Hard carbon is the most promising anode for sodium-ion battery applications due to the wide availability and low work voltage.However,it often delivers worse electrochemical performance in ester-based electrolytes.Her...Hard carbon is the most promising anode for sodium-ion battery applications due to the wide availability and low work voltage.However,it often delivers worse electrochemical performance in ester-based electrolytes.Herein,a hierarchically porous loose sponge-like hard carbon with a highly disordered phase,prepared from the biomass of platanus bark,exhibits superior rate performance with a capacity of 165 mAh·g-1 at a high current of1 A·g-1,and high retention of 71.5%after 2000 cycles in an ester-based electrolyte.The effect of the hierarchically porous loose sponge-like structure on the formation dynamics of solid electrolyte interphase(SEI),and related properties,was studied via cyclic voltammetry(CV),galvanostatic intermittent titration technique(GITT),X-ray photoelectron spectroscope(XPS),Fourier transform infrared spectroscopy(FTIR)and electrochemical impedance spectroscopy(EIS)analysis.These results reveal that the hierarchically porous structure can construct continued connecting channels and accelerate the electrolyte transport,which is beneficial to the reaction kinetics of SEI.Moreover,the mesoporous structure is conducive to good contact between electrolyte and materials and shortens the Na+diffusion path,which in turn facilitates the charge transfer kinetics in the material.展开更多
Nanoscale hierarchically porous metal–organic frameworks(NHP-MOFs)have received unprecedented attention in many fields owing to their integration of the strengths of nanoscale size(<1μm)and hierarchical porous st...Nanoscale hierarchically porous metal–organic frameworks(NHP-MOFs)have received unprecedented attention in many fields owing to their integration of the strengths of nanoscale size(<1μm)and hierarchical porous structure(micro-,meso-and/or macro-pores)of MOFs.This review focuses on recent advances in the main synthetic strategies for NHP-MOFs based on different metal ions(e.g.,Cu,Fe,Co,Zn,Al,Zr,and Cr),including the template method,composite technology,post-synthetic modification,in situ growth and the grind method.In addition,the mechanisms of synthesis,regulation techniques and the advantages and disadvantages of various methods are discussed.Finally,the challenges and prospects of the commercialisation of promising NHP-MOFs are also presented.The purpose of this review is to provide a road map for future design and development of NHP-MOFs for practical application.展开更多
A carbon-based sulfonated catalyst was prepared by direct sulfonation and carbonization （in moderate conditions：200 ＆#176;C, 12 h） of red liquor solids, a by-product of paper-making process. The prepared sulfonate...A carbon-based sulfonated catalyst was prepared by direct sulfonation and carbonization （in moderate conditions：200 ＆#176;C, 12 h） of red liquor solids, a by-product of paper-making process. The prepared sulfonated cata-lyst （SC） had aromatic structure, composed of carbon enriched inner core, and oxygen-containing （SO3H, COOH, OH） groups enriched surface. The SO3H, COOH, OH groups amounted to 0.74 mmol·g^-1, 0.78 mmol·g^-1, 2.18 mmol·g^-1, respectively. The fresh SC showed much higher catalytic activity than that of the traditional solid acid catalysts （strong-acid 732 cation exchange resin, hydrogen type zeolite socony mobile-five （HZSM-5）, sulfated zir-conia） in esterification of oleic acid. SC was deactivated during the reactions, through the mechanisms of leaching of sulfonated species and formation of sulfonate esters. Two regeneration methods were developed, and the catalytic activity can be mostly regenerated by regeneration Method 1 and be fully regenerated by regeneration Method 2, respectively.展开更多
Searching for inexpensive,efficient and durable electrocatalysts with earth-abundant elements toward the hydrogen evolution reaction(HER)is of vital importance for the future sustainable hydrogen economy,yet still rem...Searching for inexpensive,efficient and durable electrocatalysts with earth-abundant elements toward the hydrogen evolution reaction(HER)is of vital importance for the future sustainable hydrogen economy,yet still remains a formidable challenge.Herein,a facile template-engaged strategy is demonstrated for the direct in-situ growth of Ni nanoparticles and N-doped carbon nanotubes on carbon nanorod substrates,forming a hierarchically branched architecture(abbreviated as Ni@N-C NT/NRs hereafter).The elaborate construction of such unique hierarchical structure with tightly encapsulated Ni nanoparticles and open configuration endows the as-fabricated Ni@N-C NT/NRs with abundant well-dispersed active sites,enlarged surface area,reduced resistances of charge transfer and mass diffusion,and reinforced mechanical robustness.As a consequence,the optimal Ni@N-C NT/NR catalyst demonstrates superior electrocatalytic activity with relatively low overpotential of 134 mV to deliver a current density of 10 mA·cm^-2 and excellent stability for HER in 0.1 M KOH,holding a great promise for practical scalable H2 production.More importantly,this work offers a reliable methodology for feasible fabrication of robust high-performance carbon-based hierarchical architectures for a variety of electrochemical applications.展开更多
