TL;DR: It is shown that water and related processes of MXene hydrolysis play the main role in the phenomena leading to complete transformations of 2D titanium carbide MXenes into titania in aqueous environments.
Abstract: Although oxidation was deemed as the main factor responsible for the instability of MXenes in aqueous colloids, here we put forward and test a hypothesis about the central role of water as the prim...
TL;DR: The MOF can sensitively and selectively sense acetylacetone (acac) via a fluorescence enhancement effect with a detection limit of 0.10 ppm and good reusability, which demonstrates the first example of a MOF-based turn-on fluorescent sensor for acac.
Abstract: A ZnII-based metal-organic framework (MOF) with a rare tcj topology has been solvothermally synthesized and displays relatively good thermal and chemical stabilities. Interestingly, the MOF can sensitively and selectively sense acetylacetone (acac) via a fluorescence enhancement effect with a detection limit of 0.10 ppm and good reusability, which demonstrates the first example of a MOF-based turn-on fluorescent sensor for acac.
TL;DR: MOF-808, a plausible mechanism concerning on Zr-OH(H2O) groups promoting the H2O2 decomposion in to both •O2- and •OH, represents a new benchmark catalyst for catalytic oxidative desulfurization.
Abstract: The restriction of sulfur content in fuels has become increasingly stringent as a result of the growing environmental concerns. Although several MOF-derived materials like POM@MOF composites have shown the ability to catalyze oxidative desulfurization (ODS), their catalytic activities inevitably obstructed by the encapsulated catalytic sites like POM due to the blockage of cavities. Therefore, MOFs with intrinsic and accessible catalytic sites are highly desirable for their applications in ultradeep ODS. Herein, four representative Zr-based MOFs (Zr-MOFs), namely, UiO-66, UiO-67, NU-1000, and MOF-808, were assessed for catalytic ODS. These MOFs were confirmed that they have peroxidase-like activity and can catalyze ODS with H2O2 as oxidant. Among them, MOF-808 showed the highest catalytic activity and it can fully desulfurize dibenzothiophene (DBT) in a model gasoline with a S concentration of 1000 ppm under 40 °C within 5 min. An extremely low apparent Arrhenius activation energy (22.0 KJ·mol-1) and an extraordinarily high TOF value (42.7 h-1) were obtained, ranking MOF-808 among the best catalysts for the catalytic DBT oxidation. Further studies confirmed that the excellent catalytic activity is mainly responsible for the high concentration of the accessible Zr-OH(H2O) catalytic sites decorated in MOF-808. The superoxide radicals (•O2-) and hydroxyl radicals (•OH) were identified and were proved to involve in the DBT oxidation. Besides, the effects of Bronsted and lewis acidity to the catalytic efficiency were also discussed. Based on the experimental results, a plausible mechanism concerning on Zr-OH(H2O) groups promoting the H2O2 decomposion in to both •O2- and •OH was first proposed. Moreover, MOF-808 can be facilely reused for at least eight runs without significant loss of its catalytic activity. By the integration of facile synthesis, high catalytic efficiency, and good stability, MOF-808 thus represents a new benchmark catalyst for catalytic oxidative desulfurization.
TL;DR: Characterization results demonstrated that the high capture capability of MOF-74 (Ni) materials can be attributed to the synergistic effect of abundant narrow micropore channels and rich five-coordinated Ni2+ open metal sites which are beneficial for the trapping of CO2 molecules.
Abstract: In the present work, a series of MOF-74 (Ni) materials with narrow micropore channels and abundant unsaturated metal sites was respectively prepared via hydrothermal (HT), condensation reflux (CE), and microwave-assisted (MW) methods. The physicochemical properties of synthesized materials were characterized by powder X-ray diffraction, N2-sorption, field-emission scanning electron microscopy, Fourier-transform infrared (FTIR), thermogravimetric (TG)/TG-FTIR, X-ray photoelectron spectroscopy, UV-vis-near infrared, NH3/CO2-temperature programmed desorption, and in situ diffuse reflectance infrared Fourier transform spectroscopy. Their CO2/N2 adsorption performances were evaluated by isotherm adsorption and dynamic adsorption experiments. We found that the MW is a rapid and facile protocol for the synthesis of MOF-74 (Ni) materials with highly efficient CO2 capture capacity. The well-shaped MW-140 adsorbent with superior CO2 adsorption capacity of 5.22 mmol/g at 25 °C can be obtained within 60 min by the MW process, almost 6 times higher than that of the commercial activated carbon (0.89 mmol/g). Results of dynamic adsorption experiments showed that the MW-140 material possesses the highest CO2 adsorption capacity of 3.37 mmol/g under humid conditions (RH = 90%). Importantly, MW-140 has excellent adsorption stability and recyclability, superior CO2 capture selectivity (CO2/N2 = 31), and appropriate isosteric heat in CO2 adsorption (21-38 kJ/mol), making it a promising and potential material for industrial CO2 capture. Characterization results demonstrated that the high capture capability of MOF-74 (Ni) materials can be attributed to the synergistic effect of abundant narrow micropore channels and rich five-coordinated Ni2+ open metal sites which are beneficial for the trapping of CO2 molecules.
