We report herein a new alkaline earth metal ion organic framework[Mg_(2)(NH_(2)BDC)_(2)(HNO_(3))]·9H_(2)O(AEMOF-7),which shows a 3-D microporous structure with several unusual features,such as the rare trigonal p...We report herein a new alkaline earth metal ion organic framework[Mg_(2)(NH_(2)BDC)_(2)(HNO_(3))]·9H_(2)O(AEMOF-7),which shows a 3-D microporous structure with several unusual features,such as the rare trigonal prismatic coordination geometry of one of the crystallographically unique Mg^(2+)centers and the existence of a bridging HNO_(3)ligand.The H^(+)ions of the HNO_(3)ligand are dissociable as demonstrated via proton conductivity measurements.AEMOF-7 displays relatively high selectivity for CO_(2)vs.CH_(4)and negligible N_(2)uptake.Interestingly,this compound was found to be capable of single-crystal-to-single-crystal(SCSC)exchange of Mg^(2+)by Cu^(2+)ions,which was observed for the first time in a MOF material.AEMOF-7 is also luminescent and its photophysical properties were investigated via solid state UV-Vis,steady-state and time-resolved luminescence studies.展开更多
Voltammetric analytical techniques combine exceptional sensitivity,low cost,portability and capability for simultaneous determination of multiple analytes.The sensitivity of voltammetric analysis is largely determined...Voltammetric analytical techniques combine exceptional sensitivity,low cost,portability and capability for simultaneous determination of multiple analytes.The sensitivity of voltammetric analysis is largely determined by the efficiency of the working electrode.Electrodes modified with metal organic frameworks(MOFs)seem particularly promising for use in the analysis of a series of important inorganic and organic analytes.Nevertheless,research on chemically modified electrodes with MOFs is still in its infancy.In this critical review,we present the current status of research related to MOF-modified electrodes highlighting the respective MOF-modified electrodes which are based on MOFs that show exceptional chemical stability or/and sorption capability towards the targeted analytes.We also provide perspectives for future research aiming at motivating additional scientists to be involved in this exciting field of MOF-based electroanalytical sensors.展开更多
Heavy metal ions represent hazardous and harmful contaminants for living organisms and the environment and thus,it is of urgent need to develop new materials sufficient to detect and remove them efficiently.Herein,we ...Heavy metal ions represent hazardous and harmful contaminants for living organisms and the environment and thus,it is of urgent need to develop new materials sufficient to detect and remove them efficiently.Herein,we report the metal sulfide ion exchanger(MSIE)H_(x)Ga_(x)Ge_(4−x)S_(8)·yH_(2)O(protonated UCR-20,p-UCR-20)which demonstrates exceptional capability for both detection and removal of heavy metals from aqueous samples.展开更多
The ever-increasing need to determine and monitor the chemical constituents of the constantly evolving environment has led the global scientific community to invest considerable research effort in the development of e...The ever-increasing need to determine and monitor the chemical constituents of the constantly evolving environment has led the global scientific community to invest considerable research effort in the development of efficient and user-friendly chemical sensors.The development of improved chemical sensors largely depends on the synthesis of novel materials with the ability to transform a molecular recognition event into a readable signal.Among the various types of sensory materials,those where analyte detection is based on the change of a luminescence signal are gaining increasing attention due to the extremely high sensitivities which can be achieved in combination with new technological advances enabling the integration of optical detection systems in small,portable and easy to use devices.In this critical review we approach the emerging field of sensory materials based on luminescent metal–organic frameworks(LMOFs)by beginning with a survey of the general principles of luminescence-based sensing.In particular,after a brief overview,we first focus on the working principles and successes of well established sensory materials based on small molecules and conjugated polymers.Subsequently,we concentrate on the special features of LMOFs which make them promising sensory materials and we discuss best practices which researchers in the field should follow in order to prove the sensing ability of LMOFs and avoid common misconceptions and errors.We continue with presenting selected examples of LMOF-based sensors for nitroaromatics,humidity and heavy metal ions from the recent literature and we conclude with a summary of the state-of-the-art of LMOF sensors.Finally,we propose some directions for future research on LMOF sensors.展开更多
