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The multistep synthesis of novel bis-terephthalthioamides based on methyl esters of amino acids (AAs) was proposed using conventional heating and microwave-assisted approaches. In fact, the comparative case study on the thionation of new symmetrical diamides with Lawesson’s reagent (LR) was performed. The microwave-accelerated small-scale methodology was successfully employed on the whole pathway from substrates (Gly, Ala, Val, Tyr, Ser) to products (symmetrical dithioamides of terephthalic acid), resulting in significantly reduced reaction time, energy requirements, and slightly increased reaction yields when compared to conventional heating. Moreover, the intermolecular similarity of novel terephthalic acid derivatives was estimated in the multidimensional space (mDS) of the structure/property-related in silico descriptors using principal component analysis (PCA) and hierarchical clustering analysis (HCA). The distance-oriented structure/property distribution was also correlated with the experimental lipophilic data.

Supramolecular 3D Zn(II) coordination polymer {[Zn(bim)(bdc)]⋅0.8DMF⋅0.4EtOH⋅0.1H2O }n (Zn-MOF), constructed from Zn2+ ions, bis(imidazol-1-yl)methane (bim) and terephthalate (bdc2−) anions, was synthesized and structurally characterized. Zn-MOF crystallizes in the tetragonal crystal system, space group P42/n. Each Zn(II) ion coordinates two neutral bim molecules in a bridging bidentate coordination mode via nitrogen atoms at position 3 of the imidazole rings and two bdc2− anions, with monodentate coordination of the carboxylate group for one of them and bidentate coordination for another. Zn(II) cations are in a distorted square pyramidal ZnN2O3 coordination environment. Metal cations are alternately linked by the bim and bdc2− ligands, forming a two-dimensional layered structure along the crystallographic plane ab. As a result of layer interpenetration, a supramolecular 3D network is formed. Zn-MOF demonstrated blue (aquamarine) emission with a maximum at 430 nm upon excitation at 325 nm. The luminescence lifetime of 6 ns is characteristic for ligand-centered fluorescence. The luminescent sensing properties of Zn-MOF in ethanol suspension toward inorganic cations and anions were evaluated and an emission quenching response was observed for Fe3+ and chromate/dichromate ions. Photoinduced electron transfer from Zn-MOF to Fe3+ was elucidated as a possible quenching mechanism on the basis of DFT calculations.

The purification of terephthalic acid recovered from an alkali-reduction wastewater by reactive crystallization was investigated. The crude terephthalic acid was reacted with sodium hydroxide solution to form a salt of disodium terephthalate, then acidified with sulfuric acid to get the terephthalic acid with higher purity. Effects of time, pH, concentration, and flow rate of secondary feed solutions, temperature, and stirring rate on Crystal Size Distribution (CSD) of terephthalic acid precipitate were investigated. The results showed that CSD was influenced by the concentration of reactants and the pH solution. On the other hand, time, temperature, flow rate of secondary solution, and stirring rate had no significant effects on the CSD, which the mean size of crystals ±3 μm. The mean size of crystals at solution pH 5, 4, and 3 were 6.03, 9.42, and 10.34 μm, respectively; meanwhile, at concentrations of 0.5, 0.3, and 0.1 M, were 7.57, 3.24, and 3.09 μm, respectively. The semi-batch reactive crystallization with double-feeding at constant pH and temperature produced monodispersed crystals. However, this method needs to be carried out more than once for terephthalic acid purification, which is intended for polyethylene terephthalate (PET) polymerization.

Poly(ethylene terephthalate) polyester represents the most common class of thermoplastic polymers widely used in the textile, bottling, and packaging industries. Terephthalic acid and ethylene glycol, both of petrochemical origin, are polymerized to yield the polyester. However, an earlier report suggests that polymerization of methoxyterephthalic acid with ethylene glycol provides a methoxy-polyester with similar properties. Currently, there are no established biobased synthetic routes toward the methoxyterephthalic acid monomer. Here, we show a viable route to the dicarboxylic acid from various tree species involving three catalytic steps. We demonstrate that sawdust can be converted to valuable aryl nitrile intermediates through hydrogenolysis, followed by an efficient fluorosulfation-catalytic cyanation sequence (>90%) and then converted to methoxyterephthalic acid by hydrolysis and oxidation. A preliminary polymerization result indicates a methoxy-polyester with acceptable thermal properties.