TL;DR: Two new three-dimensional MOFs with high porosity were prepared successfully by the electron-rich tetrakis(4-pyridylphenyl)ethylene (tppe) as ligands, showing the high sensitivity and selectivity toward nitro-antibiotics in an aqueous media and the best detection efficiency for furazolidone (FZD) among the reported luminescent sensors.
Abstract: The highly porous luminescent metal–organic frameworks (MOFs) can act as fluorescent probes for the detection of nitro compounds and can also serve as containers and energy transfer platforms to co...
TL;DR: A cobalt(II) coordination polymer with an unusual 4,4,4-connected network was hydrothermally synthesized and observed with high thermal, solvent, and pH stabilities and can serve as the first dual-responsive fluorescent chemosensor for the selective detection of acetylacetone and Cr2O72- ion in aqueous systems.
Abstract: A cobalt(II) coordination polymer with an unusual 4,4,4-connected network was hydrothermally synthesized and observed with high thermal, solvent, and pH stabilities. This polymer can serve as the first dual-responsive fluorescent chemosensor for the selective detection of acetylacetone and Cr2O72- ion (pH 3.0) in aqueous systems.
TL;DR: The proposed mediator-free Z-scheme-oriented electron-hole migration route is well supported by photoluminescence, and the scavenger test well explains the better charge-carrier separation and high catalytic performance of the prepared composite.
Abstract: The abolition of environmental pollutants and production of hydrogen (H2) from water using a heterogeneous photocatalyst is a demanding science of the current scenario to solve the increasing environmental pollution and worldwide energy catastrophe in modern life. To validate this purpose, the design of low-cost and durable semiconductor-based photocatalysts with great light absorption capacity becomes the most challenging issue for researchers. Regarding this, herein the phosphotungstic acid (HPW)-anchored Zr6O4(OH)4(BDC)6 (UiO-66) metal-organic framework (MOF), i.e., HPW@UiO-66, has been prepared by a hydrothermal method and is efficient, stable, and capable of harvesting solar energy toward the degradation of tetracycline hydrochloride (TCH) and H2 production in the presence of a sacrificial donor. The ionic interaction between HPW and UiO-66 plays a key role toward the photostability and charge-transfer mechanism of the composite and is well characterized with X-ray diffraction, UV diffuse-reflectance spectroscopy, Fourier transform infrared, and X-ray photoelectron spectroscopy. A total of 30 wt % HPW@UiO-66 shows a maximum degradation of about 87.24% of a 20 ppm TCH solution in 60 min of solar-light irradiation and about 353.89 μmol/h of H2 production. The conduction- and valence-band potentials are well characterized with Mott-Schottky measurement and a delay charge recombination process through electrochemical impedance spectroscopy. The proposed mediator-free Z-scheme-oriented electron-hole migration route is well supported by photoluminescence, and the scavenger test well explains the better charge-carrier separation and high catalytic performance of the prepared composite. This research will bestow an advantageous blueprint to fabricate novel and challenging photocatalysts toward the photocatalytic treatment of environmental pollutants and H2 evolution.
TL;DR: This work emphasizes the rational portable assembly of biocompatible nanozymes like CS-MoSe2 NS for the field detection of Hg2+ in food, biological, and environmental samples and shows high specificity and anti-interfering ability over other ions and great practiseability in real water and serum samples.
Abstract: The nanozyme-based strategy is currently one of the frontiers in the detection of toxic heavy metal ions. However, the utilization of noble metal free nanozymes to construct an economically and environmentally sustainable methodology remains largely unknown. Here, chitosan-functionalized molybdenum(IV) selenide nanosheets (CS-MoSe2 NS), greenly synthesized by an ionic liquid-assisted grinding method, were exploited for the colorimetric sensing of mercury ions (Hg2+). The sensing principle was based on the activating effect of Hg2+ on CS-MoSe2 NS nanozyme activities, triggered by the in situ reduction of chitosan-captured Hg2+ ions on a MoSe2 NS surface. Using 3,3',5,5'-tetramethylbenzidine (TMB) as a colorimetric indicator, the concentrations of activator-like Hg2+ ions could be quantitatively and selectively monitored, reaching a limit of detection of 3.5 nM with the ultraviolet-visible spectrophotometer. In addition, the integration system of CS-MoSe2 NS with a smartphone achieved a portable detection limit as low as 8.4 nM Hg2+ within 15 min and showed high specificity and anti-interfering ability over other ions and great practicability in real water and serum samples. The eco-friendly properties of such sensing system were also confirmed. This work emphasizes the rational portable assembly of biocompatible nanozymes like CS-MoSe2 NS for the field detection of Hg2+ in food, biological, and environmental samples.
