Electrocatalytic hydrogen production from seawater holds enormous promise for clean energy generation.Nevertheless,the direct electrolysis of seawater encounters significant challenges due to poor anodic stability cau...Electrocatalytic hydrogen production from seawater holds enormous promise for clean energy generation.Nevertheless,the direct electrolysis of seawater encounters significant challenges due to poor anodic stability caused by detrimental chlorine chemistry.Herein,we present our recent discovery that the incorporation of Ce into Ni Fe layered double hydroxide nanosheet array on Ni foam(Ce-Ni Fe LDH/NF)emerges as a robust electrocatalyst for seawater oxidation.During the seawater oxidation process,CeO_(2)is generated,effectively repelling Cl^(-)and inhibiting the formation of Cl O-,resulting in a notable enhancement in the oxidation activity and stability of alkaline seawater.The prepared Ce-Ni Fe LDH/NF requires only overpotential of 390 m V to achieve the current density of 1 A cm^(-2),while maintaining long-term stability for 500 h,outperforming the performance of Ni Fe LDH/NF(430 m V,150 h)by a significant margin.This study highlights the effectiveness of a Ce-doping strategy in augmenting the activity and stability of materials based on Ni Fe LDH in seawater electrolysis for oxygen evolution.展开更多
Multi-metal hydroxides possess unique physical and chemical properties,making them promising candidates for supercapacitor working electrodes.Enhancing their electrochemical performance can be achieved through a combi...Multi-metal hydroxides possess unique physical and chemical properties,making them promising candidates for supercapacitor working electrodes.Enhancing their electrochemical performance can be achieved through a combination with carbon materials.In this study,we synthesized a composite material by hydrothermally dispersed 4,6,and 10 wt%carbon nanotubes(CNT)into ternary cobaltbismuth-samarium hydroxide(CoBiSm-TOH).These nanocomposites were employed as the material for the working electrode in a supercapacitor.The findings reveal that at 1.5 A/g,the specific capacitance of CNT3@CoBiSm-TOH,using a three-electrode system,was found to be 852.91 F/g,higher than that of CoBi-BOH,CoBiSm-TOH,CNT1@CoBiSm-TOH and CNT5@CoBiSm-TOH-measuring 699.69,750.34,789.54 and 817.79 F/g,respectively.Moreover,CNT3@CoBiSm-TOH electrodes exhibited a capacitance retention of around 88%over 10,000 cycles.To demonstrate practical applicability,CNT3@CoBiSm-TOH was grown on woven carbon fiber(WCF),and a solid-state supercapacitor device was developed using the VARTM(vacuum-assisted resin transfer molding).This device displayed a specific capacitance of 272.67 F/g at 2.25 A/g.Notably,it achieved a maximum energy density of 53.01 Wh/kg at a power density of 750 W/kg and sustained excellent cycle stability over 50,000 cycles,maintaining 70%of its initial capacitance.These results underscore the importance of interfacial nanoengineering and provide crucial insights for the development of future energy storage devices.展开更多
Urea generation through electrochemical CO_(2) and NO_(3)~-co-reduction reaction(CO_(2)NO_(3)RR)is still limited by either the low selectivity or yield rate of urea.Herein,we report copper carbonate hydroxide(Cu_2(OH)...Urea generation through electrochemical CO_(2) and NO_(3)~-co-reduction reaction(CO_(2)NO_(3)RR)is still limited by either the low selectivity or yield rate of urea.Herein,we report copper carbonate hydroxide(Cu_2(OH)_2CO_(3))as an efficient CO_(2)NO_(3)RR electrocatalyst with an impressive urea Faradaic efficiency of45.2%±2.1%and a high yield rate of 1564.5±145.2μg h~(-1)mg_(cat)~(-1).More importantly,H_(2) evolution is fully inhibited on this electrocatalyst over a wide potential range between-0.3 and-0.8 V versus reversible hydrogen electrode.Our thermodynamic simulation reveals that the first C-N coupling follows a unique pathway on Cu_2(OH)_2CO_(3) by combining the two intermediates,~*COOH and~*NHO.This work demonstrates that high selectivity and yield rate of urea can be simultaneously achieved on simple Cu-based electrocatalysts in CO_(2)NO_(3)RR,and provide guidance for rational design of more advanced catalysts.展开更多
Designing efficient and long-lasting non-metal electrocatalysts is an urgent task for addressing the issue of kinetic hysteresis in electrochemical oxidation reactions.The bimetallic hydroxides,catalyzing the oxygen e...Designing efficient and long-lasting non-metal electrocatalysts is an urgent task for addressing the issue of kinetic hysteresis in electrochemical oxidation reactions.The bimetallic hydroxides,catalyzing the oxygen evolution reaction(OER),have significant research potential because hydroxide reconstruction to generate an active phase is a remarkable advantage.Herein,the complete reconstruction of ultrathin CoNi(OH)_(2) nanosheets was achieved by embedding Ag nanoparticles into the hydroxide to induce a spontaneous redox reaction(SRR),forming heterojunction Ag@CoNi(OH)_(2) for bifunctional hydrolysis.Theoretical calculations and in situ Raman and ex situ characterizations revealed that the inductive effect of the Ag cation redistributed the charge to promote phase transformation to highly activate Ag-modified hydroxides.The Co-Ni dual sites in Co/NiOOH serve as novel active sites for optimizing the intermediates,thereby weakening the barrier formed by OOH^*.Ag@CoNi(OH)_(2) required a potential of 1.55 V to drive water splitting at a current density of 10 mA cm^(-2),with nearly 98.6% Faraday efficiency.Through ion induction and triggering of electron regulation in the OER via the synergistic action of the heterogeneous interface and surface reconstruction,this strategic design can overcome the limited capacity of bimetallic hydroxides and bridge the gap between the basic theory and industrialization of water decomposition.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