Approximately 400 billion PET bottles are produced annually in the world, of which from 8 to 9 million tons are discarded in oceans. This requires developing strategies to urgently recycle them. PET recycling can be carried out using the microbial hydrolysis of polymers when monomers and oligomers are released. Exploring the metabolic activity of fungi is an environmentally friendly way to treat harmful polymeric waste and obtain the production of monomers. The present study addressed: (i) the investigation of potential of strains with the potential for the depolymerization of PET bottles from different manufacturers (crystallinity of 35.5 and 10.4%); (ii) the search for a culture medium that favors the depolymerization process; and (iii) gaining more knowledge on fungal enzymes that can be applied to PET recycling. Four strains (from 100 fungal strains) were found as promising for conversion into terephthalic acid from PET nanoparticles (npPET): Curvularia trifolii CBMAI 2111, Trichoderma sp. CBMAI 2071, Trichoderma atroviride CBMAI 2073, and Cladosporium cladosporioides CBMAI 2075. The fermentation assays in the presence of PET led to the release of terephthalic acid in concentrations above 12 ppm. Biodegradation was also confirmed using mass variation analyses (reducing mass), scanning electron microscopy (SEM) that showed evidence of material roughness, FTIR analysis that showed band modification, enzymatic activities detected for lipase, and esterase and cutinase, confirmed by monomers/oligomers quantification using high performance liquid chromatography (HPLC-UV). Based on the microbial strains PET depolymerization, the results are promising for the exploration of the selected microbial strain.

There is a need for more sustainable recycling technologies for mixed textile waste, including the two main fibers poly(ethylene terephthalate) (PET) and cotton but also containing other fiber types. Hydrothermal liquefaction has been shown to be a promising technology to recycle textile waste containing cotton and PET into bio-oil and terephthalic acid (TPA). However, the practically accumulated composition of textile waste is more complex and features more than two fibers. In the present study we investigated the effect of eight different fabrics individually in ternary mixtures with a fixed ratio of cotton and PET and in a complex mixture reflecting the global fiber production. It was found that between 3 and 12 wt% bio-oil and 17–77 wt% TPA can be obtained depending on composition and temperature. Fibers with a high nitrogen content, such as suede, acrylic and nylon, significantly decreased the TPA yields due to the formation of terephthalic amides.

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.

Excess fluoride in water poses a threat to ecology and human health, which has attracted global attention. In this study, a series of lanthanum-based metal–organic frameworks (La-MOFs) were synthesized by varying the organic ligands (i.e., terephthalic acid (BDC), trimesic acid (BTC), biphenyl-4,4-dicarboxylic acid (BPDC), 2,5-dihydroxyterephthalic acid (BHTA), and 1,2,4,5-benzenetetracarboxylic acid (PMA)) to control the microscopic structure of the MOFs and subsequently apply them for the removal of fluoride in water. The maximum capture capacities of La-BTC, La-BPDC, La-BHTA, La-PMA, and La-BDC at 298 K are 105.2, 125.9, 145.5, 158.9, and 171.7 mg g−1, respectively. The adsorption capacity is greater than most reported adsorbents. The adsorption isotherms of La-MOFs for fluoride are well fit to the Langmuir isotherm model. In addition, the adsorption kinetics of La-BTC, La-BPDC, La-BHTA, La-PMA, and La-BDC follows the pseudo-second-order kinetic model, and the kinetic rate-limiting step of adsorption is chemical adsorption. Thermodynamics revealed that temperature is favorable for the adsorption of fluoride. Meanwhile, La-BTC, La-BPDC, La-BHTA, La-PMA, and La-BDC are suitable for the removal of fluoride in a relatively wide pH range (4.0–9.0). Simultaneously, from X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) analysis, electrostatic attraction and ligand exchange are identified as the main action mechanisms for the adsorption of fluoride of La-MOFs. The prepared La-MOFs are used as efficient adsorbents for removal of fluoride in actual water, indicating that they have great potential in removing fluoride in real and complex environmental water. This work provides a new strategy for designing adsorbents with adjustable microstructure and expected function to effectively recover fluorosis in water.

Spiro[3.3]heptane-2,6-dicarboxylic acid (Fecht's acid, H2SHDC) is examined as a non-aromatic terephthalic acid isostere for the first time. The rigid spirocyclic backbone provides greater steric bulk than conventional aromatic dicarboxylates with consequences for pore chemistry and control of interpenetration, presented here in the structures of two new MOFs. Complex 1 is a three-dimensional rod packed structure consisting of Yb-carboxylate chains bridged by SHDC linkers which, although non-porous, exhibits a surprisingly high thermal stability for a spirocyclic cyclobutane derivative. Complex 2 is a co-ligand complex of SHDC with trans-1,2-bis(4-pyridyl)ethene (bpe) which contains linear solvent channels despite fourfold interpenetration. Although the framework does not retain its structure following evacuation, a clear difference is observed in the extended structure compared to the structurally related terephthalate species. This observation suggests the non-aromatic backbone of Fecht's acid and other rigid aliphatic linkers may prove an effective means to disfavour deleterious close inter-framework contacts which prevail in interpenetrated aromatic MOFs.

