability of synthesized OCLDHs were analyzed. Then the OCLDHs were added into bitumen to evaluate the storage stability and anti-UV aging property of OCLDHs/bitumen composites.The results show that the organic anions are inserted into the interlayers of LDHs, the intercalation expands the interlayer distance of LDHs, makes the particle shapes become more irregular and complicated, and enhances the absorption ability within the range from 200 to 300 nm while has little influence on the UV reflection ability.Result of high temperature storage stability indicates the organic modification ameliorates the compatibility of LDHs with bitumen. Compared with LDHs, OCLDHs decrease the deteriorations of bitumen’s properties during UV exposure test, exhibiting better effect in enhancing anti-UV aging performance of bitumen. Furthermore,among the three OCLDHs, LDHs intercalated by SDBS exhibit the most effective improvement due to the best compatibility with bitumen and comparatively good UV shielding effect.
基金the financial support by the National Natural Science Foundation of China (No. 20973022 and No. 11472048)
文摘This article presents a detailed structural study of a new spherical Mg Cl2-supported Ti Cl4 Ziegler-Natta catalyst for isotactic propylene polymerization, and researches on the relationship between catalyst structure and polymer properties. The spherical support with the chemical composition of CH3CH2 OMg OCH(CH2Cl)2 has been synthesized from a new dispersion system and is used as the supporting material to prepare Ziegler-Natta catalyst. The XRD analysis indicates that the catalyst is fully activated with δ-Mg Cl2 in the active catalyst. The far-IR spectrometric results confirm again the presence of δ-Mg Cl2 in the active catalyst. Textural property of the active catalyst exhibits high surface area coupled with high porosity. The high activity in propylene polymerization is mainly ascribed to the full activation and the porous structure of the catalyst. Scanning electron microscopy/energy dispersive spectrometer mapping results indicate a uniform titanium distribution throughout the catalyst particles. Particle size analysis shows that the catalyst has a narrow particle size distribution. The perfect spherical shape, uniform titanium distribution and narrow particle size distribution of the catalyst confirm the advantage of polymer particles production with less fines. The solid state 13 C NMR and mid-IR spectroscopic analyses indicate that there exists strong complexation between diisobutyl phthalate and Mg Cl2, which leads to the high isotacticity of polypropylene.
基金Project(51604303) supported by the National Natural Science Foundation of China
文摘To extract selenium(Ⅵ)from the highly caustic leachate of copper anode slime,the Ca-Al-Cl layered double hydroxides(Ca-Al-Cl-LDHs)with a formula of Ca2 Al(OH)6 Cl·2 H2 O by three co-precipitation methods were synthesized.A plate-like morphology and hexagonal crystal structure with typical mineral phases and functional groups were identified by the FESEM,XRD,FTIR,BET and XPS analysis.The forward feeding sample exhibits the best adsorption capacity of Se(Ⅵ).The factor experiments then reveal a favorable adsorption process with low temperature,low NaOH concentration and high adsorbent dosage.Furthermore,the adsorption kinetics and isotherm parameters can be well described by the Langmuir isotherm and the pseudo-second-order models,respectively.Accordingly,the maximum adsorption amount of Se(Ⅵ)onto Ca-Al-Cl-LDHs reaches188.6 mg/g at 50 ℃.
基金supported by the National Natural Science Foundation of China(Grant Nos.21701043,21825201 and U19A2017)the Provincial Natural Science Foundation of Hunan(2019GK2031)+1 种基金the Open Project Program of Key Laboratory of Low Dimensional Materials&Application Technology(Xiangtan University),Ministry of Education,China(No.KF20180202)the China Postdoctoral Science Foundation(Grant Nos.2019 M662766,2019 M662759,2020 M682549,and 2020 M672473)。
文摘One of the fundamental driving forces in the materials science community is the hunt for new materials with specific properties that meet the requirements of rapidly evolving technology.
