Aqueous Zinc-ion batteries(ZIB) are attracting immense attention because of their merits of excellent safety and quite cheap properties compared with lithium-ion batteries(LIB).Manganese oxide is one of the most impor...Aqueous Zinc-ion batteries(ZIB) are attracting immense attention because of their merits of excellent safety and quite cheap properties compared with lithium-ion batteries(LIB).Manganese oxide is one of the most important cathode materials of ZIB.In this paper,α-Mn2O3 used as cathode of ZIB is synthesized via Metal-Organic Framework(MOF)-derived method,which delivers a high specific capacity of225 mAh g^(-1) at 0.05 A g^(-1) and 92.7 mAh g^(-1) after 1700 cycles at 2 A g^(-1).The charge storage mechanism of α-Mn2O3 cathode is found to greatly depend on the discharge current density.At lower current density discharging,the H+ and Zn2+ are successively intercalated into the α-Mn2O3 before and after the "turning point" of discharge voltage and their discharging products present obviously different morphologies changing from flower-like to large plate-like products.At a higher current density,the low-voltage plateau after the turning point disappears due to the decrease of amount of Zn2+ intercalation and the H+intercalation is dominated in α-Mn2 O3.This study provides significant understanding for future design and research of high-performance Mn-based cathodes of ZIB.展开更多
Water induced decomposition of Cu3（BTC）2 （BTC= benzene-l,3,5-tricarboxylate） metal-organic framework （MOF） was studied using dynamic water vapour adsorption. Small-angle X-ray scattering, Fourier transform infra...Water induced decomposition of Cu3（BTC）2 （BTC= benzene-l,3,5-tricarboxylate） metal-organic framework （MOF） was studied using dynamic water vapour adsorption. Small-angle X-ray scattering, Fourier transform infrared spectroscopy and differential scanning calorimetry analyses revealed that the underlying mechanism of Cu3（BTC）2 MOF decomposition under humid streams is the interpenetration of water molecules into Cu-BTC coordination to displace organic linkers （BTC） from Cu centres.展开更多
The synthesis of wide bandwidth,thin thickness,and high performance microwave absorbing materials has become a hot topic of current research.Metal-organic frameworks with heterojunctions and porous structures are cons...The synthesis of wide bandwidth,thin thickness,and high performance microwave absorbing materials has become a hot topic of current research.Metal-organic frameworks with heterojunctions and porous structures are considered as suitable candidates to meet these characteristics.Herein,heterogeneous CoFe@N-doped porous carbon polyhedron composites were successfully synthesized via Fe^(2+)to replace Co in zeolite imidazole frame-67.The dielectric properties of composites were enhanced by the replacement of Fe^(2+),and the synergistic effect of dielectric loss and magnetic loss was realized.The petal-like lamellar structure increases the travel of electromagnetic(EM)waves,and the formation of porous structures improves impedance matching.Specifically,a reflection loss of−67.30 dB was obtained at a thickness of 2.88 mm,and an ultrabroad wide effective absorption bandwidth of 8.40 GHz was obtained,covering most of the X-band(8–12 GHz)and the whole Ku-band(12–18 GHz).The radar cross section(RCS)reduction value can reach 29.4 dB·m^(2),which means that the radar detector has a smaller probability of detecting targets.This work describes the unique advantages of metal ion replacement metal-organic frameworks derived materials in structural design,impedance matching,and performance adjustment,and provides a new reference for the field of electromagnetic wave absorption.展开更多