Poly-p-phenylene terephthamide (PPTA) is widely applied in bulletproof products and composite materials because of its high strength, high modulus, high temperature resistance and creep resistance. The PPTA molecule with highly symmetrical and regular structure is linear structure formed by the alternating connection of benzene ring and amide bond, and the amide bonds between the molecular chains form strong hydrogen bonds. Therefore, the dissolution and depolymerization of PPTA is very challenging. In this work, an efficient catalytic system was developed for the controllable degradation of waste PPTA, and the high-value added monomers terephthalic acid (TPA) and p-phenylenediamine (PPD) were recovered. The results show that the amide bonds of PPTA can be selectively cleaved by the strong Bronsted base catalysts in alcohols, especially in the NaOH/n-butanol system. Under the optimal degradation conditions (5 wt% NaOH in n-butanol, 180 °C, 6 h), the percentage degradation of PPTA is 100%, and the yields of TPA and PPD are 92.0% and 91.5%, respectively. In addition, it is found that the wettability of n-alcohols on PPTA monofilament and the addition of a small amount of water have important influences on the degradation of PPTA. The work elucidates the degradation mechanism of PPTA, and reveals the important factors affecting the depolymerization of PPTA.

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...

open access article A terephthalic acid-modified chitosan−magnetic nanocomposite (Cs−Tp@Fe3O4) was synthesized and characterized. The synthesized Cs−Tp@Fe3O4wasused in a batch process for the adsorptive removal of the acid blue 25 (AB-25) dye inaqueous solutions. The kinetic data were subjected to the pseudo-first-order, pseudo-second-order, Elovich, and intra-particle diffusion models, while the equilibrium datawere evaluated with the Langmuir, Freundlich, Temkin, and Dubinin−Radushkevichisotherm models. The effects of the initial dye concentration, contact time, andadsorbent dosage, as well as their interactions, on the removal efficiency wereinvestigated using the design of experiments based on a central composite design, andthe resultant data were modeled with the response surface methodology (RSM),artificial neural network (ANN), adaptive neuro-fuzzy inference system (ANFIS), andmultiple linear regression (MLR) approaches. The adsorption process followedpseudo-first-order with good agreement between the experimentalQe(exp)andcalculatedQe(cal.)amounts of dye adsorbed, as well as the values of correlation coefficient,R2(0.999) and percentage of sumsquare error, % SSE (0.640). All the investigated adsorption isothermsfitted all models well in the order of Dubinin−Radushkevich> Langmuir > Freundlich > Temkin withR2> 0.9 with the monolayer maximum adsorption capacity of 440.24 mg/g obtained fromthe Langmuir isotherm. The RSM model predicted the maximum removal efficiency at an optimum initial dye concentration of19.11 mg/L, a contact time of 95.3 min, and an adsorbent dosage of 0.18 g. Statistically, the models werefitted in the order of RSM> ANN > ANFIS > MLR. These results indicated that the prepared Cs−Tp@Fe3O4is an efficient adsorbent for the AB-25 dyeremoval with excellent stability for water treatment applications. (8) (PDF) Chitosan–Terephthalic Acid–Magnetic Composite Beads for Effective Removal of the Acid Blue Dye from Aqueous Solutions: Kinetics, Isotherm, and Statistical Modeling. Available from: https://www.researchgate.net/publication/355954648_Chitosan-Terephthalic_Acid-Magnetic_Composite_Beads_for_Effective_Removal_of_the_Acid_Blue_Dye_from_Aqueous_Solutions_Kinetics_Isotherm_and_Statistical_Modeling [accessed Nov 25 2021].

Lignin is the only renewable aromatic material in nature and contains a large number of oxygen-containing functional groups. High-value and green utilization of "lignin-to-chemicals" can be realized via using lignin to produce fine chemicals such as phenols and carboxylic acids, which can not only reduce the waste of lignin in the process of lignocellulosic biomass treatment, but gradually make the substitution of traditional fossil fuels come true. The hydrogenolysis process under catalysis of metal catalyst has high product selectivity and less impurity, which is suitable for the production of same type or single fine chemicals. Hydrogenolysis of lignin via metal catalysts to produce lignin oil, and further modification of functional groups (e.g. methoxyl, alkyl and hydroxyl group) of depolymerized monomers in the bio-oil to yeild phenols and terephthalic acid are reviewed, and catalytic mechanisms are briefly summarized in this paper. Finally, the problems of lignin catalytic conversion existing currently are investigated, and the future development of this field is also prospected.

Direct aerobic oxidation of p-xylene using cobalt, manganese and bromide ion catalyst system, named the Amoco method, is a fundamentally important process to produce terephthalic acid in industry. However, it still suffers from harsh conditions and potential environmental pollution. Herein, we disclose an aerobic oxidation of alkyl aromatics to carboxylic acids through decatungstate photocatalysis featuring mild and green conditions (i.e., ambient temperature, visible light irradiation and atmospheric O2 as the green oxidant). It is scalable for the synthesis of terephthalic acid, which shows a significant potential for industrial production. Various substituted toluene derivatives were well applicable, thus furnishing acid and ester products in good yields.