Electrochemical CO_(2) reduction is a promising technology for solving the CO_(2) emission problems and producing value-added products. Here, we report a hierarchically porous Cu1Au single-atom alloy(SAA) as an effici...Electrochemical CO_(2) reduction is a promising technology for solving the CO_(2) emission problems and producing value-added products. Here, we report a hierarchically porous Cu1Au single-atom alloy(SAA) as an efficient electrocatalyst for CO_(2) reduction. Benefiting from the hierarchically porous architectures with abundant vacancies as well as three-dimensional accessible active sites, the as-prepared nanoporous Cu1Au SAA catalyst shows remarkable CO_(2) reduction performance with nearly 100% CO Faraday efficiency in a wide potential range(-0.4 to -0.9 V vs. reversible hydrogen electrode. The in-situ X-ray absorption spectroscopy studies and density functional theory calculations reveal that the Cu-Au interface sites serve as the intrinsic active centers,which can facilitate the activated adsorption of CO_(2) and stabilize the *COOH intermediate.展开更多
Stable non-noble metal bifunctional electrocatalysts are one of the challenges to the fluctuating overall water splitting driven by re-newable energy.Herein,a novel self-supporting hierarchically porous Ni_(x)Fe-S/NiF...Stable non-noble metal bifunctional electrocatalysts are one of the challenges to the fluctuating overall water splitting driven by re-newable energy.Herein,a novel self-supporting hierarchically porous Ni_(x)Fe-S/NiFe_(2)O_(4) heterostructure as bifunctional electrocatalyst was constructed based on porous Ni-Fe electrodeposition on three-dimensional(3D)carbon fiber cloth,in situ oxidation,and chemical sulfuration.Results showed that the Ni_(x)Fe-S/NiFe_(2)O_(4) heterostructure with a large specific surface area exhibits good bifunctional activity and stability for both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)because of the abundance of active sites,synergistic effect of the heterostructure,superhydrophilic surface,and stable,self-supporting structure.The results further confirmed that the Ni_(x)Fe-S phase in the heterostructure is transformed into metal oxides/hydroxides and Ni_(3)S_(2) during OER.Compared with the commercial 20wt%Pt/C||IrO_(2)-Ta_(2)O_(5) electrolyzer,the self-supporting Ni1/5Fe-S/NiFe_(2)O_(4)||Ni1/2Fe-S/NiFe_(2)O_(4) electrolyzer exhibits better stability and lower cell voltage in the fluctu-ating current density range of 10-500 mA/cm^(2).Particularly,the cell voltage of Ni1/5Fe-S/NiFe_(2)O_(4)||Ni1/2Fe-S/NiFe_(2)O_(4) is only approximately 3.91 V at an industrial current density of 500 mA/cm^(2),which is lower than that of the 20wt%Pt/C||IrO_(2)-Ta_(2)O_(5) electrolyzer(i.e.,approximately 4.79 V).This work provides a promising strategy to develop excellent bifunctional electrocatalysts for fluctuating overall water splitting.展开更多
The rational design and construction of hierarchically porous nanostructure for oxygen reduction reaction (ORR) electrocatalysts is crucial to facilitate the exposure of accessible active sites and promote the mass/el...The rational design and construction of hierarchically porous nanostructure for oxygen reduction reaction (ORR) electrocatalysts is crucial to facilitate the exposure of accessible active sites and promote the mass/electron transfer under the gas-solid-liquid triple-phase condition. Herein, an ingenious method through the pyrolysis of creative polyvinylimidazole coordination with Zn/Fe salt precursors is developed to fabricate hierarchically porous Fe-N-doped carbon framework as efficient ORR electrocatalyst. The volatilization of Zn species combined with the nanoscale Kirkendall effect of Fe dopants during the pyrolysis build the hierarchical micro-, meso-, and macroporous nanostructure with a high specific surface area (1,586 m^(2)·g^(−1)), which provide sufficient exposed active sites and multiscale mass/charge transport channels. The optimized electrocatalyst exhibits superior ORR activity and robust stability in both alkaline and acidic electrolytes. The Zn-air battery fabricated by such attractive electrocatalyst as air cathode displays a higher peak power density than that of Pt/C-based Zn-air battery, suggesting the great potential of this electrocatalyst for Zn-air batteries.展开更多
Lithium metal is one of the most promising anode materials for next-generation electrochemical energy storage due to low electrochemical potential and high specific capacity.However,large volume change and uncontrolla...Lithium metal is one of the most promising anode materials for next-generation electrochemical energy storage due to low electrochemical potential and high specific capacity.However,large volume change and uncontrollable formation of lithium dendrite during cycling severely hinder the practical application of rechargeable Li metal batteries.Herein,we report a hierarchically porous Cu covered with lithiophilic CuxO(HPCu-CuxO) via femtosecond laser strategy in about 2 min as current collector for highperformance Li metal batteries.With precisely tunable pore volume and depth as well as lithiophilic CuxO interphase,the HPCu-CuxO not only guides homogeneous Li nucleation,resulting in a smooth and dendrite-free lithium surface,but also provides space to alleviate the volume expansion of Li metal anode,achieving excellent structure stability.Consequently,highly stable Coulombic efficiency and ultralow overpotential of 15 mV even up to 1000 h were achieved at the current density of 1 mA cm^(-2).Moreover,the resultant Li@HPCu-CuxO//LiFePO_(4) full battery delivered outstanding cycle stability and rate capability.These results offer a pathway toward high-energy-density and safe rechargeable Li metal batteries.展开更多