Layered double hydroxides(LDHs)have attracted tremendous research interest in widely spreading applications.Most notably,transition-metal-bearing LDHs are expected to serve as highly active electrocatalysts for oxygen...Layered double hydroxides(LDHs)have attracted tremendous research interest in widely spreading applications.Most notably,transition-metal-bearing LDHs are expected to serve as highly active electrocatalysts for oxygen evolution reaction(OER)due to their layered structure combined with versatile com-positions.Furthermore,reducing the thickness of platelet LDH crystals to nanometer or even molecular scale via cleavage or delamination provides an important clue to enhance the activity.In this review,recent progresses on rational design of LDH nanosheets are reviewed,including direct synthesis via traditional coprecipitation,homogeneous precipitation,and newly developed topochemical oxidation as well as chemical exfoliation of parent LDH crystals.In addition,diverse strategies are introduced to modulate their electrochemical activity by tuning the composition of host metal cations and intercalated counter-anions,and incorporating dopants,cavi-ties,and single atoms.In particular,hybridizing LDHs with conductive components or in situ growing them on conductive substrates to produce freestanding electrodes can further enhance their intrinsic catalytic activity.A brief discussion on future research directions and prospects is also summarized.展开更多
With exhaustion of fossil fuels and the deterioration of global environment,widespread and intensive researches have been concentrated on clean and sustainable alternative energy sources,such as metal-air batteries[1]...With exhaustion of fossil fuels and the deterioration of global environment,widespread and intensive researches have been concentrated on clean and sustainable alternative energy sources,such as metal-air batteries[1],fuel cells[2]and water splitting devices[3].Electrocatalytic oxidation of water to O2(oxygen evolution reaction,OER)is a vital chemical process involved in energy storage and conversion from renewable sources in form of molecular fuels such as H2 via water electrolysis,which has attracted a great amount of research efforts in the past few years[4,5].Nowadays,RuO2 and IrO2 are widely used as typical excellent OER electrocatalysts.However,their high-cost and scarce nature restricts the broadly commercial application of those materials[6,7].Hence,there is an urgent demand to develop low cost,highly efficient,and superb stable OER catalysts.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
The high energy demand we currently face in society and the subsequent large consumption of fossil fuels cause its depletion and increase the pollution levels.The quest for the production of clean energy from renewabl...The high energy demand we currently face in society and the subsequent large consumption of fossil fuels cause its depletion and increase the pollution levels.The quest for the production of clean energy from renewable and sustainable sources remains open.The conversion of solar energy into hydrogen via the water-splitting process,assisted by pho tores pons ive semiconductor catalysts,is one of the most promising technologies.Significant progress has been made on water splitting in the past few years and a variety of photocatalysts active not only under ultra-violet(UV) light but especially with the visible part of the electromagnetic spectrum have been developed.Layered double hydroxides(LDH)-based materials have emerged as a promising class of nanomaterials for solar energy applications owing to their unique layered structure,compositional flexibility,tunable bandgaps,ease of synthesis and low manufacturing costs.This review covers the most recent research dedicated to LDH materials for photocatalytic water-splitting applications and encompasses a range of synthetic strategies and post-modifications used to enhance their performance.Moreover,we provide a thorough discussion of the experimental conditions crucial to obtaining improved photoactivity and highlight the impact of some specific parameters,namely,catalysts loading,cocatalysts,sacrificial agents,and irradiation sources.This review provides the necessary tools to select the election technique for adequately enhancing the photoactivity of LDH and modified LDH-based materials and concludes with a critical summary that outlines further research directions.展开更多
The Na2CO3-modified HZSM-5 zeolites were further treated by tetrapropylammonium hydroxide(TPAOH) solution. The effect of TPAOH concentration on the secondary crystallization process was investigated. The resulting sam...The Na2CO3-modified HZSM-5 zeolites were further treated by tetrapropylammonium hydroxide(TPAOH) solution. The effect of TPAOH concentration on the secondary crystallization process was investigated. The resulting samples were characterized by a complementary combination of X-ray diffraction, N2 adsorption/desorption, scanning electron microscopy, X-ray fluorescence spectroscopy, XPS, 27 Al and 29 Si magic-angle spinning nuclear magnetic resonance spectroscopy, BET and temperature-programmed desorption techniques. The results showed that the secondary crystallization of the HZSM-5 zeolite could result in migration of non-framework species from the internal channels to the zeolite surface and their transformation into framework species. The catalytic activity of these modified samples for thiophene alkylation was evaluated. Both the activity and stability of the catalysts were improved after secondary crystallization.展开更多
