Rational Design of MIL-68(In) Derived Multiple Sulfides with Well Confined Quantum Dots and the Promoted Photocatalytic Hydrogen Generation.

Quantum dots (QDs) of metal sulfides were proven to be excellent cocatalysts in visible-light-driven photocatalytic reactions. Metal organic frameworks (MOFs) possess a 3D porous channel that effectively confines small QDs and preserves their high catalytic activity by preventing their aggregation. In order to precisely construct the ternary metal sulfides of ZnS/ZnIn2S4/In2S3 with well-maintained Zn-AgInS2 (ZAIS) QDs, an in situ sulfurization combining a subsequent Zn(II)-exchange strategy was employed in this work. First, the ZAIS QDs were incorporated into MIL-68(In), which were then used as the precursors to precisely construct the ternary metal sulfides of ZnS/ZnIn2S4/In2S3 with well maintained ZAIS QDs through an in situ sulfurization combining subsequent Zn(II)-exchange strategy. When the optimized nanocomposites (QDs@M-t-Zn, where t is the sulfurization time) were applied in visible light-induced photocatalytic hydrogen generation, the resulting QDs@M-24h-Zn showed a significantly improved hydrogen evolution rate of 448.96 µmol g-1 h-1, which values are clearly higher than those of MIL-68(In), QDs@MIL-68(In), and M-24h-Zn without the presence of ZAIS QDs. To elucidate the increased photocatalytic mechanism, the optical patterns and the batch electrochemical investigations were combined. It has been discovered that the matching band potentials and the close contact heterojunction enhance interface charge transfer, which in turn encourages photocatalytic hydrogen production. This study demonstrates the well-thought-out design of the uniform confinement architecture inherited from MOF QD-assisted multinary metal sulfides photocatalysts.

Multi-component carbon-based composites containing high crystallinity NiBDC as high-performance electrodes for supercapacitors.

Herein, we propose a strategy combining in situ sol-gel hydrothermal growth and annealing treatment for preparing multi-component carbon-based composites with high crystallinity of NiBDC (C-Ni/NiO/NiBDC). The C-Ni/NiO/NiBDC can be used by both positive and negative materials to build a supercapacitor that shows superior capacitance over the wide potential range of 0-1.8 V, resulting from the high crystallinity of NiBDC and synergistic effect of NiBDC, Ni and NiO, as well as their mutual intimate interfacial contact.

Interface synthesis of Cu-BTC/PVDF hybrid membranes and their selective adsorption activity toward Congo red.

Considering the surface affinity of MOFs and separation advantages of polymer membranes, herein, a one-step interface synthesis strategy is used in the construction of Cu-BTC/PVDF hybrid membranes, in which Cu2+ ions and 1,3,5-benzenetricarboxylic acid (H3BTC) were dissolved in ionized water and n-octanol separately, and polyvinylidene fluoride (PVDF) films were laid at the interface of two immiscible solvents. As a result, Cu-BTC was generated and readily self-assembled inside the PVDF films. Scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA) and the Brunauer-Emmett-Teller (BET) method were used to characterize Cu-BTC/PVDF hybrid membranes, and Congo red (CR) was selected as the target dye to evaluate the surface adsorption activity of the hybrid membranes. Batch adsorption tests under various conditions were conducted to optimize the adsorption capacity, adsorption kinetics, isotherms and thermodynamics, which were analyzed to further explore the adsorption behavior. Based on this, the adsorption mechanism was discussed. It is worth noting that because of the π-π stacking interaction and hydrogen bonding, an extraordinary adsorption capacity of CR was achieved, and the good separation advantage and the cyclic adsorption performances endow the resulting Cu-BTC/PVDF hybrid membranes with promising applications in the removal of organic dyes from practical wastewater.

Co-adsorption and Fenton-like oxidation in the efficient removal of methylene blue by MIL-88B@UiO-66 nanoflowers.

