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
Amorphous two-dimensional transition metal oxide/(oxy)hydroxide(2D TMO/TMHO)nanomaterials(NMs)have the properties of both 2D and amorphous materials,displaying outstanding physicochemical qualities.Therefore,they demo...Amorphous two-dimensional transition metal oxide/(oxy)hydroxide(2D TMO/TMHO)nanomaterials(NMs)have the properties of both 2D and amorphous materials,displaying outstanding physicochemical qualities.Therefore,they demonstrate considerable promise for use in electrocatalytic water splitting applications.Here,the primary amorphization strategies for achieving the 2D TMO/TMHO NMs are comprehensively reviewed,including low-temperature reaction,rapid reaction,exchange/doping effect,ligand modulation,and interfacial energy confinement.By integrating these strategies with various physicochemical synthesis methods,it is feasible to control the amorphization of TMO/TMHO NMs while maintaining the distinctive benefits of their 2D structures.Furthermore,it delves into the structural advantages of amorphous 2D TMO/TMHO NMs in electrocatalytic water splitting,particularly emphasizing recent advancements in enhancing their electrocatalytic performance through interface engineering.The challenges and potential future directions for the precise synthesis and practical application of amorphous 2D TMO/TMHO NMs are also provided.This review aims to establish a theoretical foundation and offer experimental instructions for developing effective and enduring electrocatalysts for water splitting.展开更多
Rare earth metal elements include lanthanide elements as well as scandium and yttrium,totaling seventeen metal elements.Due to the wide application prospects of rare earth metal elements in various fields such as lumi...Rare earth metal elements include lanthanide elements as well as scandium and yttrium,totaling seventeen metal elements.Due to the wide application prospects of rare earth metal elements in various fields such as luminescent materials,magnetic materials,catalytic materials,electronic devices,they have an important strategic position.In the field of electrocatalysis,rare earth metal elements have great potential for development due to their unique 4f electron layer structure,spin orbit coupling,high reactivity,controllable coordination number,and rich optical properties.However,there is currently a lack of systematic reviews on the modification strategies of rare earth metal elements and the latest developments in electrocatalysis.Therefore,in order to stimulate the enthusiasm of researchers,this review focuses on the application progress of rare earth metal element modified metal oxides in multiple fields such as wastewater treatment,hydrogen peroxide synthesis,hydrogen evolution reaction(HER),carbon dioxide reduction reaction(CO_(2)RR),nitrogen reduction reaction(NRR)and machine learning assisted research.In depth analysis of its electrocatalytic mechanism in various application scenarios and key factors affecting electrocatalytic performance.This review is of great significance for further developing high-performance and multifunctional electrocatalysts,and is expected to provide strong support for the development of energy,environment,and chemical industries.展开更多
Although the powder Fenton-like catalysts have exhibited high catalytic performances towards pollutant degradation,they cannot be directly used for Fenton-like industrialization considering the problems of loss and re...Although the powder Fenton-like catalysts have exhibited high catalytic performances towards pollutant degradation,they cannot be directly used for Fenton-like industrialization considering the problems of loss and recovery.Therefore,the membrane fixation of catalyst is an important step to realize the actual application of Fenton-like catalysts.In this work,an efficient catalyst was developed with Co-N_(x)configuration facilely reconstructed on the surface of Co_(3)O_(4)(Co-N_(x)/Co_(3)O_(4)),which exhibited superior catalytic activity.We further fixed the highly efficient Co-N_(x)/Co_(3)O_(4)onto three kinds of organic membranes and one kind of inorganic ceramic membrane installing with the residual PMS treatment device to investigate its catalytic stability and sustainability.Results indicated that the inorganic ceramic membrane(CM)can achieve high water flux of 710 L m-2h-1,and the similar water flux can be achieved by Co-N_(x)/Co_(3)O_(4)/CM even without the pressure extraction.We also employed the Co-N_(x)/Co_(3)O_(4)/CM system to the wastewater secondary effluent,and the pollutant in complicated secondary effluent could be highly removed by the Co-N_(x)/Co_(3)O_(4)/CM system.This paper provides a new point of view for the application of metal-based catalysts with M-N_(x)coordination in catalytic reaction device.展开更多
The use of metal oxides has been extensively documented in the literature and applied in a variety of contexts,including but not limited to energy storage,chemical sensors,and biomedical applications.One of the most s...The use of metal oxides has been extensively documented in the literature and applied in a variety of contexts,including but not limited to energy storage,chemical sensors,and biomedical applications.One of the most significant applications of metal oxides is heterogeneous catalysis,which represents a pivotal technology in industrial production on a global scale.Catalysts serve as the primary enabling agents for chemical reactions,and among the plethora of catalysts,metal oxides including magnesium oxide(MgO),ceria(CeO_(2))and titania(TiO_(2)),have been identified to be particularly effective in catalyzing a variety of reactions[1].Theoretical calculations based on density functional theory(DFT)and a multitude of other quantum chemistry methods have proven invaluable in elucidating the mechanisms of metal-oxide-catalyzed reactions,thereby facilitating the design of high-performance catalysts[2].展开更多