Developing advanced oxygen reduction reaction(ORR)electrocatalysts with rapid mass/electron transport as well as conducting relevant kinetics investigations is essential for energy technologies,but both still face ong...Developing advanced oxygen reduction reaction(ORR)electrocatalysts with rapid mass/electron transport as well as conducting relevant kinetics investigations is essential for energy technologies,but both still face ongoing challenges.Herein,a facile approach was reported for achieving the highly dispersed Co nanoparticles anchored hierarchically porous N-doped carbon fibers(Co@N-HPCFs),which were assembled by core-shell MOFs-derived hollow polyhedrons.Notably,the unique one-dimensional(1D)carbon fibers with hierarchical porosity can effectively improve the exposure of active sites and facilitate the electron transfer and mass transfer,resulting in the enhanced reaction kinetics.As a result,the ORR performance of the optimal Co@N-HPCF catalysts remarkably outperforms that of commercial Pt/C in alkaline solution,reaching a limited diffusion current density(J)of 5.85 m A cm^(-2)and a half-wave potential(E_(1/2))of 0.831 V.Particularly,the prepared Co@N-HPCF catalysts can be used as an excellent air-cathode for liquid/solid-state Zn-air batteries,exhibiting great potentiality in portable/wearable energy devices.Furthermore,the reaction kinetic during ORR process is deeply explored by finite element simulation,so as to intuitively grasp the kinetic control region,diffusion control region,and mixing control region of the ORR process,and accurately obtain the relevant kinetic parameters.This work offers an effective strategy and a reliable theoretical basis for the engineering of first-class ORR electrocatalysts with fast electronic/mass transport.展开更多
Self‐supporting ZSM‐5crystals with hierarchical porosity were prepared through a steam‐assisted crystallization method using sponges as rigid scaffolds.The synthesized materials were characterized by X‐ray diffrac...Self‐supporting ZSM‐5crystals with hierarchical porosity were prepared through a steam‐assisted crystallization method using sponges as rigid scaffolds.The synthesized materials were characterized by X‐ray diffraction,nitrogen sorption,scanning electron microscopy,transmission electron microscopy,solid‐state nuclear magnetic resonance spectroscopy and ammonia temperature‐programmed desorption.The ZSM‐5monoliths exhibited high crystallinities,hierarchical porous structures and strong acidities.They showed superior catalytic performance in the liquid‐phase esterification reaction between benzyl alcohol and hexanoic acid.展开更多
Hollow zeolite microspheres have recently attracted much attention for their applications in catalysis,microreactors and biomedicine.Herein,we present hierarchically structured zeolite ZSM-5 microspheres with unique,a...Hollow zeolite microspheres have recently attracted much attention for their applications in catalysis,microreactors and biomedicine.Herein,we present hierarchically structured zeolite ZSM-5 microspheres with unique,abundant macropores that allow more efficient use for catalysis.The hierarchically macroporous zeolite ZSM-5 microspheres are synthesized under the assistance of water/oil emulsions and using polystyrene nanospheres as templates.The zeolite microsphere is assembled by uniform hollow zeolite nanospheres.Their large inner cavities and thin zeolite shells lead to smaller diffusion channel and higher improved accessibility to active sites,contributing to high catalytic performance in the catalytic conversion of benzyl alcohol in mesitylene.Such novel zeolite microspheres with impressive performance will be applied to numerous other industrial catalytic reactions.展开更多
Exploring electrode materials with attractive specific capacity and prominent cyclic durability is of the essence for promoting lithium ion batteries(LIBs).In2O3 has shown an extraordinary promise for LIBs with advant...Exploring electrode materials with attractive specific capacity and prominent cyclic durability is of the essence for promoting lithium ion batteries(LIBs).In2O3 has shown an extraordinary promise for LIBs with advantageous gravimetric capacity(theoretically 965 mA h g-1) and low working voltage.However,In2O3 still suffers from the inherent weaknesses of metal oxides in practical application,especially low conductivity and incorrigible volume expansion upon the cycling process.Here,we demonstrate the architecture of metal-organic framework(MOF)-derived In2O3 nanocrystals/hierarchically porous nitrogen-doped carbon composite(In2O3/HPNC) for ultra-stable LIBs anode.This hierarchically porous structure(micro/meso/macro-pores) with nitrogen doping not only ensures exceptional mechanical strength and accommodates the volume expansion of In2O3 nanocrystals,but also offers electrons and lithium ions efficient interpenetrating pathways to migrate rapidly during charge/discharge processes.Thus,In2O3/HPNC exhibits excellent cyclic stability with a high specific capacity of 623 mA h g-1 over2000 cycles at 1000 mA g-1,corresponding to an ultra-low specific capacity decay of 0.017% per cycle(the best among the ln203-based anode for LIBs),and outstanding rate performance,suggesting a critical step toward achieving long-life and high-rate LIBs in practical devices.展开更多
The rational design and synthesis of hierarchically hollow nanostructures with controlled spatial architecture and composition are significant in electrocatalysis owing to their abundant active sites and the expedited...The rational design and synthesis of hierarchically hollow nanostructures with controlled spatial architecture and composition are significant in electrocatalysis owing to their abundant active sites and the expedited electron/mass transfer.Electrocatalytic nitrate reduction to ammonia is of great interest from the points of environmental protection and energy saving.However,the development of this technology is hindered by the lack of efficient nitrate-toammonia electrocatalysts and the kinetically sluggish oxygen evolution reaction at the anode.Herein,a novel self-template conversion method was developed for the synthesis of Co3O4@Ni O hierarchical nanotubes(Co3O4@Ni O HNTs)with Ni O porous nanosheets assembled on Co3O4nanotubes.The as-obtained Co3O4@Ni O HNTs exhibited an outstanding performance for both the cathodic nitrate electroreduction to ammonia reaction and the anodic tetrahydroisoquinolines(THIQs)semi-dehydrogenation to dihydroisoquinolines(DHIQs).Importantly,a two-electrode system of Co3O4@Ni O HNTs||Co3O4@Ni O HNTs was constructed for the simultaneous synthesis of ammonia and DHIQs with high selectivity and robust stability.展开更多