Development of binary MOF-on-MOF heterostructures is a research hotspot in MOFs chemistry due to the advantages elicited by a closely connected interface, which may endow more abundant functionality and even broader applications in interface chemistry. A MOF-on-MOF heterostructure was constructed by in situ growth of MIL-88B on the outer surface of UiO-66. The resultant MIL-88B@UiO-66 produced had an interesting flower-like morphology composed of MIL-88B (petal) on tetrahedral UiO-66 (core). The MIL-88B@UiO-66 heterostructure showed adsorption and Fenton-like oxidation abilities, with distinctly improved structural stability in aqueous solution compared with that of single MIL-88B. Methylene blue (MB) was selected as the target molecule to evaluate the adsorption and Fenton-like oxidation activities. The efficiency of total removal of MB was studied systematically under various operating conditions and the influencing factors were optimized. The kinetics of adsorption and catalytic oxidation were simulated to explore the interactions between MB and MIL-88B@UiO-66. The mechanisms of enhanced adsorption and Fenton-like oxidation were suggested. The cyclic removal performance and structural stability of MIL-88B@UiO-66 were also determined.

Construction of Ni3+-rich nanograss arrays for boosting alkaline water oxidation.

The rational design of high-efficiency electrocatalysts for application in water oxidation in alkaline media remains a great challenge. In this paper, Ni3+-rich nanograss-like Mo-doped Ni3S2/NiS/VS arrays grown on nickel foam (denoted as Mo-NiVS@NF) have been successfully constructed through a hydro/solvothermal method. Interestingly, Mo-NiVS@NF exhibits superior catalytic OER performance, needing an overpotential of 217 mV to drive a current density of 10 mA cm-2, outperforming most previously reported NiS-based electrocatalysts. The result indicates that the Ni3+-rich active sites caused by the modulation of the electronic structure environment via the introduction of V and high-valency Mo play an important role in the high activity for the OER. Moreover, this catalyst shows high long-term electrochemical durability.

Nanosized CuO encapsulated Ni/Co bimetal Prussian blue with high anti-interference and stability for electrochemical non-enzymatic glucose detection.

Non-enzymatic glucose sensors based on metal oxides are receiving remarkable attention owing to their outstanding characteristics of being easy-to use, low cost, and reusability. However, the disadvantage of weak anti-interference associated with poor selectivity significantly restricts their applicability. Herein, we report a two-step in situ fabrication of nanosized CuO encapsulated Ni/Co bimetal Prussian blue (PB) with a typical core-shell structure, which can be efficiently used for non-enzymatic glucose detection, ascribing to the permeability and abundant active sites of out-shelled crystalline porous Ni/Co PB and the high catalytic activity and conductivity of embedded CuO nanoparticles, afforded by their mutual synergistic interactions. The glassy carbon electrode modified with the hybrid of the CuO-encapsulated Ni/Co PB (simplified as the Ni/Co-PB/CuO/GCE electrode) exhibited a high glucose sensitivity of 600 µA mM-1 cm-2 with a low detection limit of 0.69 µM (S/N = 3), a fast response time (less than 3 s), and excellent long-term stability. In addition, the CuO-encapsulated Ni/Co PB showed favorable anti-interference ability in the presence of ascorbic acid (AA), L-lysine (Lys), dopamine (DA), cysteine (Cys), dopamine (DA), and KCl interferences. The reusability and long-term stability, as well as the practicability of the Ni/Co-PB/CuO/GCE sensing electrode verified by testing real serum samples were also investigated, and the experimental results demonstrated the applicability of the core-shell NiCo-PB/CuO based flexible electrochemical sensor for non-enzymatic glucose sensing in practical applications.

Synergistic adsorption and photocatalytic degradation of persist synthetic dyes by capsule-like porphyrin-based MOFs.

The synergistic effects involving surface adsorption and photocatalytic degradation commonly play significant roles in the removal of persistent synthetic organics from wastewater in the case of porous semiconductors. Inspired by the visible-light harvesting advantages of porphyrin-based MOFs, a capsule-like bimetallic porphyrin-based MOF (PCN-222(Ni/Hf)) has been successfully constructed through a facile hydrothermal method. In which, the Hf (IV) ions were exactly bonded to the carboxyl groups substituted on the porphyrin rings, meanwhile the Ni (II) ions were finely bonded to the -N inside the porphyrin rings. The adsorption/photocatalytic performances were assessed by using four persistent dyes including rhodamine B (RhB), basic violet 14 (BV14), crystal violet, and acid black 210 (AB210) as the target substances, and enhanced total removal efficiency was obtained by the bimetallic PCN-222(Ni/Hf) in comparison with that of single PCN-222(Hf). The electrochemical analyses and the sacrificial agent capture experiments were carried out to elucidate the photocatalytic mechanism, and the adsorption/photocatalytic stability of PCN-222(Ni/Hf) is also investigated. The work has broadened the applications of porphyrin-based MOFs in the removal of organics by combining their excellent surface adsorption capacity and photocatalytic activities.