TL;DR: The smart NH2-MIL-53(Al) nanohexahedron has a great potential for simultaneous Hg2+ detection and removal from water.
Abstract: The worsening pollution due to mercury species makes it inevitable to explore prospective versatile materials, which not only can detect mercury ions (Hg2+) with high sensitivity but also possesses efficient capture and removal ability. In this study, a series of classic organic ligand-based luminescence MOFs materials with high oxidation state central metals (Al3+, Zr4+, Cr3+, Fe3+, and Ti4+) were synthesized and were screened to achieve simultaneously Hg2+ detection and removal through the strong coordination of amino groups or nitrogen centers with Hg2+ and the intrinsic fluorescence intensity of MOFs regulated by the ligand-to-metal charge transfer (LMCT) effect. Among these checked materials, NH2-MIL-53(Al) exhibited the excellent ability for Hg2+ detection with wide response interval (1-17.3 μM), low detection limit (0.15 μM), good selectivity, wide pH adaptation (4.0-10.0), and strong anti-interference ability. Meanwhile, the resultant NH2-MIL-53(Al) possessed an efficient removal capability toward Hg2+, accompanied by a fast uptake kinetics (within 60 min) and large loading capacity (153.85 mg g-1). Furthermore, NH2-MIL-53(Al) also displayed satisfactory stability before and after Hg2+ treatment because of the formation of strong coordination bonds between high oxidation state aluminum (Al3+) and organic carboxylate ligands. Notably, the prepared NH2-MIL-53(Al) had no significant loss of adsorption performance even after being reused four times. All of these superior properties render the smart NH2-MIL-53(Al) nanohexahedron a great potential for simultaneous Hg2+ detection and removal from water.
TL;DR: Past and recent works on the possible biological and cellular applications of these promising ruthenium(II) polypyridine complexes are explored, with a focus on their use as bioimaging reagents, biomolecular probes, and phototherapeutic agents.
Abstract: Ruthenium(II) polypyridine complexes are one of the most extensively studied and developed systems in the family of luminescent transition-metal complexes. Notably, there has been a large amount of interest in the biological applications of these luminescent ruthenium(II) complexes because of their rich photophysical and photochemical properties. In this Viewpoint, we explore past and recent works on the possible biological and cellular applications of these promising complexes, with a focus on their use as bioimaging reagents, biomolecular probes, and phototherapeutic agents.
TL;DR: Zn- MOFs exhibit interesting stimuli-responsive luminescence enhancement after the encapsulation of a series of IIIB cations stimulated different luminescent emitting and intensity enhancement through host-guest processes of the pores in MOFs, especially for two distinct responses of Zn-MOF on a Tb3+ cation.
Abstract: Three water-stable luminescent MOFs [Zn4(bptc)2(NMP)3(DMF)(H2O)2]n (1-a), [Cd4(bptc)2(NMP)3(DMF)2(H2O)1]n (1-b), and {[Zn2(bptc)(DMA)(H2O)2]·(DMA)2·H2O}n (2), possessing similar chemical components (M2:L1:Sol3) and topology structures, were synthesized by solvents control. Their excellent sensing on iron(III) cation and nitroaromatic explosives (NACs) with great selectivity, sensitivity and a high Ksv (4.54 × 104 for 1-b on PNP) were observed by quenching effects. Furthermore, Zn-MOFs exhibit interesting stimuli-responsive luminescence enhancement after the encapsulation of a series of IIIB cations stimulated different luminescent emitting and intensity enhancement through host–guest processes of the pores in MOFs, especially for two distinct responses of Zn-MOF on a Tb3+ cation.
TL;DR: A mixed-valence Ce-MOF (Ce-BPyDC) that can exhibit both oxidase- like and peroxidase-like activities and establish a colorimetric biosensing platform using 3,3',5,5'-tetramethylbenzidine as a color reagent for ascorbic acid detection.