This paper describes the synthesis and characterization of Zn2+ decorated (adipic and terephthalic acid as linkers) piperazine-based metal-organic framework (P-MOFs) and their extraction behavior toward the Chicago sky blue (CSB) dye. The formation of Zn2+-decorated P-MOFs was confirmed by FT-IR spectroscopy, energy-dispersive spectroscopy, X-ray diffraction, BET surface area analysis and TGA. Adsorption behavior of the synthesized P-MOFs was explored through solid-phase adsorption (batch method) prior to UV-Vis spectrophotometric determination. Adsorption parameters, including adsorbent dosage, pH of solution, dye concentration, and time, were optimized. Excellent percentage removal of 94% and 95% for AP-Zn-MOF and TP-Zn-MOF, respectively, was achieved at pH 7.5. Kinetics studies indicated that the synthesized adsorbents AP-Zn-MOF and TP-Zn-MOF followed the pseudo-second-order rate model with R2 value 0.9989. The Freundlich isotherm with high R2 value as compared to Langmuir isotherm indicated that CSB adsorption for the synthesized MOFs follows multilayer adsorption.

Mercury (Hg) causes serious health issues in its all forms. Deficiency as well as excess of copper ion (Cu2+) in human body is hazardous. A series of four compounds have been derived from carboxylated benzoic acids (benzoic acid, isophthalic acid, terephthalic acid and phthalic acid) and 4H-1,2,4 triazole-4-amine and characterized. Fluorescencce detection of Hg2+ was recorded by the derivates with benzoic acid and isophthalic acid while the derivatives of terephthalic acid and phthalic acid detect Cu2+ by fluorescence “off” mode. Metal ions like Li+, Na+, K+, Zn2+, Al3+, Mg2+, Mn2+, Co2+, Ni2+, Cu2+, Cd2+, Pb2+ and Hg2+ found not to interfere. The stoichiometry of binding is 1:1 for the benzoic acid derivative with Hg2+ while it is 1:2 for the other three derivatives. The binding constants are ca. 10− 4.5 between the sensors and Hg2+ or Cu2+ and detection limits are around 10− 5.5 M. DFT calculation provided optimized geometries of the sensors and confirmed the stoichiometry of binding with Hg2+/Cu2+.

Upcycling of spent plastics has become a more emergent topic than ever before due to the rapid generation of plastic waste associated with the change of lifestyles of the human society. Polyethylene terephthalate (PET) is a major aromatic plastic and herein, the conversion of PET back into arenes was demonstrated in a one-pot reaction combining depolymerization and hydrodeoxygenation (HDO) over a Co/TiO2 catalyst. The effectiveness of the Co/TiO2 catalyst in HDO and the underlining reaction pathway were established using the PET monomer terephthalic acid (TPA) as the substrate. Quantitative TPA conversion together with 75.2 mol% xylene and toluene selectivity under 30 bar initial H2 pressure at 340 °C was achieved after 4 h reaction. More encouragingly, the catalyst induced both depolymerization and HDO reaction via C-O bond cleavage when PET was used as a substrate. 78.9 mol% arenes (toluene and xylene) was obtained under optimized conditions.

The design of efficient nanostructured catalysts is highly desirable for promoting the hydrogenation of 4-carboxybenzaldehyde (4-CBA), which are the key process of hydrorefining of crude terephthalic acid (CTA) to pure terephthalic acid (PTA). Herein, the Pt-FeNi@C, Pt-Fe@C and Pt-Ni@C catalysts were developed and proved to be active for the selective hydrogenation of 4-CBA. As a result, the excellent 4-hydroxymethylbenzoic acid (4-HMBA) selectivity (85%) and benzoic acid (BA) selectivity (88%) were achieved on Pt-FeNi@C and Pt/C, respectively. In comparison with the commercial Pd/C catalyst, the Pt-FeNi@C catalyst exhibits excellent activity (97%) and reduces the occurrence of decarbonylation. Moreover, the Pt-FeNi@C catalyst exhibits excellent recyclability: the catalytic activity did not decrease significantly after four reaction cycles. In combination with detailed characterization, the Pt-FeNi@C catalyst has porous graphene core-shell architecture and remarkable electron transfer capacity. This work may provide some inspirations for the exploration of new PTA hydrofining catalysts.

The asymmetric unit of the polymeric title compound {[Co2(C12H7NO8)(H2O)2]·1.6H2O} n comprises two CoII ions, which are coordinated by fully deprotonated 2-aminodiacetic terephthalic acid (adtp4–) and terminal water molecules in distorted octahedral N1O5 and O6 coordination environments. The title compound features tetranuclear CoII units bridged by κ 3 O:O:O′- and κ 3 O:O,O′-carboxylate groups, which are joined into ribbons via syn–anti carboxylate bridges. The parallel adtp4– ligands with an alternately reversed arrangement further link adjacent CoII ribbons into (010) layers, which are assembled into a three-dimensional supramolecular network via intermolecular hydrogen bonds. The disordered water solvent molecules are situated in channels parallel to [100]. Magnetic measurements and analyses reveal that the title compound displays antiferromagnetic behaviour. The purity of the title compound was characterized by X-ray powder diffraction.