The development of novel nanozymes for environmental contamination remediation is a worthwhile research direction.However,most of the reported nanozymes cannot degrade efficiently due to the limitation of the internal...The development of novel nanozymes for environmental contamination remediation is a worthwhile research direction.However,most of the reported nanozymes cannot degrade efficiently due to the limitation of the internal active sites not being able to come into direct contact with contaminants.Therefore,we reported Fe-N-C single-atom nanozymes(SAzymes)with atomically dispersed FeN4 active sites anchored on a three-dimensional hierarchically ordered microporous-mesoporous-macroporous nitrogen doped carbon matrix(3DOM Fe-N-C)for the degradation of a targeted environmental pollutant(rhodamine B(RhB)).The three-dimensional(3D)hierarchically ordered porous structure may accelerate mass transfer and improve the accessibility of active sites.This structure and high metal atom utilization endow Fe-N-C SAzyme with enhanced tri-enzyme-mimic activities,comprising oxidase-mimic,peroxidase-mimic,and catalase-mimic activities.Based on its excellent peroxidase-mimic activity,3DOM Fe-N-C can degrade RhB by hydroxyl radicals(·OH)generated in the presence of hydrogen peroxide.This study provides a new idea for designing porous Fe-N-C SAzymes for environmental contamination remediation.展开更多
Developing large-scale and highly efficient oxygen reduction reaction(ORR)catalysts acts a vital role in realizing wide application of metal–air batteries.Here,we propose a gas-foaming strategy to fabricate sustainab...Developing large-scale and highly efficient oxygen reduction reaction(ORR)catalysts acts a vital role in realizing wide application of metal–air batteries.Here,we propose a gas-foaming strategy to fabricate sustainable and 3D hierarchically porous N-doped carbon with high specific surface area and abundant defects sites derived from biomass.The obtained catalyst exhibits prominent ORR property with higher half-wave potential(0.861 V)and slightly lower kinetic current density(32.44 m A cm^-2),compared to Pt/C(0.856 V and 43.61 m A cm^-1).Furthermore,employing it as catalyst of air cathode,the Al–air battery delivers remarkable discharge performance with excellent power density of 401 m W cm^-2,distinguished energy density of 2453.4 Wh kg^-1 and extremely high open-circuit voltage of 1.85 V among the reported metal–air batteries in the literatures.This gas-foaming strategy for full utilization of biomass affords a chance to explore scalable advanced catalysts in metal–air battery.展开更多
Nitrogen-rich porous carbonaceous materials have shown great potential in energy storage and conversion applications due to their facile fabrication,high electronic conductivity,and improved hydrophilic property.Herei...Nitrogen-rich porous carbonaceous materials have shown great potential in energy storage and conversion applications due to their facile fabrication,high electronic conductivity,and improved hydrophilic property.Herein,three-dimensional porous N-rich carbon foams are fabricated through a one-step carbonization-activation method of the commercial melamine foam,and displaying hierarchically porous structure(macro-,meso-,and micro-pores),large surface area(1686.5 m2 g^-1),high N-containing level(3.3 at%),and excellent compressibility.The as-prepared carbon foams as electrodes for quasi-solid-state supercapacitors exhibit enhanced energy storage ability with 210 F g^-1 and 2.48c at 0.1 A g^-1,and150 F g^-1 and 1.77 F cm^-2 at 1 A g^-1,respectively.Moreover,as an electrode for lithium-based dual-ion capacitor,this distinctive porous carbon also delivers remarkable specific capacitance with 143.6 F g^-1 at0.1 A g^-1 and 116.2 F g^-1 at 1 A g^-1.The simple preparation method and the fascinating electrochemical performance endow the N-rich porous carbon foams great prospects as high-performance electrodes for electrochemical energy storage.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.U1804129,21771164,21671205 and U1804126)Zhongyuan Youth Talent Support Program of Henan Province and Zhengzhou University Youth Innovation Program。
文摘Hard carbon is the most promising anode for sodium-ion battery applications due to the wide availability and low work voltage.However,it often delivers worse electrochemical performance in ester-based electrolytes.Herein,a hierarchically porous loose sponge-like hard carbon with a highly disordered phase,prepared from the biomass of platanus bark,exhibits superior rate performance with a capacity of 165 mAh·g-1 at a high current of1 A·g-1,and high retention of 71.5%after 2000 cycles in an ester-based electrolyte.The effect of the hierarchically porous loose sponge-like structure on the formation dynamics of solid electrolyte interphase(SEI),and related properties,was studied via cyclic voltammetry(CV),galvanostatic intermittent titration technique(GITT),X-ray photoelectron spectroscope(XPS),Fourier transform infrared spectroscopy(FTIR)and electrochemical impedance spectroscopy(EIS)analysis.These results reveal that the hierarchically porous structure can construct continued connecting channels and accelerate the electrolyte transport,which is beneficial to the reaction kinetics of SEI.Moreover,the mesoporous structure is conducive to good contact between electrolyte and materials and shortens the Na+diffusion path,which in turn facilitates the charge transfer kinetics in the material.