Abstract: Enzyme-like metal-organic frameworks (MOFs) are currently one type of starring material in the fields of artificial enzymes and analytical sensing. However, there has been little progress in making use of the MOF structures based on the catalytically active metal center with multiple valences. Herein, we report a mixed-valence Ce-MOF (Ce-BPyDC) that can exhibit both oxidase-like and peroxidase-like activities. Ce-BPyDC was synthesized by a facile hydrothermal method, which preserves the rare coexistence of Ce(III) and Ce(IV) in the MOF structure. The enzymatic studies demonstrated the enzyme-like activities of Ce-BPyDC follow the Michaelis-Menten kinetics and are strongly dependent on temperature, pH, and reaction time. Ce-BPyDC was also revealed to exert high catalytic activity that could transcend horseradish peroxidase and other MOF nanozymes, due to the redox-active Ce(III)/Ce(IV) cycles inside. Furthermore, the simple synthesis, high nanozyme activity, and great stability of Ce-BPyDC motivated us to establish a colorimetric biosensing platform using 3,3',5,5'-tetramethylbenzidine as a color reagent. Adopting this strategy, we established a visual, sensitive, and selective colorimetric method for ascorbic acid (AA) detection, for which the linear interval and limit of detection were 1-20 and 0.28 μM, respectively. The successful AA detection in real juice samples implies the promising use of such mixed-valence MOF nanozymes in food and biomedical samples.
TL;DR: The results show that the pristine MOFs have great potential toward improving different high-performance electrochemical energy storage devices, without requiring the pyrolysis or calcination stages and are very promising for future advancement of the energy field.
Abstract: In this work, a new 3D metal-organic framework (MOF) {[Co3(μ4-tpa)3(μ-dapz)(DMF)2]·2DMF}n (Co(II)-TMU-63; H2tpa = terephthalic acid, dapz = pyrazine-2,5-diamine, DMF = dimethylformamide) containing low-cost and readily available ligands was generated, fully characterized, and used as an electrode material in supercapacitors without the need for a calcination process. Thus, the synthesis of this material represents an economical and cost-effective method in the energy field. The crystal structure of Co(II)-TMU-63 is assembled from two types of organic building blocks (μ4-tpa2- and μ-dapz ligands), which arrange the cobalt nodes into a complex layer-pillared net with an unreported 4,4,4,6T14 topology. The presence of open sites in this MOF is promising for studying electrochemical activity and other types of applications. In fact, Co(II)-TMU-63 as a novel electrode material when comparing with pristine MOFs shows great cycling stability, large capacity, and high energy density and so acts as an excellent supercapacitor (384 F g-1 at 6 A g-1). In addition, there was a stable cycling performance (90% capacitance) following 6000 cycles at 12 A g-1 current density. Also, the Co(II)-TMU-63//activated carbon (AC) asymmetric supercapacitor acted in a broad potential window of 1.7 V (0-1.7 V), exhibiting a high performance with 4.42 kW kg-1 power density (PD) and 24.13 Whkg-1 energy density (ED). These results show that the pristine MOFs have great potential toward improving different high-performance electrochemical energy storage devices, without requiring the pyrolysis or calcination stages. Hence, such materials are very promising for future advancement of the energy field.
TL;DR: A fast, switchable, and highly selective fluorescent sensor platform for different organic solvents based on the luminescence of (C9NH20)2MnBr4 has been developed and it is believed that the hybrid metal halides with high PLQE and the exploration of these as a fluorescence sensor will expand the applications scope of bulk 0D materials for future development.
Abstract: Organic-inorganic hybrid metal halides with zero-dimensional (0D) structure has emerged as a new class of light-emitting materials. Herein, a new lead-free compound (C9NH20)2MnBr4 has been discovered and a temperature-dependent phase transition has been identified for two phases (space group P21/c and C2/c) in which individual [MnBr4]2- anions connect with organic cations, (C9NH20+) (1-buty-1-methylpyrrolidinium+), forming periodic structure with 0D blocks. A green emission band, peaking at 528 nm with a high photoluminescence quantum efficiency (PLQE) of 81.08%, has been observed at room temperature, which is originated from the 4T1(G) to 6A1 transition of tetrahedrally coordinated Mn2+ ions, as also elaborated by density functional theory calculation. Accordingly, a fast, switchable, and highly selective fluorescent sensor platform for different organic solvents based on the luminescence of (C9NH20)2MnBr4 has been developed. We believe that the hybrid metal halides with high PLQE and the exploration of these as a fluorescence sensor will expand the applications scope of bulk 0D materials for future development.
TL;DR: A Au-MoS2/ZnIn2S4 heterojunction photocatalyst is designed for the first time by adopting a simple one-pot hydrothermal technique, followed by a deposition-precipitation method, which represents the synergetic enhancement of photocatalytic activity through the p-n heteroj junction as well as the hot-electron participation by the metal nanocatalyst, which is an inspiration for developing efficient photoc atalysts.
