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Copper (Cu) provides a cost-effective means of producing value-added fuels through the electrochemical reduction of carbon dioxide (CO2RR). However, we observed the production of hydrocarbons via CO2RR on commercial Cu films is less efficient because of the surface impurities, i.e., Fe. Carbon monoxide (CO), a reaction intermediate of CO2RR to hydrocarbons, binds strongly to the Fe sites and interrupts the production of hydrocarbons, resulting in an active hydrogen evolution reaction (HER). Herein, we report a method of blocking the effect of Fe impurities on the Cu surface through the preferential growth of nano-sized metal-organic frameworks (MOFs) on Fe site. When zirconium (Zr)-based MOFs (UiO-66) forms a compensating layer on Cu film via the terephthalic acid (TPA)-Fe coordination bond, the UiO-66 coated Cu film (UiO-66@Cu) presents significantly improved hydrocarbon Faradaic efficiency (FE) of 37.59% compared to 14.68% FE on commercial Cu film (99.9% purity) by suppressing HER. According to X-ray photoelectron spectroscopy (XPS) analysis, the UiO-66 ligand binds to entire metallic Fe site on the Cu surface, while metallic Cu is retained. Thus, UiO-66@Cu provides active sites of Cu for CO2RR and leads to highly efficient and selective production of hydrocarbons.

A series of wholly aromatic copolyesters P-IPAx with low melting point (Tm) derived from hydroxybenzoic acid (HBA), 6-hydroxy-2-naphthoic acid (HNA), 4,4'-dihydroxy-biphenyl (BP), terephthalic acid...

Protective fabrics with air-permeable and flexible features are crucial for practical application in the detoxification of chemical warfare agents (CWAs). Zr-based metal-organic frameworks (Zr-MOFs) are desirable to exhibit outstanding degradation toward CWAs. However, generally, MOFs with powders cannot afford the utilization as a protective layer directly; meanwhile, it is still a puzzling challenge to integrate MOFs with textiles efficiently. Herein, we develop a scalable and controllable strategy to fabricate UiO-66-NH2 on electrospun polyacrylonitrile nanofibers (UiO-66-NH2 fabrics) firmly and uniformly to capture and catalyze 2-chloroethyl ethyl sulfide (CEES) effectively for self-detoxification. The obtained UiO-66-NH2 fabrics are greatly capable of specific surface area, ample porosity, excellent crystallinity, and abundant catalytic active sites. Consequently, CEES can be removed efficiently up to 97.7% after 48 h by reaction and adsorption. The degradation products mainly including ethyl-2-hydroxyethyl sulfide, ether, bis[2-(ethylthio)ethyl], and 2-(2-(ethylthio)ethylamino) terephthalic acid are detected. Moreover, the obtained nanofibrous fabrics possess air-permeable, washable, and flexible as well as lightweight merits, totally ensuring their promising engineering applications for protective clothing.

The electrochemical synthesis of metal-organic frameworks (MOFs) has been widely explored but has involved indirect routes, including anodic dissolution of solid metal electrodes or the use of interfacial redox chemistry to generate base equivalents and drive MOF assembly. These methods are limited in scope, as the former relies on the use of an anode consisting of the metal ion to be incorporated into the MOF, and the latter relies on the compatibility of the metal/ligand solution with the probase that is subsequently oxidized or reduced. We report the facile, direct electrochemical syntheses of four iron-based MOFs via controlled potential oxidation of dissolved metal cations. Oxidation of Fe(II) at +0.75 V (vs Ag/Ag+) in a solution containing 2,6-lutidine and terephthalic acid affords highly crystalline Fe-MIL-101. Controlled potential electrolysis with carboxy-functionalized ITO affords Fe-MIL-101 grown directly on the surface of modified electrodes. The methods we report herein represent the first general routes that employ interfacial electrochemistry to alter the oxidation state of metal ions dissolved in solution to directly trigger MOF formation. The reported method is functional group tolerant and will be broadly applicable to the bulk synthesis or surface growth of a range of MOFs based on metal ions with accessible oxidation states.

Fe-MIL-88B was prepared by a method that utilizes ferric nitrate and terephthalic acid (TPA or H2BDC) as precursors. The catalyst was characterized by TEM, SEM, FTIR, XRD, BET, and TGA. The pyrolyzed MOF (Fe-MIL-88B/C) was then tested for FTS at 300 psi, 300/340°C and H2/CO=1 after reduction under flow of hydrogen at 400°C for 4 hours. GC product results show promising FTS performance and stability compared to previously reported Fe-MOF derived catalysts with CO conversion of 96.90% at 340°C for 40 hours and 97.45% at 300°C for 26 hours.

Fe/Co metal–organic frameworks (Fe/Co-MOFs) were synthesized by a solvothermal method using terephthalic acid (BDC) and N,N-dimethylformamide (DMF), and the removal of tetracycline (TC) was accomplished with high efficiency. We explored the influence of Co content on the characteristics of the bimetallic MOFs. The structures of the Fe/Co-MOFs were characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy (FTIR), and nitrogen physisorption analysis. The results showed that Co2+ was well loaded in the Fe-MOFs. Due to the different coordination behaviors of Co2+ and Fe3+ with BDC, the Fe/Co-MOFs formed a new 3D structure with a spike ball-like morphology. The morphology changed dramatically, leading to a large specific surface area, and the activity of the Lewis acid sites was greatly enhanced. Through FTIR and XPS analysis before and after adsorption, the adsorption process was mainly affected by coordination action. The largest TC adsorption capacity was observed when the Fe/Co ratio was equal to 1:3, and the saturated adsorption capacity was 139.8 mg g−1.

