The large-scale synthesis of platinum-free electrocatalysts for the oxygen reduction reaction(ORR)remains a grand challenge.We report the large-scale production of stable and active ORR electrocatalysts based on iron,...The large-scale synthesis of platinum-free electrocatalysts for the oxygen reduction reaction(ORR)remains a grand challenge.We report the large-scale production of stable and active ORR electrocatalysts based on iron,an earth-abundant element.A core–shell zeolitic imidazolate framework–tannic acid coordination polymer composite(ZIF-8@K-TA)was utilized as the catalyst precursor,which was transformed into iron atoms dispersed in hollow porous nitrogen-doped carbon capsules(H-Fe-N_(x)-C)through ion exchange and pyrolysis.H-Fe-N_(x)-C fea-tures site-isolated single-atom iron centers coordinated to nitrogen in graphitic layers,high levels of nitrogen doping,and high permeability to incoming gases.Benefiting from these characteristics,H-Fe-N_(x)-C demonstrated efficient electrocatalytic activity(E_(1/2)=0.92 V,vs.RHE)and stability towards the ORR in both alkaline and acidic media.In ORR performance,it surpassed the majority of recently reported Fe-N-C catalysts and the standard Pt/C catalyst.In addition,H-Fe-N_(x)-C showed outstanding tolerance to methanol.展开更多
The rational design and construction of inexpensive and highly active electrocatalysts for hydrogen evolution reaction(HER)is of great importance for water splitting.Herein,we develop a facile approach for preparation...The rational design and construction of inexpensive and highly active electrocatalysts for hydrogen evolution reaction(HER)is of great importance for water splitting.Herein,we develop a facile approach for preparation of porous carbon-confined Ru-doped Cu nanoparticles(denoted as Ru-Cu@C)by direct pyrolysis of the Ru-exchanged Cu-BTC metal–organic framework.When served as the electrocatalyst for HER,strikingly,the obtained Ru-Cu@C catalyst exhibits an ultralow overpotential(only 20 mV at 10 mA cm^(-2))with a small Tafel slope of 37 m V dec^(-1)in alkaline electrolyte.The excellent performance is comparable or even superior to that of commercial Pt/C catalyst.Density functional theory(DFT)calculations confirm that introducing Ru atoms into Cu nanocrystals can significantly alter the desorption of H_(2) to achieve a close-to-zero hydrogen adsorption energy and thereby boost the HER process.This strategy gives a fresh impetus to explore low-cost and high-performance catalysts for HER in alkaline media.展开更多
In the present paper, a metal–organic framework Cr-BDC was prepared and used as adsorbent for adsorption of o-nitrophenol(ONP) and p-nitrophenol(PNP) from aqueous solutions. Cr-BDC was characterized by scanning elect...In the present paper, a metal–organic framework Cr-BDC was prepared and used as adsorbent for adsorption of o-nitrophenol(ONP) and p-nitrophenol(PNP) from aqueous solutions. Cr-BDC was characterized by scanning electron microscopy, transmission electron microscope, X-ray diffraction and BET methods. The results indicate that Cr-BDC gets a very large specific surface area of 4128 m^2·g^(-1)and pore sizes are concentrated in 1 nm, which is a benefit for using for wastewater treatment. The influences of the adsorption conditions, such as temperature,solution concentration, adsorption time and reusability on adsorption performance were investigated. Cr-BDC exhibited an encouraging uptake capacity of 310.0 mg·g^(-1)for ONP, and adsorption capacity of Cr-BDC for ONP is significantly higher than that for PNP under suitable adsorption conditions. The characterizations of adsorption process were examined with the Lagergren pseudo-first-order, the pseudo-second-order kinetic model, and the intra-particular diffusion model. Kinetics experiments indicated that the pseudo-second-order model displayed the best correlation with adsorption kinetics data. Furthermore, our adsorption equilibrium data could be better described by the Freundlich equation. The results indicate that the as-prepared Cr-BDC is promising for use as an effective and economical adsorbent for ONP removal.展开更多
Cu-based materials are seldom reported as oxygen evolution reaction(OER)electrocatalysts due to their inherent electron orbital configuration,which makes them difficult to adsorb oxygen-intermediates during OER.Reason...Cu-based materials are seldom reported as oxygen evolution reaction(OER)electrocatalysts due to their inherent electron orbital configuration,which makes them difficult to adsorb oxygen-intermediates during OER.Reasonably engineering the hierarchical architectures and the electronic structures can improve the performance of Cu-based OER catalysts,such as constructing multilevel morphology,inducing the porous materials,improving the Cu valence,building heterostructures,doping heteroatoms,etc.In this work,copper-1,3,5-benzenetricarboxylate(HKUST-1)octahedra in-situ grow on the Cu nanorod(NR)-supported N-doped carbon microplates,meanwhile an active layer of Cu(OH)_(2)forms on the surface of the original conductive Cu NRs.The octahedral HKUST-1,serving as a spacer between the microplates,greatly improves the porosity and increases the available active sites,facilitating the mass transport and electron transfer,thus resulting in greatly enhanced OER performance.展开更多
