Water splitting powered by clean electricity is a sustainable and promising approach to produce green hydrogen.Currently,noble metal(e.g.Iridium,Ruthenium,Platinum)-based catalysts are most widely used for water split...Water splitting powered by clean electricity is a sustainable and promising approach to produce green hydrogen.Currently,noble metal(e.g.Iridium,Ruthenium,Platinum)-based catalysts are most widely used for water splitting electrolysis.However,noble metal-based catalysts often suffer from multiple disadvantages,including high cost,low selectivity and poor durability.The emergence of metal-organic framework nanosheets(MOFNSs)attracts significant attention due to their unique advantages.Here,a concise,yet comprehensive and critical,review of recent advances in the field of MOFNSs is provided.This review explains the fundamental oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)catalytic mechanisms as well as key characterization techniques for the structure-activity relationship study are discussed.Moreover,it discusses efficient design strategies and the brief research advances of MOFNSs in HER,OER,and bifunctional electrocatalysis,along with some challenges and opportunities.展开更多
Metal–organic frameworks(MOFs)represent a unique class of porous materialswith tremendous potential for diverse applications.A key factor contributing totheir versatility is their ability to precisely introduce funct...Metal–organic frameworks(MOFs)represent a unique class of porous materialswith tremendous potential for diverse applications.A key factor contributing totheir versatility is their ability to precisely introduce functional groups at specificpositions within pores and crystals.This review explores two prominent strategiesfor achieving the positional functionalization of MOFs:post-synthetic ligand exchange(PSE)and MOF-on-MOF.In PSE,the existing ligands within solid-stateMOFs can be selectively replaced by the desired functional groups in solutionthrough ligand dynamics.This invasive functionalization provides a flexibleapproach to fine-tuning the surface of the MOFs with the target functionality.Conversely,MOF-on-MOF strategies are additive methodologies involving thecontrolled growth of one MOF layer onto another.The functionality of the core andshell(or surface)can be independently controlled.This review critically examinesthe examples,strengths,limitations,and applications of these strategies,emphasizingtheir significance in advancing the field of MOF functionalization andpaving the way for tailored multifunctional materials with precise and specificproperties.展开更多
The controllable construction of two-dimensional(2D)metal–organic framework(MOF)nanosheets with favorable electrochemical performances is greatly challenging for energy storage.Here,we design an in situ induced growt...The controllable construction of two-dimensional(2D)metal–organic framework(MOF)nanosheets with favorable electrochemical performances is greatly challenging for energy storage.Here,we design an in situ induced growth strategy to construct the ultrathin carboxylated carbon nanotubes(C-CNTs)interpenetrated nickel MOF(Ni-MOF/C-CNTs)nanosheets.The deliberate thickness and specific surface area of novel 2D hybrid nanosheets can be effectively tuned via finely controlling C-CNTs involvement.Due to the unique microstructure,the integrated 2D hybrid nanosheets are endowed with plentiful electroactive sites to promote the electrochemical performances greatly.The prepared Ni-MOF/C-CNTs nanosheets exhibit superior specific capacity of 680 C g^−1 at 1 A g^−1 and good capacity retention.The assembled hybrid device demonstrated the maximum energy density of 44.4 Wh kg^−1 at a power density of 440 W kg^−1.Our novel strategy to construct ultrathin 2D MOF with unique properties can be extended to synthesize various MOF-based functional materials for diverse applications.展开更多
We report the synthesis of nitridation-induced NiFe-MOF through post-synthetic functionalization of terminal ligand in NiFe-MOF nanosheet.We directly identify the key factor of amino ligand in N-NiFe-MOF for boosting ...We report the synthesis of nitridation-induced NiFe-MOF through post-synthetic functionalization of terminal ligand in NiFe-MOF nanosheet.We directly identify the key factor of amino ligand in N-NiFe-MOF for boosting the OER performance through combining single X-ray crystallographic characterization and in-situ Raman tracking,as well as ex-situ spectroscopy analysis.Density functional theory(DFT)calculations and experime ntal results indicate irreversible phase rec on structio n from amino ligand oxidation prior to OER could lead to the optimized ΔG_(-O),resulting in the remarkable OER performance with an overpotential of 258 mV to obtain the current density of 100 mA cm^(-2) in 1.0 M KOH solution.Our work will provide new strategy for rational designing advanced MOF-based OER electrocatalysts.展开更多
During the last decade, metal-organic frameworks(MOFs) have been applied in various fields due to their unique chemical and functional advantages. One of the widespread research hotspots is MOF-based membranes for sep...During the last decade, metal-organic frameworks(MOFs) have been applied in various fields due to their unique chemical and functional advantages. One of the widespread research hotspots is MOF-based membranes for separations, specifically continuous defect-free MOF membranes, which are usually grown on porous substrates. The substrate not only serves as the MOF layer support but also has a great influence on the membrane fabrication process and the final separation performance of the resultant membrane. In this review, we mainly introduce the progress focused on the substrates for MOF membranes fabrication. The substrate modifications and seeding methods aimed at synthesizing highquality MOF membranes are also summarized systematically.展开更多