Cryogenic magnetic cooling based on the principle of the magnetocaloric effects(MCEs)of magnetic solids has been recognized as an alternative cooling technology due to its significant economic and social benefits.Desi...Cryogenic magnetic cooling based on the principle of the magnetocaloric effects(MCEs)of magnetic solids has been recognized as an alternative cooling technology due to its significant economic and social benefits.Designing novel magnetic materials with good magnetocaloric performance is a prerequisite for practical applications.In this study,three gadolinium-transition metal-based high entropy oxides(HEOs)of Gd(Fe_(1/4)Ni_(1/4)Al_(1/4)Cr_(1/4))O_(3),Gd(Fe_(1/5)Ni_(1/5)Al_(1/5)Cr_(1/5)Co_(1/5))O_(3),and Gd(Fe_(1/6)Ni_(1/6)Al_(1/6)Cr_(1/6)Co_(1/6)Mn_(1/6))O_(3)were designed and systematically characterized regarding their structural and cryogenic magnetic properties.These HEOs were confirmed to crystallize into a single-phase perovskite-type orthorhombic structure with a homogeneous microstructure,reveal a second-order magnetic transition at low temperatures,and exhibit significant cryogenic MCEs.The magnetocaloric performances of the present HEOs,identified by magnetic entropy changes,relative cooling power,and temperature-averaged entropy changes,were com-parable with recently reported candidate materials.The present study indicates potential applications for cryogenic magnetic cooling of the present HEOs and provides meaningful clues for designing and exploring HEOs with good cryogenic magnetocaloric performances.展开更多
Selective oxidation of amines to imines through electrocatalysis is an attractive and efficient way for the chemical industry to produce nitrile compounds,but it is limited by the difficulty of designing efficient cat...Selective oxidation of amines to imines through electrocatalysis is an attractive and efficient way for the chemical industry to produce nitrile compounds,but it is limited by the difficulty of designing efficient catalysts and lack of understanding the mechanism of catalysis.Herein,we demonstrate a novel strategy by generation of oxyhydroxide layers on two-dimensional iron-doped layered nickel phosphorus trisulfides(Ni1-xFexPS_(3))during the oxidation of benzylamine(BA).In-depth structural and surface chemical characterizations during the electrocatalytic process combined with theoretical calculations reveal that Ni(1-x)FexPS_(3) undergoes surface reconstruction under alkaline conditions to form the metal oxyhydroxide/phosphorus trichalcogenide(NiFeOOH/Ni1-xFexPS_(3))heterostructure.Interestingly,the generated heterointerface facilitates BA oxidation with a low onset potential of 1.39 V and Faradaic efficiency of 53%for benzonitrile(BN)synthesis.Theoretical calculations further indicate that the as-formed NiFeOOH/Ni1-xFexPS_(3) heterostructure could offer optimum free energy for BA adsorption and BN desorption,resulting in promising BN synthesis.展开更多
Following publication of the original article[1],the authors found that they pasted the same data when drawing XRD for sample NCO-1 and NCO-2 in Fig.2a,however,the XRD of all four samples in the manuscript was tested,...Following publication of the original article[1],the authors found that they pasted the same data when drawing XRD for sample NCO-1 and NCO-2 in Fig.2a,however,the XRD of all four samples in the manuscript was tested,and XRD raw data were kept and can be offered.The correct Fig.2 has been provided in this Correction.展开更多
The reaction characteristics of calcium-based materials during calcium looping(CaL)process are pivotal in the efficiency of CaL thermochemical energy storage(TCES)and CO_(2)capture systems.Currently,metal oxide doping...The reaction characteristics of calcium-based materials during calcium looping(CaL)process are pivotal in the efficiency of CaL thermochemical energy storage(TCES)and CO_(2)capture systems.Currently,metal oxide doping is the primary method to enhance the reaction characteristics of calcium-based materials over multiple cycles.In particular,co-doping with variable-valence metal oxides(VVMOs)can effectively increase the oxygen vacancy content in calcium-based materials,significantly improving their cyclic reaction characteristics.However,there are so numerous VVMOs co-doping schemes that the experimental screening process is complex,consuming considerable time and economic costs.Density functional theory(DFT)calculations have been widely used to reveal the impact of metal oxide doping on the cyclic reaction characteristics of calcium-based materials,with calculation results showing good agreement with experimental conclusions.Nevertheless,there is still a lack of research on utilizing DFT to screen calcium-based materials,and a systematic research methodology has not yet been established.In this study,a systematic DFT-based screening methodology for calcium-based materials was proposed.A series of key parameters for DFT calculations including CO_(2)adsorption energy,oxygen vacancy formation energy,and sintering resistance were proposed.Furthermore,a preliminary mathematical model to predict the CaL TCES and CO_(2)capture performance of calcium-based materials was introduced.The aforementioned DFT method was employed to screen for VVMOs co-doped calcium-based materials.The results revealed that Mn and Ce co-doped calcium-based materials exhibited superior DFT-predicted reaction characteristics.These DFT predictions were validated through experimental assessments of cyclic thermochemical energy storage,CO_(2)capture,and relevant characterization.The outcomes demonstrate a high degree of consistency among DFT-based predictions,experimental results,and characterization.Hence,the DFT-based screening methodology for calcium-based materials proposed herein is a viable solution,poised to offer theoretical insights for the efficient design of calcium-based materials.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