A Cd-containing metal–organic framework（Cd L）, formula as {[Cd_3（L）_2（H_2O）_6] 1.5DMF}, has been synthesized under solvothermal condition by the reaction of 4,40,400-（methylsilanetriyl）tribenzoic acid（H_3L）...A Cd-containing metal–organic framework（Cd L）, formula as {[Cd_3（L）_2（H_2O）_6] 1.5DMF}, has been synthesized under solvothermal condition by the reaction of 4,40,400-（methylsilanetriyl）tribenzoic acid（H_3L） and Cd^（2＋）ion. Single-crystal X-ray diffraction reveals that Cd L displays a three-dimensional framework with 2-fold interpenetration and DMF molecules locate in the void space of the channels. A topological analysis of the framework indicates Cd Lisa 3,4-connected pto net. The photoluminescence properties of Cd L are systematically studied in detail. Impressively, Cd L shows excellent detection performance towards Fe^（3＋）ion and acetone in the sensing experiments, which undoubtedly demonstrates the great potential of Cd L as a highly selective multi-responsive luminescent sensor for the detection of organic solvents and metal ions.展开更多
As promising catalysts for the degradation of organic pollutants,metal–organic frameworks(MOFs)often face limitations due to the particle agglomeration and challenging recovery in liquid-catalysis application,stemmin...As promising catalysts for the degradation of organic pollutants,metal–organic frameworks(MOFs)often face limitations due to the particle agglomeration and challenging recovery in liquid-catalysis application,stemming from their powdery nature.Engineering macroscopic structures from pulverous MOF is thus of great importance for broadening their practical applications.In this study,three-dimensional porous MOF aerogel catalysts were successfully fabricated for degrading organic dyes by activating peroxymonosulfate(PMS).MOF/gelatin aerogel(MOF/GA)catalysts were prepared by directly integrating bimetallic FeCo-BDC with gelatin solutions,followed by freeze-drying and low-temperature calcination.The FeCo-BDC-0.15/GA/PMS system exhibited remarkable performance in degrading various organic dyes,eliminating 99.2%of rhodamine B within a mere 5 min.Compared to the GA/PMS system,there was over a 300-fold increase in the reaction rate constant.Remarkably,high removal efficiency was maintained across varying conditions,including different solution pH,co-existing inorganic anions,and natural water matrices.Radical trapping experiments and electron paramagnetic resonance analysis revealed that the degradation involved radical(SO_(4)^(-)·)and non-radical routes(^(1)O_(2)),of which ^(1)O_(2) was dominant.Furthermore,even after a continuous 400-min reaction in a fixed-bed reactor at a liquid hourly space velocity of 27 h^(-1),the FeCo-BDC/GA composite sustained a degradation efficiency exceeding 98.7%.This work presents highly active MOF-gelatin aerogels for dye degradation and expands the potential for their large-scale,continuous treatment application in organic dye wastewater management.展开更多
Two-dimensional metal–organic frameworks(2D MOFs),as a new type of 2D materials,have been widely applied in various applications because of their unique structures and exposed active sites.Herein,we reported two low-...Two-dimensional metal–organic frameworks(2D MOFs),as a new type of 2D materials,have been widely applied in various applications because of their unique structures and exposed active sites.Herein,we reported two low-cost 2D MOFs constructed by a raw chemical succinic acid(SA),M-SA(M=Ni or Co),which served as efficient photocatalysts for the reduction of CO_(2)to CO.Taking advantage of the thinness and open metal sites,the ultrathin Ni-SA nanosheets(ca.3.6 nm)exhibited excellent CO production of 6.96(7)mmol·g^(−1)·h^(−1)and CO selectivity of 96.6%.Photoelectrochemical tests and theoretical calculations further confirmed the higher charge transfer efficiency and unsaturated metal sites for promoting photocatalytic performances.More importantly,Ni-SA can also be synthesized in large-scale by an energy-saving method under room temperature,strongly suggesting its promising future and potential for practical applications.展开更多
Metal–organic frameworks(MOFs) packed in the column have been a promising candidate as the stationary phase for high performance liquid chromatography(HPLC). However, the direct packing of irregular MOF powder could ...Metal–organic frameworks(MOFs) packed in the column have been a promising candidate as the stationary phase for high performance liquid chromatography(HPLC). However, the direct packing of irregular MOF powder could raise some problems like high back pressure and low column efficiency in the HPLC separation. In this work, UiO-66 capable of separating xylenes was supported effectively on the surface of the monodisperse spherical silica microspheres by one-pot method. The hybridization of Ui O-66 and silica microspheres(termed UiO-66@SiO2 shell–core composite) was prepared by stirring the suspension of the precursors of Ui O-66 and\\COOH terminated silica in the N,N-dimethylformamide with heating. The shell–core composite material UiO66@SiO2 was characterized by SEM, TEM, PXRD and FTIR. Then, it was used as a packing material for the chromatographic separation of xylene isomers. Xylene isomers including o-xylene, m-xylene and p-xylene were efficiently separated on the column with high resolution and good reproducibility. Moreover, the Ui O-66@SiO2 shell–core composites packed column still remained reverse shape selectivity as Ui O-66 possessed, and the retention of xylenes was probably ascribed to the hydrophobic effect between analytes and the aromatic rings of the Ui O-66 shell. The Ui O-66@SiO2 shell–core composites obtained in this study have some potential for the separation of structural isomers in HPLC.展开更多