The electrodeposition approach is significant in electrode fabrication for practical application.Herein,the electrodeposited amorphous NiFe hydroxide species for oxygen evolution reaction (OER) in water splitting reac...The electrodeposition approach is significant in electrode fabrication for practical application.Herein,the electrodeposited amorphous NiFe hydroxide species for oxygen evolution reaction (OER) in water splitting reaction is demonstrated by revealing the synergistic effect influenced by the support electrode of Fe and Ni foil and the contents of Fe and Ni in the electrolyte.All the electrodeposited samples have an amorphous structure and similar profiles of binding energy and chemical states for Fe and Ni as characterized by the spectroscopic techniques.While the support effect and Fe/Ni synergistic effect are indeed observed for the varied catalytic performances observed for the different electrodes;the Ni foil supported catalyst exhibits much higher performance than that of the Fe foil supported catalyst,and the different redox potentials of Ni species in the different Fe/Ni electrode resulting from the Fe–Ni synergism are observed in the cyclic voltammetry curve analysis.The surface roughness and the electrochemical surface area are also influenced by the support effect and the Fe/Ni ratio in the plating electrolyte.The optimal electrode shows a very low overpotential of~200 mV to reach 10 mA cm^(-2),and very high catalytic stability by the consecutive cyclic voltammetry measurements and 20 h stability test.Though it has the largest electrochemical surface area,the highest catalytic efficiency for these active sites is also indicated by the specific activity and turnover frequency polarization curves.The current work shows the effective experience for the electrodeposited Fe/Ni based catalysts in large-scale fabrication,which can be more practical for hydrogen generation in the alkaline water electrolysis.展开更多
For many two-dimensional(2D)materials,low coordination edges and corner sites offer greatly enhanced catalytic performance compared to basal sites,motivating the search for new synthetic approaches towards ultrathin a...For many two-dimensional(2D)materials,low coordination edges and corner sites offer greatly enhanced catalytic performance compared to basal sites,motivating the search for new synthetic approaches towards ultrathin and ultrafine 2D nanomaterials with high specific surface areas.To date,the synthesis of catalysts that are both ultrathin(monolayer)and ultrafine(lateral size<10nm)has proven extremely challenging.Herein,using a facile ultrasonic exfoliation procedure,we describe the successful synthesis of ultrafine ZnCo-LDH nanosheets(denoted as ZnCo-UF)with a size^3.5 nm and thickness^0.5 nm.The single layer ZnCo-UF nanosheets possess an abundance of oxygen vacancies(Vo)and unsaturated coordination s让es,thereby affording outstanding electrocatalytic water oxidation performance.DFT calculations confirmed that Vo on the surface of ZnCo-UF enhanced H20 adsorption via increasing the electropositivity of the nanosheets.展开更多
Layered double hydroxides (LDHs), a class of anionic clays consisting of brucite-like host layers and interlayer anions, have been widely investigated in the last decade due to their promising applications in many are...Layered double hydroxides (LDHs), a class of anionic clays consisting of brucite-like host layers and interlayer anions, have been widely investigated in the last decade due to their promising applications in many areas such as catalysis, ion separation and adsorption. Owing to the highly tunable compositi on and uniform distribution of metal cations in the brucite-like layers, as well as the facile exchangeability of intercalated anions, LDHs can be modified and functionalized to form various nanostructures/composites through versatile processes such as anion intercalation and exfoliation, decoration of nanoparticles, selfassembly with other two-dimensional (2D) materials, and controlled growth on conductive supports (e.g., nanowire arrays, nano tubes, 3D foams). In this article, we briefly review the recent advances on both the LDH nano structures and functionalized composites toward the applications in energy conversion, especially for water oxidation.展开更多
Photocatalytic reduction of CO2 with H2 O to syngas is an effective way for producing high value-added chemical feedstocks such as methanol and light olefins in industry.Nevertheless,the precise control of CO/H2 ratio...Photocatalytic reduction of CO2 with H2 O to syngas is an effective way for producing high value-added chemical feedstocks such as methanol and light olefins in industry.Nevertheless,the precise control of CO/H2 ratio from photocatalytic CO2 reduction reaction still poses a great challenge for the further application.Herein,we prepared a series of highly efficient heterostructure based on highly dispersed palladium supported on ultrathin Co Al-layered double hydroxide(LDH).In conjunction with a Ru-complex sensitizer,the molar ratios of CO/H2 can be tuned from 1:0.74 to 1:3 under visible-light irradiation(λ>400 nm).More interestingly,the syngas can be obtained under light irradiation atλ>600 nm.Structure characterization and density functional theory calculations revealed that the remarkable catalytic activity can be due to the supported palladium,which improved the charge transfer efficiency.Meanwhile,more H atoms were used to generate H2 on the supported palladium for further tunable CO/H2 ratio.This work demonstrates a new strategy for harnessing abundant solar-energy to produce syngas from a CO2 feedstock.展开更多
Compared with noble metal catalyst, Co3O4-based electrocatalysts have attracted considerable interesting as low-cost alternatives for oxygen evolution reaction (OER). However, the poor electrocatalytic activity still ...Compared with noble metal catalyst, Co3O4-based electrocatalysts have attracted considerable interesting as low-cost alternatives for oxygen evolution reaction (OER). However, the poor electrocatalytic activity still remains a huge challenge. Herein, we demonstrate a feasible approach through oxidation of CoFe layered double hydroxide (CoFe-LDH) to synthesize Fe-doped Co3O4@C nanopmrticles with size of about 30-50 nm. As OER catalyst, the as-synthesized Fe-doped Co3O4@C nanoparticles exhibited superior OER performance with a small overpotential of 260 mV at the current density of 20 mA cm^-2, a small Tafel slope of 70 mV dec^-1 and long-term durability (there was no obviously OER current density degradation for 100 h) in alkaline solution. The present work opens a new avenue to the exploration of cost-effective and excellent electrocatalysts based on transition metal oxide materials to substitute precious metal materials for water splitting.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
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.