Branched polyesters based on the polyethylene terephthalate were synthesized by incorporating isophthalic acid (IPA) and trimellitic anhydride (TMA). TMA has the branching agent role. During the esterification step, only terephthalic acid, IPA, and ethylene glycol were reacted and TMA was added at the beginning of the polycondensation step. Reaction progress was studied using water production and mixing torque increase during esterification and polycondensation steps, respectively. Polycondensation time increases with IPA and decreases with TMA. Fourier transform infrared spectroscopy spectrum shows the production of polyester. Randomness and sequence length were studied using 13CNMR. Results reveal that randomness increases with TMA. Crystallinity and morphology of samples were studied using differential scanning microscopy (DSC). DSC thermograms show that samples turn to an amorphous structure by adding IPA and TMA with decreasing glass transition temperature, Tg. X-ray diffraction spectra approve changing nature similar to DSC results. Dynamic light scattering results present that with an increase in TMA, some size-increasing particles were detected. The rheological behavior of samples was studied using RMS. By adding TMA, the elastic behavior of samples changes to viscous behaviors.

The combination of cobalt sulfide and carbon can effectively stabilize the structure of the anode material and reduce the capacity decay. Co1−xS/C anode material was synthesized by two-step method of solvothermal and solid-phase sintering, in which cobalt chloride hexahydrate, selenourea and glucose are cobalt, sulfur and carbon sources, respectively. The discharge specific discharge capacity of Co1−xS/C anode material is stable at 216.7 mAh g−1 at 50 mA g−1 after 100 cycles. The 3D network-like Co9S8@C anode material was synthesized by solid-phase template method. The precursor (Co-based Metal organic Frameworks) template was prepared using cobaltous nitrate hexahydrate and terephthalic acid as cobalt source and organic ligand, respectively. Co9S8@C anode material is a network structure composed of uniformly sized spherical particles, which has the characteristics of high specific surface area and high porosity. The discharge specific capacity at the 10th cycle is as high as 1246.2 mAh g−1 at 50 mA g−1. After 100 cycles, the capacity decays to 1032.6 mAh g−1, and the capacity retention rate is 82.85%.

Iron terephthalate metal-organic framework (MOF-235) was used as an additive in preparation and modification of perovskite layer of solar cells (PSCs). MOF-235 with the chemical formula [Fe3O(1,4-BDC)3(DMF)3][FeCl4](DMF)3] was used by the one-step solution method with the solvent engineering technique in perovskite precursor solution to synthesize the perovskite layer by solvothermal method. The perovskite layer film was characterized by XRD and FE-SEM analyzing methods to consider the effect of additive on stability and morphology of synthesized crystal layer after annealing processes. The results showed the incorporation of 5 wt% of MOF-235 increased the open-circuit voltage (Voc) of PCS from 0.99 ± 0.03 to 1.03 ± 0.02 V. Therefore, the power efficiency improved from 8.34 ± 0.37% to 9.56 ± 0.12%. As a result, the addition of MOF-235 improves the coverage of perovskite film on TiO2 layer that contributes to the stability of perovskite solar cells, due to the effects of rigidity and π–π bond of benzene ring in terephthalic acid.

The development of graphene oxide/rare earth complexes luminescent materials is limited due to the strong quenching ability of graphene oxide. However, the hybrid materials with pyromellitic acid (PMA) as ligand not only have better performance, but also have stronger luminescence intensity. Herein we tested the effect of the carboxylic acid structure of PMA on the luminescence intensity of graphene oxide/rare earth complexes hybrid materials. Phthalic acid (PA), Isophthalic acid (i-PA) and Terephthalic acid (p-PA) are selected as test ligand, representing the o-position, meta-position and para-position effects of PMA. By comparing the luminescence intensity, we found that o-position effect is helpful for the ligand to sensitize rare earth ions, and meta-position and para-position effects are helpful for the graphene oxide sheets (GOSs) to improve the luminescence intensity of hybrid materials and inhibit the quenching effect of the GOSs. Furthermore, we speculate on the relationship between the distance of π-π stacking of GOSs and rare earth complexes and luminescence intensity of hybrid materials. This work provides an important reference for the design of graphene oxide/rare-earth aromatic carboxylic acid hybrid luminescent materials.

Aims: The aim of this work was to investigate the impact of light modulation parameters on the degradation of terephthalic acid, an organic model pollutant, within a heterogeneous photocatalytic system under visible light. For this purpose, a fixed bed photocatalytic reactor, irradiated by white-light LEDs matrix controlled by a system for light dimming, was used. The bed consisted of a nitrogen-doped titania photocatalyst deposited on polystyrene pellets. Background: Wastewater containing TPA can be treated into conventional aerobic biological units. However, the mineralization of TPA is slow and inefficient and its presence negatively influences the biodegradation efficiency because this pollutant inhibits microbial growth. Nowadays, innovative technologies named advanced oxidation processes (AOPs), such as heterogeneous photocatalysis with UV and visible light, ozonation, and Fenton oxidation, have gained popularity for effective organic destruction of TPA from wastewater. The heterogeneous photocatalytic oxidation process of the TPA under visible light is the most advantageous process in terms of both fixed and operating costs. Objective: In this work, the successful application of light modulation techniques for degradation of TPA using a photocatalytic system with supported visible active photocatalysts (N-doped TiO2) immobilized on polystyrene pellets is reported. In particular, sinusoidal lighting has been used analyzing the influence of the period of oscillation and the amplitude of light modulation on the reaction kinetics, in such a way as to minimize the times and energy costs for the process. Methods: To evaluate the influence of light modulation on the efficiency of the TPA removal, a discontinuous system composed of a Recirculating Photocatalytic Fixed Bed Reactor (RPFBR) irradiated by a matrix of white light LEDs was used. The flat geometry of the photoreactor guarantees the efficient excitation of the photocatalyst. An amount of 250 mL of aqueous solution with the initial TPA concentration of 12.5 ppm was applied in the photocatalytic tests lasting 180 min of irradiation fixed or sinusoidal modulated. Results: The results show that the variation of the oscillation period of the sinusoidal modulation has a pertinent influence on the photodegradation of TPA and a maximum value of the apparent kinetic constant, 0.0045 min-1 is found when the period of oscillation is 0.24 s. The sinusoidal modulation with optimal amplitude occurs with current between 50-200 mA, that shows the highest value of the apparent kinetic constant equal to 0.0046 min-1. The optimal sinusoidal modulation, as a consequence is with current between 50-200 mA and period of 0.24 s. From the data collected from the tests, it is possible to evaluate the energy cost necessary to obtain the reduction of 90% of the terephthalic acid in 1 m3 of polluted water for each modulation (E E/O), and compare these values with other tests for TPA degradation reported in the literature. The internal comparison with the three systems of literature shows that the optima sinusoidal modulation of LEDs matrix permits a strong reduction in the electrical energy consumption. Conclusion: Photocatalytic tests have demonstrated the improvement of the process energy efficiency using the light modulation technique. A further confirmation of the advantage of light modulation was obtained by comparing the energy costs required for the abatement of 90% of the terephthalic acid in 1m 3 of the photocatalytic system. Finally, a mathematical model for photocatalytic degradation of terephthalic acid within the recirculating fixed bed photocatalytic reactor, irradiated by white-light LEDs was developed.