Zinc manganese oxide(ZMO)system represents a notable family of mixed transition metal oxides(MTMOs)because of their superiority of the high theoretical capacity,adequacy of natural content,and low cost.However,the met...Zinc manganese oxide(ZMO)system represents a notable family of mixed transition metal oxides(MTMOs)because of their superiority of the high theoretical capacity,adequacy of natural content,and low cost.However,the methods to match both the reliable synthesis and the designable construction of large-sized two-dimensional(2D)ZMO nanosheets are still considered as grand challenges.Herein,we have successfully realized the preparation of 2D ZMO nanosheets with large lateral sizes up to~20 mm by simple pyrolysis of 2D metal–organic framework(MOF)nanosheets precursor.The growth mechanism of 2D MOF is proposed to be based on the lamellar micelles formed by polyvinyl pyrrolidone(PVP).The obtained 2D and porous ZMO nanosheets exhibit high specific capacity as well as good rate capability.More importantly,the as-prepared ZMO electrode shows a remarkable capacity increment upon cycling(from 832 mAh g^(-1) at the 2nd cycle to 1418 mAh g^(-1) at the 700th cycle,at 1 A g^(-1)).Through simple adjustment of the calcination temperature,the valence state of Mn species in the yielding ZMO samples can be fine-tuned.Through systematic investigation towards these ZMOs containing different Mn species,the extra specific capacity is revealed to be chiefly on account of the arising of the valence state of Mn upon the cycling process.Moreover,it is disclosed that the higher-valent Mn the pristine ZMO contains,the more additional capacity it gains upon cycling.We believe that this work will inspire more detailed analysis on the relationship between the valence state of Mn and extra capacity.展开更多
Electrochemical CO_(2) reduction into CO or high-value products is regarded as a feasible pathway for energy conversion,which has attracted universal attention in recent years [1-3].However,the reduction of CO_(2) mol...Electrochemical CO_(2) reduction into CO or high-value products is regarded as a feasible pathway for energy conversion,which has attracted universal attention in recent years [1-3].However,the reduction of CO_(2) molecule is a thermodynamically uphill process,which involves multiple elemental steps and the competition of hydrogen evolution reaction(HER) in aqueous solution.展开更多
Developing laminar composite solid electrolyte with ultrathin thickness and continuous conduction channels in vertical direction holds great promise for all-solid-state lithium batteries.Herein,a thin,laminar solid el...Developing laminar composite solid electrolyte with ultrathin thickness and continuous conduction channels in vertical direction holds great promise for all-solid-state lithium batteries.Herein,a thin,laminar solid electrolyte is synthesized by filtrating–NH 2 functionalized metal-organic framework nanosheets and then being threaded with poly(ethylene oxide)chains induced by the hydrogen-bonding interaction from–NH_(2) groups.It is demonstrated that the threaded poly(ethylene oxide)chains lock the adjacent metal-organic framework nanosheets,giving highly enhanced structural stability(Young’s modulus,1.3 GPa)to 7.5-μm-thick laminar composite solid electrolyte.Importantly,these poly(ethylene oxide)chains with stretching structure serve as continuous conduction pathways along the chains in pores.It makes the non-conduction laminar metal-organic framework electrolyte highly conductive:3.97×10^(−5) S cm^(−1) at 25℃,which is even over 25 times higher than that of pure poly(ethylene oxide)electrolyte.The assembled lithium cell,thus,acquires superior cycling stability,initial discharge capacity(148 mAh g^(−1) at 0.5 C and 60℃),and retention(94% after 150 cycles).Besides,the pore size of nanosheet is tailored(24.5–40.9˚A)to evaluate the mechanisms of chain conformation and ion transport in confined space.It shows that the confined pore only with proper size could facilitate the stretching of poly(ethylene oxide)chains,and meanwhile inhibit their disorder degree.Specifically,the pore size of 33.8˚A shows optimized confinement effect with trans-poly(ethylene oxide)and cis-poly(ethylene oxide)conformation,which offers great significance in ion conduction.Our design of poly(ethylene oxide)-threaded architecture provides a platform and paves a way to the rational design of next-generation high-performance porous electrolytes.展开更多
文摘Water splitting powered by clean electricity is a sustainable and promising approach to produce green hydrogen.Currently,noble metal(e.g.Iridium,Ruthenium,Platinum)-based catalysts are most widely used for water splitting electrolysis.However,noble metal-based catalysts often suffer from multiple disadvantages,including high cost,low selectivity and poor durability.The emergence of metal-organic framework nanosheets(MOFNSs)attracts significant attention due to their unique advantages.Here,a concise,yet comprehensive and critical,review of recent advances in the field of MOFNSs is provided.This review explains the fundamental oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)catalytic mechanisms as well as key characterization techniques for the structure-activity relationship study are discussed.Moreover,it discusses efficient design strategies and the brief research advances of MOFNSs in HER,OER,and bifunctional electrocatalysis,along with some challenges and opportunities.