A new solvothermal post-synthesis treatment for preparing high aspect ratio magnesium aluminium layered double hydroxides(Mg Al–LDHs) has been developed. Treating laurate-intercalated Mg Al–LDHs in pure ethanol in a...A new solvothermal post-synthesis treatment for preparing high aspect ratio magnesium aluminium layered double hydroxides(Mg Al–LDHs) has been developed. Treating laurate-intercalated Mg Al–LDHs in pure ethanol in an autoclave for 48 h at 150 °C was found to produce delaminated MgA l–LDH nanosheets with a thickness of ~2.6 nm and an aspect ratio of ~105. It is proposed that the high pressure solvothermal process promotes the insertion of ethanol molecules into the LDH interlayer space, thereby facilitating delamination. This new post-synthesis treatment provides the opportunity for a facile, large scale route to highly delaminated high aspect ratio LDHs, which might be of interest towards novel nanomaterials for energy conversion and storage.展开更多
Oxygen evolution reaction(OER) plays an indispensable role in developing renewable clean energy resources. One of the critical bottlenecks for the reaction is the development of highly efficient electrocatalyst to dec...Oxygen evolution reaction(OER) plays an indispensable role in developing renewable clean energy resources. One of the critical bottlenecks for the reaction is the development of highly efficient electrocatalyst to decrease the high overpotentials of four-electron transfer process of OER. Recently, layered double hydroxides(LDHs) have been widely investigated among the most promising electrocatalysts for OER due to their high intrinsic activity, excellent stability as well as low-cost. However, it remains unclear how the exposed facet of the LDHs affects their electrocatalytic activity. Here we elucidate the active edge facet of LDHs towards OER by combining the finely control of edge facet ratio coupled with molecular probe method and computational calculation. The LDHs with higher edge facet area ratio show superior activity with low onset potential as well as decreased Tafel slope. The active edge site is further proved by blocking the unsaturated edge sites with cyanate probe anion, of which the adsorption largely inhibits OER activity. Furthermore, based on density functional theory(DFT) calculation, twodimensional map of theoretical overpotentials as a function of Gibbs free energy reveals that the edge(100) facet exhibits a much higher OER activity than basal plane(001) facet.展开更多
The hierarchical structure of molybdenum disulfide(MoS2)nanosheet arrays stemmed from nickelcobalt layered double hydroxide(NiCo-LDH)/carbon cloth was prepared by growing the MoS_(2) nanosheet arrays onto the NiCo-LDH...The hierarchical structure of molybdenum disulfide(MoS2)nanosheet arrays stemmed from nickelcobalt layered double hydroxide(NiCo-LDH)/carbon cloth was prepared by growing the MoS_(2) nanosheet arrays onto the NiCo-LDH template which was pre-deposited onto the carbon cloth substrate.In this electrode configuration,carbon cloth is the three dimensional and conductive skeleton;NiCo-LDH nanosheets,as the template,ensure the oriented growth of MoS2 nanosheet arrays.Therefore,more MoS_(2) active sites are exposed and the catalyst exhibits good hydrogen evolution reaction activity.展开更多
基金support from the Free Exploration Project of Frontier Technology for Laoshan Laboratory(No.16-02)the National Natural Science Foundation of China(Nos.22072015 and 21927811)。
文摘Electrocatalytic hydrogen production from seawater holds enormous promise for clean energy generation.Nevertheless,the direct electrolysis of seawater encounters significant challenges due to poor anodic stability caused by detrimental chlorine chemistry.Herein,we present our recent discovery that the incorporation of Ce into Ni Fe layered double hydroxide nanosheet array on Ni foam(Ce-Ni Fe LDH/NF)emerges as a robust electrocatalyst for seawater oxidation.During the seawater oxidation process,CeO_(2)is generated,effectively repelling Cl^(-)and inhibiting the formation of Cl O-,resulting in a notable enhancement in the oxidation activity and stability of alkaline seawater.The prepared Ce-Ni Fe LDH/NF requires only overpotential of 390 m V to achieve the current density of 1 A cm^(-2),while maintaining long-term stability for 500 h,outperforming the performance of Ni Fe LDH/NF(430 m V,150 h)by a significant margin.This study highlights the effectiveness of a Ce-doping strategy in augmenting the activity and stability of materials based on Ni Fe LDH in seawater electrolysis for oxygen evolution.