Public health concerns associated with the potential leaching of substances from Polyethylene terephthalate (PET) packaging have been raised due to the role of phthalates as endocrine-disrupting chemicals or obesogens. In particular, changes in the environment such as pH, temperature, and irradiation can improve contaminant migration from PET food packaging. In this study, the in vitro effects of p-phthalates terephthalic acid (TPA) and dimethyl terephthalate (DMT) on murine adipocytes (3T3-L1) were evaluated using concentrations that might be obtained in adult humans exposed to contaminated sources. TPA and, in particular, DMT exposure during 3T3-L1 differentiation increased the cellular lipid content and induced adipogenic markers PPAR-γ, C/EBPß, FABP4, and FASN, starting from low nanomolar concentrations. Interestingly, the adipogenic action of TPA- and DMT-induced PPAR-γ was reverted by ICI 182,780, a specific antagonist of the estrogen receptor. Furthermore, TPA and DMT affected adipocytes’ thermogenic program, reducing pAMPK and PGC-1α levels, and induced the NF-κB proinflammatory pathway. Given the observed effects of biologically relevant chronic concentrations of these p-phthalates and taking into account humans’ close and constant contact with plastics, it seems appropriate that ascertaining safe levels of TPA and DMT exposure is considered a high priority.

In this study, we investigate the hydrothermal liquefaction (HTL) of PET separated from a densified postconsumer plastic mix, with the aim of recovering its monomer. This second raw material is made up of 90% polyolefin, while the remaining 10% is made up of PET, traces of metals, paper, and glass. After preliminary separation by density in water, two batch experiments were performed on the sunken fraction (composed mainly of PET) in a stainless steel autoclave at 345 °C for 30 and 20 min. Both trials resulted in similar yields of the three phases. In particular, the solid yield is around 76% by weight. After a purification step, this phase was analyzed by UV–Vis, 1H-NMR, and FTIR spectroscopy and resulted to be constituted by terephthalic acid (TPA), a product of considerable industrial interest. The study proved that the hydrothermal liquefaction process coupled with density separation in water is effective for obtaining TPA from a densified postconsumer plastic mix, which can be used for new PET synthesis.

A three-component reaction between the 1,4-benzenedicarboxylic (terephthalic) acid (H2bdc), bis(1,2,4-triazol-1-yl)methane (btrm) and zinc nitrate was studied, and three new coordination polymers were isolated by a careful selection of the reaction conditions. Coordination polymers {[Zn3(DMF)(btrm)(bdc)3]·nDMF}∞ and {[Zn3(btrm)(bdc)3]·nDMF}∞ containing trinuclear {Zn3(bdc)3} secondary building units are joined by btrm auxiliary linkers into three-dimensional metal–organic frameworks. The coordination polymer {[Zn(bdc)(btrm)]∙nDMF}∞ consists of Zn2+ cations joined by bdc2− and btrm linkers into a two-fold interpenetrated network. Upon activation, MOF [Zn3(btrm)(bdc)3]∞ demonstrated CO2/N2 adsorption selectivity with an ideal adsorbed solution theory (IAST) factor of 21. All three MOF demonstrated photoluminescence with a maximum near 435–440 nm upon excitation at 330 nm.

Fast fashion trends lead to significant quantities of textiles produced and discarded, its waste is incinerated or landfilled due to a lack of recycling technologies for mixed textiles. Recycling of mixed textiles by hydrothermal liquefaction (HTL) is a novel approach to produce bio-oil and monomers, as no prior sorting or color removal is required. Herein, post-consumer polyester (polyethylene terephthalate (PET)) and cotton garments were subjected to HTL to produce bio-oil and terephthalic acid (TPA). The effects of blending ratio of PET and cotton, temperature and alkali catalyst on the product distributions are investigated. A maximum bio-oil yield of 26% was attained at 325 °C for a 95% Cotton/ 5% PET mix under alkali conditions. TPA yields ranged from 48 to 91%, where 50/50% PET/cotton resulted in a higher TPA yield than 95/5% PET/cotton textile wastes. The results obtained contribute to the development of sustainable recycling processes of mixed textiles.