基金the financial support from the National Natural Science Foundation of China(22008032,22108034,and 22102026)the Guangdong Basic and Applied Basic Research Foundation(2019A1515110706)+2 种基金the Guangdong Provincial Key Lab of Green Chemical Product Technology(GC202111)the Medical Science and Technology Research Foundation of Guangdong Province(A2021189)the Shandong Provincial Natural Science Foundation(ZR2018ZC1458)。
文摘Nanoscale hierarchically porous metal–organic frameworks(NHP-MOFs)have received unprecedented attention in many fields owing to their integration of the strengths of nanoscale size(<1μm)and hierarchical porous structure(micro-,meso-and/or macro-pores)of MOFs.This review focuses on recent advances in the main synthetic strategies for NHP-MOFs based on different metal ions(e.g.,Cu,Fe,Co,Zn,Al,Zr,and Cr),including the template method,composite technology,post-synthetic modification,in situ growth and the grind method.In addition,the mechanisms of synthesis,regulation techniques and the advantages and disadvantages of various methods are discussed.Finally,the challenges and prospects of the commercialisation of promising NHP-MOFs are also presented.The purpose of this review is to provide a road map for future design and development of NHP-MOFs for practical application.
基金Supported by the National Natural Science Foundation of China(21276076)the Fundamental Research Funds for the Central Universities of China(WA1014003)State Key Laboratory of Chemical Engineering(SKL-ChE-10C06)
文摘A carbon-based sulfonated catalyst was prepared by direct sulfonation and carbonization （in moderate conditions：200 ＆#176;C, 12 h） of red liquor solids, a by-product of paper-making process. The prepared sulfonated cata-lyst （SC） had aromatic structure, composed of carbon enriched inner core, and oxygen-containing （SO3H, COOH, OH） groups enriched surface. The SO3H, COOH, OH groups amounted to 0.74 mmol·g^-1, 0.78 mmol·g^-1, 2.18 mmol·g^-1, respectively. The fresh SC showed much higher catalytic activity than that of the traditional solid acid catalysts （strong-acid 732 cation exchange resin, hydrogen type zeolite socony mobile-five （HZSM-5）, sulfated zir-conia） in esterification of oleic acid. SC was deactivated during the reactions, through the mechanisms of leaching of sulfonated species and formation of sulfonate esters. Two regeneration methods were developed, and the catalytic activity can be mostly regenerated by regeneration Method 1 and be fully regenerated by regeneration Method 2, respectively.
基金The work was financially supported by the National Natural Science Foundation of China(Nos.21972068,21875112,21576139,51871060,51672049)Natural Science Foundation of Jiangsu Province(No.BK20171473).The authors also thank the supports from National and Local Joint Engineering Research Center of Biomedical Functional Materials and a project sponsored by the Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘Searching for inexpensive,efficient and durable electrocatalysts with earth-abundant elements toward the hydrogen evolution reaction(HER)is of vital importance for the future sustainable hydrogen economy,yet still remains a formidable challenge.Herein,a facile template-engaged strategy is demonstrated for the direct in-situ growth of Ni nanoparticles and N-doped carbon nanotubes on carbon nanorod substrates,forming a hierarchically branched architecture(abbreviated as Ni@N-C NT/NRs hereafter).The elaborate construction of such unique hierarchical structure with tightly encapsulated Ni nanoparticles and open configuration endows the as-fabricated Ni@N-C NT/NRs with abundant well-dispersed active sites,enlarged surface area,reduced resistances of charge transfer and mass diffusion,and reinforced mechanical robustness.As a consequence,the optimal Ni@N-C NT/NR catalyst demonstrates superior electrocatalytic activity with relatively low overpotential of 134 mV to deliver a current density of 10 mA·cm^-2 and excellent stability for HER in 0.1 M KOH,holding a great promise for practical scalable H2 production.More importantly,this work offers a reliable methodology for feasible fabrication of robust high-performance carbon-based hierarchical architectures for a variety of electrochemical applications.