基金supported by the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT(2022R1A2C1009706).
文摘Metal–organic frameworks(MOFs)represent a unique class of porous materialswith tremendous potential for diverse applications.A key factor contributing totheir versatility is their ability to precisely introduce functional groups at specificpositions within pores and crystals.This review explores two prominent strategiesfor achieving the positional functionalization of MOFs:post-synthetic ligand exchange(PSE)and MOF-on-MOF.In PSE,the existing ligands within solid-stateMOFs can be selectively replaced by the desired functional groups in solutionthrough ligand dynamics.This invasive functionalization provides a flexibleapproach to fine-tuning the surface of the MOFs with the target functionality.Conversely,MOF-on-MOF strategies are additive methodologies involving thecontrolled growth of one MOF layer onto another.The functionality of the core andshell(or surface)can be independently controlled.This review critically examinesthe examples,strengths,limitations,and applications of these strategies,emphasizingtheir significance in advancing the field of MOF functionalization andpaving the way for tailored multifunctional materials with precise and specificproperties.
基金supported by National Natural Science Foundation of China(21878062)
文摘The controllable construction of two-dimensional(2D)metal–organic framework(MOF)nanosheets with favorable electrochemical performances is greatly challenging for energy storage.Here,we design an in situ induced growth strategy to construct the ultrathin carboxylated carbon nanotubes(C-CNTs)interpenetrated nickel MOF(Ni-MOF/C-CNTs)nanosheets.The deliberate thickness and specific surface area of novel 2D hybrid nanosheets can be effectively tuned via finely controlling C-CNTs involvement.Due to the unique microstructure,the integrated 2D hybrid nanosheets are endowed with plentiful electroactive sites to promote the electrochemical performances greatly.The prepared Ni-MOF/C-CNTs nanosheets exhibit superior specific capacity of 680 C g^−1 at 1 A g^−1 and good capacity retention.The assembled hybrid device demonstrated the maximum energy density of 44.4 Wh kg^−1 at a power density of 440 W kg^−1.Our novel strategy to construct ultrathin 2D MOF with unique properties can be extended to synthesize various MOF-based functional materials for diverse applications.
基金supported by the National Natural Science Foundation of China(21972107 and 51202127)the National Natural Science Foundation of Hubei Province(2020CFA095 and 2016CFB382)+1 种基金the Fundamental Research Funds for the Central Universities(2042017kf0227,2042019kf0205)the National Natural Science Foundation of Jiangsu Province(BK20191186)。
文摘We report the synthesis of nitridation-induced NiFe-MOF through post-synthetic functionalization of terminal ligand in NiFe-MOF nanosheet.We directly identify the key factor of amino ligand in N-NiFe-MOF for boosting the OER performance through combining single X-ray crystallographic characterization and in-situ Raman tracking,as well as ex-situ spectroscopy analysis.Density functional theory(DFT)calculations and experime ntal results indicate irreversible phase rec on structio n from amino ligand oxidation prior to OER could lead to the optimized ΔG_(-O),resulting in the remarkable OER performance with an overpotential of 258 mV to obtain the current density of 100 mA cm^(-2) in 1.0 M KOH solution.Our work will provide new strategy for rational designing advanced MOF-based OER electrocatalysts.
基金the funding from the National Natural Science Foundation of China (22078107, 22022805)the National Key Research and Development Program (2021YFB3802500)。
文摘During the last decade, metal-organic frameworks(MOFs) have been applied in various fields due to their unique chemical and functional advantages. One of the widespread research hotspots is MOF-based membranes for separations, specifically continuous defect-free MOF membranes, which are usually grown on porous substrates. The substrate not only serves as the MOF layer support but also has a great influence on the membrane fabrication process and the final separation performance of the resultant membrane. In this review, we mainly introduce the progress focused on the substrates for MOF membranes fabrication. The substrate modifications and seeding methods aimed at synthesizing highquality MOF membranes are also summarized systematically.