The use of metal-organic frameworks(MOFs)as solid adsorption materials for carbon capture is promising,but achieving efficient and reversible adsorption with a balance of capacity and selectivity for carbon dioxide(CO...The use of metal-organic frameworks(MOFs)as solid adsorption materials for carbon capture is promising,but achieving efficient and reversible adsorption with a balance of capacity and selectivity for carbon dioxide(CO_(2))over N_(2) remains a challenge.To take full advantage of the strong channel traffic and robustness of MOFs with relatively small pores,it is highly necessary to employ a defect-engineering strategy to construct a broader channel structure that can facilitate the loading of functional motif-rich amino acids(AAs).This strategy can greatly enhance the CO_(2) adsorption performance of MOF.In this study,motif-rich amino acids are loaded into the defective and robust porous frameworks via combined defect-engineering and post-synthetic methods.The defective Zr/Hf-MOF-808s modified with AAs,especially for the 18 mol%4-nitroisophthalic acid,generated defective products allowing for the loading of L-serine(L-Ser).This modification resulted in a significant improvement in both the adsorption capacity(248%improvement at 298 K,100 kPa)and the selectivity of CO_(2)/N_(2) using the ideal adsorbed solution theory(IAST),with the selectivity increasing to 120.55 and 38.27 at 15 and 100 kPa,respectively,while maintaining good cycling performance.Density functional theory(DFT)simulation,CO_(2) temperature-programmed desorption(CO_(2)-TPD),and in situ Fourier transform infrared spectroscopy(FTIR)were further employed to have a better understanding of the enhanced CO_(2) adsorption capacity.Interestingly,unlike the AAs loaded pristine MOF-808s that showed the best CO_(2) adsorption capacity with the loading of short and small glycine(Gly),the broadened channel size in our work enables the loading of functional motif-rich L-serine,which brings more active binding sites,improving CO_(2) adsorption.展开更多
Despite various 2H-MoS/carbon hybrid nanostructures have been constructed and committed to improve the performance for sodium-ion batteries(SIBs),they still show the limited cycle stability due to the relatively large...Despite various 2H-MoS/carbon hybrid nanostructures have been constructed and committed to improve the performance for sodium-ion batteries(SIBs),they still show the limited cycle stability due to the relatively large volumetric expansion during the charge-discharge process Herein,we report the construction of cobalt-doped few-layered 1T-MoS2 nanosheets embedded in N,S-doped carbon(CMS/NSC)nanobowls derived from metal-organic framework(MOF)precursor via a simple in situ sulfurization process.This unique hierarchical structure enables the uniformly dispersed Co-doped 1T-MoS2 nanosheets intimately couple with the highly conductive carbon nanobowls,thus efficiently preventing the aggregation.In particular,the Co-doping plays a crucial role in maintaining the integrity of structure for MoS2 during cycling tests,confirmed by first-principles calculations.Compared with pristine MoS2,the volume deformation of Co-doped MoS2 can be shrunk by a prominent value of 52%during cycling.Furthermore,the few-layered MoS2 nanosheets with 1T metalic phase endow higher conductivity,and thus can surpass its counterpart 2H semiconducting phase in battery performance.By virtue of the synergistic effect of stable structure,appropriate doping and high conductivity,the resulting CMS/NSC hybrid shows superior rate capability and cycle stability.The capacity of CMS/NSC can still be 235.9 mAh·g^-1 even at 25 A·g^-1,which is 51.3%of the capacity at 0.2 A·g^-1.Moreover,the capacity can still remain 218.6 mAh·g^-1 even over 8,240 cycles at 5 Ag·g^-1 with a low decay of 0.0044%per cycle,one of the best performances among the reportec MoS2-based anode materials for SIBs.展开更多
Reactive oxygen species(ROS)plays important roles in living organisms.While ROS is a double-edged sword,which can eliminate drug-resistant bacteria,but excessive levels can cause oxidative damage to cells.A core–shel...Reactive oxygen species(ROS)plays important roles in living organisms.While ROS is a double-edged sword,which can eliminate drug-resistant bacteria,but excessive levels can cause oxidative damage to cells.A core–shell nanozyme,Ce O_(2)@ZIF-8/Au,has been crafted,spontaneously activating both ROS generating and scavenging functions,achieving the multifaceted functions of eliminating bacteria,reducing inflammation,and promoting wound healing.The Au Nanoparticles(NPs)on the shell exhibit high-efficiency peroxidase-like activity,producing ROS to kill bacteria.Meanwhile,the encapsulation of Ce O_(2) core within ZIF-8 provides a seal for temporarily limiting the superoxide dismutase and catalase-like activities of Ce O_(2) nanoparticles.Subsequently,as the ZIF-8 structure decomposes in the acidic microenvironment,the Ce O_(2) core is gradually released,exerting its ROS scavenging activity to eliminate excess ROS produced by the Au NPs.These two functions automatically and continuously regulate the balance of ROS levels,ultimately achieving the function of killing bacteria,reducing inflammation,and promoting wound healing.Such innovative ROS spontaneous regulators hold immense potential for revolutionizing the field of antibacterial agents and therapies.展开更多