Abstract: Developing effective and simple one-pot synthetic strategies regarding the formation of heterojunction photocatalytic semiconductors remains an intense challenge in research pursuits. Further scheming of the p-n heterojunction has sustained renewed interest in catalysis, photocatalysis, energy storage, and conversion because they easily accelerate the bulk charge separation efficiency. Thus we have successfully designed a Au-MoS2/ZnIn2S4 heterojunction photocatalyst for the first time by adopting a simple one-pot hydrothermal technique, followed by a deposition-precipitation method. By adjusting the mole ratio of Mo with that of Zn and In precursors, we have fabricated a MoS2/ZnIn2S4 p-n heterojunction photocatalyst, and the established p-n heterojunction between MoS2 and ZnIn2S4 is demonstrated by various physicochemical and morphological characterizations. An interfacial junction is created between MoS2 and ZnIn2S4 at the depletion region via an in situ formation mechanism, leading to the enhancement of the charge separation through the p-n heterojunction and thus improving the photocatalytic activity. Moreover, the photocatalytic activity is projected to further improve by the incorporation of Au nanodots on the surface of MoS2/ZnIn2S4 photocatalysts. The increase in activity is due to the generation and participation of a large number of direct-electron-transfer-induced hot electrons in the photochemical reaction. From the experimental results, Au-MoS2/ZnIn2S4 heterojunction photocatalysts with only 1% MoS2 and 1% Au loading content displayed a 561.25 μmol/h H2 evolution rate and 84% degradation of phenol, which are nearly 15 and 6 times higher than those neat ZnIn2S4. In addition Au-MoS2/ZnIn2S4 photocatalysts exhibit a photocurrent density of ∼2.56 mAcm-2, which is nearly 2.4 times higher than that of the MoS2/ZnIn2S4 heterojunction photocatalyst. This exertion represents the synergetic enhancement of photocatalytic activity through the p-n heterojunction as well as the hot-electron participation by the metal nanocatalyst, which is an inspiration for developing efficient photocatalysts.
TL;DR: The excellent adsorption and separation properties of SCNU-Z1-Cl is attribute to the cationic framework, large tubular channel, as well as the high positive Zeta potential.
Abstract: Cationic framework materials capable of removing anionic pollutants from wastewater are highly desirable but relatively rarely reported. Herein, a cationic MOF (SCNU-Z1-Cl) possessing tubular channels with diameter of 1.5 nm based on Ni(II) and a nitrogen-containing ligand has been synthesized and applied to capture hazardous anionic contaminants from water. The SCNU-Z1-Cl exhibits high BET surface area of 1636 m2/g, and shows high hydrolytically stability in pH range from 4 to 10. Owing to the large tubular channels and the uncoordinated anions in the framework, the aqueous-phase anion-exchange applications of SCNU-Z1-Cl were explored with environmentally toxic oxo-anions including CrO42-, Cr2O72-, MnO4-, and ReO4-, and organic dyes. The adsorption of oxoanions exhibits high uptake kinetics and the adsorption capacities of CrO42-, Cr2O72-, MnO4-, and ReO4- are 126, 241, 292, and 318 mg/g, respectively, which were some of the highest values in the field of MOF/COF. In additional, the selectively is high when other concurrent anions are exist. The anionic dyes with different sizes including methyl orange, acid orange A, congo red, as well as methyl blue can be adsorbed by SCNU-Z1-Cl in few minutes to about 1 h. The adsorption capacities for them are 285, 180, 585, and 262 mg/g, respectively. In contrast, the adsorption kinetics for catinionic dyes with different sizes is obviously lower and exhibit a size-selectively adsorption that only cationic dye with suitable size (rhodamine B) can be adsorbed by SCNU-Z1-Cl. Consequently, SCNU-Z1-Cl can sepearate organic dyes in three different modes: size-dependent, charge-dependent, and kinetics-dependent selective adsorption. The excellent adsorption and separation properties of SCNU-Z1-Cl is attribute to the cationic framework, large tubular channel, as well as the high positive Zeta potential.
TL;DR: Rational design of rare examples of 3D polyhedral MOFs composed of Lewis acidic and basic sites exhibiting efficient co-catalyst-free conversion of CO2 has been demonstrated.
Abstract: Highly porous, polyhedral metal–organic frameworks (MOFs) of Co(II)/Ni(II), {[M6(TATAB)4(DABCO)3(H2O)3]·12DMF·9H2O}n (where M = Co(II) (1)/Ni(II) (2), H3TATAB = 4,4′,4″-s-triazine-1,3,5-triyl-tri-p...
TL;DR: These Co(II) compounds act as heterogeneous catalysts for the oxidation of alcohols with tBuOOH ( tert-butylhydroperoxide) under mild conditions and broaden a still very small number of CPs or MOFs driven by the present type of multifunctional pyridine-carboxylic acids.
