Copper Benzene Tricarboxylate Research Articles

Solvothermal Synthesis of Cu3(BTC)2 Metal Organic Framework

For the last two decades the research with Metal Organic Framework (MOF) is proving to be most fruitful, due to their crystalline-inorganic hybrid material with uniform porous structure, high environmental stability and tuneable matrices. With these unique properties of MOFs material have vast applications in storage, chemical separation, catalysis, drug delivery. In present investigation we have reported the chemical synthesis of copper benzenetricarboxylate. In Teflon-lined stainless-steel autoclave at 80oC for 20hr. The resulting Copper benzenetricarboxylate (Cu-BTC) is further characterised by Fourier Transform Infrared Spectroscopy and X-ray diffraction (XRD)

Enhanced detection of heavy metal ions using Ag nanoparticles and single-walled carbon nanotubes within Cu-based metal-organic frameworks

Heavy metal ions (HMIs) are major water pollutants, and their toxicity for humans is a great concern for scientists and environmentalists. They are harmful to health even at trace levels; therefore, identifying and removing heavy metals from water is critical. Herein, we report highly selective and sensitive multi-analyte detection of HMIs in water using an electrochemical sensor probe based on Ag nanoparticles and single-walled carbon nanotubes incorporating copper benzene tri-carboxylate metal–organic frameworks (Ag/SWNTs@CuBTC-MOFs). The materials were characterized using FTIR, XPS, XRD, and FE-SEM with EDX mapping, TEM, TG-DTA, BET surface area, CV, and EIS. The Ag/SWNTs@CuBTC-MOF electrochemical sensor was tested by differential pulse voltammetry over a pH range of 3–10 for various HMIs. It shows high pH-dependent sensitivity towards Hg2+ (pH-5.0), Ni2+ (pH-7.0), and Fe3+ (pH-10.0) ions and a limit of detection of 1.39 nM, 2.6 nM, and 3.03 nM, respectively. The fabricated sensor probe exhibits high selectivity, good linearity, and a limit of detection below the maximum contamination limit, as the US Environmental Protection Agency suggested.

Single-Walled Carbon Nanotubes-Copper Metal-Organic Framework Composite for the Sensitive Detection of Lead Ions in Aqueous Solutions

Lead (Pb) is a hazardous heavy metal extensively employed in various industrial applications, often resulting in the presence of its ionic form (Pb2+) in water resources. Due to its profound toxicity to humans and the environment, the reliable detection and removal of Pb2+ ions from water are imperative. In this study, we have successfully synthesized a composite material consisting of single-walled carbon nanotubes (SWNTs) incorporated into a copper-based metal-organic framework (MOF) known as copper benzene tricarboxylate (CuBTC). This composite denoted as SWNTs@CuBTC, was synthesized via a solvothermal route. Comprehensive characterizations, including Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) with energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET) surface area analysis, and thermogravimetric analysis (TGA), were conducted to elucidate its structural and morphological properties. Electrochemical assessments, specifically cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were carried out to evaluate the electrochemical behaviour of the SWNTs@CuBTC composite. Subsequently, a sensor utilizing SWNTs@CuBTC was constructed by modifying glassy carbon electrodes (GCE) through a drop-casting technique. The sensing capabilities of this sensor were systematically examined using the differential pulse voltammetry (DPV) technique. Our sensor exhibited exceptional sensitivity towards Pb2+ ions, with a remarkable limit of detection (LOD) of 25 nM and a sensitivity of 0.1499 μA/nM, showcasing its potential for highly sensitive detection of Pb2+ ions in aqueous solutions.