Modulation of metal sites coordination can significantly refine the electronic architecture of catalysts,thereby improving their catalytic performance.This work successfully developed a core–shell Co@N-doped porous c...Modulation of metal sites coordination can significantly refine the electronic architecture of catalysts,thereby improving their catalytic performance.This work successfully developed a core–shell Co@N-doped porous carbon(Co@NC)catalyst by pyrolyzing the COF/MOF(IISERP-COF3/ZIF-67)composite in an inert atmosphere.The Co@NC catalyst exhibited impressive oxygen evolution reaction(OER)performance,with a small overpotential of 304 mV and a modest Tafel slope of 88.6 mV·dec^(−1) in a 1 M KOH,alongside remarkable stability,maintaining 98.5%of its activity over 13 h.The role of IISERP-COF3 was pivotal in preventing Co atom aggregation during the ZIF-67 pyrolysis,which facilitated the creation of mesopores for enhanced mass transport and conductivity.Moreover,it effectively modulated the Co-N coordination to fine-tune the electronic structure,thereby optimizing the catalyst's capacity for adsorption of intermediates and boosting its intrinsic activity.Density functional theory(DFT)studies corroborate that the exceptional OER efficiency of Co@NC can be linked to the enhanced Co-N coordination,optimizing the localized electronic structure at the Co active sites.This study not only proposes an innovative approach for optimizing COF/MOF as effective electrocatalysts but also clears the path for the emergence of affordable,high-performance alternatives to precious metal-based catalysts,marking a significant advancement in sustainable energy technologies.展开更多
Metal-organic framework(MOF)nanosheets and covalent organic framework(COF)nanosheets as emerging porous materials nanosheets have captured increasing attention owing to their attractive properties originating from the...Metal-organic framework(MOF)nanosheets and covalent organic framework(COF)nanosheets as emerging porous materials nanosheets have captured increasing attention owing to their attractive properties originating from the advantages of large lateral size,ultrathin thickness,tailorable physiochemical environment,flexibility and highly accessible active sites on surface,and the applications of them have been explored in a wide range of fields.Although MOF and COF nanosheets own many similar properties,their applications in various fields show significant differences,probably due to their different compositions and bonding modes.Hence,we summarize the recent progress of MOF and COF nanosheets by comparative analysis on their advantages and limitations in synthesis and applications,providing a more profound and full-scale perspective for researchers or beginners to understand this field.Herein,the categories of preparation methods of MOF and COF nanosheets are firstly discussed,including top-down and bottom-up methods.Secondly,the applications of MOF and COF nanosheets for separation,catalysis,sensing and energy storage are summarized.Finally,based on current achievements,we put forward our personal insights into the challenges and outlooks on the synthesis,characterizations,and promising applications for future research of MOF and COF nanosheets.展开更多