基金financially supported by 2024 Gyeongbuk Green Environment Support Center。
文摘Multi-metal hydroxides possess unique physical and chemical properties,making them promising candidates for supercapacitor working electrodes.Enhancing their electrochemical performance can be achieved through a combination with carbon materials.In this study,we synthesized a composite material by hydrothermally dispersed 4,6,and 10 wt%carbon nanotubes(CNT)into ternary cobaltbismuth-samarium hydroxide(CoBiSm-TOH).These nanocomposites were employed as the material for the working electrode in a supercapacitor.The findings reveal that at 1.5 A/g,the specific capacitance of CNT3@CoBiSm-TOH,using a three-electrode system,was found to be 852.91 F/g,higher than that of CoBi-BOH,CoBiSm-TOH,CNT1@CoBiSm-TOH and CNT5@CoBiSm-TOH-measuring 699.69,750.34,789.54 and 817.79 F/g,respectively.Moreover,CNT3@CoBiSm-TOH electrodes exhibited a capacitance retention of around 88%over 10,000 cycles.To demonstrate practical applicability,CNT3@CoBiSm-TOH was grown on woven carbon fiber(WCF),and a solid-state supercapacitor device was developed using the VARTM(vacuum-assisted resin transfer molding).This device displayed a specific capacitance of 272.67 F/g at 2.25 A/g.Notably,it achieved a maximum energy density of 53.01 Wh/kg at a power density of 750 W/kg and sustained excellent cycle stability over 50,000 cycles,maintaining 70%of its initial capacitance.These results underscore the importance of interfacial nanoengineering and provide crucial insights for the development of future energy storage devices.
基金supported by the Research Grants Council(26206115,16304821 and 16309418)the Southern Marine Science and Engineering Guangdong Laboratory(Guangzhou)(SMSEGL20SC01)+2 种基金the Innovation and Technology Commission(grant no.ITC-CNERC14EG03)of the Hong Kong Special Administrative Regionthe Hong Kong Postdoctoral Fellowship Scheme(HKUST PDFS2021-4S12 and HKUST PDFS2021-6S08)the support from the Shenzhen fundamental research funding(JCYJ20210324115809026,20200925154115001,JCYJ20200109141216566)。
文摘Urea generation through electrochemical CO_(2) and NO_(3)~-co-reduction reaction(CO_(2)NO_(3)RR)is still limited by either the low selectivity or yield rate of urea.Herein,we report copper carbonate hydroxide(Cu_2(OH)_2CO_(3))as an efficient CO_(2)NO_(3)RR electrocatalyst with an impressive urea Faradaic efficiency of45.2%±2.1%and a high yield rate of 1564.5±145.2μg h~(-1)mg_(cat)~(-1).More importantly,H_(2) evolution is fully inhibited on this electrocatalyst over a wide potential range between-0.3 and-0.8 V versus reversible hydrogen electrode.Our thermodynamic simulation reveals that the first C-N coupling follows a unique pathway on Cu_2(OH)_2CO_(3) by combining the two intermediates,~*COOH and~*NHO.This work demonstrates that high selectivity and yield rate of urea can be simultaneously achieved on simple Cu-based electrocatalysts in CO_(2)NO_(3)RR,and provide guidance for rational design of more advanced catalysts.
基金supported by the Inner Mongolia R&D Program Plan(2021ZD0042,2021EEDSCXSFQZD006)the National Natural Science Foundation of China(21902123)the Natural Science Basic Research Program of Shaanxi(2023-JC-ZD-22)。
文摘Designing efficient and long-lasting non-metal electrocatalysts is an urgent task for addressing the issue of kinetic hysteresis in electrochemical oxidation reactions.The bimetallic hydroxides,catalyzing the oxygen evolution reaction(OER),have significant research potential because hydroxide reconstruction to generate an active phase is a remarkable advantage.Herein,the complete reconstruction of ultrathin CoNi(OH)_(2) nanosheets was achieved by embedding Ag nanoparticles into the hydroxide to induce a spontaneous redox reaction(SRR),forming heterojunction Ag@CoNi(OH)_(2) for bifunctional hydrolysis.Theoretical calculations and in situ Raman and ex situ characterizations revealed that the inductive effect of the Ag cation redistributed the charge to promote phase transformation to highly activate Ag-modified hydroxides.The Co-Ni dual sites in Co/NiOOH serve as novel active sites for optimizing the intermediates,thereby weakening the barrier formed by OOH^*.Ag@CoNi(OH)_(2) required a potential of 1.55 V to drive water splitting at a current density of 10 mA cm^(-2),with nearly 98.6% Faraday efficiency.Through ion induction and triggering of electron regulation in the OER via the synergistic action of the heterogeneous interface and surface reconstruction,this strategic design can overcome the limited capacity of bimetallic hydroxides and bridge the gap between the basic theory and industrialization of water decomposition.