Developing isolated single atomic noble metal catalysts is one of the most effective methods to maximize noble metal atom utilization efficiency and enhance catalytic performances.Layered double hydroxides(LDHs)are tw...Developing isolated single atomic noble metal catalysts is one of the most effective methods to maximize noble metal atom utilization efficiency and enhance catalytic performances.Layered double hydroxides(LDHs)are two-dimensional nanoarchitectures in which M^(3+) and M^(2+) sites are atomically isolated due to static repulsions,providing special anchoring sites for single noble metal atoms and enabling the tuning of catalytic activity.Herein,a comprehensive review of the advances in LDHs supported single-atom catalysts(M/LDH SACs)is presented,focusing on the synthetic strategies,structure characterization,and application of M/LDH SACs in energy devices.Strong electronic coupling between single atomic noble metal atoms and corresponding anchoring sites of LDHs determines not only the catalytic activity of M/LDH SACs but also the stability during catalytic reactions.Furthermore,a perspective is proposed to highlight the challenges and opportunities for understanding the reaction mechanism and development of highly efficient M/LDH SACs.展开更多
The aggregation and fractal structure of mixed metal hydroxides ( MMH ) agglomerates with increasing ionic strength have been studied by dynamic light scattering ( DLS ) and SEM techniques. The experiments indicate th...The aggregation and fractal structure of mixed metal hydroxides ( MMH ) agglomerates with increasing ionic strength have been studied by dynamic light scattering ( DLS ) and SEM techniques. The experiments indicate that the MMH agglomerates have two different structures in RLA regime and DLA regime, and also give the proof that the transition region between RLA and DLA may occur.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
Metal hydroxides （MAH） consisting of magnesium hydroxide and aluminum hydroxide with a mass ratio of 1：2 were surface-modified by y-diethoxyphosphorous ester propyldiethoxymethylsilane, boric acid and diphenylsilan...Metal hydroxides （MAH） consisting of magnesium hydroxide and aluminum hydroxide with a mass ratio of 1：2 were surface-modified by y-diethoxyphosphorous ester propyldiethoxymethylsilane, boric acid and diphenylsilanediol in xylene under dibutyl tin dilaurate catalyst at 140 ℃. Phosphorus, silicon and boron elements covalently bonded to metal hydroxide particles were detected by X-ray photoelectron spectroscopy. The degradation behavior of the surface-modified MAH was characterized by thermogravimetric analysis. The results show that linear low density polyethylene （LLDPE） composite, filled with 50% （mass fraction） of MAH modified by 5.0% （mass fraction） of modifiers, passes the V-0 rating of UL-94 test and shows the limited oxygen index of 34%, and its heat release rate and average effective heat combustion in a cone calorimeter measurement decrease obviously; The mechanical properties of MAH can be improved by surface-modification. The uniform dispersion of particles and strong interfacial bonding between particles and matrix are obtained.展开更多
Two strains of Fe/Mn oxidizing bacteria tolerant to high concentrations of multiple heavy metal(loid)s and efficient decontamination for them were screened.The surface of the bio-Fe/Mn oxides produced by the oxidation...Two strains of Fe/Mn oxidizing bacteria tolerant to high concentrations of multiple heavy metal(loid)s and efficient decontamination for them were screened.The surface of the bio-Fe/Mn oxides produced by the oxidation of Fe(II)and Mn(II)by Pseudomonas taiwanensis(marked as P4)and Pseudomonas plecoglossicida(marked as G1)contains rich reactive oxygen functional groups,which play critical roles in the removal efficiency and immobilization of heavymetal(loid)s in co-contamination system.The isolated strains P4 and G1 can growwell in the following environments:pH 5-9,NaCl 0-4%,and temperature 20-30℃.The removal efficiencies of Fe,Pb,As,Zn,Cd,Cu,and Mn are effective after inoculation of the strains P4 and G1 in the simulated water system(the initial concentrations of heavy metal(loid)were 1 mg/L),approximately reaching 96%,92%,85%,67%,70%,54%and 15%,respectively.The exchangeable and carbonate bound As,Cd,Pb and Cu are more inclined to convert to the Fe-Mn oxide bound fractions in P4 and G1 treated soil,thereby reducing the phytoavailability and bioaccessible of heavy metal(loid)s.This research provides alternatives method to treat water and soil containing high concentrations of multi-heavy metal(loid)s.展开更多
To improve the efficiency of oxygen electrolysis,exploiting bifunctional electrocatalysts with excellent activity and stability is extremely important due to the four-electron transfer dynamics of oxygen evolution rea...To improve the efficiency of oxygen electrolysis,exploiting bifunctional electrocatalysts with excellent activity and stability is extremely important due to the four-electron transfer dynamics of oxygen evolution reaction(OER)and oxygen reduction reaction(ORR).Herein,a series of yolk-shell hollow polyhedrons(YHPs)embedded with NiCoFe ternary alloy and metal oxides,which are named YHP-x(x=1,2,3,4),were reported.By controlled etching multi-layered zeolitic imidazolate frameworks and following pyrolytic integration,YHPs are endowed with mass transfer tunnels,accessible inner active sites,and good electrical conductivity.Due to the synergetic effect of the alloy,metal oxides and the yolk-shell structure,YHP-1 exhibits excellent ORR performance with a half-wave potential of 0.79 V and YHP-2 displays superior OER performance with a low overpotential of 257 mV at 10 mA cm−2.The strategy described in this work can be extended to a number of hollow/yolk-shell electrocatalysts for water splitting and metal–air batteries.展开更多