Although metal–organic frameworks have been heavily tested as the anode materials for lithium-ion batteries(LIBs),the poorer conductivity,easy collapse of frameworks,and serious volume expansion limit their further a...Although metal–organic frameworks have been heavily tested as the anode materials for lithium-ion batteries(LIBs),the poorer conductivity,easy collapse of frameworks,and serious volume expansion limit their further application in LIBs.Herein,we report a facile approach to obtain MXene-encapsulated porous Ni-naphthalene dicarboxylic acid(Ni-NDC)nanosheets by hybridizing ultrathin Ti_(3)C_(2)MXene and three-dimensional(3D)Ni-NDC nanosheet aggregates.In the structure of Ni-NDC/MXene hybrids,the interlayer hydrogen-bond interaction between Ni-NDC and MXene can effectively increase the interlayer spacing and further inhibit the oxidation of pure MXene.Hence,the introduction of MXene(a conductive matrix)could further improve the conductivity of Ni-NDC,avoid self-agglomeration,and buffer the volume expansion of Ni-NDC nanosheets.Benefiting from the synergistic effects between Ni-NDC and MXene,Ni-NDC/MXene hybrid electrode exhibits a reversible discharge capacity(579.8 mA∙h∙g^(−1)at 100 mA∙g^(−1)after 100 cycles)and good long-term cycling performance(310 mA∙h∙g^(−1)at 1 A∙g^(−1)after 500 cycles).展开更多
In this work,we report that high catalytic performance of metal–organic frameworks(MOFs)can be obtained through a synergistic effect of postsynthetic modification of MOF nanoparticles and liquid superwetting and conf...In this work,we report that high catalytic performance of metal–organic frameworks(MOFs)can be obtained through a synergistic effect of postsynthetic modification of MOF nanoparticles and liquid superwetting and confinement in the MOF coating.Specifically,2-ureido-4[1H]pyrimidinone(UPy)functionalized polysiloxanes were covalently appended onto the UiO-66 nanoparticles via a postsynthetic approach,which were further anchored onto different porous films through multivalent hydrogen bonding of the UPy motifs.The hydrophobic MOF coating can preserve the porosity of the solid substrates,enable rapid liquid superwetting and confinement within the porous substrates.Using the Knoevenagel condensation as a modeled system,robust and highly catalytic performances of the MOF coating were observed on a range of aldehyde substrates.Gram-scale production of chromene,a pharmaceutical which is typically synthesized via expensive catalysis,was successfully demonstrated on the MOF coating with high yielding rates,demonstrating the great potential of the MOF coating in pharmaceutical synthesis.展开更多
Metal–organic framework-based compounds have recently gained great attention because of their unique porous structure,ordered porosity,and high specific surface area.Benefiting from these superior properties,metal–o...Metal–organic framework-based compounds have recently gained great attention because of their unique porous structure,ordered porosity,and high specific surface area.Benefiting from these superior properties,metal–organic framework-based compounds have been proven to be one of the most potential candidates for environmental governance and remediation.In this review,the different types of metal–organic framework-based compounds are first summarized.Further,the various environmental applications of metal–organic framework-based compounds including organic pollutant removal,toxic and hazardous gas capture,heavy metal ion detection,gas separation,water harvesting,air purification,and carbon dioxide reduction reactions are discussed in detail.In the end,the opportunities and challenges for the future development of metal–organic framework-based compounds for environmental applications are highlighted.展开更多
The separation of C2H4from C_(2)H_(6)/C_(2)H_(4)mixture is of great importance but difficult and energy intensive. Adsorptive separation provides an alternative approach to ameliorate this situation. Here, we report a...The separation of C2H4from C_(2)H_(6)/C_(2)H_(4)mixture is of great importance but difficult and energy intensive. Adsorptive separation provides an alternative approach to ameliorate this situation. Here, we report a microporous metal–organic framework(MOF) BUT-315-a as a C_(2)H_(6)-selective adsorbent for the separation of C2H6/C2H4gas mixture. BUT-315-a combines good IAST selectivity of 2.35 with high C_(2)H_(6)uptake of 97.5 cm^(3)g^(-1), giving superior high separation potential ΔQ(2226 mmol L^(-1)) for equimolar C_(2)H_(6)/C_(2)H_(4) at 298 K. Impressively, such excellent performance can be preserved at higher temperatures of 313 and 323 K to accommodate industrial conditions. Efficient dynamic separation performance of BUT-315-a has been demonstrated by column breakthrough experiments under varied temperatures and gas ratios. Theoretical calculations further reveal multiple synergistic interactions between C_(2)H_(6) and the framework. This work highlights a new benchmark material for C_(2)H_(6)/C_(2)H_(4)separation and provides guidance for designing adsorbent for separation applications.展开更多