Surface modification of Cu2O with stabilized Cu+ for highly efficient and stable CO2 electroreduction to C2+ chemicals

Copper (Cu)-based materials are known as the most attractive catalysts for electrochemical carbon dioxide reduction reaction (CO2RR), especially the Cu+ species (e.g., Cu2O), which show excellent capability for catalyzing CO2 to C2+ chemicals because of their unique electronic structure. However, the active Cu+ species are prone to be reduced to metallic Cu under an electroreduction environment, thus resulting in fast deactivation and poor selectivity. Here, we developed an advanced surface modification strategy to maintain the active Cu+ species via assembling a protective layer of metal–organic framework (copper benzenetricarboxylate, CuBTC) on the surface of Cu2O octahedron (Cu2O@CuBTC). It's encouraging to see that the Cu2O@CuBTC heterostructure outperforms the bare Cu2O octahedron in catalyzing CO2 to C2+ chemicals and dramatically enhances the ratio of C2H4/CH4 products. A systematic study reveals that the introduced CuBTC shell plays a critical role in maintaining the active Cu+ species in Cu2O@CuBTC heterostructure under reductive conditions. This work offers a practical strategy for improving the catalytic performance of CO2RR over copper oxides and also establishes a route to maintain the state of valence-sensitive catalysts.

Direct detection of TNF-α by copper benzene tricarboxylate MOFs/gold nanoparticles modified electrochemical label-free immunosensor using FFT admittance voltammetry

A new simple label-free electrochemical immunosensor was designed for sensitive and selective determination of tumor necrosis factor-alpha (TNF-α), through gold nanoparticles (GNPs) incorporated copper benzene tricarboxylate metal organic frameworks (HKUST-1) modified gold electrode, where TNF-α specific monoclonal antibody was bonded to the electrode surface through shaped self-assembled monolayer (SAM) of mercapto compounds. The fabrication steps were monitored by field emission scanning electron microscopy (FE-SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Under optimized experimental conditions, fast Fourier transform admittance voltammetry (FFTADV) used for TNF-α measurement. A wide linear range of current response towards the TNF-α concentration from 0.0005 to 50 ng/mL and LOD value of 0.15 pg/mL were achieved using FFTADV. The described immunosensor had adequate sensitivity and selectivity towards direct determination of TNF-α in complex biological matrix.

Metal‐Organic‐Framework‐Based Electrochemical Nanosensor for Hydrogen Peroxide

AbstractElectrochemical applications of metal organic frameworks (MOFs) are of considerable current interest. Due to the large surface area exposed to solution, MOFs are potentially useful electrode materials for sensing inner‐sphere analytes, such as reactive oxygen species. Herein, we electrodeposited copper benzene tricarboxylate MOF (HKUST‐1) into the cavity of an open carbon nanopipette (CNP) to produce a CNP‐MOF nanoelectrode. Unlike electronically conductive metal or carbon electrodes, the electrochemical response of CNP–MOFs relies on oxidation/reduction of Cu(I)/Cu(II) nodes in the porous nanostructure. Nevertheless, sigmoidal steady‐state voltammograms with a well‐defined plateau current have been recorded for simple redox mediators, for example, ferrocenemethanol. A linear calibration curve obtained for the hydrogen peroxide reduction suggests that CNP–MOFs can potentially be useful as nanosensors for peroxide.

Simulation and Experimental Studies of Size Effects on Plasmonic Gas Sensing with Nanohole Arrays

Simulation and Experimental Studies of Size Effects on Plasmonic Gas Sensing with Nanohole Arrays

Electrocatalytic detection of l-cysteine using molybdenum POM doped-HKUST-1 metal organic frameworks

Glass carbon electrodes (GCE) were modified with metal organic frameworks (MOFs) containing molybdenum polyoxometallates (Mo POMs) in a copper benzene tricarboxylate framework (HKUST-1). The Mo POMs were introduced via one-pot synthesis (Mo2) and post-synthetic modification (Mo1) techniques. The electrode modifiers were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and thermal analysis. The modified electrodes’ oxidation capacity toward l-cysteine was studied. Mo POMs significantly improved electron transfer kinetics compared to the bare GCE. The best Mo POM doped electrode (Mo1-GCE) had a catalytic rate constant of 2.2 × 104 M−1 s−1 and a limit of detection of 3.07 × 10−7 M. Under the employed experimental conditions, the detection response for l-cysteine was very fast (within 0.1 s) for all the modified electrodes and selective toward l-cysteine in the presence of other amino acids.