Thermal expansion of an organic salt, prepared by solvent-drop grinding of terephthalic acid and imidazole in a 1:2 ratio, has been studied over a wide range of temperature 100–430 K. Restricted mo...

A new bimetallic metal–organic framework (Cd/Zr-MOF) was successfully synthesized via microwave hydrothermal method using Zr4+ and Cd2+ as two metal ions and terephthalic acid (H2BDC) as organic ligand. The effects of Cd/Zr molar ratio and the reaction temperature on the Cd/Zr-MOF structure and its photocatalytic performance to degrade Rhodamine B (RhB) under simulated sunlight were explored in detail. The results show that the Cd/Zr-MOF with Cd/Zr molar ratio of 5:1 obtained at the reaction temperature of 160 °C exhibits the best photocatalytic performance, and the photocatalytic efficiency can reach 95.82% after 105 min irradiation, which is much higher than that of pure UiO-66 or pure Cd-MOF. The result of Mott–Schottky tests certified the formation of n–n heterojunction between Cd-MOF and UiO-66, which is conducive to the transfer and separation of photogenerated electrons and holes and is the main reason of the enhanced photocatalytic performance. In addition, the mechanism of photocatalytic degradation of Cd/Zr-MOF was studied by adding different eliminating agents. The photodegradation of RhB was mainly caused by superoxide ion (·O2−) and electron hole (h+). The Cd/Zr-MOF composites with excellent photocatalytic activity to Rhodamine B were synthesized via one-step microwave hydrothermal method.

Capability of pulsed laser ablation (PLA) in liquid environment as a physical bottom-up method to synthesis metal–organic framework MOF-5 has been investigated experimentally for the first time. In this experiment, a high-purity zinc (Zn) target was irradiated by the fundamental wavelength of a pulsed Nd:YAG laser in a solution of dimethylformamide (DMF) containing terephthalic acid. A variety of diagnostics were employed to investigate the properties of MOF-5 nanostructures and to study the effects of laser fluence and concentration of acid on their characteristics. The porous and rod structure of synthesized MOF-5s observed in SEM images and their cubic shape observed in TEM microimages in good agreement with XRD and FTIR spectra confirm the production of MOF-5 nanostructures by PLA method. Results show that size of synthesized MOF-5 nanostructures was decreased with increasing the laser fluence. Furthermore, an amount of produced nanostructures was increased with increasing the ligand concentration in the liquid environment of ablation and laser fluence.

Recycling of polyester waste has become a focus of global attention in recent years. Herein, a novel bimetallic catalyst, CoMo@NC derived from Mo@ZIF-CoZn, has been prepared, which can be applied in hydrogenolysis for recycling terephthalate-based polyesters (polyethylene terephthalate (PET) and polybutylene terephthalate (PBT)), converting PET to the valuable monomer terephthalic acid (PTA) in high yield within 10 hours at 260 °C, under atmospheric H2. A distinct enhancement in the catalytic performance of this catalyst is observed when compared with monometallic catalysts, which can be ascribed to the “synergistic catalysis” between Mo-sites and Co-sites inside the bimetallic catalyst. The recyclability test indicated that this catalyst could be reused for at least six times with stable activity. This work highlights new possibilities for bimetallic catalysts applied in sustainable chemistry.

MIL-53 is a metal organic framework (MOF) belonging to the MIL (Material Institute Lavoisier) group. It is a 3-D framework, built up by the combination of metal salt (Al, Fe, Cr) and linker (terephthalic acid). It is well known for its flexibility in structure and the phenomenon of breathing. It was first synthesized in the year 2002 by Gerard Ferey using chromium salt and widely used for adsorption/separation applications due to its remarkable flexibility and porous structure. In the formation of MIL-53, different ranges of metal ions and linker are used which provides the possibility of the formation of different compositional variety. From the literatures reported in this paper, it was found that the researchers have used just three synthesis routes solvothermal, electrochemical, and microwave-assisted methods for the synthesis of MIL-53 and found to have only few applications. This paper aims to appraise the methods being used for synthesis of MIL-53 and its several applications.

Mesoporous KIT-5 was functionalized with g-C3N4 nanoparticles using trichloroacetic acid and terephthalic acid as acid modulators under hydrothermal conditions. The surface morphology, elemental composition, stability, surface area, pore size and pore volume of the functionalized KIT-5-g-C3N4 nanomaterial were determined using SEM, EDAX, Zeta potential analysis and BET surface area analysis respectively. The functionalized mesoporous KIT-5 material was screened for cationic dye degradation. The material was found to decolorize and degrade the cationic dye methylene blue completely under visible light conditions. The adsorption and degradation of the dye by functionalized KIT-5-g-C3N4 nanomaterial were studied using UV spectrophotometer. The photo degradation efficiency of the functionalized KIT-5-g-C3N4 nanomaterial was found to be 85.5%. The recyclability and reusability of the functionalized KIT-5-g-C3N4 nanomaterial in dye degradation was studied. The mechanism for the successful dye degradation by functionalized KIT-5-g-C3N4 nanomaterial was also discussed based on electro static interaction.