Short-chain perfluorocarboxylic acids(PFCAs) are a class of persistent organic pollutants that are widely used as substitutes for long-chain PFCAs. However, they also pose a non-negligible risk to ecosystems. In this ...Short-chain perfluorocarboxylic acids(PFCAs) are a class of persistent organic pollutants that are widely used as substitutes for long-chain PFCAs. However, they also pose a non-negligible risk to ecosystems. In this study, we demonstrated that a fluorescent metal–organic framework(MOF)(named V-101) constructed from In^(3+)and an aromatic-rich tetratopic carboxylate ligand 5-[2,6-bis(4-carboxyphenyl) pyridin-4-yl] isophthalic acid(H4BCPIA) exhibited highly efficient turn-off and turn-on fluorescence responses toward five short-chain PFCAs in water and methanol, respectively. The limits of detection of V-101 toward five short-chain PFCAs are down to μg/L level, and it showed good anti-interference abilities toward short-chain PFCAs in the presence of common metal ions. The major mechanisms associated with fluorescence responses were molecular collisions and interactions between V-101 and short-chain PFCAs. This work demonstrates that the structure variety of MOFs imparts them with the potential of MOFs in the detection of short-chain PFCAs for pollution control.展开更多
A porous three-dimensional copper(Ⅱ) metal-organic framework (MOF) {[Cu2(tci)(OH)(pip)0.5(H2O)]·6H2O}n (1) [tci = tris (2-carboxyethyl)isocyanurate, pip = piperazine] has been generated under hydrothermal condit...A porous three-dimensional copper(Ⅱ) metal-organic framework (MOF) {[Cu2(tci)(OH)(pip)0.5(H2O)]·6H2O}n (1) [tci = tris (2-carboxyethyl)isocyanurate, pip = piperazine] has been generated under hydrothermal conditions at 120 °C. Single crystal X-ray diffraction reveals that the polymer exhibits a novel three-dimensional framework based on planar tetranuclear copper(Ⅱ) cluster units. The variable temperature magnetic susceptibility data in the range 2-280 K show antiferromagnetic spin-spin coupling in the tetranuclear unit in complex 1. A theoretical fitting of the magnetic data gives J values of -31.3 cm-1, -30.8 cm-1, and 13.5 cm-1.展开更多
Inexpensive and abundant sodium resources make energy storage systems using sodium chemistry promising replacements for typical lithium-ion rechargeable batteries(LIBs).Fortuitously,aqueous sodium-ion rechargeable bat...Inexpensive and abundant sodium resources make energy storage systems using sodium chemistry promising replacements for typical lithium-ion rechargeable batteries(LIBs).Fortuitously,aqueous sodium-ion rechargeable batteries(ASIBs),which operate in aqueous electrolytes,are cheaper,safer,and more ionically conductive than batteries that operate in conventional organic electrolytes;furthermore,they are suitable for grid-scale energy storage applications.As electrode materials for storing Na~+ ions in ASIBs,a variety of multifunctional metal-organic frameworks(MOFs) have demonstrated great potential in terms of having porous 3 D crystal structures,compatibility with aqueous solutions,long cycle lives(≥1000 cycles),and ease of synthesis.The present review describes MOF-derived technologies for the successful application of MOFs to ASIBs and suggests future challenges in this area of research based on the current understanding.展开更多
Reliable estimation of the pore size distribution(PSD) in porous materials such as metal–organic frameworks(MOFs) and zeolitic imidazolate frameworks(ZIFs) is crucial for accurately assessing adsorption capacity and ...Reliable estimation of the pore size distribution(PSD) in porous materials such as metal–organic frameworks(MOFs) and zeolitic imidazolate frameworks(ZIFs) is crucial for accurately assessing adsorption capacity and corresponding selectivity. In this study, the so-called zeolitic imidazolate framework-7(ZIF-7) is successfully synthesized via relatively fast and convenient microwave technique. The morphology and structure of the obtained MOF were characterized by XRD, SEM and N_2 and CO_2adsorption/desorption isotherms at 77 K and0 °C respectively. Then, to determine the PSD of the fabricated MOF, carbon dioxide isotherms are experimentally measured at various temperatures up to atmospheric pressure. Afterward, the experimental CO_2 isotherms data are utilized in two recently proposed in-house algorithms of SHN1 and SHN2 to extract the true PSD of manufactured ZIF-7. The obtained results revealed that median pore diameter of the fabricated ZIF-7 is estimated around 0.404 nm and 0.370 nm by using CO_2 isotherms at 273 K and 298 K respectively. These values are in good agreement with the real pore diameter of 0.42 nm. Moreover, experimental data of water adsorption isotherms over four different MOFs, borrowed from literature, are employed to illustrate further effectiveness of the above algorithms on successful determination of the corresponding pore size distributions. All predicted PSDs are proved to be in good agreement with those obtained from independent methods such as topology and morphology studies.展开更多
基金Foundation(B?0027)(SM),National Science Foundation of China(Grants 22006036)North China Electric Power University(XM2112307)(HY and XW)+1 种基金GINW is supported by a James Cook Research Fellowship from New Zealand Government funding,administered by the Royal Society Te Aparangisupport from the XAS beamline scientists of the Australian Synchrotron and the 14 W station of the Shanghai Synchrotron Radiation Facility(SSRF).