In recent years,since water pollution has aroused great public concern,various carbon materials have already been widely applied for water treatment.In this respect,tremendous effort has been made to provide different...In recent years,since water pollution has aroused great public concern,various carbon materials have already been widely applied for water treatment.In this respect,tremendous effort has been made to provide different synthesis methods of carbon materials.Among all carbon materials,metal-organic framework(MOF)derived carbon has always been favored as it possesses several appealing merits such as high specific surface area,large pore volume,and outstanding chemical stability.This review presents the latest development of MOFs as templates and precursors for the fabrication of various carbon materials,including porous carbon,nanocarbon,and graphene,which are pyrolyzed at different temperatures.The article also emphasizes on their future trends and perspectives on the application of water treatment.展开更多
基金supported by the National Natural Science Foundation of China (51672156)Local Innovative Research Teams Project of Guangdong Pearl River Talents Program (No. 2017BT01N111)+2 种基金Guangdong Province Technical Plan Project (2017B010119001)Shenzhen Technical Plan Project (JCYJ20170817161221958 and JCYJ20170412170706047)Shenzhen Graphene Manufacturing Innovation Center (201901161513)。
文摘Aqueous Zinc-ion batteries(ZIB) are attracting immense attention because of their merits of excellent safety and quite cheap properties compared with lithium-ion batteries(LIB).Manganese oxide is one of the most important cathode materials of ZIB.In this paper,α-Mn2O3 used as cathode of ZIB is synthesized via Metal-Organic Framework(MOF)-derived method,which delivers a high specific capacity of225 mAh g^(-1) at 0.05 A g^(-1) and 92.7 mAh g^(-1) after 1700 cycles at 2 A g^(-1).The charge storage mechanism of α-Mn2O3 cathode is found to greatly depend on the discharge current density.At lower current density discharging,the H+ and Zn2+ are successively intercalated into the α-Mn2O3 before and after the "turning point" of discharge voltage and their discharging products present obviously different morphologies changing from flower-like to large plate-like products.At a higher current density,the low-voltage plateau after the turning point disappears due to the decrease of amount of Zn2+ intercalation and the H+intercalation is dominated in α-Mn2 O3.This study provides significant understanding for future design and research of high-performance Mn-based cathodes of ZIB.
文摘Water induced decomposition of Cu3（BTC）2 （BTC= benzene-l,3,5-tricarboxylate） metal-organic framework （MOF） was studied using dynamic water vapour adsorption. Small-angle X-ray scattering, Fourier transform infrared spectroscopy and differential scanning calorimetry analyses revealed that the underlying mechanism of Cu3（BTC）2 MOF decomposition under humid streams is the interpenetration of water molecules into Cu-BTC coordination to displace organic linkers （BTC） from Cu centres.
基金supported by the National Natural Science Foundation of China(No.52102036)the Sichuan Science and Technology Program(No.2021JDRC0099).
文摘The synthesis of wide bandwidth,thin thickness,and high performance microwave absorbing materials has become a hot topic of current research.Metal-organic frameworks with heterojunctions and porous structures are considered as suitable candidates to meet these characteristics.Herein,heterogeneous CoFe@N-doped porous carbon polyhedron composites were successfully synthesized via Fe^(2+)to replace Co in zeolite imidazole frame-67.The dielectric properties of composites were enhanced by the replacement of Fe^(2+),and the synergistic effect of dielectric loss and magnetic loss was realized.The petal-like lamellar structure increases the travel of electromagnetic(EM)waves,and the formation of porous structures improves impedance matching.Specifically,a reflection loss of−67.30 dB was obtained at a thickness of 2.88 mm,and an ultrabroad wide effective absorption bandwidth of 8.40 GHz was obtained,covering most of the X-band(8–12 GHz)and the whole Ku-band(12–18 GHz).The radar cross section(RCS)reduction value can reach 29.4 dB·m^(2),which means that the radar detector has a smaller probability of detecting targets.This work describes the unique advantages of metal ion replacement metal-organic frameworks derived materials in structural design,impedance matching,and performance adjustment,and provides a new reference for the field of electromagnetic wave absorption.
基金supported by the National Natural Science Foundation of China(Nos.52170119 and 22178357)the Youth Innovation Promotion Association of the Chinese Academy of Sciences(No.2021044).