This review provides insight into the current research trend in transition metal oxides(TMOs)-based photocatalysis in removing the organic colouring matters from water.For easy understanding,the research progress has ...This review provides insight into the current research trend in transition metal oxides(TMOs)-based photocatalysis in removing the organic colouring matters from water.For easy understanding,the research progress has been presented in four generations according to the catalyst composition and mode of application,viz:single component TMOs(the firstgeneration),doped TMOs/binary TMOs/doped binary TMOs(the second-generation),inactive/active support-immobilized TMOs(the third-generation),and ternary/quaternary compositions(the fourth-generation).The first two generations represent suspended catalysts,the third generation is supported catalysts,and the fourth generation can be suspended or supported.The review provides an elaborated comparison between suspended and supported catalysts,their general/specific requirements,key factors controlling degradation,and the methodologies for performance evaluation.All the plausible fundamental and advanced dye degradation mechanisms involved in each generation of catalysts were demonstrated.The existing challenges in TMOs-based photocatalysis and how the researchers approach the hitch to resolve it effectively are discussed.Future research trends are also presented.展开更多
The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous me...The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.展开更多
Precipitation is often used for the preparation of La(OH)_(3)with precipitants of liquid alkali and ammonia.To solve the problems of high cost and wastewater pollution caused by common precipitants,the active MgO synt...Precipitation is often used for the preparation of La(OH)_(3)with precipitants of liquid alkali and ammonia.To solve the problems of high cost and wastewater pollution caused by common precipitants,the active MgO synthesized by pyrolysis was used as the precipitant to prepare La(OH)_(3).The species distribution of LaCl_(3)and LaCl_(3)-MgCl_(2)mixed system solution was calculated,and the kinetic analysis of the precipi-tation process was carried out to confirm the key factors influencing the precipitation of La(OH)_(3).The results show that La(OH)_(3)with D_(50)of 5.57μm,a specific surface area of 25.70 m^(2)/g,a rod-like shape,and MgO content of 0.044 wt%,was successfully prepared by adding active MgO.The precipitation ratio of La reaches 99.92%.The La(OH)_(3)precipitation is controlled by the diffusion process.The activity of MgO has a significant influence on MgO content in the precipitate.The preparation of La(OH)_(3)by active MgO provides a potential way for an eco-friendly preparation method of rare earth.展开更多
Two-dimensional(2D)metal oxides(2DMOs),such as MoO_(2),have made impressive strides in recent years,and their applicability in a number of fields such as electronic devices,optoelectronic devices and lasers has been d...Two-dimensional(2D)metal oxides(2DMOs),such as MoO_(2),have made impressive strides in recent years,and their applicability in a number of fields such as electronic devices,optoelectronic devices and lasers has been demonstrated.However,2DMOs present challenges in their synthesis using conventional methods due to their non-van der Waals nature.We report that KCl acts as a flux to prepare large-area 2DMOs with sub-millimeter scale.We systematically investigate the effects of temperature,homogeneous time and cooling rate on the products in the flux method,demonstrating that in this reaction a saturated homogenous solution is obtained upon the melting of the salt and precursor.Afterward,the cooling rate was adjusted to regulate the thickness of the target crystals,leading to the precipitation of 2D non-layered material from the supersaturated solution;by applying this method,the highly crystalline non-layered 2D MoO_(2)flakes with so far the largest lateral size of up to sub-millimeter scale(~464μm)were yielded.Electrical studies have revealed that the 2D MoO_(2)features metallic properties,with an excellent sheet resistance as low as 99Ω·square^(-1 )at room temperature,and exhibits a property of charge density wave in the measurement of resistivity as a function of temperature.展开更多
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 the National Key Research and Development Program of China(No.2018YFA0703700)the National Natural Science Foundation of China(No.12034002)the Interdisciplinary Research Project for Young Teachers of USTB(Fundamental Research Funds for the Central Universities,No.FRF-IDRY-23-033)。
文摘Amorphous two-dimensional transition metal oxide/(oxy)hydroxide(2D TMO/TMHO)nanomaterials(NMs)have the properties of both 2D and amorphous materials,displaying outstanding physicochemical qualities.Therefore,they demonstrate considerable promise for use in electrocatalytic water splitting applications.Here,the primary amorphization strategies for achieving the 2D TMO/TMHO NMs are comprehensively reviewed,including low-temperature reaction,rapid reaction,exchange/doping effect,ligand modulation,and interfacial energy confinement.By integrating these strategies with various physicochemical synthesis methods,it is feasible to control the amorphization of TMO/TMHO NMs while maintaining the distinctive benefits of their 2D structures.Furthermore,it delves into the structural advantages of amorphous 2D TMO/TMHO NMs in electrocatalytic water splitting,particularly emphasizing recent advancements in enhancing their electrocatalytic performance through interface engineering.The challenges and potential future directions for the precise synthesis and practical application of amorphous 2D TMO/TMHO NMs are also provided.This review aims to establish a theoretical foundation and offer experimental instructions for developing effective and enduring electrocatalysts for water splitting.