文摘The large-scale synthesis of platinum-free electrocatalysts for the oxygen reduction reaction(ORR)remains a grand challenge.We report the large-scale production of stable and active ORR electrocatalysts based on iron,an earth-abundant element.A core–shell zeolitic imidazolate framework–tannic acid coordination polymer composite(ZIF-8@K-TA)was utilized as the catalyst precursor,which was transformed into iron atoms dispersed in hollow porous nitrogen-doped carbon capsules(H-Fe-N_(x)-C)through ion exchange and pyrolysis.H-Fe-N_(x)-C fea-tures site-isolated single-atom iron centers coordinated to nitrogen in graphitic layers,high levels of nitrogen doping,and high permeability to incoming gases.Benefiting from these characteristics,H-Fe-N_(x)-C demonstrated efficient electrocatalytic activity(E_(1/2)=0.92 V,vs.RHE)and stability towards the ORR in both alkaline and acidic media.In ORR performance,it surpassed the majority of recently reported Fe-N-C catalysts and the standard Pt/C catalyst.In addition,H-Fe-N_(x)-C showed outstanding tolerance to methanol.
基金the National Key R&D Program of China(2018YFB0605700)the National Natural Science Foundation of China(51778570,51879230,21725101,21871244,21521001,and 21703145)+1 种基金China Postdoctoral Science Foundation(2019TQ0298,2019M660151)Fujian Institute of Innovation(CAS)。
文摘The rational design and construction of inexpensive and highly active electrocatalysts for hydrogen evolution reaction(HER)is of great importance for water splitting.Herein,we develop a facile approach for preparation of porous carbon-confined Ru-doped Cu nanoparticles(denoted as Ru-Cu@C)by direct pyrolysis of the Ru-exchanged Cu-BTC metal–organic framework.When served as the electrocatalyst for HER,strikingly,the obtained Ru-Cu@C catalyst exhibits an ultralow overpotential(only 20 mV at 10 mA cm^(-2))with a small Tafel slope of 37 m V dec^(-1)in alkaline electrolyte.The excellent performance is comparable or even superior to that of commercial Pt/C catalyst.Density functional theory(DFT)calculations confirm that introducing Ru atoms into Cu nanocrystals can significantly alter the desorption of H_(2) to achieve a close-to-zero hydrogen adsorption energy and thereby boost the HER process.This strategy gives a fresh impetus to explore low-cost and high-performance catalysts for HER in alkaline media.
基金Supported by the National Natural Science Foundation of China(No.21676133)the Natural Science Foundation of Fujian Province(2014J01051)
文摘In the present paper, a metal–organic framework Cr-BDC was prepared and used as adsorbent for adsorption of o-nitrophenol(ONP) and p-nitrophenol(PNP) from aqueous solutions. Cr-BDC was characterized by scanning electron microscopy, transmission electron microscope, X-ray diffraction and BET methods. The results indicate that Cr-BDC gets a very large specific surface area of 4128 m^2·g^(-1)and pore sizes are concentrated in 1 nm, which is a benefit for using for wastewater treatment. The influences of the adsorption conditions, such as temperature,solution concentration, adsorption time and reusability on adsorption performance were investigated. Cr-BDC exhibited an encouraging uptake capacity of 310.0 mg·g^(-1)for ONP, and adsorption capacity of Cr-BDC for ONP is significantly higher than that for PNP under suitable adsorption conditions. The characterizations of adsorption process were examined with the Lagergren pseudo-first-order, the pseudo-second-order kinetic model, and the intra-particular diffusion model. Kinetics experiments indicated that the pseudo-second-order model displayed the best correlation with adsorption kinetics data. Furthermore, our adsorption equilibrium data could be better described by the Freundlich equation. The results indicate that the as-prepared Cr-BDC is promising for use as an effective and economical adsorbent for ONP removal.
基金the National Natural Science Foundation of China(Nos.U1904215 and 21875207)the Natural Science Foundation of Jiangsu Province(No.BK20200044)the Shenzhen Key Laboratory of Micro/Nano-Porous Functional Materials(SKLPM,No.ZDSYS20210709112802010).
文摘Cu-based materials are seldom reported as oxygen evolution reaction(OER)electrocatalysts due to their inherent electron orbital configuration,which makes them difficult to adsorb oxygen-intermediates during OER.Reasonably engineering the hierarchical architectures and the electronic structures can improve the performance of Cu-based OER catalysts,such as constructing multilevel morphology,inducing the porous materials,improving the Cu valence,building heterostructures,doping heteroatoms,etc.In this work,copper-1,3,5-benzenetricarboxylate(HKUST-1)octahedra in-situ grow on the Cu nanorod(NR)-supported N-doped carbon microplates,meanwhile an active layer of Cu(OH)_(2)forms on the surface of the original conductive Cu NRs.The octahedral HKUST-1,serving as a spacer between the microplates,greatly improves the porosity and increases the available active sites,facilitating the mass transport and electron transfer,thus resulting in greatly enhanced OER performance.