Enantioselective sensing of chiral molecules is an important issue for both biomedical research and the pharmaceutical industry. Here, an enantioselective photoelectrochemical (PEC) sensor was constructed by integrating TiO2 nanotubes (NTs) with metal-organic frameworks (MOFs) for the identification of enantiomers. TiO2 NTs prepared by electrochemical anodization can not only be used as the PEC platform but also as the metal-ion precursor to react with terephthalic acid (BDC) to form MIL-125(Ti) in situ. A postsynthetic exchange (PSE) method was used for exchanging the ligand of MIL-125 by 2-aminoterephthalic acid (BDC-NH2) for further functionalization. Homochirality was then successfully introduced into achiral MIL-125-NH2 by postsynthetic modification (PSM) with l-histidine (l-His). The resulting homochiral metal-organic frameworks (MOF)-in-NT architecture exhibits excellent discrimination ability for the chiral recognition of 3,4-dihydroxyphenylalanine (l/d-DOPA) enantiomers. Moreover, by adjusting the charge-carrier separation-induced photocurrent variation mechanism, the as-proposed homochiral PEC electrode exhibits a broad application potential for the discrimination of enantiomers. Because of the construction of binder-free monochiral MOF-in-NT structure directly on a Ti-metal substrate, the valuable feature is that the PEC sensing platform can be used directly, thereby providing a stable, simplified, and low-cost sensing device for the recognition of chiral enantiomers.

Organics including terephthalic acid and glucose are added to selectively adsorb on iron oxide or graphene oxide, which can further modify the structure properties and metal-support interaction of iron oxide/reduced graphene oxide catalysts. The proper metal-support interaction is favorable for the reduction and carburization of iron oxide to form more active sites for CO hydrogenation. Thus, higher CO conversion and heavier hydrocarbons are achieved over organics modified catalysts. This simple, eco-friendly and economic viable method opens a new avenue from molecular level for the design of highly active supported catalysts.

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.

MOF based on cobalt terephthalate and 1,10-phenanthroline was synthesized according to a modified procedure by the interaction of cobalt nitrate, terephthalic acid, and 1,10-phenanthroline in the presence of alkali. MOF has been used to extract the organic Congo red and methylene blue dyes from their aqueous solutions. The degree of removal depends on temperature and reaches values close to 100% within 60 min at 291 and 308 K. The limiting adsorption is 40 mg/g, and the Langmuir model is in good agreement with the experimental results. The antioxidant activity of MOF was evaluated on a model solution of adrenalin hydrochloride in an alkaline medium with a maximum inhibition of the oxidation of the model compound of 87.05%. The antibacterial activity of MOF against Escherichia coli (E. coli) was assessed as satisfactory, which is explained by the release of metal cations and organic ligand, and the long period of action is due to their synergistic action.

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.

Chemo‐biological upcycling of poly(ethylene terephthalate) (PET) developed in this study includes the following key steps: chemo‐enzymatic PET depolymerization, biotransformation of terephthalic acid (TPA) into catechol, and its application as a coating agent. Monomeric units were first produced through PET glycolysis into bis(2‐hydroxyethyl) terephthalate (BHET), mono(2‐hydroxyethyl) terephthalate (MHET), and PET oligomers, and enzymatic hydrolysis of these glycolyzed products using Bacillus subtilis esterase (Bs2Est). Bs2Est efficiently hydrolyzed glycolyzed products into TPA as a key enzyme for chemo‐enzymatic depolymerization. Furthermore, catechol solution produced from TPA via a whole‐cell biotransformation (Escherichia coli) could be directly used for functional coating on various substrates after simple cell removal from the culture medium without further purification and water‐evaporation. This work demonstrates a proof‐of‐concept of a PET upcycling strategy via a combination of chemo‐biological conversion of PET waste into multifunctional coating materials., PETit four: A proof‐of‐concept upcycling strategy to convert poly(ethylene terephthalate) (PET) into multifunctional catechol coating materials is presented: (1) PET glycolysis without purification; (2) one‐step enzymatic hydrolysis of glycolyzed products into terephthalic acid (TPA); (3) whole‐cell biotransformation of TPA into catechol using an engineered Escherichia coli; (4) application of crude catechol solution as a multifunctional coating material without purification.

This paper reports that the optical properties of anthraquinone (AQ) and its photo-catalytic performance in the visible light-driven p-xylene (PX) oxidation can be fine-tuned and improved through varying its skeleton substituents at the molecular level, and the electron-withdrawing substituent exhibits a better improvement effect than the electron-donating one. The best catalyst 2-carboxyanthraquinone (AQ-COOH) can achieve 70.9% PX conversion and 88.2% p-toluic acid selectivity under visible light illumination and 1 atm O2 pressure. The addition of benzenesulfonic acid in the above photocatalytic system can further increase PX conversion to 86.7%, along with a significant improvement in the selectivity of p-carboxybenzaldehyde and terephthalic acid, which likely originates from the unique recombination behavior of the photo-generated charge carriers of the catalyst and the additive driven by the strong interactions between their aromatic skeletons and acidic substituents. Furthermore, AQ-COOH can achieve almost quantitative yield of acetylacetone in ethylbenzene photooxidation and the regulating effect of toluene's para-position substituents on its reactivity is also reported in the AQ-COOH photocatalysis system. Based on quenching tests and EPR spectral characterizations, the oxygen vacancies (h+), superoxide free radicals (O2•-) and singlet oxygen (1O2) as the photo-generated active species are involved in the proposed photo-catalysis mechanism.