基金supported by the National Key Research and Development Program of China(No.2023YFC3708005)The Fundamental Research Funds for the Central Universities,Nankai University(No.63241208)supported by the National Natural Science Foundation of China(Nos.21872102 and 22172080)。
文摘Rare earth metal elements include lanthanide elements as well as scandium and yttrium,totaling seventeen metal elements.Due to the wide application prospects of rare earth metal elements in various fields such as luminescent materials,magnetic materials,catalytic materials,electronic devices,they have an important strategic position.In the field of electrocatalysis,rare earth metal elements have great potential for development due to their unique 4f electron layer structure,spin orbit coupling,high reactivity,controllable coordination number,and rich optical properties.However,there is currently a lack of systematic reviews on the modification strategies of rare earth metal elements and the latest developments in electrocatalysis.Therefore,in order to stimulate the enthusiasm of researchers,this review focuses on the application progress of rare earth metal element modified metal oxides in multiple fields such as wastewater treatment,hydrogen peroxide synthesis,hydrogen evolution reaction(HER),carbon dioxide reduction reaction(CO_(2)RR),nitrogen reduction reaction(NRR)and machine learning assisted research.In depth analysis of its electrocatalytic mechanism in various application scenarios and key factors affecting electrocatalytic performance.This review is of great significance for further developing high-performance and multifunctional electrocatalysts,and is expected to provide strong support for the development of energy,environment,and chemical industries.
基金supported by National Natural Science Fundation of China(Nos.52170086,22308194,U22A20423)Natural Science Foundation of Shandong Province(No.ZR2021ME013)+1 种基金Taishan Scholars Program of Shandong Province(No.tsqn202211012)Shandong Provincial Excellent Youth(No.ZR2022YQ47)。
文摘Although the powder Fenton-like catalysts have exhibited high catalytic performances towards pollutant degradation,they cannot be directly used for Fenton-like industrialization considering the problems of loss and recovery.Therefore,the membrane fixation of catalyst is an important step to realize the actual application of Fenton-like catalysts.In this work,an efficient catalyst was developed with Co-N_(x)configuration facilely reconstructed on the surface of Co_(3)O_(4)(Co-N_(x)/Co_(3)O_(4)),which exhibited superior catalytic activity.We further fixed the highly efficient Co-N_(x)/Co_(3)O_(4)onto three kinds of organic membranes and one kind of inorganic ceramic membrane installing with the residual PMS treatment device to investigate its catalytic stability and sustainability.Results indicated that the inorganic ceramic membrane(CM)can achieve high water flux of 710 L m-2h-1,and the similar water flux can be achieved by Co-N_(x)/Co_(3)O_(4)/CM even without the pressure extraction.We also employed the Co-N_(x)/Co_(3)O_(4)/CM system to the wastewater secondary effluent,and the pollutant in complicated secondary effluent could be highly removed by the Co-N_(x)/Co_(3)O_(4)/CM system.This paper provides a new point of view for the application of metal-based catalysts with M-N_(x)coordination in catalytic reaction device.
基金financial support from the National Key R&D Program of China(2021YFB3500700)the National Natural Science Foundation of China(22473042,22003016,and 92145302).
文摘The use of metal oxides has been extensively documented in the literature and applied in a variety of contexts,including but not limited to energy storage,chemical sensors,and biomedical applications.One of the most significant applications of metal oxides is heterogeneous catalysis,which represents a pivotal technology in industrial production on a global scale.Catalysts serve as the primary enabling agents for chemical reactions,and among the plethora of catalysts,metal oxides including magnesium oxide(MgO),ceria(CeO_(2))and titania(TiO_(2)),have been identified to be particularly effective in catalyzing a variety of reactions[1].Theoretical calculations based on density functional theory(DFT)and a multitude of other quantum chemistry methods have proven invaluable in elucidating the mechanisms of metal-oxide-catalyzed reactions,thereby facilitating the design of high-performance catalysts[2].