基金supported by the National Natural Science Foundation of China (51771072)the Youth 1000 Talent Program of China (799229034)+3 种基金the Outstanding Youth Scientist Foundation of Hunan Province (2020JJ2006)the Fundamental Research Funds for the Central UniversitiesHunan University State Key Laboratory of Advanced Design and Manufacturing for Vehicle Body Independent Research Project (71860007)Hunan Provincial Innovation Foundation for Postgraduate (CX20190312)。
文摘Electrochemical CO_(2) reduction is a promising technology for solving the CO_(2) emission problems and producing value-added products. Here, we report a hierarchically porous Cu1Au single-atom alloy(SAA) as an efficient electrocatalyst for CO_(2) reduction. Benefiting from the hierarchically porous architectures with abundant vacancies as well as three-dimensional accessible active sites, the as-prepared nanoporous Cu1Au SAA catalyst shows remarkable CO_(2) reduction performance with nearly 100% CO Faraday efficiency in a wide potential range(-0.4 to -0.9 V vs. reversible hydrogen electrode. The in-situ X-ray absorption spectroscopy studies and density functional theory calculations reveal that the Cu-Au interface sites serve as the intrinsic active centers,which can facilitate the activated adsorption of CO_(2) and stabilize the *COOH intermediate.
基金financially supported by the National Natural Science Foundation of China (Nos. 51874020 and 52004022)
文摘Stable non-noble metal bifunctional electrocatalysts are one of the challenges to the fluctuating overall water splitting driven by re-newable energy.Herein,a novel self-supporting hierarchically porous Ni_(x)Fe-S/NiFe_(2)O_(4) heterostructure as bifunctional electrocatalyst was constructed based on porous Ni-Fe electrodeposition on three-dimensional(3D)carbon fiber cloth,in situ oxidation,and chemical sulfuration.Results showed that the Ni_(x)Fe-S/NiFe_(2)O_(4) heterostructure with a large specific surface area exhibits good bifunctional activity and stability for both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)because of the abundance of active sites,synergistic effect of the heterostructure,superhydrophilic surface,and stable,self-supporting structure.The results further confirmed that the Ni_(x)Fe-S phase in the heterostructure is transformed into metal oxides/hydroxides and Ni_(3)S_(2) during OER.Compared with the commercial 20wt%Pt/C||IrO_(2)-Ta_(2)O_(5) electrolyzer,the self-supporting Ni1/5Fe-S/NiFe_(2)O_(4)||Ni1/2Fe-S/NiFe_(2)O_(4) electrolyzer exhibits better stability and lower cell voltage in the fluctu-ating current density range of 10-500 mA/cm^(2).Particularly,the cell voltage of Ni1/5Fe-S/NiFe_(2)O_(4)||Ni1/2Fe-S/NiFe_(2)O_(4) is only approximately 3.91 V at an industrial current density of 500 mA/cm^(2),which is lower than that of the 20wt%Pt/C||IrO_(2)-Ta_(2)O_(5) electrolyzer(i.e.,approximately 4.79 V).This work provides a promising strategy to develop excellent bifunctional electrocatalysts for fluctuating overall water splitting.
基金This work was supported by the National Natural Science Foundation of China(No.51976143)the National Key Research and Development Program of China(No.2018YFA0702001)Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory(No.XHD2020-002).
文摘The rational design and construction of hierarchically porous nanostructure for oxygen reduction reaction (ORR) electrocatalysts is crucial to facilitate the exposure of accessible active sites and promote the mass/electron transfer under the gas-solid-liquid triple-phase condition. Herein, an ingenious method through the pyrolysis of creative polyvinylimidazole coordination with Zn/Fe salt precursors is developed to fabricate hierarchically porous Fe-N-doped carbon framework as efficient ORR electrocatalyst. The volatilization of Zn species combined with the nanoscale Kirkendall effect of Fe dopants during the pyrolysis build the hierarchical micro-, meso-, and macroporous nanostructure with a high specific surface area (1,586 m^(2)·g^(−1)), which provide sufficient exposed active sites and multiscale mass/charge transport channels. The optimized electrocatalyst exhibits superior ORR activity and robust stability in both alkaline and acidic electrolytes. The Zn-air battery fabricated by such attractive electrocatalyst as air cathode displays a higher peak power density than that of Pt/C-based Zn-air battery, suggesting the great potential of this electrocatalyst for Zn-air batteries.
基金financially supported by the Fundamental Research Funds of the Central Universities(no.531107051048)the support from the Hunan Key Laboratory of Two-Dimensional Materials(No.801200005)。
文摘Lithium metal is one of the most promising anode materials for next-generation electrochemical energy storage due to low electrochemical potential and high specific capacity.However,large volume change and uncontrollable formation of lithium dendrite during cycling severely hinder the practical application of rechargeable Li metal batteries.Herein,we report a hierarchically porous Cu covered with lithiophilic CuxO(HPCu-CuxO) via femtosecond laser strategy in about 2 min as current collector for highperformance Li metal batteries.With precisely tunable pore volume and depth as well as lithiophilic CuxO interphase,the HPCu-CuxO not only guides homogeneous Li nucleation,resulting in a smooth and dendrite-free lithium surface,but also provides space to alleviate the volume expansion of Li metal anode,achieving excellent structure stability.Consequently,highly stable Coulombic efficiency and ultralow overpotential of 15 mV even up to 1000 h were achieved at the current density of 1 mA cm^(-2).Moreover,the resultant Li@HPCu-CuxO//LiFePO_(4) full battery delivered outstanding cycle stability and rate capability.These results offer a pathway toward high-energy-density and safe rechargeable Li metal batteries.