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 in part by the WPIMANA,Ministry of Education,Culture,Sports,Science and TechnologyCREST of the Japan Science and Technology Agency(JST)(Grant No.JPMJCR17N1)the support from JSPS KAKENNHI grant 15H02004 and 18H03869.
文摘Layered double hydroxides(LDHs)have attracted tremendous research interest in widely spreading applications.Most notably,transition-metal-bearing LDHs are expected to serve as highly active electrocatalysts for oxygen evolution reaction(OER)due to their layered structure combined with versatile com-positions.Furthermore,reducing the thickness of platelet LDH crystals to nanometer or even molecular scale via cleavage or delamination provides an important clue to enhance the activity.In this review,recent progresses on rational design of LDH nanosheets are reviewed,including direct synthesis via traditional coprecipitation,homogeneous precipitation,and newly developed topochemical oxidation as well as chemical exfoliation of parent LDH crystals.In addition,diverse strategies are introduced to modulate their electrochemical activity by tuning the composition of host metal cations and intercalated counter-anions,and incorporating dopants,cavi-ties,and single atoms.In particular,hybridizing LDHs with conductive components or in situ growing them on conductive substrates to produce freestanding electrodes can further enhance their intrinsic catalytic activity.A brief discussion on future research directions and prospects is also summarized.
基金financially supported by the National Natural Science Foundation of China(U1707603,21521005,21975013,21901017)the National Key Research and Development Program of China(2017YFA0206500,2018YFA0702000)+2 种基金Beijing Natural Science Foundation(2172042)PetroChina Innovation Foundationthe Fundamental Research Funds for the Central Universities。
文摘With exhaustion of fossil fuels and the deterioration of global environment,widespread and intensive researches have been concentrated on clean and sustainable alternative energy sources,such as metal-air batteries[1],fuel cells[2]and water splitting devices[3].Electrocatalytic oxidation of water to O2(oxygen evolution reaction,OER)is a vital chemical process involved in energy storage and conversion from renewable sources in form of molecular fuels such as H2 via water electrolysis,which has attracted a great amount of research efforts in the past few years[4,5].Nowadays,RuO2 and IrO2 are widely used as typical excellent OER electrocatalysts.However,their high-cost and scarce nature restricts the broadly commercial application of those materials[6,7].Hence,there is an urgent demand to develop low cost,highly efficient,and superb stable OER catalysts.
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financially supported by: the Base Funding–UIDB/50020/2020 of the Associate Laboratory LSRE-LCM–funded by national funds through FCT/MCTES (PIDDAC) and project 2DMAT4FUEL (POCI-01-0145-FEDER-029600-COMPETE2020-FCT/ MCTES-PIDDAC, Portugal)Oea D-Ernst Mach Grant worldwide, Vienna, Austriathe support of the Austrian Science Fund (FWF), project number P32801.
文摘The high energy demand we currently face in society and the subsequent large consumption of fossil fuels cause its depletion and increase the pollution levels.The quest for the production of clean energy from renewable and sustainable sources remains open.The conversion of solar energy into hydrogen via the water-splitting process,assisted by pho tores pons ive semiconductor catalysts,is one of the most promising technologies.Significant progress has been made on water splitting in the past few years and a variety of photocatalysts active not only under ultra-violet(UV) light but especially with the visible part of the electromagnetic spectrum have been developed.Layered double hydroxides(LDH)-based materials have emerged as a promising class of nanomaterials for solar energy applications owing to their unique layered structure,compositional flexibility,tunable bandgaps,ease of synthesis and low manufacturing costs.This review covers the most recent research dedicated to LDH materials for photocatalytic water-splitting applications and encompasses a range of synthetic strategies and post-modifications used to enhance their performance.Moreover,we provide a thorough discussion of the experimental conditions crucial to obtaining improved photoactivity and highlight the impact of some specific parameters,namely,catalysts loading,cocatalysts,sacrificial agents,and irradiation sources.This review provides the necessary tools to select the election technique for adequately enhancing the photoactivity of LDH and modified LDH-based materials and concludes with a critical summary that outlines further research directions.
基金the financial support by the Natural Science Foundation of Liaoning Province of China (Grant No.201202126)the National Natural Science Foundation of China (Grant Nos. 21276253 and 21401093)
文摘The Na2CO3-modified HZSM-5 zeolites were further treated by tetrapropylammonium hydroxide(TPAOH) solution. The effect of TPAOH concentration on the secondary crystallization process was investigated. The resulting samples were characterized by a complementary combination of X-ray diffraction, N2 adsorption/desorption, scanning electron microscopy, X-ray fluorescence spectroscopy, XPS, 27 Al and 29 Si magic-angle spinning nuclear magnetic resonance spectroscopy, BET and temperature-programmed desorption techniques. The results showed that the secondary crystallization of the HZSM-5 zeolite could result in migration of non-framework species from the internal channels to the zeolite surface and their transformation into framework species. The catalytic activity of these modified samples for thiophene alkylation was evaluated. Both the activity and stability of the catalysts were improved after secondary crystallization.