Detection of Pb(II): Au Nanoparticle Incorporated CuBTC MOFs.

In the present investigation, copper benzene tricarboxylate metal organic frameworks (CuBTC MOF) and Au nanoparticle incorporated CuBTC MOF (Au@CuBTC) were synthesized by the conventional solvothermal method in a round bottom flask at 105°C and kept in an oil bath. The synthesized CuBTC MOF and Au@CuBTC MOFs were characterized by structure using X-ray diffraction (XRD) spectroscopic methods including Fourier Transform Infrared spectroscopy, Raman Spectroscopy, X-ray Photoelectron Spectroscopy (XPS), and Energy dispersive spectroscopy (EDS). We also characterized them using morphological techniques such as Field emission scanning electron microscopy (FE-SEM), and electrochemical approaches that included cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). We examined thermal stability by thermogravimetric analysis (TG/DTA) and N2 adsorption—desorption isotherm by Brunauer-Emmett-Teller (BET) surface area method. Both materials were tested for the detection of lead (II) ions in aqueous media. Au nanoparticle incorporated CuBTC MOF showed great affinity and selectivity toward Pb2+ ions and achieved a lower detection limit (LOD) of 1 nM/L by differential pulse voltammetry (DPV) technique, which is far below than MCL for Pb2+ ions (0.03 μM/L) suggested by the United States (U.S.) Environmental Protection Agency (EPA) drinking water regulations.

Selective and sensitive detection of lead Pb(II) ions: Au/SWNT nanocomposite-embedded MOF-199

Metal organic frameworks (MOFs) are best known for their highly crystalline structures, ultrahigh porosity with considerable surface area and tunable physicochemical properties. The promising architecture of MOFs, where central metal atoms are surrounded by organic ligands secures their prominent candidature for advanced sensor technology. In this work, we have synthesized gold (Au) nanoparticles and single-walled carbon nanotube (SWNTs) nanocomposite-incorporated copper benzene tricarboxylate (MOF-199) MOF (Au/SWNTs@MOF-199) by solvothermal route. The synthesized Au/SWNTs@ MOF-199 has rigorously characterized with spectroscopic, morphological, structural, electrochemical, thermal, Brunauer–Emmett–Teller (BET) surface area using N2 adsorption isotherm methods. The proposed Au/SWNTs@MOF-199 nanocomposite exhibited excellent electrochemical characteristics and sensing performance towards Pb2+ ions. The calibration plot for the electrochemical response of Au/SWNTs@MOF-199 towards Pb2+ ions was recorded for the range of 0.1 mM–1 pM (R2 = 99.58)) with a limit of detection of 25 pM/L and a rapid response time of a few seconds with high sensitivity, selectivity, repeatability and reproducibility as determined by error bar diagram. These results indicate the significant potential of Au/SWNTs@MOF-199 nanocomposites as highly sensitive Pb2+ ion sensor.

Rapid defect engineering of UiO-67 (Zr) via microwave-assisted continuous-flow synthesis: Effects of modulator species and concentration on the toluene adsorption

Abstract Defect engineering is a promising approach for tailoring the physicochemical properties, such as stability, pore structure, and surface area, of metal–organic frameworks (MOFs). In this study, some defective Zr-based biphenyl dicarboxylate (UiO-67 (Zr)) MOFs were prepared via fast modulated synthesis under microwave-assisted continuous flow by using HCOOH, CH3COOH, CH3CH2COOH, and C6H5COOH as modulators. A surface-modified UiO-67(Zr) framework with high porosity and crystallinity could be rapidly produced in a few minutes due to the incomplete exchange between the bridging ligand and the modulator. The defect concentration in the products was tuned by controlling both the modulator species and concentrations utilized. The adsorption ability toward toluene of the prepared UiO-67(Zr) MOFs was found to be related to their structural defects; the defective UiO-67(Zr) MOF synthesized with HCOOH as the modulator exhibited the highest toluene adsorption capacity (467 mg g−1), surpassing also most of the previously reported adsorbent materials, such as zeolites, activated carbon, Zr-based dicarboxybenzene (UiO-66(Zr)), H2N-UiO-66(Zr), zeolitic imidazolates, and copper benzenetricarboxylate. Moreover, the experimental dynamic adsorption data were mathematically modeled to predict the adsorption behaviors of defective UiO-67(Zr) MOFs.