We acknowledge the funding from Academy of Finland (Profi 3), and the use of the RawMatTERS Finland Infrastructure (RAMI) at Aalto University. The measured data of RIXS will be available for public after three years period following DOI: 10.15151/ESRF-ES-438677278. Atomic/molecular layer deposition (ALD/MLD) is currently strongly emerging as an intriguing route for novel metal–organic thin-film materials. This approach already covers a variety of metal and organic components, and potential applications related to e.g. sustainable energy technologies. Among the 3d metal components, nickel has remained unexplored so far. Here we report a robust and efficient ALD/MLD process for the growth of high-quality nickel terephthalate thin films. The films are deposited from Ni(thd)2 (thd: 2,2,6,6-tetramethyl-3,5-heptanedionate) and terephthalic acid (1,4-benzenedicarboxylic acid) precursors in the temperature range of 180–280 °C, with appreciably high growth rates up to 2.3 Å per cycle at 200 °C. The films are amorphous but the local structure and chemical state of the films are addressed based on XRR, FTIR and RIXS techniques.

Herein, effective optical band gap engineering of a robust Zr12 oxo-based hcp UiO-66 has been realized through linker functionalization. A versatile mixed solvent-based solvothermal process was employed to synthesize the pristine hcp UiO-66 and the designed functional analogues (hcp UiO-66-CH3, hcp UiO-66-NH2 and hcp UiO-66-NDC). Optical band gaps determined from diffuse reflectance spectra (DRS) showed that hcp UiO-66 had a large band gap of 4.07 eV and a slightly narrower value of 3.93 eV was derived after the introduction of methyl groups. By embellishing the linker with an amino group possessing a strong electron-donating property, the band gap was drastically reduced to 2.92 eV. Surprisingly, the value could be further lowered to 2.48 eV by substituting the terephthalic acid (TPA) ligand of hcp UiO-66 with bulkier 1,4-naphthalic acid (1,4-NDC). In view of the tremendous influence of ligand functionalization on band gap energy, we also investigated the photoluminescence (PL) properties of the materials. It was found that the PL performance of hcp UiO-66 could also be significantly tuned by using substituted ligands: hcp UiO-66-NH2 and hcp UiO-66-NDC, which exhibited obvious red shifted PL compared to the pristine hcp UiO-66. The origins of both band gap variation and luminescence tunability were discussed accordingly.

The effects of concentration and an oriented external electric field on the transformations of hydrogen-bonded structures of trimesic acid (TMA) and terephthalic acid (TPA) have been investigated at a liquid–solid interface by scanning tunneling microscopy (STM). The triangular periodic TMA framework can be transformed into a flower-like structure by changing the STM sample bias sign in situ. Networks of TMA and TPA are porous at a negative substrate bias, but typically change to relatively compact forms when the polarity of the applied bias is reversed. This change is reversible if the applied bias is reversed. The effects have potentials to locally control the capture and release of analytes in host-guest systems and the 2D morphology in multicomponent layers.

Control of product quality plays a crucial role in petrochemical industries. In this paper, we propose a new strategy to control the quality of purified terephthalic acid (PTA) product. In this approach, the PTA quality is controlled by monitoring the concentration of the main impurity in the hydropurification process, which is 4-carboxybenzaldehyde (4-CBA) in the crude terephthalic acid (CTA) powder. To attain the research objectives, a dynamic dispersion model is developed in the face of catalyst deactivation, considering the vital operating parameters. The CTA powder streams with low and high 4-CBA concentrations can be effectively used through a proper (and controlled) mixing procedure. This strategy can be applied by controlling the ratio of the mass flowrates of the two streams, having high and low concentrations. The positive effect of H2 partial pressure on the system performance can be implemented by a small decrease in reactor temperature. Off-spec PTA powder can be used with the CTA powder having a high 4-CBA concentration. Increasing temperature accelerates the reduction rate of the Pd/C catalyst surface area, leading to an unfavorable sintering phenomenon. The decreased activity of Pd/C catalyst is in good agreement with the normalized ratio of decrease in the surface area of pure Pd with increasing temperature.

Luminescent materials enable warm white LEDs, molecular tagging, enhanced optoelectronics and can improve energy harvesting. With the recent development of multi-step processes like down- and upconversion and the difficulty in sensitizing these, it is clear that optimizing all properties simultaneously is not possible within a single material class. In this work, we have utilized the layer-by-layer approach of atomic layer deposition to combine broad absorption from an aromatic molecule with the high emission yields of crystalline multi-layer lanthanide fluorides in a single-step nanocomposite process. This approach results in complete energy transfer from the organic molecule while providing inorganic fluoride-like lanthanide luminescence. Sm3+ is easily quenched by organic sensitizers, but in our case we obtain strong fluoride-like Sm3+ emission sensitized by strong UV absorption of terephthalic acid. This design allows combinations of otherwise incompatible species, both with respect to normally incompatible synthesis requirements and in controlling energy transfer and quenching routes. Aromatic molecules often afford strong and tunable absorption, desirable for lighting applications, but incorporating them in inorganic structures without luminescence quenching is challenging. Here the broad absorption from terephthalic acid is combined with inorganic fluoride-like lanthanide luminescence in a composite material.

Two new different metal–organic frameworks (MOFs) [Ba(L1)(H2O)2]n·nH2O (MOF 1) and [Ba(L2)(H2O)2]n·0.5nDMF·0.5nH2O (MOF 2) were yielded by the assembly of oxygen-friendly Ba(II) ions and two similar linkers, namely 2-(imidazol-1-yl)terephthalic acid (H2L1) and 2-(1H-1,2,4-triazol-1-yl) terephthalic acid (H2L2). Single-crystal X-ray diffractions (XRD) indicate that MOF 1 is a new three-dimensional (3D) stacking dense network formed by the one-dimensional (1D) rod-shaped chains and L1 linkers, whereas MOF 2 presents a 3D nanotube porous framework with cylindrical tunnels based on the 1D loop chains as the secondary building units (SBUs) by replacing the imidazole group in H2L1 with the triazole group in H2L2. As a result, MOF 2 has a higher density of active sites and Lewis acid sites in the porous surface of nanotube than MOF 1. Thereby, the CO2 capture and separation capacity of MOF 2 is great higher than that of CH4 at 298 K.