A hierarchical hollow Ni/Co-functionalized MoS2 architecture with highly sensitive non-enzymatic glucose sensing activity.

A hierarchical hollow Ni/Co-codoped MoS2 architecture was successfully prepared using a Ni/Co Prussian Blue analogue as the precursor followed by the solvothermal-assisted insertion of MoS42- and extraction of [Co(CN)6]3- at 200 °C for 32 h. The obtained Ni/Co-codoped MoS2 composite exhibited a hollow microcubic structural characteristic, and the morphology, structure, and chemical compositions were carefully characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS), respectively. The Ni/Co-codoped MoS2 composite used as an electrode material featured excellent glucose sensing activity and a high sensitivity of 2546 µA mM-1 cm-2 with a relatively low detection limit of 0.69 µM (S/N = 3). In addition, the Ni/Co-codoped MoS2 composite showed good anti-interference sensing performance in the presence of ascorbic acid (AA), lysine (Lys), cysteine (Cys), urea, H2O2, KCl, and other interferents. These experimental results revealed that the composite is a promising electrode material for enzyme-free glucose sensing, and the feasible synthetic strategy may provide an effective and controlled route to prepare other multi-metal substituted sulfide-based hierarchical structures with high electrochemical sensing performance.

Selective adsorption of malachite green (MG) and fuchsin acid (FA) by ZIF-67 hybridized polyvinylidene fluoride (PVDF) membranes.

MOF/polymer hybrid membranes integrate the surface activity of MOFs and the advantages of PVDF membranes, and can be used as adsorption membranes in the efficient removal of target organics. In this work, a new hybrid membrane of ZIF-67/PVDF with varying ZIF-67 dosages has been fabricated through a facile mechanical blending followed by a lyotropic phase transition. Methods including field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), FT-IR analyses and surface hydrophobicity/hydrophilicity measurements are applied to characterize the structure, physicochemical properties and membrane performances. Two synthetic triarylmethane dyes, cationic malachite green (MG) and anionic fuchsin acid (FA), are chosen as the main adsorption targets to evaluate the adsorption capacities of the resulting ZIF-67/PVDF hybrid membranes. Interestingly, all of the ZIF-67/PVDF hybrid membranes exhibit distinctly favorable efficiencies and selectivities toward MG and FA compared to pristine PVDF, which proves the positive roles of ZIF-67 in the adsorption ability of the hybrid membranes. The adsorption conditions are optimized and the adsorption kinetics and thermodynamics are analysed to study the adsorption mechanism. The reusability and the structural stability of the hybrid membranes undergoing cyclic adsorption processes are also discussed. To the best of our knowledge, this is the first time that good adsorption capacities for MG and FA for these MOF/PVDF membranes have been reported. This work highlights the prospective applications of MOF/PVDF hybrid membranes in the rapid and effective removal of target organics in the treatment of waste water.

CdS/Ag2S/g-C3N4 ternary composites with superior photocatalytic performance for hydrogen evolution under visible light irradiation.

CdS/Ag2S/g-C3N4 ternary composites as photocatalysts with different amounts of Ag2S were successfully synthesized through a simple chemical deposition method. These photocatalysts were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX) mapping and X-ray photoelectron spectroscopy (XPS) to obtain the information of the structure and composition. Compared with the pure samples and binary composites, CdS/Ag2S/g-C3N4 ternary composites showed enhanced hydrogen production activities, and the maximum hydrogen production rate of CdS/Ag2S(2%)/CN is about 1020.54 µmol g-1 h-1 in Na2S-Na2SO3 solution. Based on the photoluminescence and electrochemical results, the improved photocatalytic activity could be attributed not only to the synergic effect of ternary components in the composite, but also to the introduction of Ag2S that provided abundant active sites for H2 production. A possible mechanism was investigated in detail.