文摘The use of metal-organic frameworks(MOFs)as solid adsorption materials for carbon capture is promising,but achieving efficient and reversible adsorption with a balance of capacity and selectivity for carbon dioxide(CO_(2))over N_(2) remains a challenge.To take full advantage of the strong channel traffic and robustness of MOFs with relatively small pores,it is highly necessary to employ a defect-engineering strategy to construct a broader channel structure that can facilitate the loading of functional motif-rich amino acids(AAs).This strategy can greatly enhance the CO_(2) adsorption performance of MOF.In this study,motif-rich amino acids are loaded into the defective and robust porous frameworks via combined defect-engineering and post-synthetic methods.The defective Zr/Hf-MOF-808s modified with AAs,especially for the 18 mol%4-nitroisophthalic acid,generated defective products allowing for the loading of L-serine(L-Ser).This modification resulted in a significant improvement in both the adsorption capacity(248%improvement at 298 K,100 kPa)and the selectivity of CO_(2)/N_(2) using the ideal adsorbed solution theory(IAST),with the selectivity increasing to 120.55 and 38.27 at 15 and 100 kPa,respectively,while maintaining good cycling performance.Density functional theory(DFT)simulation,CO_(2) temperature-programmed desorption(CO_(2)-TPD),and in situ Fourier transform infrared spectroscopy(FTIR)were further employed to have a better understanding of the enhanced CO_(2) adsorption capacity.Interestingly,unlike the AAs loaded pristine MOF-808s that showed the best CO_(2) adsorption capacity with the loading of short and small glycine(Gly),the broadened channel size in our work enables the loading of functional motif-rich L-serine,which brings more active binding sites,improving CO_(2) adsorption.
基金This work was financially supported by the National Key R&D Program of China(No.2016YFB0100200)Young Thousand Talents Program,the Open Project Foundation of State Key Laboratory of Chemical Resource Engineering,the China Postdoctoral Science Foundation(No.2017M610018)the National Natural Science Foundation of China(No.51671003),Start-up Funding from Peking University.
文摘Despite various 2H-MoS/carbon hybrid nanostructures have been constructed and committed to improve the performance for sodium-ion batteries(SIBs),they still show the limited cycle stability due to the relatively large volumetric expansion during the charge-discharge process Herein,we report the construction of cobalt-doped few-layered 1T-MoS2 nanosheets embedded in N,S-doped carbon(CMS/NSC)nanobowls derived from metal-organic framework(MOF)precursor via a simple in situ sulfurization process.This unique hierarchical structure enables the uniformly dispersed Co-doped 1T-MoS2 nanosheets intimately couple with the highly conductive carbon nanobowls,thus efficiently preventing the aggregation.In particular,the Co-doping plays a crucial role in maintaining the integrity of structure for MoS2 during cycling tests,confirmed by first-principles calculations.Compared with pristine MoS2,the volume deformation of Co-doped MoS2 can be shrunk by a prominent value of 52%during cycling.Furthermore,the few-layered MoS2 nanosheets with 1T metalic phase endow higher conductivity,and thus can surpass its counterpart 2H semiconducting phase in battery performance.By virtue of the synergistic effect of stable structure,appropriate doping and high conductivity,the resulting CMS/NSC hybrid shows superior rate capability and cycle stability.The capacity of CMS/NSC can still be 235.9 mAh·g^-1 even at 25 A·g^-1,which is 51.3%of the capacity at 0.2 A·g^-1.Moreover,the capacity can still remain 218.6 mAh·g^-1 even over 8,240 cycles at 5 Ag·g^-1 with a low decay of 0.0044%per cycle,one of the best performances among the reportec MoS2-based anode materials for SIBs.
基金supported by the Natural Science Foundation of Fujian Province of China(No.2022J01043)China Scholarship Council(201806315005 and 201703170071).
文摘Reactive oxygen species(ROS)plays important roles in living organisms.While ROS is a double-edged sword,which can eliminate drug-resistant bacteria,but excessive levels can cause oxidative damage to cells.A core–shell nanozyme,Ce O_(2)@ZIF-8/Au,has been crafted,spontaneously activating both ROS generating and scavenging functions,achieving the multifaceted functions of eliminating bacteria,reducing inflammation,and promoting wound healing.The Au Nanoparticles(NPs)on the shell exhibit high-efficiency peroxidase-like activity,producing ROS to kill bacteria.Meanwhile,the encapsulation of Ce O_(2) core within ZIF-8 provides a seal for temporarily limiting the superoxide dismutase and catalase-like activities of Ce O_(2) nanoparticles.Subsequently,as the ZIF-8 structure decomposes in the acidic microenvironment,the Ce O_(2) core is gradually released,exerting its ROS scavenging activity to eliminate excess ROS produced by the Au NPs.These two functions automatically and continuously regulate the balance of ROS levels,ultimately achieving the function of killing bacteria,reducing inflammation,and promoting wound healing.Such innovative ROS spontaneous regulators hold immense potential for revolutionizing the field of antibacterial agents and therapies.