基金This project is financially supported by National Natural Science Foundation of China(Grant No.51502060)Natural Science Foundation of Shandong Province,China(Grant No.ZR2015EQ010 and No.ZR2019MB027)the Fundamental Research Funds for the Central Universities(Grant No.2015DXGJMS004).
文摘Zinc manganese oxide(ZMO)system represents a notable family of mixed transition metal oxides(MTMOs)because of their superiority of the high theoretical capacity,adequacy of natural content,and low cost.However,the methods to match both the reliable synthesis and the designable construction of large-sized two-dimensional(2D)ZMO nanosheets are still considered as grand challenges.Herein,we have successfully realized the preparation of 2D ZMO nanosheets with large lateral sizes up to~20 mm by simple pyrolysis of 2D metal–organic framework(MOF)nanosheets precursor.The growth mechanism of 2D MOF is proposed to be based on the lamellar micelles formed by polyvinyl pyrrolidone(PVP).The obtained 2D and porous ZMO nanosheets exhibit high specific capacity as well as good rate capability.More importantly,the as-prepared ZMO electrode shows a remarkable capacity increment upon cycling(from 832 mAh g^(-1) at the 2nd cycle to 1418 mAh g^(-1) at the 700th cycle,at 1 A g^(-1)).Through simple adjustment of the calcination temperature,the valence state of Mn species in the yielding ZMO samples can be fine-tuned.Through systematic investigation towards these ZMOs containing different Mn species,the extra specific capacity is revealed to be chiefly on account of the arising of the valence state of Mn upon the cycling process.Moreover,it is disclosed that the higher-valent Mn the pristine ZMO contains,the more additional capacity it gains upon cycling.We believe that this work will inspire more detailed analysis on the relationship between the valence state of Mn and extra capacity.
基金supported by the National Natural Science Foundation of China(21875030,21908120)the Liaoning Excellent Talents in University(LR2019016)。
文摘Electrochemical CO_(2) reduction into CO or high-value products is regarded as a feasible pathway for energy conversion,which has attracted universal attention in recent years [1-3].However,the reduction of CO_(2) molecule is a thermodynamically uphill process,which involves multiple elemental steps and the competition of hydrogen evolution reaction(HER) in aqueous solution.
基金The authors would like to acknowledge the financial support from National Nat-ural Science Foundation of China (U2004199)Excellent Youth Foundation of Henan Province (202300410373)+2 种基金China Postdoctoral Science Foundation (2021T140615 and 2020M672281)Natural Science Foundation of Henan Province (212300410285)Young Talent Support Project of Henan Province(2021HYTP028).
文摘Developing laminar composite solid electrolyte with ultrathin thickness and continuous conduction channels in vertical direction holds great promise for all-solid-state lithium batteries.Herein,a thin,laminar solid electrolyte is synthesized by filtrating–NH 2 functionalized metal-organic framework nanosheets and then being threaded with poly(ethylene oxide)chains induced by the hydrogen-bonding interaction from–NH_(2) groups.It is demonstrated that the threaded poly(ethylene oxide)chains lock the adjacent metal-organic framework nanosheets,giving highly enhanced structural stability(Young’s modulus,1.3 GPa)to 7.5-μm-thick laminar composite solid electrolyte.Importantly,these poly(ethylene oxide)chains with stretching structure serve as continuous conduction pathways along the chains in pores.It makes the non-conduction laminar metal-organic framework electrolyte highly conductive:3.97×10^(−5) S cm^(−1) at 25℃,which is even over 25 times higher than that of pure poly(ethylene oxide)electrolyte.The assembled lithium cell,thus,acquires superior cycling stability,initial discharge capacity(148 mAh g^(−1) at 0.5 C and 60℃),and retention(94% after 150 cycles).Besides,the pore size of nanosheet is tailored(24.5–40.9˚A)to evaluate the mechanisms of chain conformation and ion transport in confined space.It shows that the confined pore only with proper size could facilitate the stretching of poly(ethylene oxide)chains,and meanwhile inhibit their disorder degree.Specifically,the pore size of 33.8˚A shows optimized confinement effect with trans-poly(ethylene oxide)and cis-poly(ethylene oxide)conformation,which offers great significance in ion conduction.Our design of poly(ethylene oxide)-threaded architecture provides a platform and paves a way to the rational design of next-generation high-performance porous electrolytes.