Despite significant methodological and technological advancements in chemical recycling of synthetic polymers, an efficient and quantitative conversion of post-consumer polyethylene terephthalate (PET) into terephthalic acid (TPA) under ambient conditions of temperature and pressure still remains a challenge. In this respect, the application of mechanochemistry and multiple advantages offered by solid-state ball milling and vapor-assisted aging have remained insufficiently explored. To further expand their potential, the implementation of organic solvent-free milling as a superior methodology for successful alkaline depolymerization of waste PET (e. g., bottles and textile) into TPA monomer in near-quantitative yields was reported herein. The solid-state alkaline PET hydrolysis was also shown to proceed in excellent yields under aging conditions in humid environment or in the presence of alcohol vapors. Moreover, the performance of mechanochemical ball milling and aging in the gram-scale depolymerization of PET into TPA was demonstrated.

Photocatalysis technology has received much attention on the treatment of antibiotics residues. In this paper, CdS quantum dots (QDs)-decorated TiO2 (CDS-T for short) have been prepared successfully through a photodeposition method and utilized as photocatalysts for degradation of metronidazole (MTZ). Under visible light irradiation for 60 min, the degradation ratio of MTZ over CDS-T-3 that was prepared by 3 h of photodeposition reached up to 90.9%, which was 1.5 times than that reached over commercial CdS. The decoration of CdS QDs onto TiO2 can enlarge light absorption range to visible region. Furthermore, greatly improved separation efficiency of photogenerated carriers is realized through forming heterojunction. Activity control experiments demonstrate that O2·− serve as the main active species, while ·OH and holes (h+) play secondary roles on the MTZ degradation. Moreover, electron spin resonance (ESR) technique, terephthalic acid photoluminescence (TA-PL) technique and N,N-diethyl-p-phenylenediamine (DPD) method confirm that larger amounts of active species are generated from CDS-T-3 than that from commercial CdS under visible light. This study can not only offer an easy method to prepare CdS quantum dots-decorated TiO2 but also enlarge its application in solving the problem of metronidazole contamination.

In the present work, we developed a simple, eco-friendly, and cost-effective approach to fabricate a recyclable hydrophobic/superoleophilic fabric filter using bismuth nanostructures and purified terephthalic acid (PTA)-based resin. First, different morphologies of bismuth nanostructures such as dendritic, hierarchical, flower and cactus-like were prepared by a facile one-step galvanic displacement method. Afterwards, the coating composition of Bi/PTA mixtures was applied on the surface of fabric filters by a simple hand brushing route. The results indicated that the water and oil contact angles of the modified hydrophobic-superoleophilic fabric filter were about 135° and 0°, respectively. The various oil/water mixtures can be successfully separated by a facile gravity-driven filtration using the as-coated hydrophobic filter with the separation efficiency above 93% and repeatability for at least 10 times. Also, the improved hydrophobic filter showed excellent self-cleaning performance for the removal of surface contaminants. The advantages of scalable production, high efficiency, cost-effective, time saving, sustainable and excellent reusability for the prepared hydrophobic-superoleophilic filter make it to be a potential candidate for oil/water separation and self-cleaning applications.

In the present work, we report the effect of the addition of platinum (Pt loading 1 wt%) on photocatalysts based on TiO2 and its incorporation in a SiO2 matrix using the sol gel method. The photocatalyst/silica matrix ratio was w(TiO2)/w(SiO2) of 15/85. The characterization of the samples was carried out with X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), specific surface area by N2 physisorption (BET) and UV–Vis diffuse reflectance spectroscopy (UV–Vis DRS). The photoactivity of the samples was evaluated in the photodegradation of 2,4-dichlorophenoxyacetic acid (2,4-D). The production of hydroxyl radicals (•OH) on the surface of the samples irradiated with UV light was detected by the fluorescence technique using terephthalic acid as a test molecule. The resulting supported catalyst showed enhanced photocatalytic activity towards 2,4-D degradation, almost 97% of the 2, 4-D was degraded with Pt/TiM–Si sample in 180 min compared to pure commercial TiO2 P25 under UV radiation. The increase in photoactivity can be attributed to the extended band gap energy, large surface area, and a better charge separation and more efficient transfer of the photogenerated charges (e−–h+) due to the presence of Pt ions on the surface of the photocatalyst. Finally, stability and reusability test of the samples was estimated using recycling experiments, indicating its remarkable efficiency in contaminated water treatment.

Metal organic frameworks (MOFs) are considered as very promising positive electrode materials for supercapacitors. To achieve good electrochemical performance, in this work, we report a mixed-ligand approach to prepare modified Ni-MOF by using trimesic acid (BTC) as the modulator to partially replace the terephthalic acid (PTA) ligands. The introduction of BTC can induce the formation of nanosheets with inserted albizia flower-like spheres, where the nanowires on the albizia flower-like spheres can provide rich redox reaction sites and the “spacer” spheres between the layers can hinder the aggregation of the 2D nanosheets to provide fast transport pathways. Moreover, adsorption simulation shows that the adsorption energy of OH− on the mixed organic ligands is increased after introducing the BTC ligands, which may improve the reversible redox reaction kinetics in the electrode materials. The as-obtained albizia flower-like spheres@nanosheets structured Ni-MOF with the optimized amount of BTC exhibits a high capacitance of 920 F g−1 at 1 A g−1, good rate capability of 61% at 20 A g−1, and an excellent cycling stability in 6 M KOH electrolyte. This work may provide helpful guidance for controlling the structure and surface property of MOFs to improve the electrochemical performance for supercapacitors.

A new core-shell nanocomposite was designed by functionalization of Co3O4 quantum dots (Co3O4-QDs) core with terephthalic acid (TPA) and growth of Fe-infinite coordination polymer (Fe-ICP) shell on...