There is a need for high‐performance applications for terephthalic acid (TPA) polyesters with high heat resistance, impact toughness, and optical clarity. Bisphenol A (BPA) based polycarbonates and polyarylates have such properties, but BPA is an endocrine disruptor. Therefore, new TPA polyesters that are less hazardous to health and the environment are becoming popular. Tetramethylcyclobutanediol (TMCD) is a difunctional monomer that can be polymerized with TPA and other diols to yield copolyesters with superior properties to conventional TPA polyesters. It has a cyclobutyl ring that makes it more rigid than cyclohexanedimethanol (CHDM) and EG. Thus, TMCD containing TPA copolyesters can have high heat resistance and impact strength. TPA can be made from abundantly available upcycled polyethylene terephthalate (PET). Therefore, this review discusses the synthesis of monomers and copolyesters, the impact of diol composition on material properties, molecular weight, effects of photodegradation, health safety, and substitution of cyclobutane diols for future polyesters., High‐performance plastics: Tetramethylcyclobutanediol containing terephthalic acid based copolyesters can give high heat resistance and impact toughness which are useful in the manufacturing of high‐performance plastic parts.

Polyfluoroalkyl phosphate diesters (diPAPs) are widely used for paper and cardboard impregnation and discharged via waste streams from production processes and consumer products. To improve the knowledge about the environmental fate of diPAPs, electrochemical oxidation (EO) was used to characterize the transformation pathways and reaction kinetics. 6:2 diPAP was transformed electrochemically to perfluorocarboxylic acids (C5-C7 PFCAs) and two intermediates (6:2 fluorotelomer carboxylic acid, FTCA, and 6:2 fluorotelomer unsaturated carboxylic acid, FTUCA). EO of potential intermediates 6:2 monoPAP and 6:2 fluorotelomer alcohol (FTOH) showed similar transformation products but with different ratios. We show that 6:2 diPAP is initiated by OH radical (•OH) reactions, as evidenced by the measured steady-state concentrations of •OH with the probe molecule terephthalic acid, quenching experiments, and pH dependency of the reaction. PFHpA was the main product of 6:2 diPAP oxidation, and it was formed in a pseudo-first-order reaction for which a bimolecular rate constant was estimated to be kO•H,diPAPformPFHpA = 9.4(±1.4) × 107 M-1 s-1 by an initial rate approach. This can be utilized to estimate the environmental half-life of 6:2 diPAP for the reaction with •OH and the formation kinetics of persistent PFCAs.

The cobalt-based metal organic frameworks (Co-MOFs) catalyst has been prepared with using terephthalic acid and 4,4′-bipyridine as organic linkers by facile solvothermal method for one pot oxidative esterification. The prepared catalyst was pyrolysed at different temperature and then applied for oxidation of aldehyde using molecular oxygen as benign oxidant under mild conditions. The Co-MOFs pyrolysed at 800 °C (denoted as Co-MOFs-800) catalyst exhibited excellent catalytic activity, selectivity and recyclability toward the oxidative esterification of benzaldehydes. Furthermore, it can be reused up to 5 runs without significant loss of activity.

Efficient gas separation and purification play a vital role in the current advanced development of industry, and the application of MOF adsorbents in this area with highly technical materials shows obvious advantages. On the basis of reticular chemistry, the 4-c lvt MOF adsorbent [CuDTTA]·3DMF·CH3CN has been constructed (CuDTTA; H2DTTA = 2,5-bis(1H-1,2,4-triazol-1-yl)terephthalic acid). CuDTTA reveals a multiple-micropore system and high-density active sites decorated on the channel surfaces, which are conducive to its extraordinary selectivity of CO2/CH4 and C2H2/CH4 (29 and 166, 1:1). In combination with an analysis of Qst values, CuDTTA possesses the synergistic effect of size sieving and abundant functional sites, significantly improving the gas adsorption and separation performance. Meanwhile, the results also reveal that functional sites have a stronger binding affinity toward C2H2 with respect to CO2. Such a conclusion renders CuDTTA to be a promising adsorbent material for industrial applications.

The crude glycerol is the main by-product of biodiesel production and contains large amounts of potassium (or sodium) soap. These alkaline compounds may be reacted with ester groups of polyethylene terephthalate (PET) to form the corresponding terephthalic acid salts. In this work, the process of PET depolymerization with crude glycerol with a high content of potassium salts was studied. Depolymerization is the multistage process and proceeds through the formation of oligomers of various molecular weights. Subsequently, the resulting intermediate compounds decompose to low molecular weight oligomers (dimers and trimers), up to dipotassium terephthalate (DPT). A general reaction scheme and a mathematical model of the process are represented, and rate constants of all reactions are estimated.

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.