基金supported by National Natural Science Foundation of China (Nos. 21171162, 21471144)Jilin Province Youth Foundation (No. 20130522132JH)+1 种基金Jilin Province Natural Science Foundation (No. 20150101181JC)Changchun Science and Technology Plan (No. 2013059)
文摘A Cd-containing metal–organic framework（Cd L）, formula as {[Cd_3（L）_2（H_2O）_6] 1.5DMF}, has been synthesized under solvothermal condition by the reaction of 4,40,400-（methylsilanetriyl）tribenzoic acid（H_3L） and Cd^（2＋）ion. Single-crystal X-ray diffraction reveals that Cd L displays a three-dimensional framework with 2-fold interpenetration and DMF molecules locate in the void space of the channels. A topological analysis of the framework indicates Cd Lisa 3,4-connected pto net. The photoluminescence properties of Cd L are systematically studied in detail. Impressively, Cd L shows excellent detection performance towards Fe^（3＋）ion and acetone in the sensing experiments, which undoubtedly demonstrates the great potential of Cd L as a highly selective multi-responsive luminescent sensor for the detection of organic solvents and metal ions.
基金funded by the Natural Science Foundation of Fujian Province(2023J05180)the President's Foundation of Minnan Normal University(KJ2021011).
文摘As promising catalysts for the degradation of organic pollutants,metal–organic frameworks(MOFs)often face limitations due to the particle agglomeration and challenging recovery in liquid-catalysis application,stemming from their powdery nature.Engineering macroscopic structures from pulverous MOF is thus of great importance for broadening their practical applications.In this study,three-dimensional porous MOF aerogel catalysts were successfully fabricated for degrading organic dyes by activating peroxymonosulfate(PMS).MOF/gelatin aerogel(MOF/GA)catalysts were prepared by directly integrating bimetallic FeCo-BDC with gelatin solutions,followed by freeze-drying and low-temperature calcination.The FeCo-BDC-0.15/GA/PMS system exhibited remarkable performance in degrading various organic dyes,eliminating 99.2%of rhodamine B within a mere 5 min.Compared to the GA/PMS system,there was over a 300-fold increase in the reaction rate constant.Remarkably,high removal efficiency was maintained across varying conditions,including different solution pH,co-existing inorganic anions,and natural water matrices.Radical trapping experiments and electron paramagnetic resonance analysis revealed that the degradation involved radical(SO_(4)^(-)·)and non-radical routes(^(1)O_(2)),of which ^(1)O_(2) was dominant.Furthermore,even after a continuous 400-min reaction in a fixed-bed reactor at a liquid hourly space velocity of 27 h^(-1),the FeCo-BDC/GA composite sustained a degradation efficiency exceeding 98.7%.This work presents highly active MOF-gelatin aerogels for dye degradation and expands the potential for their large-scale,continuous treatment application in organic dye wastewater management.
基金Shenzhen Key Laboratory of Micro/Nano-Porous Functional Materials(SKLPM)(No.ZDSYS20210709112802010)China Postdoctoral Science Foundation(No.2022M711483).
文摘Two-dimensional metal–organic frameworks(2D MOFs),as a new type of 2D materials,have been widely applied in various applications because of their unique structures and exposed active sites.Herein,we reported two low-cost 2D MOFs constructed by a raw chemical succinic acid(SA),M-SA(M=Ni or Co),which served as efficient photocatalysts for the reduction of CO_(2)to CO.Taking advantage of the thinness and open metal sites,the ultrathin Ni-SA nanosheets(ca.3.6 nm)exhibited excellent CO production of 6.96(7)mmol·g^(−1)·h^(−1)and CO selectivity of 96.6%.Photoelectrochemical tests and theoretical calculations further confirmed the higher charge transfer efficiency and unsaturated metal sites for promoting photocatalytic performances.More importantly,Ni-SA can also be synthesized in large-scale by an energy-saving method under room temperature,strongly suggesting its promising future and potential for practical applications.
基金Supported by the National Natural Science Foundation of China(21722609,21776240)Zhejiang Provincial Natural Science Foundation of China(LR17B060001)
文摘Metal–organic frameworks(MOFs) packed in the column have been a promising candidate as the stationary phase for high performance liquid chromatography(HPLC). However, the direct packing of irregular MOF powder could raise some problems like high back pressure and low column efficiency in the HPLC separation. In this work, UiO-66 capable of separating xylenes was supported effectively on the surface of the monodisperse spherical silica microspheres by one-pot method. The hybridization of Ui O-66 and silica microspheres(termed UiO-66@SiO2 shell–core composite) was prepared by stirring the suspension of the precursors of Ui O-66 and\\COOH terminated silica in the N,N-dimethylformamide with heating. The shell–core composite material UiO66@SiO2 was characterized by SEM, TEM, PXRD and FTIR. Then, it was used as a packing material for the chromatographic separation of xylene isomers. Xylene isomers including o-xylene, m-xylene and p-xylene were efficiently separated on the column with high resolution and good reproducibility. Moreover, the Ui O-66@SiO2 shell–core composites packed column still remained reverse shape selectivity as Ui O-66 possessed, and the retention of xylenes was probably ascribed to the hydrophobic effect between analytes and the aromatic rings of the Ui O-66 shell. The Ui O-66@SiO2 shell–core composites obtained in this study have some potential for the separation of structural isomers in HPLC.