A series of four polyol macromers with similar hydroxyl number was prepared by reacting palm fatty acid distillate with neopentaglycol, pentaerythritol, and separate equimolar amounts of isophthalic acid (IPA), terephthalic acid (TPA), phthalic anhydride (PA), and adipic acid (AA). Each macromer was then copolymerized with 2-hydroxylethyl acrylate (2-HEA) and toluene diisocyanate to produce the UV curable resins labeled as UA–IPA, UA–TPA, UA–PA, and UA–AA, respectively. The glass transition temperature (Tg), pendulum hardness, and adhesion properties of the cured films were studied. In general, all the resins produced coatings with high gloss and good adhesion. When accelerated weathering tests were carried out, films of UA–TPA could withstand UVA exposure up to 1500 h. When subjected to methyl ethyl ketone double rub test, cured films of UA–IPA and UA–TPA could withstand the highest double rubs at 90 times, followed by UA–PA and UA–AA at 45 and 15 times, respectively. Under salt spray corrosion test for 720 h, cured films showed good corrosion resistance with no observable blistering, except for UA–AA that showed slight blistering. Excellent water resistance was achieved by all cured films with good adhesion and minimal gloss reduction.

The work reports a study of the properties of tautomeric O–H⋯O hydrogen bonding (τ-bonding). The Raman spectra of crystalline and polycrystalline samples of terephthalic acid chains, benzoic acid dimers, and ibuprofen dimers are studied in the temperature region of 5-300 K. The protons on τ-bonds in terephthalic acid and ibuprofen are substituted by deuterium. Temperature dependences of the frequencies of τ-bond translational vibrations are analyzed, their relation to tunneling and proton hopping is discussed. It is shown that the propagation of the proton (deuteron) density distribution function into the neighboring empty potential well increases hydrogen bonding, while physical motion of the particle through the barrier or hopping over the barrier affect the ω(T) dependence of the vibration of the C=O bond in the τ-ring. On the example of ibuprofen, asymmetric τ-bonds are analyzed and the energy difference between L- and R-tautomers are measured.

In this work, a holmium oxide (Ho2O3/CNT) photocatalysts were successfully synthesized through a MOF assisted route for the first time. The effects of the morphology and purity on the photocatalytic behavior of the products, were investigated by determining various physicochemical properties. The Ho2O3/CNT nanocomposite was systematically analyzed by powder X-ray diffraction (P-XRD), transmission electron microscopy (TEM), ultraviolet–visible diffuse reflectance spectroscopy (UV–vis DRS), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy studies. The Ho2O3 derived from a MOF assisted synthetic route using Ho(NO3)3·5H2O and terephthalic acid with a 1:1 M ratio at a temperature of 750 °C for 3 h prove the most advantageous, 98% degradation of 20 mg/L aqueous tetracycline pollutant was observed within 60 min. The elevated photocatalytic activity was mainly attributable to the unique synthetic route, improved crystallinity, wide UV-light absorption rate and excellent adsorption capabilities of CNT, as well as enhanced oxygen deficiency. The photocatalytic results confirm that the Ho2O3/CNT nanocomposite is an efficient photocatalyst for the degradation of toxic tetracycline pollutant and is thus suitable for use in environmental remediation.

In this study, wholly aromatic phosphorus-containing thermotropic liquid crystal polymers (TLCP) derived from 6-hydroxy-2-naphthenic acid (HNA), terephthalic acid (TA) and 10-(2,5-Dihydroxypheny)-1...

The purpose of the work was to determine the properties of poly(vinyl chloride) (PVC) plasticized with a new linear and oligomeric terephthalic acid esters and aliphatic acids in terms of their application as an innovative non-phthalate plasticizers. On the basis of analysis of PVC grain swelling shows that these compounds have plasticizing properties. Plastographometric tests were performed, the glass transition temperature and thermal stability time were analyzed. The mass flow rate (MFR) and mechanical properties of plasticized PVC was determined. Based on the analysis of the results obtained, it can be concluded that both assessed oligoesters can be successfully used for the production of plasticized PVC with utility indicators similar to those of plasticized PVC produced so far.

Mixed-ligand metal–organic frameworks (MIXMOFs) containing two or more organic linkers that exhibit functionalities can show improved selective gas adsorption and separation properties with respect to those of the conventional MOFs. In this study, the mixed-ligand UiO–66(Zr) framework was rapidly prepared by employing a microwave-assisted continuous-flow method, which can be easily scaled up for efficient mass production. A microfluidic syringe pump system was used to introduce the precursor solutions of zirconium metal salt and ligand mixture (terephthalic acid and 2-amino terephthalic acid) into a polytetrafluoroethylene tubular reactor kept under microwave irradiation. MIXMOFs were obtained within 10 min, a much shorter time than the reaction time required by the conventional heating method. The prepared samples were characterized by N2 porosimetry, field-emission scanning electron microscopy, Fourier transform infrared spectrometry, thermogravimetric, and powder X-ray diffraction analyses to elucidate the effects of the ligand ratios. Furthermore, the toluene adsorption–desorption tests were conducted using the synthesized mixed-ligand UiO–66(Zr) adsorbents at different temperatures.

openaire: EC/H2020/765378/EU//HYCOAT Two series of ZnO-organic superlattice thin films are fabricated with systematically controlled frequencies of monomolecular hydroquinone (HQ) or terephthalic acid (TPA) based organic layers within the ZnO matrix using the atomic/molecular layer deposition (ALD/MLD) technique. The two different organic components turn the film orientation to different directions and affect the electrical transport properties differently. While the TPA layers enhance the c-axis orientation of the ZnO layers and act as electrical barriers depressing the electrical conductivity even in low concentrations, adding the HQ layers enhances the a-axis orientation and initially increases the carrier concentration, effective mass, and electrical conductivity. The work thus demonstrates the intriguing but little exploited role of the organic component in controlling the properties of the inorganic matrix in advanced layer-engineered inorganic-organic superlattices.