基金supported by the Platform of Science and Technology and Talent Team Plan of Guizhou province(No.GCC[2023]007)the National Natural Science Foundation of China(No.52062003).
文摘Modulation of metal sites coordination can significantly refine the electronic architecture of catalysts,thereby improving their catalytic performance.This work successfully developed a core–shell Co@N-doped porous carbon(Co@NC)catalyst by pyrolyzing the COF/MOF(IISERP-COF3/ZIF-67)composite in an inert atmosphere.The Co@NC catalyst exhibited impressive oxygen evolution reaction(OER)performance,with a small overpotential of 304 mV and a modest Tafel slope of 88.6 mV·dec^(−1) in a 1 M KOH,alongside remarkable stability,maintaining 98.5%of its activity over 13 h.The role of IISERP-COF3 was pivotal in preventing Co atom aggregation during the ZIF-67 pyrolysis,which facilitated the creation of mesopores for enhanced mass transport and conductivity.Moreover,it effectively modulated the Co-N coordination to fine-tune the electronic structure,thereby optimizing the catalyst's capacity for adsorption of intermediates and boosting its intrinsic activity.Density functional theory(DFT)studies corroborate that the exceptional OER efficiency of Co@NC can be linked to the enhanced Co-N coordination,optimizing the localized electronic structure at the Co active sites.This study not only proposes an innovative approach for optimizing COF/MOF as effective electrocatalysts but also clears the path for the emergence of affordable,high-performance alternatives to precious metal-based catalysts,marking a significant advancement in sustainable energy technologies.
基金the National Natural Science Foundation of China for Distinguished Young Scholars(No.21625401)the National Natural Science Foundation of China(Nos.21727808,21971114).
文摘Metal-organic framework(MOF)nanosheets and covalent organic framework(COF)nanosheets as emerging porous materials nanosheets have captured increasing attention owing to their attractive properties originating from the advantages of large lateral size,ultrathin thickness,tailorable physiochemical environment,flexibility and highly accessible active sites on surface,and the applications of them have been explored in a wide range of fields.Although MOF and COF nanosheets own many similar properties,their applications in various fields show significant differences,probably due to their different compositions and bonding modes.Hence,we summarize the recent progress of MOF and COF nanosheets by comparative analysis on their advantages and limitations in synthesis and applications,providing a more profound and full-scale perspective for researchers or beginners to understand this field.Herein,the categories of preparation methods of MOF and COF nanosheets are firstly discussed,including top-down and bottom-up methods.Secondly,the applications of MOF and COF nanosheets for separation,catalysis,sensing and energy storage are summarized.Finally,based on current achievements,we put forward our personal insights into the challenges and outlooks on the synthesis,characterizations,and promising applications for future research of MOF and COF nanosheets.
基金the National Natural Science Foundation of China(Nos.U1904215 and 21875207)the Natural Science Foundation of Jiangsu Province(No.BK20200044)Changjiang scholars program of the Ministry of Education(No.Q2018270).
文摘In recent years,since water pollution has aroused great public concern,various carbon materials have already been widely applied for water treatment.In this respect,tremendous effort has been made to provide different synthesis methods of carbon materials.Among all carbon materials,metal-organic framework(MOF)derived carbon has always been favored as it possesses several appealing merits such as high specific surface area,large pore volume,and outstanding chemical stability.This review presents the latest development of MOFs as templates and precursors for the fabrication of various carbon materials,including porous carbon,nanocarbon,and graphene,which are pyrolyzed at different temperatures.The article also emphasizes on their future trends and perspectives on the application of water treatment.