基金supported by the National Natural Science Foundation of China(No.52171174).The authors acknowledge Dr.Chao Zhang from the Instrumentation Service Center for Physical Sciences at Westlake University for magnetization measurements.
文摘Cryogenic magnetic cooling based on the principle of the magnetocaloric effects(MCEs)of magnetic solids has been recognized as an alternative cooling technology due to its significant economic and social benefits.Designing novel magnetic materials with good magnetocaloric performance is a prerequisite for practical applications.In this study,three gadolinium-transition metal-based high entropy oxides(HEOs)of Gd(Fe_(1/4)Ni_(1/4)Al_(1/4)Cr_(1/4))O_(3),Gd(Fe_(1/5)Ni_(1/5)Al_(1/5)Cr_(1/5)Co_(1/5))O_(3),and Gd(Fe_(1/6)Ni_(1/6)Al_(1/6)Cr_(1/6)Co_(1/6)Mn_(1/6))O_(3)were designed and systematically characterized regarding their structural and cryogenic magnetic properties.These HEOs were confirmed to crystallize into a single-phase perovskite-type orthorhombic structure with a homogeneous microstructure,reveal a second-order magnetic transition at low temperatures,and exhibit significant cryogenic MCEs.The magnetocaloric performances of the present HEOs,identified by magnetic entropy changes,relative cooling power,and temperature-averaged entropy changes,were com-parable with recently reported candidate materials.The present study indicates potential applications for cryogenic magnetic cooling of the present HEOs and provides meaningful clues for designing and exploring HEOs with good cryogenic magnetocaloric performances.
基金National Natural Science Foundation of China,Grant/Award Number:22179029Fundamental Research Funds for the Central Universities,Grant/Award Number:buctrc202324+2 种基金Young Elite Scientists Sponsorship Program by BAST,Grant/Award Number:BYESS2023093Ministero dell'Istruzione,dell'Universitàe della Ricerca,Grant/Award Number:2022FNL89YKempestiftelserna。
文摘Selective oxidation of amines to imines through electrocatalysis is an attractive and efficient way for the chemical industry to produce nitrile compounds,but it is limited by the difficulty of designing efficient catalysts and lack of understanding the mechanism of catalysis.Herein,we demonstrate a novel strategy by generation of oxyhydroxide layers on two-dimensional iron-doped layered nickel phosphorus trisulfides(Ni1-xFexPS_(3))during the oxidation of benzylamine(BA).In-depth structural and surface chemical characterizations during the electrocatalytic process combined with theoretical calculations reveal that Ni(1-x)FexPS_(3) undergoes surface reconstruction under alkaline conditions to form the metal oxyhydroxide/phosphorus trichalcogenide(NiFeOOH/Ni1-xFexPS_(3))heterostructure.Interestingly,the generated heterointerface facilitates BA oxidation with a low onset potential of 1.39 V and Faradaic efficiency of 53%for benzonitrile(BN)synthesis.Theoretical calculations further indicate that the as-formed NiFeOOH/Ni1-xFexPS_(3) heterostructure could offer optimum free energy for BA adsorption and BN desorption,resulting in promising BN synthesis.
文摘Following publication of the original article[1],the authors found that they pasted the same data when drawing XRD for sample NCO-1 and NCO-2 in Fig.2a,however,the XRD of all four samples in the manuscript was tested,and XRD raw data were kept and can be offered.The correct Fig.2 has been provided in this Correction.
基金supported by the National Natural Science Foundation of China(52276204 and U22A20435)。
文摘The reaction characteristics of calcium-based materials during calcium looping(CaL)process are pivotal in the efficiency of CaL thermochemical energy storage(TCES)and CO_(2)capture systems.Currently,metal oxide doping is the primary method to enhance the reaction characteristics of calcium-based materials over multiple cycles.In particular,co-doping with variable-valence metal oxides(VVMOs)can effectively increase the oxygen vacancy content in calcium-based materials,significantly improving their cyclic reaction characteristics.However,there are so numerous VVMOs co-doping schemes that the experimental screening process is complex,consuming considerable time and economic costs.Density functional theory(DFT)calculations have been widely used to reveal the impact of metal oxide doping on the cyclic reaction characteristics of calcium-based materials,with calculation results showing good agreement with experimental conclusions.Nevertheless,there is still a lack of research on utilizing DFT to screen calcium-based materials,and a systematic research methodology has not yet been established.In this study,a systematic DFT-based screening methodology for calcium-based materials was proposed.A series of key parameters for DFT calculations including CO_(2)adsorption energy,oxygen vacancy formation energy,and sintering resistance were proposed.Furthermore,a preliminary mathematical model to predict the CaL TCES and CO_(2)capture performance of calcium-based materials was introduced.The aforementioned DFT method was employed to screen for VVMOs co-doped calcium-based materials.The results revealed that Mn and Ce co-doped calcium-based materials exhibited superior DFT-predicted reaction characteristics.These DFT predictions were validated through experimental assessments of cyclic thermochemical energy storage,CO_(2)capture,and relevant characterization.The outcomes demonstrate a high degree of consistency among DFT-based predictions,experimental results,and characterization.Hence,the DFT-based screening methodology for calcium-based materials proposed herein is a viable solution,poised to offer theoretical insights for the efficient design of calcium-based materials.