Yolk-shell (Cu,Zn)Fe2O4 ferrite nano-microspheres with highly selective triethylamine gas-sensing properties.

Multicomponent spinel ferrites are essential to be used in high-performance gas-sensing materials. Herein, multinary (Cu,Zn)Fe2O4 spinel nano-microspheres with tunable internal structures, including solid, core-shell, and yolk-shell, were successfully synthesized by a simple self-templated solvothermal method combined with a subsequent annealing strategy. The internal structures of the (Cu,Zn)Fe2O4 nano-microspheres significantly rely on the heating rates of the precursors, which show promising selective response towards trimethylamine gas. Among them, the as-formed yolk-shell (Cu,Zn)Fe2O4 nano-microspheres exhibited high response to triethylamine with excellent selectivity of STEA/SX = 1.86 at 160 °C, fast response-recovery rate (58 s/136 s), and long-term repeatability and stability of more than one month. The corresponding triethylamine gas-sensing mechanism with the special microstructures is discussed. This work provides new insights into the rational design of interior structure and the modulation of high gas response and selectivity of multinary spinel ferrites in gas-sensing applications.

Synergetic Effect of Tetraethylammonium Bromide Addition on the Morphology Evolution and Enhanced Photoluminescence of Rare-Earth Metal-Organic Frameworks.

Controlled synthesis of rare-earth metal-organic frameworks (RE-MOFs) is of great significance to match their emerging multifunctional luminescence applications. Herein, we propose a green and general solvent-free synthetic strategy for the adjustment of morphology and dimension of various RE-MOFs (RE = Eu, Tb, Er, Dy, Y, Tm) by using a tetraethylammonium bromide-assisted thermal-heating method. These self-assembled RE-MOF materials possess controllable morphologies and hierarchical structures while retaining the structural topology of MIL-78, proving that the strategy is a feasible and effective way in opening up large-scale synthesis of RE-MOFs. It is further found that the tetraethylammonium could be carbonized into carbon dots and encapsulated in Eu/Tb-MIL-78 to enhance the fluorescence emission intensities significantly, making the hierarchical Eu/Tb-MIL-78 MOF materials good candidates for the latent fingerprints recognition application. This work provides a novel strategy for effectively controlling the morphology and dimension of RE-MOFs materials with enhanced photoluminescence and has great potential in their scaling-up syntheses and exploring the new luminescence applications.

A facile synthesis of a ZIF-derived ZnS/ZnIn2S4 heterojunction and enhanced photocatalytic hydrogen evolution.

A facile synthetic route, by using rhombic dodecahedral zeolitic imidazolate framework-8 (ZIF-8) as the structure template, is devoted to fabricating the ZnS/ZnIn2S4 hybrid heterojunction; the compact heterostructure was produced by combining the sulfurization of ZIF-8 and the in situ precipitation of ZnIn2S4 in one pot. The resulting ZnS nanoparticles of about 100 nm were uniformly dispersed in the folds of flower-like ZnIn2S4, whose structure is beneficial for charge transfer at the heterointerface. The additional quantities of ZIF-8 are varied to find an optimum ratio of the two components to obtain the best photocatalytic activity. In the photocatalytic hydrogen generation irradiated by simulated solar light, all the ZnS/ZnIn2S4 hybrid photocatalysts displayed improved hydrogen production rates compared to single ZnS or ZnIn2S4, and the best hydrogen production rate of 453.4 µmol h-1 g-1 is obtained by ZnS/ZIS-20, whose value is approximately 4 times higher than that of single ZnIn2S4. The electrochemical properties of the ZnS/ZnIn2S4 hybrid photocatalysts were measured to explore the charge transfer mode at the interface, and the band structure and enhanced photocatalytic hydrogen generation mechanism have been proposed. The excellent recycling properties of hydrogen production indicated the prospective applications of this kind of ZIF-derived metal sulfide in photocatalytic reactions.

Exerting Spatial Control During Nanoparticle Occlusion within Calcite Crystals.