Abstract: New coordination polymers of cobalt(II), namely, [Co(μ4-cpna)(H2O)2]n (1), [Co(μ3-cpna)(phen)(H2O)]n·nH2O (2), [Co3(μ4-dppa)2(H2O)6]n·2nH2O (3), and [Co3(μ5-dppa)2(μ-4,4′-bipy)(H2O)2]n·4nH2O (4), h...
TL;DR: Benefiting from the uncoordinated carboxylate sites in the framework, JLU-MOF71 not only can sensitively detect trace amounts of individual Fe3+ and 2,4,6-trinitrophenol (TNP) through luminescence quenching but also exhibits high selectivity when other competing analytes exist.
Abstract: By using the mixed-linker strategy, a new pillar-layered luminescence Zn-LMOF (JLU-MOF71) ([Zn2Na2(TPHC)(4,4-Bipy)(DMF)]·8H2O) (TPHC = [1,1′:2′,1″-terphenyl]-3,3″,4,4′,4″,5′-hexacarboxylic acid, 4,...
TL;DR: An exceptionally stable metal-organic framework based on one-dimensional TbIII chains with significant green emission under excitation energy, which can detect NFAs in water from bovine serum samples and can be easily prepared and used with excellent stability and recursitivity.
Abstract: An exceptionally stable metal-organic framework based on one-dimensional (1D) TbIII chains with significant green emission under excitation energy, {[Tb(TATMA)(H2O)·2H2O} n (namely, 1), has been fabricated successfully under hydrothermal conditions. By virtue of the spectral overlap between the absorbance spectra of nitrofurans (NFAs) and the excitation spectrum of MOF 1, the resultant sample exhibits outstandingly sensitive and selective luminescence detectability for NFT ( Ksv = 3.35 × 104 M-1) and NFZ ( Ksv = 3.00 × 104 M-1) by quenching phenomenon. More importantly, it can detect NFAs in water from bovine serum samples. The portable MOF film can be easily prepared and used with excellent stability and recursitivity.
TL;DR: Two types of isostructural Ln3+-based metal-organic frameworks (LnMOFs) under solvothermal conditions, where two structurally similar pyridine-containing dicarboxylate ligands were used as the organic linkers, exhibit an excellent S-shaped response for temperatures in the range of 25-300 K, with favorable relative sensitivity and temperature uncertainty.
Abstract: In this work, we prepared two types of isostructural Ln3+-based metal-organic frameworks (LnMOFs) under solvothermal conditions, where two structurally similar pyridine-containing dicarboxylate ligands, 6-(4-carboxyphenyl)nicotinic acid and [2,2'-bipyridine]-5,5'-dicarboxylic acid, were used as the organic linkers. The as-synthesized LnMOF compounds were characterized using single-crystal X-ray diffraction (XRD), powder XRD, and thermogravimetric analysis. With the lanthanide co-doping approach, two mixed LnMOFs, Tb0.95Eu0.05cpna and Tb0.95Eu0.05bpydc, were obtained and evaluated for application as potential ratiometric luminescence thermometers. The temperature-dependent luminescence of the two materials was investigated, and their emission intensities, luminescence lifetimes, and thermometric parameters were compared. They exhibit an excellent S-shaped response for temperatures in the range of 25-300 K, with favorable relative sensitivity and temperature uncertainty. Moreover, their color changes from green at 25 K to red at 300 K, so that they are also suitable as colorimetric luminescent probes.
TL;DR: Densely populated acidic and basic sites in both Zn(II)/Cd(II) MOFs facilitated the conversion of ECH to ECH carbonate in high yields and showed comparable or even higher catalytic activity than other previously reported MOFs.
Abstract: We synthesized two new adenine-based Zn(II)/Cd(II) metal-organic frameworks (MOFs), namely, [Zn2(H2O)(stdb)2(5H-Ade)(9H-Ade)2]n (PNU-21) and [Cd2(Hstdb)(stdb)(8H-Ade)(Ade)]n (PNU-22), containing auxiliary dicarboxylate ligand (stdb = 4,4'-stilbenedicarboxylate). Both MOFs were characterized by multiple analytical techniques such as single-crystal X-ray diffraction (SXRD), powder X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, thermogravimetric analysis, scanning electron microscopy, as well as temperature program desorption and Brunauer-Emmett-Teller measurements. Both MOFs were structurally robust and possessed unsaturated Lewis acidic metal centers [Zn(II) and Cd(II)] and free basic N atoms of adenine molecules. They were used as heterogeneous catalysts for the fixation of CO2 into five-membered cyclic carbonates. Significant conversion of epichlorohydrin (ECH) was attained at a low CO2 pressure (0.4 MPa) and moderate catalyst (0.6 mol %)/cocatalyst (0.3 mol %) amounts, with over 99% selectivity toward the ECH carbonate. They showed comparable or even higher catalytic activity than other previously reported MOFs. Because of high thermal stability and robust architecture of PNU-21/PNU-22, both catalysts could be reused with simple separation up to five successive cycles without any considerable loss of their catalytic activity. Densely populated acidic and basic sites in both Zn(II)/Cd(II) MOFs facilitated the conversion of ECH to ECH carbonate in high yields. The reaction mechanism of the cycloaddition reaction between ECH and CO2 is described by possible intermediates, transition states, and pathways, from the density functional theory calculation in correlation with the SXRD structure of PNU-21.