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This work was supported by the National Natural Science Foundation of China,the National Key Research and Development Project(2021YFA1502200)the Royal Society and Newton Fund through a Newton Advanced Fellowship award(NAF\R1\191294)+3 种基金the Program for Changjiang Scholars and Innovation Research Team in the University(IRT1205)the Fundamental Research Funds for the Central Universities,the starting-up foundation from Beijing University of Chemical Tech-nology,the fellowship of China Postdoctoral Science Foundation(2020M670107)the Natural Science Foundation of Beijing,China(2214062)the China Scholarship Council and a long-term subsidy from China's Ministry of Finance and the Ministry of Education.
文摘Developing isolated single atomic noble metal catalysts is one of the most effective methods to maximize noble metal atom utilization efficiency and enhance catalytic performances.Layered double hydroxides(LDHs)are two-dimensional nanoarchitectures in which M^(3+) and M^(2+) sites are atomically isolated due to static repulsions,providing special anchoring sites for single noble metal atoms and enabling the tuning of catalytic activity.Herein,a comprehensive review of the advances in LDHs supported single-atom catalysts(M/LDH SACs)is presented,focusing on the synthetic strategies,structure characterization,and application of M/LDH SACs in energy devices.Strong electronic coupling between single atomic noble metal atoms and corresponding anchoring sites of LDHs determines not only the catalytic activity of M/LDH SACs but also the stability during catalytic reactions.Furthermore,a perspective is proposed to highlight the challenges and opportunities for understanding the reaction mechanism and development of highly efficient M/LDH SACs.
基金supported by the National Natural Science Foundation of China(No.20273041)the Ministry of the Education.
文摘The aggregation and fractal structure of mixed metal hydroxides ( MMH ) agglomerates with increasing ionic strength have been studied by dynamic light scattering ( DLS ) and SEM techniques. The experiments indicate that the MMH agglomerates have two different structures in RLA regime and DLA regime, and also give the proof that the transition region between RLA and DLA may occur.
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Project(20574020) supported by the National Natural Science Foundation of ChinaProject(20061001) supported by the Opening Project of the Key Laboratory of Polymer Processing Engineering, Ministry of Education, ChinaProject (20060106-2) supported by Guangdong Key Projects
文摘Metal hydroxides （MAH） consisting of magnesium hydroxide and aluminum hydroxide with a mass ratio of 1：2 were surface-modified by y-diethoxyphosphorous ester propyldiethoxymethylsilane, boric acid and diphenylsilanediol in xylene under dibutyl tin dilaurate catalyst at 140 ℃. Phosphorus, silicon and boron elements covalently bonded to metal hydroxide particles were detected by X-ray photoelectron spectroscopy. The degradation behavior of the surface-modified MAH was characterized by thermogravimetric analysis. The results show that linear low density polyethylene （LLDPE） composite, filled with 50% （mass fraction） of MAH modified by 5.0% （mass fraction） of modifiers, passes the V-0 rating of UL-94 test and shows the limited oxygen index of 34%, and its heat release rate and average effective heat combustion in a cone calorimeter measurement decrease obviously; The mechanical properties of MAH can be improved by surface-modification. The uniform dispersion of particles and strong interfacial bonding between particles and matrix are obtained.
基金supported d by the National Key Research and Development Program of China(No.2018YFC1802905).
文摘Two strains of Fe/Mn oxidizing bacteria tolerant to high concentrations of multiple heavy metal(loid)s and efficient decontamination for them were screened.The surface of the bio-Fe/Mn oxides produced by the oxidation of Fe(II)and Mn(II)by Pseudomonas taiwanensis(marked as P4)and Pseudomonas plecoglossicida(marked as G1)contains rich reactive oxygen functional groups,which play critical roles in the removal efficiency and immobilization of heavymetal(loid)s in co-contamination system.The isolated strains P4 and G1 can growwell in the following environments:pH 5-9,NaCl 0-4%,and temperature 20-30℃.The removal efficiencies of Fe,Pb,As,Zn,Cd,Cu,and Mn are effective after inoculation of the strains P4 and G1 in the simulated water system(the initial concentrations of heavy metal(loid)were 1 mg/L),approximately reaching 96%,92%,85%,67%,70%,54%and 15%,respectively.The exchangeable and carbonate bound As,Cd,Pb and Cu are more inclined to convert to the Fe-Mn oxide bound fractions in P4 and G1 treated soil,thereby reducing the phytoavailability and bioaccessible of heavy metal(loid)s.This research provides alternatives method to treat water and soil containing high concentrations of multi-heavy metal(loid)s.
基金This study was financially supported by the Program for the National Natural Science Foundation of China(Nos.NSFC-21901221,21671170,21673203 and U1904215)the Natural Science Foundation of Jiangsu Province(No.BK20190870)+1 种基金Changjiang Scholars Program of the Ministry of Education(No.Q2018270)the Top Talent Project of Yangzhou University.