Simulated and Experimental Studies of Size Effects on Plasmonic Gas Sensing with Nanohole Arrays

Simulated and Experimental Studies of Size Effects on Plasmonic Gas Sensing with Nanohole Arrays

Field effect transistor based on proton conductive metal organic framework (CuBTC)

Metal organic frameworks (MOFs) are crystalline materials with ultrahigh porosity and tunable physico-chemical properties. But most MOFs are electrical insulators which restricts their use in electronic devices. In the present study, a field effect transistor (FET) based on a proton-conductive MOF was investigated. Imidazole was used as a proton conductor to increase the conductivity of the copper benzene tricarboxylate (CuBTC) MOF and, further, it was used to develop the FET. The CuBTC was synthesized using the traditional solvothermal method. The proton-conductive MOF was synthesized by post-modification of the CuBTC via the pore filling method using imidazole molecules, which achieved a proton conductivity of ~1.04 × 10−4 S cm−1 at 70 °C (anhydrous conditions). The proton conductive MOF was characterized by various techniques; spectroscopically by Fourier transform infrared spectroscopy, x-ray photoelectron spectroscopy, x-ray absorption spectroscopy, energy dispersive spectroscopy, alternating current (a.c.) impedance spectroscopy; thermally using thermogravimetric analysis; structurally using powder x-ray diffraction; morphologically using field emission scanning electron microscopy; electrically by FETs.

Direct Electrochemistry and Electrocatalysis of Myoglobin with Copper Benzenetricarboxylate Metal-Organic Frameworks@Nitrogen-Doped Graphene Composite Modified Electrode

Direct Electrochemistry and Electrocatalysis of Myoglobin with Copper Benzenetricarboxylate Metal-Organic Frameworks@Nitrogen-Doped Graphene Composite Modified Electrode

Enhancement of the Water Adsorptivity of Metal–Organic Frameworks upon Hybridization with Layered Double Hydroxide Nanosheets

Efficient water adsorbents with improved hydrostability can be synthesized by the hybridization of metal–organic framework (MOF) compounds with exfoliated layered double hydroxide (LDH) 2D nanosheets. The self-assembly between copper benzene tricarboxylate (Cu-BTC) MOF nanocrystals and exfoliated Mg–Al-LDH nanosheets leads to the nanoscale mixing of the MOF and LDH components, as well as to the prevention of the formation of aggregated secondary MOF particles. In the resulting nanohybrids, spherical Cu-BTC nanocrystals with small particle sizes of ∼5–10 nm are uniformly anchored on the surface of Mg–Al-LDH 2D nanosheets with the dimensions of several hundred nanometers. At the optimal composition, the surface area of the resulting nanohybrid becomes greater than that of pristine Cu-BTC, which is attributable to the suppression of the self-aggregation of MOF nanocrystals and to the formation of the mesoporous stacking structure of the LDH nanosheets. Of prime importance is that both the water adsorption ab...

Synthesis and Transport Properties of Novel MOF/PIM-1/MOF Sandwich Membranes for Gas Separation.