Mesoporous polymeric metal-organic frameworks (mesoporous polymeric MOFs) are prepared on fluorine-doped tin oxide (FTO) substrate using hydrophilic terephthalic acid as the ligands, titanium isopropoxide as polymeric MOF precursors, and amphiphilic graft copolymers (i.e., poly(vinyl chloride)-graft-poly(oxyethylene methacrylate) (PVC-g-POEM) as structure-directing agents. The hydrophilic POEM chains in amphiphilic graft copolymers interact with the hydrophilic ligands and polymeric MOF precursors. Following thermal treatment at 500 °C, mesoporous polymeric MOFs are transformed to mesoporous TiO2 with high specific surface area and crystallinity, suitable for photovoltaic and photocatalytic applications. Solid-state dye-sensitized solar cells (ssDSSCs) and dye-sensitized solar cells (DSSCs) fabricated with mesoporous TiO2 photoanodes have efficiencies of 7.45 and 8.43 % at 100 mW/cm2, which is much higher than that of ssDSSCs and DSSCs with photoanodes of conventional TiO2 (5.36 and 7.14 %), respectively. The enhanced efficiency is attributed to good interconnectivity, larger surface area, and high porosity of the mesoporous TiO2, which results in suppressed interfacial charge recombination loss, enhanced electron transport, increased dye loading, and facilitated penetration of the electrolytes. Mesoporous TiO2 shows excellent activity as a photocatalyst for the degradation of humic acid under UV light irradiation.

A type of leaf-shaped cobalt-based metal-organic framework material is synthesized by solvothermal method with 1.3:1 cobalt and terephthalic acid ratio and uses as the air electrode catalyst for lithium-oxygen batteries working at high discharge current density. Physical characterization displays that the interaction between cobalt and terephthalic acid can produce a crystal material and the different proportions have a certain influence on their structure and crystallinity. In addition, micromorphology with cobalt and terephthalic acid 1.3:1 shows a leaf-like structure, and synaptic structure on the leaf surface may be beneficial to improve the catalytic activity. Electrochemical tests present that air electrode using this leaf-like structure catalyst materials has good reversibility and the specific discharge capacities can achieve to 3573.90 mAh g−1 at 0.5 mA cm−2 current densities. However, compared with existing catalysts, these leaf-shaped catalyst materials have no obvious advantage in improving the cycle life.

The layered vanadium pentoxide (V2O5) application has a good development potential in lithium-ion battery cathode materials. In this paper, vanadium chloride (VCl3), terephthalic acid, and ethanol were served as crude materials to produce precursors of vanadium-based metal organic frameworks by simple solvothermal method. Porous vanadium oxides were synthesized by heat treatment at different temperatures. The results show that the vanadium pentoxide cathode material has a better electrochemical charge and discharge performance and steady cycle by heat treatment of the precursor at 600 °C. The specific capacity of first discharge of the vanadium pentoxide cathode material obtained by heat treatment at 600 °C reached to 324 mAh/g, and when the current density is 50 mA/g, the capacity retention ratio is still 50.6% after 100 cycles. The capacity retention ratio was increased by 16.6% compared to the heat treatment temperature at 400 °C.

2,5-Furandicarboxylic acid (FDCA) is a promising renewable building block, which can replace conventional petroleum-derived terephthalic acid (TPA). Here, we develop and evaluate a new catalytic process for the production of a renewable plastic monomer (FDCA) from lignocellulosic biomass-derived cellulose. In this process, cellulose is converted into FDCA (38.6% carbon yield) via a two-step catalytic conversion: dehydration of cellulose to 5-hydroxymethylfurfural (HMF, 42% molar yield) and oxidation of HMF to FDCA (93.6% molar yield). To effectively recover the products as well as recycle the solvent, we designed a detailed separation subsystem, which is integrated with the reaction subsystem. Importantly, to effectively minimize the required energy consumption, a heat pump is employed and heat integration is conducted. In addition, pioneer plant analysis is conducted to investigate the broad range of economic feasibility. In our techno-economic analysis, the integrated process leads to a minimum selling price of $1532 per ton of FDCA, meaning that the cellulose-derived FDCA has the potential to replace petroleum-derived TPA. In addition, sensitivity analysis reveals that the feedstock price and catalyst price are important parameters for the process. Furthermore, according to life-cycle assessment, the biomass-derived FDCA production is more environmentally favorable than the petroleum-derived TPA production.

Polybenzimidazole (PBI) random co-polymers containing alicyclic and aromatic backbones were synthesized using two different dicarboxylic acids (viz., cyclohexane dicarboxylic acid and terephthalic acid) by varying their molar ratios. The synthesized co-polymers were characterized by inherent viscosity (IV) measurements, Fourier transform infrared spectroscopy (FTIR), 1H nuclear magnetic resonance (1H NMR) spectroscopy, X-ray diffraction (XRD) and thermo-gravimetric analysis (TGA). The co-polymer composition was determined by 1H NMR spectroscopy. The cyclohexyl based PBI possessed a lower proton conductivity (114 mS cm−1) than terephthalic acid based PBI (220 mS cm−1). The aromatic PBI had a high tensile modulus of 11 GPa, whereas the modulus of cyclohexyl PBI was only 2 GPa. By suitably selecting the monomer concentration, the co-polymer properties can be altered (both proton conductivity and mechanical properties). Among different co-polymers, one synthesized using 30 mol% cyclohexane dicarboxylic acid and 70 mol% terephthalic acid exhibited good elongation (8%) and modulus (10.5 GPa) values and improved proton conductivity (242 mS cm−1). In the doped condition, the co-polymer registered an elongation of 52% and a tensile modulus of 170 MPa. The high conductivity of this composition is attributed to the presence of ordered domains (shown by field emission scanning electron microscopy) present in the co-polymer in the doped condition. The co-polymers are thermally stable and the thermal stability increased with an increase in the aromatic content. Thus, alicyclic–aromatic co-polymerization is a viable technique to prepare high-temperature proton exchange membranes.