The rational design of semiconductor nanostructures is of utmost importance for efficient solar energy conversion and environmental remediation.In this article,we report high-surface-area mesoporous networks consistin...The rational design of semiconductor nanostructures is of utmost importance for efficient solar energy conversion and environmental remediation.In this article,we report high-surface-area mesoporous networks consisting of Ni-implanted cubic CoO(Co_(1−x)Ni_(x)O)nanoparticles as promising catalysts for the detoxification of aqueous Cr(VI)solutions.Mechanistic studies with X-ray photoelectron,UV-vis optical absorption,fluorescence and electrochemical impedance spectroscopy and theoretical(DFT)calculations indicate that the performance enhancement of these catalysts arises from the high charge transfer kinetics and oxidation efficiency of surface-reaching holes.By tuning the chemical composition,the Co_(1−x)Ni_(x)O mesoporous catalyst at 2 atomic%Ni content imparts outstanding photocatalytic Cr(VI)reduction and water oxidation activity,corresponding to an apparent quantum yield(QY)of 1.5%atλ=375 nm irradiation light.展开更多
We describe a new synthetic method for the isolation of the UiO-66 amino-functionalized material(called metal organic resin-1,MOR-1)and its composite with alginic acid(HA).MOR-1 can be prepared in high yield(∼70%)and...We describe a new synthetic method for the isolation of the UiO-66 amino-functionalized material(called metal organic resin-1,MOR-1)and its composite with alginic acid(HA).MOR-1 can be prepared in high yield(∼70%)and purity within an hour via a reflux reaction of ZrCl4 and 2-amino-terephthalic acid in acifidied aqueous solution,whereas addition of sodium alginate to the fine suspension of MOR-1 resulting from the reflux synthesis affords the MOR-1-HA composite.This inexpensive,green and fast preparation method results in UiO-66 amino-functionalized materials(MOR-1 and MOR-1-HA)of the same quality and microporous features as those of compounds isolated with the slower solvothermal synthesis involving toxic and costly organic solvents.Field Emission-Scanning Electron Microscopy(FE-SEM)studies revealed that MOR-1 consists of spongy nanoparticles(150–300 nm in size),whereas MOR-1-HA nanoparticles are relatively compact.Thus,for the first time we could visualize the effect of alginic acid partially coating the surface of the MOR particles.The composite prepared by this method can be successfully utilized as a stationary phase,mixed with sand,in an anion-exchange column.The column shows excellent hexavalent chromium sorption properties and can be easily regenerated and reused several times with almost no loss of its initial Cr(VI)removal capacity.Remarkably,this ion exchange column is capable of eliminating Cr(VI)ions from chrome plating wastewater samples,thus indicating its potential for applications in industrial wastewater treatment.展开更多
文摘We report herein a new alkaline earth metal ion organic framework[Mg_(2)(NH_(2)BDC)_(2)(HNO_(3))]·9H_(2)O(AEMOF-7),which shows a 3-D microporous structure with several unusual features,such as the rare trigonal prismatic coordination geometry of one of the crystallographically unique Mg^(2+)centers and the existence of a bridging HNO_(3)ligand.The H^(+)ions of the HNO_(3)ligand are dissociable as demonstrated via proton conductivity measurements.AEMOF-7 displays relatively high selectivity for CO_(2)vs.CH_(4)and negligible N_(2)uptake.Interestingly,this compound was found to be capable of single-crystal-to-single-crystal(SCSC)exchange of Mg^(2+)by Cu^(2+)ions,which was observed for the first time in a MOF material.AEMOF-7 is also luminescent and its photophysical properties were investigated via solid state UV-Vis,steady-state and time-resolved luminescence studies.
文摘Voltammetric analytical techniques combine exceptional sensitivity,low cost,portability and capability for simultaneous determination of multiple analytes.The sensitivity of voltammetric analysis is largely determined by the efficiency of the working electrode.Electrodes modified with metal organic frameworks(MOFs)seem particularly promising for use in the analysis of a series of important inorganic and organic analytes.Nevertheless,research on chemically modified electrodes with MOFs is still in its infancy.In this critical review,we present the current status of research related to MOF-modified electrodes highlighting the respective MOF-modified electrodes which are based on MOFs that show exceptional chemical stability or/and sorption capability towards the targeted analytes.We also provide perspectives for future research aiming at motivating additional scientists to be involved in this exciting field of MOF-based electroanalytical sensors.