Metal-organic frameworks (MOFs) were supported on polymer membrane substrates for the fabrication of composite polymer membranes based on unmodified and modified polymer of intrinsic microporosity (PIM-1). Layers of two different MOFs, zeolitic imidazolate framework-8 (ZIF-8) and Copper benzene tricarboxylate ((HKUST-1), were grown onto neat PIM-1, amide surface-modified PIM-1 and hexamethylenediamine (HMDA) -modified PIM-1. The surface-grown crystalline MOFs were characterized by a combination of several techniques, including powder X-ray diffraction, infrared spectroscopy and scanning electron microscopy to investigate the film morphology on the neat and modified PIM-1 membranes. The pure gas permeabilities of He, H2, O2, N2, CH4, CO2 were studied to understand the effect of the surface modification on the basic transport properties and evaluate the potential use of these membranes for industrially relevant gas separations. The pure gas transport was discussed in terms of permeability and selectivity, highlighting the effect of the MOF growth on the diffusion coefficients of the gas in the new composite polymer membranes. The results confirm that the growth of MOFs on polymer membranes can enhance the selectivity of the appropriately functionalized PIM-1, without a dramatic decrease of the permeability.

Copper Benzenetricarboxylate Metal-Organic Framework Nucleation Mechanisms on Metal Oxide Powders and Thin Films formed by Atomic Layer Deposition.

Chemically functional microporous metal-organic framework (MOF) crystals are attractive for filtration and gas storage applications, and recent results show that they can be immobilized on high surface area substrates, such as fiber mats. However, fundamental knowledge is still lacking regarding initial key reaction steps in thin film MOF nucleation and growth. We find that thin inorganic nucleation layers formed by atomic layer deposition (ALD) can promote solvothermal growth of copper benzenetricarboxylate MOF (Cu-BTC) on various substrate surfaces. The nature of the ALD material affects the MOF nucleation time, crystal size and morphology, and the resulting MOF surface area per unit mass. To understand MOF nucleation mechanisms, we investigate detailed Cu-BTC MOF nucleation behavior on metal oxide powders and Al2O3, ZnO, and TiO2 layers formed by ALD on polypropylene substrates. Studying both combined and sequential MOF reactant exposure conditions, we find that during solvothermal synthesis ALD metal oxides can react with the MOF metal precursor to form double hydroxy salts that can further convert to Cu-BTC MOF. The acidic organic linker can also etch or react with the surface to form MOF from an oxide metal source, which can also function as a nucleation agent for Cu-BTC in the mixed solvothermal solution. We discuss the implications of these results for better controlled thin film MOF nucleation and growth.

Fabrication of the Microchannel by Metal-Organic Framework, Copper Benzenetricarboxylate

We successfully fabricated the metal-organic framework (MOF), copper benzenetricarboxylate on a microchannel system, which was able to solve the problems created by increased heat dissipation in small electronic equipment. The microchannel system was designed to make an entrance part that can control the reaction temperature, which was predicted through a heat transfer analysis and the finite element method with COMSOL Multiphysics. Synthetic conditions, synthesis time, temperature and microchannel size were systematically tuned for the selective fabrication of copper benzenetricarboxylate on a microchannel surface. Scanning electron microscope (SEM) images, selected area electron diffraction (SAED) pattern and Fourier transform infrared (FT-IR) data clearly demonstrated that copper benzenetricarboxylate was strongly adhered to the bottom surfaces of the microchannels. Moreover, the synthesis of MOF in the microchannel system provided a much faster growth rate and better crystallinity compared to a conventional synthesis method.

Metal–organic framework membranes with layered structure prepared within the porous support

A uniquely microstructured membrane, a metal–organic framework (MOF) layer within the porous support, was prepared by a counter-diffusion method. The MOF-based membrane prepared from the copper benzene tricarboxylate (Cu-BTC), one of the MOFs, exhibited excellent gas perm-separation properties with an ideal H2/CH4 selectivity of 153.

Exceptional function of nanoporous metal organic framework particles in emulsion stabilisation

A new concept of nanoporous metal organic framework particles stabilising emulsions was investigated. The copper benzenetricarboxylate MOF particles adsorbed at the oil/water interface play an exceptional role in stabilising both oil-in-water and water-in-oil emulsions.