TL;DR: S-MIL-101(Cr) composite can efficiently separate chloroform, toluene, petroleum ether, and n-hexane from water with excellent oil-water separation performance, with potential application in the environmental field.
Abstract: A universal strategy is developed to construct metal-organic framework (MOF)-based superhydrophobic/superoleophilic materials by the reaction of activated MOFs and octadecylamine. In particular, S-MIL-101(Cr) composite can efficiently separate chloroform, toluene, petroleum ether, and n-hexane from water with excellent oil-water separation performance, with potential application in the environmental field.
TL;DR: A thiol-functionalized metal-organic framework was successfully prepared through a post-synthesis modification procedure, and the framework intactness and porosity were well maintained after this process, and SH-MiL-68(In) exhibited selective adsorption performance for Hg(II) ions in water.
Abstract: Owing to the rapid increase of Hg(II) ions in water resources, the design and development of new adsorbents for Hg(II) removal are becoming a significant challenge in environmental protection. Herein, a thiol-functionalized metal-organic framework (SH-MiL-68(In)) was successfully prepared through a post-synthesis modification procedure, and the framework intactness and porosity were well maintained after this process. SH-MiL-68(In) exhibited selective adsorption performance for Hg(II) ions in water. Meanwhile, SH-MiL-68(In) also shows a high adsorption capacity (450 mg g-1), large adsorption rate (rate constant k2 = 1.25 g mg-1 min-1), and good recycling of adsorption capacity toward Hg(II) ions. The excellent adsorption performance resulted from the strong binding interactions between -SH soft basic groups and Hg(II) soft acidic ions.
TL;DR: A new carbon-based nanomaterial for multifunctional photodiagnostic and therapeutic agents for biological applications that show a high quantum yield of singlet oxygen, good photoinduced cytotoxicity, and effective inhibition of 3D MC growth is provided.
Abstract: Carbon dots (CDs), as an effective bioimaging agent, have aroused widespread interest. With the increasing number of CDs used in photodynamic therapy (PDT), developing efficient CDs with multiple f...
TL;DR: This work represents the first MOF-based fluorescent "switch" for the ratiometric sensing of hypochlorite and the second for ratiometry sensing of AA.
Abstract: The detection of hypochlorite (ClO-) content in tap water is extremely important because excess amounts of hypochlorite can convert into highly toxic species and inadequate amounts of hypochlorite cannot fully kill bacteria and viruses. Although several metal-organic frameworks (MOFs) have been successfully employed as fluorescent sensors for hypochlorite detection, all these sensors are based on single emission that responds to the dose of hypochlorite. Ratiometric sensors are highly desirable, which can improve the sensitivity, accuracy, and reliability via self-calibration. Herein, a nanoscale dual-emission multivariate 5-5-Eu/BPyDC@MOF-253-NH2 was synthesized by sequential mixed-ligand self-assembly and postsynthesis method. Among the two emission bands of 5-5-Eu/BPyDC@MOF-253-NH2, the strong blue emitting derived from ligands is sensitive to hypochlorite, while the red emitting derived from Eu(III) almost keeps invariable. Therefore, 5-5-Eu/BPyDC@MOF-253-NH2 was exploited as a fluorescent ratiometric nanosensor for "on-off" sensing of hypochlorite. Notably, the proposed sensing system showed an excellent performance including fast response (within 15 s), relative high specificity, wide linear range (0.1-30 μM), and low detection limit (0.094 μM). Besides, the suppressed blue emitting was recovered after the addition of ascorbic acid (AA) that consumes ClO- via the redox reaction. Therefore, 5-5-Eu/BPyDC@MOF-253-NH2 was further employed as a fluorescent ratiometric nanosensor for the "on-off-on" sensing of AA. This work represents the first MOF-based fluorescent "switch" for the ratiometric sensing of hypochlorite and the second for ratiometric sensing of AA.