2,5-Furan dicarboxylic acid (FDCA) is a promising intermediate for producing polyethylene furan dicarboxylate, an alternative to polyethylene terephthalate that combines a significantly lower greenhouse gas footprint with better mechanical and gas barrier properties. This work presents a process design and techno-economic evaluation for producing FDCA from non-edible biomass via the oxidation of furfural to furoate salt, and subsequent carboxylation to furandicarboxylate salt. Major technical uncertainties are associated with the possible polymerization of furfural in the oxidation step and the state of salt phase in the carboxylation step. Based on the furfural market price of $1400/ton this process requires a minimum selling price of 2000 ± 500 $/ton FDCA. To compete with purified terephthalic acid (PTA), it requires a premium of 100% for better performance and sustainability, or a combination of much cheaper furfural and a much lower capital expenditures (CAPEX).

A series of 1,3 and 1,4-bis[5-(R-sulfanyl)-1,2,4-triazol-3-yl)benzene derivatives were synthesized by the reaction of isophthalic and terephthalic acid hydrazides with methyl and aryl isothiocyanates, followed by base-catalyzed cyclization and alkylation of the resulting bis-triazolethiols with alkyl bromides. The suggested obesity–colorectal cancer association initiated evaluation of the antiproliferative activity of the newly synthesized compounds against a panel of obesity-related colorectal cells and inhibition of pancreatic lipase (PL). In vitro enzymatic, colorimetric, and cell culture bioassays were carried out with respective reference agents. Among the tested compounds, 1,3-bis{5-[(4-bromobenzyl)sulfanyl]-4-methyl-4H-1,2,4-triazol-3-yl}benzene showed clearly promising, though unselective, cytotoxicity in HT29, HCT116, SW620, CACO2, and SW480 cancer cells with a PL-IC50 value of 9.57±1.21 μM (

A new lanthanum complex with 2,5-bis((3-carboxylphenyl)amino)terephthalic acid is synthesized by a solvent thermal reaction. The La(III) complex monomer forms a chain by hydrogen bonding. The interaction mode of the complex with DNA is studied by fluorescence spectroscopy, and the result match the molecular docking test, the complex binds to the DNA by insertion, the fluorescence quenching constant is 0.1257. The particle size of the crystal powder is about 500 nm, which can be observed by SEM. The complex demonstrates a good anticancer activity.

Five kinds of diacid comprising ionic liquid catalyst [HO3S–(CH2)4-mim]Cl–MClx] were prepared, and their chemical structure, thermal stability and acidity were tested and analyzed. The performance evaluation of catalysts was carried out, and the process parameters were optimized. The cycling stability of the catalysts was investigated. Then, the catalytic degradation of polyethylene terephthalate (PET) was studied, and used mineral water bottles as an example. The chemical structure and molecular weight of the degradation product terephthalic acid bis(2-hydroxyethyl) ester (BHET) were analyzed. The results showed that among the catalysts synthesized, [HO3S–(CH2)4-mim]Cl–FeCl3 had the great catalytic performance and good thermal stability. According to the thermal gravimeter analysis, the decomposition temperature of the diacid ionic liquid catalyst ranges from 400 to 560 °C, while the degradation reaction temperatures in this paper are all below 250 °C, so that it has good thermal stability. At 190 °C, the PET alcoholysis rate reached 98.7% and the BHET yield reached 95.5% for 6 h, and the highest catalytic activity could still be maintained after 6 cycles, which indicate that the catalyst has excellent performance for degrading PET, and will have a great application prospect.

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%.

Polyesters synthesized from 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) and terephthalic acid (TPA) are improved alternatives to toxic polycarbonates based on bisphenol A. In this work, we use ωB97X-D/LANL2DZdp calculations, in the presence of a benzaldehyde polarizable continuum model solvent, to show that esterification of TMCD and TPA will reduce and subsequently dehydrate a dimethyl tin oxide catalyst, becoming ligands on the now four-coordinate complex. This reaction then proceeds most plausibly by an intramolecular acyl-transfer mechanism from the tin complex, aided by a coordinated proton donor such as hydronium. These findings are a key first step in understanding polyester synthesis and avoiding undesirable side reactions during production.

A stable 3-D metal–organic framework (MOF), [Cd(H2DTPA)(1.2-mbix)]n (1), has been constructed with aromatic 2,3-dihydroxy terephthalic acid (H4DTPA) and cadmium salt under solvothermal conditions. ...

Interaction of scandium(III) salts with 2,2′-bipyridine-4,4′-dicarboxylic and terephthalic acids under solvothermal conditions yields two novel metal-organic frameworks [Sc2(HCOO)2(OH)2(bpydc)]·2H2O (1) and [Sc(HCOO)(bdc)] (2), where bpydc2– is 2,2′-bipyridine-4,4′-dicarboxylate, bdc2– is terephthalate, HCOO– is formate. The crystal structures of compounds 1 and 2 are determined by single-crystal XRD. Both compounds contain formate anions as additional linkers and have a dense structure. The chemical composition and phase purity of studied compounds are confirmed by powder XRD, TG analysis, elemental analysis, and IR spectroscopy.