基金supported by the National Natural Science Foundation of China (21972124, U2002213)the Double Tops Joint Fund of the Yunnan Science and Technology Bureau and Yunnan University (2019FY003025)+1 种基金the Priority Academic Program Development of Jiangsu Higher Education Institutionthe financial support of national local joint engineering laboratory to functional adsorption material technology for the environmental protection, Soochow University (SDGC2124)。
文摘The electrodeposition approach is significant in electrode fabrication for practical application.Herein,the electrodeposited amorphous NiFe hydroxide species for oxygen evolution reaction (OER) in water splitting reaction is demonstrated by revealing the synergistic effect influenced by the support electrode of Fe and Ni foil and the contents of Fe and Ni in the electrolyte.All the electrodeposited samples have an amorphous structure and similar profiles of binding energy and chemical states for Fe and Ni as characterized by the spectroscopic techniques.While the support effect and Fe/Ni synergistic effect are indeed observed for the varied catalytic performances observed for the different electrodes;the Ni foil supported catalyst exhibits much higher performance than that of the Fe foil supported catalyst,and the different redox potentials of Ni species in the different Fe/Ni electrode resulting from the Fe–Ni synergism are observed in the cyclic voltammetry curve analysis.The surface roughness and the electrochemical surface area are also influenced by the support effect and the Fe/Ni ratio in the plating electrolyte.The optimal electrode shows a very low overpotential of~200 mV to reach 10 mA cm^(-2),and very high catalytic stability by the consecutive cyclic voltammetry measurements and 20 h stability test.Though it has the largest electrochemical surface area,the highest catalytic efficiency for these active sites is also indicated by the specific activity and turnover frequency polarization curves.The current work shows the effective experience for the electrodeposited Fe/Ni based catalysts in large-scale fabrication,which can be more practical for hydrogen generation in the alkaline water electrolysis.
基金financial support from the National Key R&D Program of China (Grant Nos.: 2017YFA0206904, 2017YFA0206900, and 2016YFB0600901)the National Program on Key Basic Research Project (Grant No.: 2014CB239402)+6 种基金the National Natural Science Foundation of China (Grant Nos.: 51772305, 51572270, U1662118, 31671489, U1332205, and 21701131)the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant No.: XDB17000000)the Royal Society Newton Advanced Fellowship (Grant No.: NA170422)the Young Elite Scientist Sponsorship Program by CAST (Grant No.: YESS20160137)the Youth Innovation Promotion Association of the CASthe Fund of Xi’an University of Science and Technology (Grant No.:2018QDJ014)funding support from the Energy Education Trust of New Zealand
文摘For many two-dimensional(2D)materials,low coordination edges and corner sites offer greatly enhanced catalytic performance compared to basal sites,motivating the search for new synthetic approaches towards ultrathin and ultrafine 2D nanomaterials with high specific surface areas.To date,the synthesis of catalysts that are both ultrathin(monolayer)and ultrafine(lateral size<10nm)has proven extremely challenging.Herein,using a facile ultrasonic exfoliation procedure,we describe the successful synthesis of ultrafine ZnCo-LDH nanosheets(denoted as ZnCo-UF)with a size^3.5 nm and thickness^0.5 nm.The single layer ZnCo-UF nanosheets possess an abundance of oxygen vacancies(Vo)and unsaturated coordination s让es,thereby affording outstanding electrocatalytic water oxidation performance.DFT calculations confirmed that Vo on the surface of ZnCo-UF enhanced H20 adsorption via increasing the electropositivity of the nanosheets.
基金supported by the National Natural Science Foundation of China(Grant Nos.21505050,51672109)the Dispatch of Faculty Abroad of the University of Jinan+2 种基金the Natural Science Foundation of Shandong Province(Grant No.ZR2016FM30)supported in part by the WPI-MANA,Ministry of Education,Culture,Sports,Science and Technology,Japansupport from JSPS KAKENNHI(18H03869)
文摘Layered double hydroxides (LDHs), a class of anionic clays consisting of brucite-like host layers and interlayer anions, have been widely investigated in the last decade due to their promising applications in many areas such as catalysis, ion separation and adsorption. Owing to the highly tunable compositi on and uniform distribution of metal cations in the brucite-like layers, as well as the facile exchangeability of intercalated anions, LDHs can be modified and functionalized to form various nanostructures/composites through versatile processes such as anion intercalation and exfoliation, decoration of nanoparticles, selfassembly with other two-dimensional (2D) materials, and controlled growth on conductive supports (e.g., nanowire arrays, nano tubes, 3D foams). In this article, we briefly review the recent advances on both the LDH nano structures and functionalized composites toward the applications in energy conversion, especially for water oxidation.