基金supported by the National Natural Science Foundation of China(Nos.62174085 and 21805136)the Program for Young Changjiang Scholars of the Ministry of Education,the Jiangsu Specially-Appointed Professors Program,the Top-notch Academic Programs Project of Jiangsu Higher Education Institutions(TAPP),the Natural Science Foundation of Jiangsu Province(No.BK20200044)the Startup Foundation for Introducing Talent of NUIST(No.2021r091).
文摘Although metal–organic frameworks have been heavily tested as the anode materials for lithium-ion batteries(LIBs),the poorer conductivity,easy collapse of frameworks,and serious volume expansion limit their further application in LIBs.Herein,we report a facile approach to obtain MXene-encapsulated porous Ni-naphthalene dicarboxylic acid(Ni-NDC)nanosheets by hybridizing ultrathin Ti_(3)C_(2)MXene and three-dimensional(3D)Ni-NDC nanosheet aggregates.In the structure of Ni-NDC/MXene hybrids,the interlayer hydrogen-bond interaction between Ni-NDC and MXene can effectively increase the interlayer spacing and further inhibit the oxidation of pure MXene.Hence,the introduction of MXene(a conductive matrix)could further improve the conductivity of Ni-NDC,avoid self-agglomeration,and buffer the volume expansion of Ni-NDC nanosheets.Benefiting from the synergistic effects between Ni-NDC and MXene,Ni-NDC/MXene hybrid electrode exhibits a reversible discharge capacity(579.8 mA∙h∙g^(−1)at 100 mA∙g^(−1)after 100 cycles)and good long-term cycling performance(310 mA∙h∙g^(−1)at 1 A∙g^(−1)after 500 cycles).
基金X.Y.acknowledges the Research Grant Council of Hong Kong(Nos.11305219 and 11307220)CityU Applied Research Grant(ARG,No.9667203)+2 种基金Shenzhen Basic Research Program(No.JCYJ20210324134009024)Z.X.acknowledges a Shenzhen-HKMacao Science and Technology Grant(type CNo.SGDX2020110309300301)from the Science,Technology,and Innovation Commission of Shenzhen Municipality.
文摘In this work,we report that high catalytic performance of metal–organic frameworks(MOFs)can be obtained through a synergistic effect of postsynthetic modification of MOF nanoparticles and liquid superwetting and confinement in the MOF coating.Specifically,2-ureido-4[1H]pyrimidinone(UPy)functionalized polysiloxanes were covalently appended onto the UiO-66 nanoparticles via a postsynthetic approach,which were further anchored onto different porous films through multivalent hydrogen bonding of the UPy motifs.The hydrophobic MOF coating can preserve the porosity of the solid substrates,enable rapid liquid superwetting and confinement within the porous substrates.Using the Knoevenagel condensation as a modeled system,robust and highly catalytic performances of the MOF coating were observed on a range of aldehyde substrates.Gram-scale production of chromene,a pharmaceutical which is typically synthesized via expensive catalysis,was successfully demonstrated on the MOF coating with high yielding rates,demonstrating the great potential of the MOF coating in pharmaceutical synthesis.
基金supported by the National Natural Science Foundation of China(NSFC-U1904215,21671170)the Top-notch Academic Programs Project of Jiangsu Higher Education Institutions(TAPP).
文摘Metal–organic framework-based compounds have recently gained great attention because of their unique porous structure,ordered porosity,and high specific surface area.Benefiting from these superior properties,metal–organic framework-based compounds have been proven to be one of the most potential candidates for environmental governance and remediation.In this review,the different types of metal–organic framework-based compounds are first summarized.Further,the various environmental applications of metal–organic framework-based compounds including organic pollutant removal,toxic and hazardous gas capture,heavy metal ion detection,gas separation,water harvesting,air purification,and carbon dioxide reduction reactions are discussed in detail.In the end,the opportunities and challenges for the future development of metal–organic framework-based compounds for environmental applications are highlighted.
基金the financial support of the National Natural Science Foundation of China (No. 22038001)。
文摘The separation of C2H4from C_(2)H_(6)/C_(2)H_(4)mixture is of great importance but difficult and energy intensive. Adsorptive separation provides an alternative approach to ameliorate this situation. Here, we report a microporous metal–organic framework(MOF) BUT-315-a as a C_(2)H_(6)-selective adsorbent for the separation of C2H6/C2H4gas mixture. BUT-315-a combines good IAST selectivity of 2.35 with high C_(2)H_(6)uptake of 97.5 cm^(3)g^(-1), giving superior high separation potential ΔQ(2226 mmol L^(-1)) for equimolar C_(2)H_(6)/C_(2)H_(4) at 298 K. Impressively, such excellent performance can be preserved at higher temperatures of 313 and 323 K to accommodate industrial conditions. Efficient dynamic separation performance of BUT-315-a has been demonstrated by column breakthrough experiments under varied temperatures and gas ratios. Theoretical calculations further reveal multiple synergistic interactions between C_(2)H_(6) and the framework. This work highlights a new benchmark material for C_(2)H_(6)/C_(2)H_(4)separation and provides guidance for designing adsorbent for separation applications.