In principle, nanoparticle occlusion within crystals provides a straightforward and efficient route to make new nanocomposite materials. However, developing a deeper understanding of the design rules underpinning this strategy is highly desirable. In particular, controlling the spatial distribution of the guest nanoparticles within the host crystalline matrix remains a formidable challenge. Herein, we show that the surface chemistry of the guest nanoparticles and the [Ca2+ ] concentration play critical roles in determining the precise spatial location of the nanoparticles within calcite crystals. Moreover, in situ studies provide important mechanistic insights regarding surface-confined nanoparticle occlusion. Overall, this study not only provides useful guidelines for efficient nanoparticle occlusion, but also enables the rational design of patterned calcite crystals using model anionic block copolymer vesicles.

Construction of an Aminated MIL-53(Al)-Functionalized Carbon Nanotube for the Efficient Removal of Bisphenol AF and Metribuzin.

A versatile organic-inorganic hybrid structure makes a metal-organic framework (MOF) an outstanding host for different kinds of guests; in addition, its easy pyrolysis nature has been proven to be useful as precursors in the construction of carbon-based materials with a special porous structure. Herein, a novel porous composite nanostructure of an aminated MIL-53(Al)@carbon nanotube (CNT) has been successfully constructed for the first time based on in situ synthesis combining the pyrolysis of ZIF-67. The resulting composite nanostructure was performed by the means of scanning electron microscopy, Brunauer-Emmett-Teller analysis, typical and high-resolution transmission electronic microscopy, X-ray photoelectron spectroscopy, etc. The results showed that a compact heterostructure has been formed between an aminated MIL-53(Al) and a CNT. The resulting composites, named N-MIL@CNT, represent distinct promoted activities in the removal of Bisphenol AF (BPAF) and Metribuzin from wastewater, and the maximum adsorption values were 274 mg/g (BPAF) and 213 mg/g (Metribuzin), which are larger than the results obtained by other MOF-based nanomaterials. The adsorption isotherm, kinetics, and thermodynamics were studied in detail, and the selective adsorption mechanism was also suggested. The excellent selectivity, reusability, and structure stability suggest the potential application of this composite nanostructure in the selective removal of BPAF or Metribuzin from the practical wastewater.

Ionothermal synthesis of a photochromic inorganic-organic complex for colorimetric and portable UV index indication and UVB detection.

Extended exposure to sunlight or artificial UV sources (particularly UVA and UVB) is a major cause of serious skin cancers and ocular diseases. A photochromic inorganic-organic complex was ionothermally synthesized via a decomposition-reassembly strategy, generated from a low-cost deep-eutectic solvent and a 4,4'-bipyridine system. Benefiting from the intrinsic synergy of the hydrogen bonding and π-π stacking interactions, the complex exhibited insensitivity towards visible light, outstanding color contrast from colorless to purple, rapid response time up to seconds, excellent reversibility and high thermal stability. UV index and UVB detection procedures indicated that the coloration performances of the complex exhibited a linear response towards UV index and UVB dose. Besides, the complex can be made to a portable test tablet, a freestanding mixed film with a cellulose paper and a mixed-matrix membrane with PVDF, which make it highly promising for portable and efficient visual UV index and detecting UVB dose.

Surface functionalization of MIL-101(Cr) by aminated mesoporous silica and improved adsorption selectivity toward special metal ions.

Developing novel solid adsorbents with high efficiency and excellent selectivity is always an important target in the removal of toxic metal ions from waste water. In this study, a composite nano-adsorbent NH2-mSiO2@MIL-101(Cr) has been fabricated and applied in the efficient removal of Pb(ii) and Cr(vi) for the first time. The nanocomposites were characterized by using field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), fourier-transform infrared (FT-IR) spectroscopy and thermal gravimetry analysis (TG). The results indicate that a typical core@shell structure has been fabricated by fully coating a mesoporous SiO2 shell over the micro/mesoporous MIL-101(Cr). As a result, the surface charge and the zeta potentials change significantly. Two toxic metal ions, namely, Pb(ii) and Cr(vi) were chosen as the main adsorption targets to evaluate the surface adsorption activities. The adsorption conditions were optimized, the influences of other coexisting ions were explored, and the adsorption selectivity was investigated. Interestingly, the NH2-mSiO2@MIL-101(Cr) nanocomposites display a prominent adsorption activity compared with the original MIL-101(Cr) and non-aminated mSiO2@MIL-101(Cr) and excellent selectivity toward Pb(ii) in the presence of other divalent metal ions. The adsorption kinetics and adsorption thermodynamics were simulated accordingly, and the enhanced adsorption mechanism was also suggested. The good reusability and adsorption selectivity of the NH2-mSiO2@MIL-101(Cr) suggest their potential applications in the selective removal of special metal ions such as Pb(ii) from the waste water.