基金supported by the Fundamental Research Funds for the Central Universities(XK1802-6,XK1902,XK1803-05,12060093063,2312018RC07)the National Natural Science Foundation of China(U1707603,21878008,21625101,20190816)。
文摘Photocatalytic reduction of CO2 with H2 O to syngas is an effective way for producing high value-added chemical feedstocks such as methanol and light olefins in industry.Nevertheless,the precise control of CO/H2 ratio from photocatalytic CO2 reduction reaction still poses a great challenge for the further application.Herein,we prepared a series of highly efficient heterostructure based on highly dispersed palladium supported on ultrathin Co Al-layered double hydroxide(LDH).In conjunction with a Ru-complex sensitizer,the molar ratios of CO/H2 can be tuned from 1:0.74 to 1:3 under visible-light irradiation(λ>400 nm).More interestingly,the syngas can be obtained under light irradiation atλ>600 nm.Structure characterization and density functional theory calculations revealed that the remarkable catalytic activity can be due to the supported palladium,which improved the charge transfer efficiency.Meanwhile,more H atoms were used to generate H2 on the supported palladium for further tunable CO/H2 ratio.This work demonstrates a new strategy for harnessing abundant solar-energy to produce syngas from a CO2 feedstock.
基金supported by the 973 Program(no.2014CB932104)the National Natural Science Foundation of China(nos:2177060378,U1707603 and 21521005)the Program for Changjiang Scholars,Innovative Research Teams in Universities(no.IRT1205)
文摘Compared with noble metal catalyst, Co3O4-based electrocatalysts have attracted considerable interesting as low-cost alternatives for oxygen evolution reaction (OER). However, the poor electrocatalytic activity still remains a huge challenge. Herein, we demonstrate a feasible approach through oxidation of CoFe layered double hydroxide (CoFe-LDH) to synthesize Fe-doped Co3O4@C nanopmrticles with size of about 30-50 nm. As OER catalyst, the as-synthesized Fe-doped Co3O4@C nanoparticles exhibited superior OER performance with a small overpotential of 260 mV at the current density of 20 mA cm^-2, a small Tafel slope of 70 mV dec^-1 and long-term durability (there was no obviously OER current density degradation for 100 h) in alkaline solution. The present work opens a new avenue to the exploration of cost-effective and excellent electrocatalysts based on transition metal oxide materials to substitute precious metal materials for water splitting.
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.
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the AdFutura Scholarship provided by the Slovene Human Resources Development and Scholarship Fund for this workthe Clarendon and Balliol Jowett Scholarships for subsequent funding+1 种基金SCG Chemicals Co., Ltd. (Thailand)SCG Packaging Co. Ltd PLC, for funding
文摘A new solvothermal post-synthesis treatment for preparing high aspect ratio magnesium aluminium layered double hydroxides(Mg Al–LDHs) has been developed. Treating laurate-intercalated Mg Al–LDHs in pure ethanol in an autoclave for 48 h at 150 °C was found to produce delaminated MgA l–LDH nanosheets with a thickness of ~2.6 nm and an aspect ratio of ~105. It is proposed that the high pressure solvothermal process promotes the insertion of ethanol molecules into the LDH interlayer space, thereby facilitating delamination. This new post-synthesis treatment provides the opportunity for a facile, large scale route to highly delaminated high aspect ratio LDHs, which might be of interest towards novel nanomaterials for energy conversion and storage.
基金supported by the National Natural Science Foundation of China (21871021, 21922501 and 21521005)the Beijing Natural Science Foundation (2192040)the Fundamental Research Funds for the Central Universities (XK1802-6 and XK1803-05)。
文摘Oxygen evolution reaction(OER) plays an indispensable role in developing renewable clean energy resources. One of the critical bottlenecks for the reaction is the development of highly efficient electrocatalyst to decrease the high overpotentials of four-electron transfer process of OER. Recently, layered double hydroxides(LDHs) have been widely investigated among the most promising electrocatalysts for OER due to their high intrinsic activity, excellent stability as well as low-cost. However, it remains unclear how the exposed facet of the LDHs affects their electrocatalytic activity. Here we elucidate the active edge facet of LDHs towards OER by combining the finely control of edge facet ratio coupled with molecular probe method and computational calculation. The LDHs with higher edge facet area ratio show superior activity with low onset potential as well as decreased Tafel slope. The active edge site is further proved by blocking the unsaturated edge sites with cyanate probe anion, of which the adsorption largely inhibits OER activity. Furthermore, based on density functional theory(DFT) calculation, twodimensional map of theoretical overpotentials as a function of Gibbs free energy reveals that the edge(100) facet exhibits a much higher OER activity than basal plane(001) facet.
基金financial support for this work from the Strategic Priority Research Program of CAS(XDB36030000)the National Natural Science Foundation of China(21422303,21573049,21872043,22002028)+3 种基金the National Basic Research Plan of China(2016YFA0201600)the Beijing Natural Science Foundation(2142036)the Youth Innovation Promotion Associationthe Special Program of “One Belt One Road”of CAS。
文摘The hierarchical structure of molybdenum disulfide(MoS2)nanosheet arrays stemmed from nickelcobalt layered double hydroxide(NiCo-LDH)/carbon cloth was prepared by growing the MoS_(2) nanosheet arrays onto the NiCo-LDH template which was pre-deposited onto the carbon cloth substrate.In this electrode configuration,carbon cloth is the three dimensional and conductive skeleton;NiCo-LDH nanosheets,as the template,ensure the oriented growth of MoS2 nanosheet arrays.Therefore,more MoS_(2) active sites are exposed and the catalyst exhibits good hydrogen evolution reaction activity.