文摘To improve the efficiency of oxygen electrolysis,exploiting bifunctional electrocatalysts with excellent activity and stability is extremely important due to the four-electron transfer dynamics of oxygen evolution reaction(OER)and oxygen reduction reaction(ORR).Herein,a series of yolk-shell hollow polyhedrons(YHPs)embedded with NiCoFe ternary alloy and metal oxides,which are named YHP-x(x=1,2,3,4),were reported.By controlled etching multi-layered zeolitic imidazolate frameworks and following pyrolytic integration,YHPs are endowed with mass transfer tunnels,accessible inner active sites,and good electrical conductivity.Due to the synergetic effect of the alloy,metal oxides and the yolk-shell structure,YHP-1 exhibits excellent ORR performance with a half-wave potential of 0.79 V and YHP-2 displays superior OER performance with a low overpotential of 257 mV at 10 mA cm−2.The strategy described in this work can be extended to a number of hollow/yolk-shell electrocatalysts for water splitting and metal–air batteries.
基金supporting us by providing technical facilities(access to journals)。
文摘This review provides insight into the current research trend in transition metal oxides(TMOs)-based photocatalysis in removing the organic colouring matters from water.For easy understanding,the research progress has been presented in four generations according to the catalyst composition and mode of application,viz:single component TMOs(the firstgeneration),doped TMOs/binary TMOs/doped binary TMOs(the second-generation),inactive/active support-immobilized TMOs(the third-generation),and ternary/quaternary compositions(the fourth-generation).The first two generations represent suspended catalysts,the third generation is supported catalysts,and the fourth generation can be suspended or supported.The review provides an elaborated comparison between suspended and supported catalysts,their general/specific requirements,key factors controlling degradation,and the methodologies for performance evaluation.All the plausible fundamental and advanced dye degradation mechanisms involved in each generation of catalysts were demonstrated.The existing challenges in TMOs-based photocatalysis and how the researchers approach the hitch to resolve it effectively are discussed.Future research trends are also presented.
基金funded by the National Natural Science Foundation of China,China (Nos.52272303 and 52073212)the General Program of Municipal Natural Science Foundation of Tianjin,China (Nos.17JCYBJC22700 and 17JCYBJC17000)the State Scholarship Fund of China Scholarship Council,China (Nos.201709345012 and 201706255009)。
文摘The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.
基金the National Key Research and Development Program of China(2022YFB3504503)the National Natural Science Foundation of China(52274355)the Gansu Province Science and Technology Major Special Project,China(22ZD6GD061).
文摘Precipitation is often used for the preparation of La(OH)_(3)with precipitants of liquid alkali and ammonia.To solve the problems of high cost and wastewater pollution caused by common precipitants,the active MgO synthesized by pyrolysis was used as the precipitant to prepare La(OH)_(3).The species distribution of LaCl_(3)and LaCl_(3)-MgCl_(2)mixed system solution was calculated,and the kinetic analysis of the precipi-tation process was carried out to confirm the key factors influencing the precipitation of La(OH)_(3).The results show that La(OH)_(3)with D_(50)of 5.57μm,a specific surface area of 25.70 m^(2)/g,a rod-like shape,and MgO content of 0.044 wt%,was successfully prepared by adding active MgO.The precipitation ratio of La reaches 99.92%.The La(OH)_(3)precipitation is controlled by the diffusion process.The activity of MgO has a significant influence on MgO content in the precipitate.The preparation of La(OH)_(3)by active MgO provides a potential way for an eco-friendly preparation method of rare earth.
基金supported by the National Key Research and Development Program of China(Nos.2023YFB3608703 and 2023YFB3608700)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(Nos.2021ZZ122 and 2020ZZ110)Fujian provincial projects(Nos.2021HZ0114 and 2021J01583).
文摘Two-dimensional(2D)metal oxides(2DMOs),such as MoO_(2),have made impressive strides in recent years,and their applicability in a number of fields such as electronic devices,optoelectronic devices and lasers has been demonstrated.However,2DMOs present challenges in their synthesis using conventional methods due to their non-van der Waals nature.We report that KCl acts as a flux to prepare large-area 2DMOs with sub-millimeter scale.We systematically investigate the effects of temperature,homogeneous time and cooling rate on the products in the flux method,demonstrating that in this reaction a saturated homogenous solution is obtained upon the melting of the salt and precursor.Afterward,the cooling rate was adjusted to regulate the thickness of the target crystals,leading to the precipitation of 2D non-layered material from the supersaturated solution;by applying this method,the highly crystalline non-layered 2D MoO_(2)flakes with so far the largest lateral size of up to sub-millimeter scale(~464μm)were yielded.Electrical studies have revealed that the 2D MoO_(2)features metallic properties,with an excellent sheet resistance as low as 99Ω·square^(-1 )at room temperature,and exhibits a property of charge density wave in the measurement of resistivity as a function of temperature.