基金The financial support of the Natural Science Foundation of China(21802079 and 22075159)the Postdoctoral Science Foundation of China(2018 M642605)+1 种基金the Youth Innovation Team Project of Shandong Provincial Education Department(2019KJC023)the Taishan Scholar Program for L.Zhang(202103058)are appreciated。
文摘Developing advanced oxygen reduction reaction(ORR)electrocatalysts with rapid mass/electron transport as well as conducting relevant kinetics investigations is essential for energy technologies,but both still face ongoing challenges.Herein,a facile approach was reported for achieving the highly dispersed Co nanoparticles anchored hierarchically porous N-doped carbon fibers(Co@N-HPCFs),which were assembled by core-shell MOFs-derived hollow polyhedrons.Notably,the unique one-dimensional(1D)carbon fibers with hierarchical porosity can effectively improve the exposure of active sites and facilitate the electron transfer and mass transfer,resulting in the enhanced reaction kinetics.As a result,the ORR performance of the optimal Co@N-HPCF catalysts remarkably outperforms that of commercial Pt/C in alkaline solution,reaching a limited diffusion current density(J)of 5.85 m A cm^(-2)and a half-wave potential(E_(1/2))of 0.831 V.Particularly,the prepared Co@N-HPCF catalysts can be used as an excellent air-cathode for liquid/solid-state Zn-air batteries,exhibiting great potentiality in portable/wearable energy devices.Furthermore,the reaction kinetic during ORR process is deeply explored by finite element simulation,so as to intuitively grasp the kinetic control region,diffusion control region,and mixing control region of the ORR process,and accurately obtain the relevant kinetic parameters.This work offers an effective strategy and a reliable theoretical basis for the engineering of first-class ORR electrocatalysts with fast electronic/mass transport.
基金supported by the National Natural Science Foundation of China(21333009)the Youth Innovation Promotion Association of CAS(2017049)~~
文摘Self‐supporting ZSM‐5crystals with hierarchical porosity were prepared through a steam‐assisted crystallization method using sponges as rigid scaffolds.The synthesized materials were characterized by X‐ray diffraction,nitrogen sorption,scanning electron microscopy,transmission electron microscopy,solid‐state nuclear magnetic resonance spectroscopy and ammonia temperature‐programmed desorption.The ZSM‐5monoliths exhibited high crystallinities,hierarchical porous structures and strong acidities.They showed superior catalytic performance in the liquid‐phase esterification reaction between benzyl alcohol and hexanoic acid.
基金supported by the National Key R&D Program of China(No.2022YFB3504000)the National Natural Science Foundation of China(Nos.22302152,U20A20122,22293020,U22B6011)+3 种基金the Fundamental Research Funds for the Central Universities,China(WUT:2024IVA090)the Program of Introducing Talents of Discipline to Universities-Plan 111(No.B20002)from the Ministry of Science and Technology and the Ministry of Education of ChinaThis research was also supported by the European Commission Interreg V France-Wallonie-Vlaanderen Project“DepollutAir”,the Program Win2Wal(No.TCHARBONACTIF:2110120)Wallonia Region of Belgium and the National Key R&D Program Intergovernmental Technological Innovation Special Cooperation Project Wallonia-Brussels/China(MOST)(No.SUB/2021/IND493971/524448).
文摘Hollow zeolite microspheres have recently attracted much attention for their applications in catalysis,microreactors and biomedicine.Herein,we present hierarchically structured zeolite ZSM-5 microspheres with unique,abundant macropores that allow more efficient use for catalysis.The hierarchically macroporous zeolite ZSM-5 microspheres are synthesized under the assistance of water/oil emulsions and using polystyrene nanospheres as templates.The zeolite microsphere is assembled by uniform hollow zeolite nanospheres.Their large inner cavities and thin zeolite shells lead to smaller diffusion channel and higher improved accessibility to active sites,contributing to high catalytic performance in the catalytic conversion of benzyl alcohol in mesitylene.Such novel zeolite microspheres with impressive performance will be applied to numerous other industrial catalytic reactions.
基金the financial support from the Fundamental Research Funds of the Central Universities(No.531118010112)the Double First-Class University Initiative of Hunan University(No.531109100004)+1 种基金the Fundamental Research Funds of the Central Universities(no.531107051048)the support from the Hunan Key Laboratory of Two-Dimensional Materials(No.801200005)
文摘Exploring electrode materials with attractive specific capacity and prominent cyclic durability is of the essence for promoting lithium ion batteries(LIBs).In2O3 has shown an extraordinary promise for LIBs with advantageous gravimetric capacity(theoretically 965 mA h g-1) and low working voltage.However,In2O3 still suffers from the inherent weaknesses of metal oxides in practical application,especially low conductivity and incorrigible volume expansion upon the cycling process.Here,we demonstrate the architecture of metal-organic framework(MOF)-derived In2O3 nanocrystals/hierarchically porous nitrogen-doped carbon composite(In2O3/HPNC) for ultra-stable LIBs anode.This hierarchically porous structure(micro/meso/macro-pores) with nitrogen doping not only ensures exceptional mechanical strength and accommodates the volume expansion of In2O3 nanocrystals,but also offers electrons and lithium ions efficient interpenetrating pathways to migrate rapidly during charge/discharge processes.Thus,In2O3/HPNC exhibits excellent cyclic stability with a high specific capacity of 623 mA h g-1 over2000 cycles at 1000 mA g-1,corresponding to an ultra-low specific capacity decay of 0.017% per cycle(the best among the ln203-based anode for LIBs),and outstanding rate performance,suggesting a critical step toward achieving long-life and high-rate LIBs in practical devices.