基金the financial support from the National Natural Science Foundation of China (Nos.22225803 and 22038001)。
文摘Short-chain perfluorocarboxylic acids(PFCAs) are a class of persistent organic pollutants that are widely used as substitutes for long-chain PFCAs. However, they also pose a non-negligible risk to ecosystems. In this study, we demonstrated that a fluorescent metal–organic framework(MOF)(named V-101) constructed from In^(3+)and an aromatic-rich tetratopic carboxylate ligand 5-[2,6-bis(4-carboxyphenyl) pyridin-4-yl] isophthalic acid(H4BCPIA) exhibited highly efficient turn-off and turn-on fluorescence responses toward five short-chain PFCAs in water and methanol, respectively. The limits of detection of V-101 toward five short-chain PFCAs are down to μg/L level, and it showed good anti-interference abilities toward short-chain PFCAs in the presence of common metal ions. The major mechanisms associated with fluorescence responses were molecular collisions and interactions between V-101 and short-chain PFCAs. This work demonstrates that the structure variety of MOFs imparts them with the potential of MOFs in the detection of short-chain PFCAs for pollution control.
基金supported by the National Natural Science Foundation of China (20971110 and J0830412)New Century Educational Talents Plan (NCET-07-0765)the Outstanding Talents Foundation of Henan Province
文摘A porous three-dimensional copper(Ⅱ) metal-organic framework (MOF) {[Cu2(tci)(OH)(pip)0.5(H2O)]·6H2O}n (1) [tci = tris (2-carboxyethyl)isocyanurate, pip = piperazine] has been generated under hydrothermal conditions at 120 °C. Single crystal X-ray diffraction reveals that the polymer exhibits a novel three-dimensional framework based on planar tetranuclear copper(Ⅱ) cluster units. The variable temperature magnetic susceptibility data in the range 2-280 K show antiferromagnetic spin-spin coupling in the tetranuclear unit in complex 1. A theoretical fitting of the magnetic data gives J values of -31.3 cm-1, -30.8 cm-1, and 13.5 cm-1.
基金supported by a National Research Foundation of Korea, South Korea (NRF) grant funded by the Korean government (MSITMinistry of Science and ICT+1 种基金Information and Communications Technologies) (NRF-2019R1F1A1042080)the Hallym University, South Korea Research Fund, 2019 (HRF-201912-013)。
文摘Inexpensive and abundant sodium resources make energy storage systems using sodium chemistry promising replacements for typical lithium-ion rechargeable batteries(LIBs).Fortuitously,aqueous sodium-ion rechargeable batteries(ASIBs),which operate in aqueous electrolytes,are cheaper,safer,and more ionically conductive than batteries that operate in conventional organic electrolytes;furthermore,they are suitable for grid-scale energy storage applications.As electrode materials for storing Na~+ ions in ASIBs,a variety of multifunctional metal-organic frameworks(MOFs) have demonstrated great potential in terms of having porous 3 D crystal structures,compatibility with aqueous solutions,long cycle lives(≥1000 cycles),and ease of synthesis.The present review describes MOF-derived technologies for the successful application of MOFs to ASIBs and suggests future challenges in this area of research based on the current understanding.
文摘Reliable estimation of the pore size distribution(PSD) in porous materials such as metal–organic frameworks(MOFs) and zeolitic imidazolate frameworks(ZIFs) is crucial for accurately assessing adsorption capacity and corresponding selectivity. In this study, the so-called zeolitic imidazolate framework-7(ZIF-7) is successfully synthesized via relatively fast and convenient microwave technique. The morphology and structure of the obtained MOF were characterized by XRD, SEM and N_2 and CO_2adsorption/desorption isotherms at 77 K and0 °C respectively. Then, to determine the PSD of the fabricated MOF, carbon dioxide isotherms are experimentally measured at various temperatures up to atmospheric pressure. Afterward, the experimental CO_2 isotherms data are utilized in two recently proposed in-house algorithms of SHN1 and SHN2 to extract the true PSD of manufactured ZIF-7. The obtained results revealed that median pore diameter of the fabricated ZIF-7 is estimated around 0.404 nm and 0.370 nm by using CO_2 isotherms at 273 K and 298 K respectively. These values are in good agreement with the real pore diameter of 0.42 nm. Moreover, experimental data of water adsorption isotherms over four different MOFs, borrowed from literature, are employed to illustrate further effectiveness of the above algorithms on successful determination of the corresponding pore size distributions. All predicted PSDs are proved to be in good agreement with those obtained from independent methods such as topology and morphology studies.