文摘Heavy metal ions represent hazardous and harmful contaminants for living organisms and the environment and thus,it is of urgent need to develop new materials sufficient to detect and remove them efficiently.Herein,we report the metal sulfide ion exchanger(MSIE)H_(x)Ga_(x)Ge_(4−x)S_(8)·yH_(2)O(protonated UCR-20,p-UCR-20)which demonstrates exceptional capability for both detection and removal of heavy metals from aqueous samples.
文摘The ever-increasing need to determine and monitor the chemical constituents of the constantly evolving environment has led the global scientific community to invest considerable research effort in the development of efficient and user-friendly chemical sensors.The development of improved chemical sensors largely depends on the synthesis of novel materials with the ability to transform a molecular recognition event into a readable signal.Among the various types of sensory materials,those where analyte detection is based on the change of a luminescence signal are gaining increasing attention due to the extremely high sensitivities which can be achieved in combination with new technological advances enabling the integration of optical detection systems in small,portable and easy to use devices.In this critical review we approach the emerging field of sensory materials based on luminescent metal–organic frameworks(LMOFs)by beginning with a survey of the general principles of luminescence-based sensing.In particular,after a brief overview,we first focus on the working principles and successes of well established sensory materials based on small molecules and conjugated polymers.Subsequently,we concentrate on the special features of LMOFs which make them promising sensory materials and we discuss best practices which researchers in the field should follow in order to prove the sensing ability of LMOFs and avoid common misconceptions and errors.We continue with presenting selected examples of LMOF-based sensors for nitroaromatics,humidity and heavy metal ions from the recent literature and we conclude with a summary of the state-of-the-art of LMOF sensors.Finally,we propose some directions for future research on LMOF sensors.
基金Special Account for Research Funds of the University of Crete(SARF UOC)(KA 10138)。
文摘The rational design of semiconductor nanostructures is of utmost importance for efficient solar energy conversion and environmental remediation.In this article,we report high-surface-area mesoporous networks consisting of Ni-implanted cubic CoO(Co_(1−x)Ni_(x)O)nanoparticles as promising catalysts for the detoxification of aqueous Cr(VI)solutions.Mechanistic studies with X-ray photoelectron,UV-vis optical absorption,fluorescence and electrochemical impedance spectroscopy and theoretical(DFT)calculations indicate that the performance enhancement of these catalysts arises from the high charge transfer kinetics and oxidation efficiency of surface-reaching holes.By tuning the chemical composition,the Co_(1−x)Ni_(x)O mesoporous catalyst at 2 atomic%Ni content imparts outstanding photocatalytic Cr(VI)reduction and water oxidation activity,corresponding to an apparent quantum yield(QY)of 1.5%atλ=375 nm irradiation light.
基金Dr M.Kaliva and Ms A.Manousaki(FORTH-IESL)for performing the FE-SEM measurements.The work performed at Northwestern University was supported by National Science Foundation grant DMR-1410169.
文摘We describe a new synthetic method for the isolation of the UiO-66 amino-functionalized material(called metal organic resin-1,MOR-1)and its composite with alginic acid(HA).MOR-1 can be prepared in high yield(∼70%)and purity within an hour via a reflux reaction of ZrCl4 and 2-amino-terephthalic acid in acifidied aqueous solution,whereas addition of sodium alginate to the fine suspension of MOR-1 resulting from the reflux synthesis affords the MOR-1-HA composite.This inexpensive,green and fast preparation method results in UiO-66 amino-functionalized materials(MOR-1 and MOR-1-HA)of the same quality and microporous features as those of compounds isolated with the slower solvothermal synthesis involving toxic and costly organic solvents.Field Emission-Scanning Electron Microscopy(FE-SEM)studies revealed that MOR-1 consists of spongy nanoparticles(150–300 nm in size),whereas MOR-1-HA nanoparticles are relatively compact.Thus,for the first time we could visualize the effect of alginic acid partially coating the surface of the MOR particles.The composite prepared by this method can be successfully utilized as a stationary phase,mixed with sand,in an anion-exchange column.The column shows excellent hexavalent chromium sorption properties and can be easily regenerated and reused several times with almost no loss of its initial Cr(VI)removal capacity.Remarkably,this ion exchange column is capable of eliminating Cr(VI)ions from chrome plating wastewater samples,thus indicating its potential for applications in industrial wastewater treatment.