TL;DR: N nanocomposites of g-C3N4@Ni-Ti layered double hydroxides with high surface areas were synthesized through an optimized hydrothermal method, in the presence of NH4F and outperform their pure g-N4 and Ni-Ti LDH components in photocatalytic degradation of AMX under visible light irradiation.
Abstract: Pollution of water resources by antibiotics is a growing environmental concern. In this work, nanocomposites of g-C3N4@Ni–Ti layered double hydroxides (g-C3N4@Ni–Ti LDH NCs) with high surface areas...
TL;DR: A facile strategy to use the polyhedral Zif-8 as a precursor for synthesizing ZIF-8-derived hybrids with different components and morphologies paves a new way in developing superior active materials in energy storage conversion etc.
Abstract: Great efforts on metal-organic framework (MOF) derived nanostructures have been devoted to modulating the compositional and structural complexities to enhance performance in various applications. However, a facile method that can simultaneously manipulate the structures of the MOF-derived material and the chemical component remains a considerable challenge. Here we report a facile strategy to use the polyhedral ZIF-8 as a precursor for synthesizing ZIF-8-derived hybrids with different components and morphologies. The synthesis involves the preparation of ZIF-8 MOF templates and sequential covering of the ZIF-8 with a interlayer of silica and then polydopamine-Ni2+ (PDA-Ni2+) and carbonizing at different high temperatures under a nitrogen atmosphere, finally leading to ZIF-8-derived hybrids with different components and structures. In the whole process, the preliminary ZIF-8 precursor play a crucial role in the morphology and structure of the final carbonized products, which can be considered as templates for silica coating and precursors of N-doped carbon layer and Zn species. We also found that the SiO2 interlayer coating is a crucial procedure for the formation of yolk-shell structured ZIF-8@SiO2@PDA-Ni2+ composites. Owing to the uniformly distributed Ni NPs and unique structures of the composites, the as-prepared Ni-based composites show high performance in the catalysis of 4-nitrophenol as well as enrichment of histidine-rich proteins. In addition, this proposed strategy for the controllable design and synthesis of ZIF-8-derived nanocomposites paves a new way in developing superior active materials in energy storage conversion etc.
TL;DR: Interestingly, an unparalleled luminescence-silent system CrO42-@Cd-MOFs was successfully fabricated by postsynthetic modification of metal-organic frameworks and represents a highly selective and sensitive turn-on luminescent responding to ascorbic acid.
Abstract: A unique three-dimensional luminescent metal-organic framework (Cd-MOFs), [Cd(tpbpc)2]·2H2O·DMF (Htpbpc = 4'-[4,2';6',4″]-terpyridin-4'-yl-biphenyl-4-carboxylic acid; DMF = dimethylformamide), was synthesized and structurally characterized; it exhibits excellent luminescent property and structural stability in aqueous solutions. Interestingly, an unparalleled luminescence-silent system CrO42-@Cd-MOFs was successfully fabricated by postsynthetic modification of metal-organic frameworks. This luminescence-silent system represents a highly selective and sensitive turn-on luminescent responding to ascorbic acid. First, this advanced fluorescent sensor displays excellent performance for CrO42- ions with a quenching of fluorescence intensity originating from fluorescence resonance energy transfer (FRET) mechanism. What's more, the fluorescent intensity of CrO42-@Cd-MOFs system can be recovered (turn-on) for sensing ascorbic acid because of the elimination of FRET process. Such a novel fabrication strategy should offer the guidance to develop various MOFs-implicated luminescence-silent systems as "turn-on" sensors for detection of specific chemicals.
TL;DR: It is revealed that replacement of Cs with Rb can offer reasonable flexibility in optoelectronic properties matching for solar cell design and optimization, while X anion exchange gives rise to large changes.
Abstract: Using density functional theory calculations, we explore the structural, electronic, and optical properties of the inorganic Ge-based halide perovskites AGeX3 (A = Cs, Rb; X = I, Br, Cl) that can possibly be used as light absorbers. We calculate the lattice parameters of the rhombohedral unit cell with an R3 m space group, frequency-dependent dielectric constants, photoabsorption coefficients, effective masses of charge carriers, exciton binding energies, and electronic band structures by use of PBEsol and HSE06 functionals with and without SOC effect. We also predict the absolute electronic energy levels with respect to the external vacuum level by using the (001) surfaces with AX and GeX2 terminations, demonstrating their strong dependence on the surface terminations. The calculated results are found to be in reasonable agreement with the available experimental data for the cases of CsGeX3, while for the cases of RbGeX3 they are predicted for the first time in this work. We reveal that replacement of Cs with Rb can offer reasonable flexibility in optoelectronic properties matching for solar cell design and optimization, while X anion exchange gives rise to large changes.