基金financially supported by the National Natural Science Foundation of China(21701122 and 21871206)。
文摘The rational design and synthesis of hierarchically hollow nanostructures with controlled spatial architecture and composition are significant in electrocatalysis owing to their abundant active sites and the expedited electron/mass transfer.Electrocatalytic nitrate reduction to ammonia is of great interest from the points of environmental protection and energy saving.However,the development of this technology is hindered by the lack of efficient nitrate-toammonia electrocatalysts and the kinetically sluggish oxygen evolution reaction at the anode.Herein,a novel self-template conversion method was developed for the synthesis of Co3O4@Ni O hierarchical nanotubes(Co3O4@Ni O HNTs)with Ni O porous nanosheets assembled on Co3O4nanotubes.The as-obtained Co3O4@Ni O HNTs exhibited an outstanding performance for both the cathodic nitrate electroreduction to ammonia reaction and the anodic tetrahydroisoquinolines(THIQs)semi-dehydrogenation to dihydroisoquinolines(DHIQs).Importantly,a two-electrode system of Co3O4@Ni O HNTs||Co3O4@Ni O HNTs was constructed for the simultaneous synthesis of ammonia and DHIQs with high selectivity and robust stability.
基金We are grateful for the support from the Ministry of Science and Technology of China(Nos.2016YFA0203203 and 2019YFA0709202)the National Natural Science Foundation of China(No.22074137).
文摘The development of novel nanozymes for environmental contamination remediation is a worthwhile research direction.However,most of the reported nanozymes cannot degrade efficiently due to the limitation of the internal active sites not being able to come into direct contact with contaminants.Therefore,we reported Fe-N-C single-atom nanozymes(SAzymes)with atomically dispersed FeN4 active sites anchored on a three-dimensional hierarchically ordered microporous-mesoporous-macroporous nitrogen doped carbon matrix(3DOM Fe-N-C)for the degradation of a targeted environmental pollutant(rhodamine B(RhB)).The three-dimensional(3D)hierarchically ordered porous structure may accelerate mass transfer and improve the accessibility of active sites.This structure and high metal atom utilization endow Fe-N-C SAzyme with enhanced tri-enzyme-mimic activities,comprising oxidase-mimic,peroxidase-mimic,and catalase-mimic activities.Based on its excellent peroxidase-mimic activity,3DOM Fe-N-C can degrade RhB by hydroxyl radicals(·OH)generated in the presence of hydrogen peroxide.This study provides a new idea for designing porous Fe-N-C SAzymes for environmental contamination remediation.
基金supported in China by the National Natural Science Foundation of China(No.51474255)the Hunan Provincial Science and Technology Plan Project,China(No.2016TP1007)the Open Sharing Fund for the Large-scale Instruments and Equipments of Central South University(CSUZC201932)。
文摘Developing large-scale and highly efficient oxygen reduction reaction(ORR)catalysts acts a vital role in realizing wide application of metal–air batteries.Here,we propose a gas-foaming strategy to fabricate sustainable and 3D hierarchically porous N-doped carbon with high specific surface area and abundant defects sites derived from biomass.The obtained catalyst exhibits prominent ORR property with higher half-wave potential(0.861 V)and slightly lower kinetic current density(32.44 m A cm^-2),compared to Pt/C(0.856 V and 43.61 m A cm^-1).Furthermore,employing it as catalyst of air cathode,the Al–air battery delivers remarkable discharge performance with excellent power density of 401 m W cm^-2,distinguished energy density of 2453.4 Wh kg^-1 and extremely high open-circuit voltage of 1.85 V among the reported metal–air batteries in the literatures.This gas-foaming strategy for full utilization of biomass affords a chance to explore scalable advanced catalysts in metal–air battery.
基金Financial supports from the National Natural Science Foundation of China(51872027)Beijing Natural Science Foundation(L172023)。
文摘Nitrogen-rich porous carbonaceous materials have shown great potential in energy storage and conversion applications due to their facile fabrication,high electronic conductivity,and improved hydrophilic property.Herein,three-dimensional porous N-rich carbon foams are fabricated through a one-step carbonization-activation method of the commercial melamine foam,and displaying hierarchically porous structure(macro-,meso-,and micro-pores),large surface area(1686.5 m2 g^-1),high N-containing level(3.3 at%),and excellent compressibility.The as-prepared carbon foams as electrodes for quasi-solid-state supercapacitors exhibit enhanced energy storage ability with 210 F g^-1 and 2.48c at 0.1 A g^-1,and150 F g^-1 and 1.77 F cm^-2 at 1 A g^-1,respectively.Moreover,as an electrode for lithium-based dual-ion capacitor,this distinctive porous carbon also delivers remarkable specific capacitance with 143.6 F g^-1 at0.1 A g^-1 and 116.2 F g^-1 at 1 A g^-1.The simple preparation method and the fascinating electrochemical performance endow the N-rich porous carbon foams great prospects as high-performance electrodes for electrochemical energy storage.