基金financially supported by the National Basic Research Program of China(No.2015CB654603)the National Natural Science Foundation of China(No.51572141,51532003)+1 种基金Beijing Nova Program(No.XX2013037)the Research fund of Science and Technology in Shenzhen(No.JSGG20150331155519130)
文摘Flexible thin-film supercapacitors with high specific capacitance are highly desirable for modern wearable or micro-sized electrical and electronic applications. In this contribution, Ni-Co hydroxides（NCH）nanosheets were deposited on top of Ni-Cu alloy（NCA）nanowire arrays forming a freestanding thin-film composite electrode with hierarchical structure for supercapacitors.During electrochemical cycling, the dissolution of Cu into Cu ions will create more active sites on NCA, and the redeposited copper oxide can be coated onto NCH, giving rise to substantial increase in specific capacitance with cycling. Meanwhile, NCA and NCH have excellent conductivity, thus leading to excellent rate performance. This flexible thin-film electrode delivers an ultrahigh initial specific capacitance of 0.63 F·cm^（-2）（or 781.3 F·cm^（-3））.During charge-discharge cycles, the specific capacitance can increase up to 1.18 F·cm^（-2）（or 1475 F·cm^（-3）） along with the“self-etching”process. The electrode presents a better specific capacitance and rate capability compared with previously reported flexible thin-film electrode, and this novel design of etching technique may expand to other binary or ternary materials.
基金supported by the Science Foundation of China University of Petroleum, Beijing (No. 2462017YJRC013)。
文摘Oxygen evolution reaction(OER) is a bottle-neck process in many sustainable energy conversion systems due to its sluggish kinetics.The development of cost-effective yet efficient electrocatalysts towards OER is highly desirable but still a great challenge at current stage.Herein,a new type of hybrid nanostructure,consisting of two-dimensional(2D) Cerium-doped NiFe-layered double hydroxide nanoflakes directly grown on the 2D Ti3C2Tx MXene surface(denoted as NiFeCe-LDH/MXene),is designed using a facile insitu coprecipitation method.The resultant NiFeCe-LDH/MXene hybrid presents a hierarchical nanoporous structure,high electrical conductivity and strong interfacial junction because of the synergistic effect of Ce doping and MXene coupling.As a result,the hybrid catalyst exhibits an excellent catalytic activity for OER,delivering a low onset overpotential of 197 mV and an overpotential of 260 mV at a current density of 10 mA·cm-2 in the alkaline medium,much lower than its pure LDH counterparts and IrO2 catalyst.Besides,the hybrid catalyst also displays a fast reaction kinetics and a remarkable stable durability.Further theoretic studies using density function theory(DFT) methods reveal that Ce doping could effectively narrow the bandgap of NiFe-LDH and reduce the overpotential in OER process.This work may shed light on the exploration of advanced electrocatalysts for renewable energy conversion and storage systems.
文摘Exploring highly efficient electrochemical water splitting catalysts has recently attracted extensive research interest from both fundamental researches and practical applications.Transition metal‐based layered double hydroxides(LDHs)have been proved to be one of the most efficient materials for oxygen evolution reaction(OER),however,still suffered from low conductivity and sluggish kinetics for hydrogen evolution reaction(HER),which largely inhibited the overall water splitting efficiency.To address this dilemma,enormous approaches including doping regulation,intercalation tuning and defect engineering are therefore rationally designed and developed.Herein,we focus on the recent exciting progress of LDHs hybridization with other two‐dimensional(2D)materials for water splitting reactions,not barely for enhancing OER efficiency but also for boosting HER activity.Particularly,the structural features,morphologies,charge transfer and synergistic effects for the heterostructure/heterointerface that influence the electrocatalytic performance are discussed in details.The hybrid 2D building blocks not only serve as additional conductivity and structural supported but also promote electron transfer at the interfaces and further enhance the electrocatalytic performance.The construction and application of the nanohybrid materials will guide a new direction in developing multifunctional materials based on LDHs,which will contribute to energy conversion and storage.