Controlled Synthesis of Porous Hierarchical ZnFe2O4 Micro-/Nanostructures with Multifunctional Photocatalytic Performance.

Engineering semiconductors with porous hierarchical micro-/nanostructures is a feasible strategy to obtain high solar-light utilization efficiency and strong photocatalytic performance. In this work, an integrated strategy of solvent evaporation and morphology-inherited annealing for the Fe-based metal-organic framework was developed to prepare the hierarchical spinel zinc ferrite (ZnFe2O4) micro-/nanostructure. The morphology and porosity of the hierarchical ZnFe2O4 structures can be adjusted by optimizing the annealing temperatures. Benefitting from magnetic separation performance, these highly visible light-responsive hierarchical ZnFe2O4 micro-/nanostructures are demonstrated to be multifunctional photocatalytic materials, and their photocatalytic activity and reproducibility were analyzed, and the photocatalytic mechanism was also investigated. This work provides a controlled and generic route for constructing novel hierarchical semiconductors with specific compositions and intriguing structures.

Magnetic carboxyl functional nanoporous polymer: synthesis, characterization and its application for methylene blue adsorption.

Magnetic carboxyl functional nanoporous polymer (MCFNP) was chemically fabricated by incorporation of magnetic Fe3O4 precursor into the carboxyl functional nanoporous polymer (CFNP). The as-synthesized MCFNP was characterized and used as an adsorbent for rapid adsorption removal of methylene blue (MB) from wastewater. Several experimental parameters affecting the adsorption efficiency were investigated including initial pH, adsorbent dosage, initial MB concentration, contact time and temperature. The adsorption behavior of MCFNP displayed that adsorption kinetics and isotherms could be well fitted to the pseudo-second-order and Langmuir models, respectively. The experimental results showed that MCFNP was an effective adsorbent with a maximum adsorption capacity of 57.74 mg g-1 for MB at 298 K. The negative free energy (ΔG) and positive enthalpy change (ΔH) confirmed that the adsorption reaction was a spontaneous and endothermic process. In addition, ethanol was used as an effective extractant for the regeneration of MCFNP, and the adsorption efficiency could remain 80% after the ninth regeneration cycle.

Immobilization of lysozyme proteins on a hierarchical zeolitic imidazolate framework (ZIF-8).

A hierarchical zeolitic imidazolate framework-8 (micro/meso-ZIF-8) was fabricated by using cetyltrimethylammonium bromide as a structure-controlling agent and l-histidine as co-templates. Compared to the conventional microporous ZIF-8 (micro-ZIF-8), the hierarchical porous structure of micro/meso-ZIF-8 contains micropores and maximum mesopores of around 35.6 nm. The as-prepared hierarchical micro/meso-ZIF-8 featured a large surface area and superior spontaneous adsorption activity than micro-ZIF-8 towards lysozyme (LZM), bovine hemoglobin (BHb) and bovine serum albumin (BSA), and the adsorption capacity increased with the decreasing of the protein size due to the molecule cutoff effects. The maximum adsorption capacity of LZM on micro/meso-ZIF-8 was higher than most of the reported results under similar adsorption conditions. The analyses of adsorption kinetics and thermodynamics implied that the adsorption mechanism mainly involved physical adsorption. Moreover, the micro/meso-ZIF-8 showed good thermal stability against temperature and excellent regeneration ability in the recycling adsorption experiments. This work proposed herein opens a broad application prospect of hierarchical MOFs in biological molecule separation, immobilization and enrichment.