Carbon nanofibers (CNFs) have been good candidates for electrode materials in supercapacitors (SPCs). It is desirable but still challenging to explore CNFs with both multiscale porous structures and high heteroatom doping. Herein, hierarchically porous CNFs (HPCNFs) are prepared with the use of poly(acrylonitrile-co-acrylic acid) (P(AN-co-AA)) and terephthalic acid (PTA). The degradation of the AA segments induces vacancy-type defects, which result in the formation of micropores inside the CNFs. In addition, the defects promote increased redox activity by increasing the N-P content. Moreover, PTA sublimation creates mesopores inside the HPCNFs, which can largely reduce ion transport resistance in the HPCNFs. The specific capacitance and area normalized capacitance (CA) of HPCNFs can reach as high as 327 F g−1 and 80.5 μF cm−2, respectively. Additionally, high capacitance retention and excellent cycling stability can be achieved. The HPCNFs with vacancy-type defects are promising for developing high-performance electrode materials for SPCs.

openaire: EC/FP7/339478/EU//LAYERENG-HYBMAT We demonstrate the fabrication of in-situ crystalline thin films of various azobenzene (AZO) based metal-organic structures using the atomic/molecular layer deposition (ALD/MLD) technique; these are highly intriguing materials as azobenzene is one of the prototype organic molecules experiencing photoisomerization. Our Li-, Ca and Fe-AZO thin films deposited from Li(thd) (thd = 2,2,6,6-tetramethyl-3,5-heptanedione), Ca(thd)2, FeCl3 and azobenzene-4,4'-dicarboxylic acid precursors in the temperature range of 250-360 °C exhibit metal-AZO structures not known from bulk samples. In all these structures, the AZO linker molecules are free to undergo the characteristic trans-cis photoisomerization reaction upon UV (360 nm) irradiation. However, this lowers the degree of crystallinity. To address the issue, we investigate hetero-organic structures where TPA (terephthalic acid) is used as another linker component together with AZO. This allows the trans-cis reaction of the AZO moieties to occur without compromising thefilm crystallinity. Finally, we demonstrate the growth of MOF-on-MOF type Ca-ADA@Ca-TPA thin films also showing the efficient photoisomerization reaction.

In this study, two new monometallic organic frameworks (MOFs), namely {[Zn1.5L(NMP)(H2O)]·H2O}n (1) and {[Pb2L2(H2O)2]·H2O}n (2), were synthesized for the first time by a new bifunctional N,O-containing 2-(1H-tetrazol-5-yl)terephthalic acid (H2L) ligand. Then, based on the HSAB principle, another porous Pb–Zn heterometallic organic framework (HMOF), namely {[PbZn0.5L(H2O)]·0.5NMP·H2O}n (3), was successfully obtained for the first time by combining Pb(II) and Zn(II) ions with H2L. The MOFs 1 and 2 are 3D densely packed frameworks, whereas the HMOF 3 is a porous 3D framework (28.9% porosity) with 1D open channels modified by Lewis basic sites (exposed N atoms) and Lewis acidic sites (unsaturated bimetallic sites). The HMOF 3 has a strong boiling water/acid–base resistance (pH = 2–12) and shows an enhanced high-efficiency catalytic effect for CO2 conversion (98%) under ambient temperature and pressure conditions. In addition, fine color regulations of the MOFs were successfully realized by doping different kinds of metal ions into them. This study aims to provide a new way and field of vision for the construction of HMOFs and their multi-functional materials.

A Ti0.7W0.3O2/TiO2 nanocomposite interfacial photocatalyst was designed and prepared for the photocatalytic degradation of phenol pollutants in wastewater. The detailed properties of the Ti0.7W0.3O2/TiO2 nanocomposite interface (NCI) were analyzed by XRD, SEM, EDX, DRS, UPS and XPS technologies, showing that anatase TiO2 nanospheres (NSs) were uniformly dispersed on the surface of rutile Ti0.7W0.3O2 nanoparticles (NPs) and formed the nanocomposite interface. The DRS and UPS results of 5 wt% Ti0.7W0.3O2/TiO2 NCI indicated a greatly broadened light response range with a wavelength shorter than 527 nm and a shorter band gap energy of 2.37 eV. The conduction band of TiO2 NSs, Ti0.7W0.3O2 NPs and 5 wt% Ti0.7W0.3O2/TiO2 NCI were measured based on the results of the valence band and band gap energy obtained via XPS and DRS, and then the energy level diagram of Ti0.7W0.3O2/TiO2 NCI was proposed. The photocatalytic degradation of phenol at Ti0.7W0.3O2/TiO2 NCI with different loading ratios of Ti0.7W0.3O2 NPs was investigated under optimum conditions (i.e., pH of 4.5, catalyst dosage of 0.45 g L−1 and phenol initial concentration of 95 ppm) under the illumination of ultraviolet visible light. Also, 5 wt% Ti0.7W0.3O2/TiO2 NCI exhibited the highest photocatalytic activity, with the initial rate constant (k) calculated as 0.09111 min−1. After recycling six times, Ti0.7W0.3O2/TiO2 NCI showed good stability and recyclability. The involvement of superoxide radicals in the initial reaction at Ti0.7W0.3O2/TiO2 NCI was evidenced by the use of a terephthalic acid (TA) fluorescent probe. Besides, UV-Vis spectroscopy, UHPLC-MS and GC-MS technologies were used to analyze the main intermediates in the photocatalytic degradation of phenol. The probable photocatalytic degradation mechanism of phenol at Ti0.7W0.3O2/TiO2 NCI was also proposed.

A microwave-assisted synthesis method for Ce(iv)-based MOFs crystallizing in the MIL-140 structure has been developed. Three different linker molecules, i.e. terephthalic acid (H2BDC), 2-chloroterephthalic acid (H2BDC-Cl) and 2,6-naphtalenedicarboxylic acid (H2NDC) that have previously been used for the synthesis of Ce-UiO-66 which contains hexanuclear Ce-O clusters as the inorganic building unit (IBU), were employed. Under solvothermal reaction conditions (140 °C) with acetonitrile as the solvent the compounds Ce-MIL-140-BDC, -BDC-Cl and -NDC, with the general composition [CeO(linker)] were obtained as microcrystalline products. For all three MOFs an extended purification process had to be carried out. The MOFs were fully characterized and the structure of Ce-MIL-140-BDC was refined against PXRD data using the Rietveld method. In contrast to Zr-MIL-140-BDC a symmetry reduction to the space group P1[combining macron] is observed. The MIL-140 structure type is built up by infinite CeO7 polyhedra that are interconnected by dicarboxylate ions to generate 1D pores. For Ce-MIL-140-BDC the highest specific surface area of asBET = 222 m2 g-1 is observed and the MOF is thermally stable up to 370 °C. This new synthetic route to Ce(iv)-MOFs avoids the formation of the previously extremely dominant hexanuclear IBU, and paves the way for higher IBU diversity in Ce(iv)-MOFs.