Biodegradable Hydrogenated Dimer Acid-Based Plasticizers for PLA with Excellent Plasticization, Thermal Stability and Gas Resistance.

The use of vegetable oil-dervied plasticizers to enhance the flexibility of polylactic acid (PLA) has received much attention due to their renewability, inexpensiveness and biodegradation. However, the double bonds in vegetable oil-based plasticizers limit their compatibility with PLA, resulting in PLA-derived products with reduced flexibility. Herein, we examined soybean oil-derived hydrogenated dimer acid-based polyethylene glycol methyl ether esters (HDA-2n, 2n = 2, 4, 6 or 8, referring to the ethoxy units) developed via the direct esterification of saturated hydrogenated dimer acid and polyethylene glycol monomethyl ethers. The resulting HDA-2n was first used as a plasticizer for PLA, and the effects of the ethoxy units in HDA-2n on the overall performance of the plasticized PLA were systematically investigated. The results showed that, compared with PLA blended with dioctyl terephthalate (DOTP), the PLA plasticized by HDA-8 with the maximum number of ethoxy units (PLA/HDA-8) exhibited better low-temperature resistance (40.1 °C vs. 15.3 °C), thermal stability (246.8 °C vs. 327.6 °C) and gas barrier properties. Additionally, the biodegradation results showed that HDA-8 could be biodegraded by directly burying it in soil. All results suggest that HDA-8 could be used as green alternative to the traditional petroleum-based plasticizer DOTP, which is applied in the PLA industry.

Single-Atom Phosphorus Defects Decorated CoP Cocatalyst Boosts Photocatalytic Hydrogen Generation Performance of Cd0.5 Zn0.5 S by Directed Separating the Photogenerated Carriers.

Design and preparation of an efficient and nonprecious cocatalysts, with structural features and functionality necessary for improving photocatalytic performance of semiconductors, remain a formidable challenge until now. Herein, for the first time, a novel CoP cocatalyst with single-atom phosphorus vacancies defects (CoP-Vp ) is synthesized and coupled with Cd0.5 Zn0.5 S to build CoP-Vp @Cd0.5 Zn0.5 S (CoP-Vp @CZS) heterojunctions photocatalysts via a liquid phase corrosion method following by an in suit growth process. The nanohybrids deliver an attractive photocatalytic hydrogen production activity of 2.05 mmol h-1 30 mg-1 under visible-light irradiation, which is 14.66 times higher than that of the pristine ZCS samples. As expected, CoP-Vp further enhances the charge-separation efficiency of ZCS, in addition to the improvement of the electron transfer efficiency, which is confirmed by the ultrafast spectroscopies. Mechanism studies based on density functional theory calculations verify that Co atoms adjacent with single-atom Vp play the key role in translation, rotation, and transformation of electrons for H2 O reduction. This scalable strategy focusing defect engineering provides a new insight into designing the highly active cocatalysts to boost the photocatalytic application.

High-Branched Organosilicon Epoxy Resin with Low Viscosity, Excellent Toughness, Hydrophobicity, and Dielectric Property.

Rapidly developing technology places higher demands on materials, thus the simultaneous improvement of materials' multiple properties is a hot research topic. In this work, a high-branched silicone epoxy resin (QSiE) was synthesized and applied to the curing system of bisphenol A epoxy resin (DGEBA) for modification investigations. When 6 wt% QSiE was added to the system, the viscosity dropped by 51.8%. The mechanical property testing results indicated that QSiE could significantly enhance the material's toughness while preserving good rigidity. The impact strength was enhanced by 1.31 times when 6wt% of QSiE was introduced. Additionally, the silicon skeleton in QSiE has low surface energy and low polarizability, which could endow the material with good hydrophobic and dielectric properties. This work provided a new idea for the preparation of high-performance epoxy resin additives, and provided a broad prospect for cutting-edge applications of epoxy resins.

BiVO4-Deposited MIL-101-NH2 for Efficient Photocatalytic Elimination of Cr(VI).

In this study, a flower-like BiVO4/MIL-101-NH2 composite is synthesized by a facile and surfactant-free process. The -COO--Bi3+ ionic bond construction was conductive to enhance the interface affinity between BiVO4 and MIL-101-NH2. Due to the highly efficient light capture and sufficient electron traps induced by oxygen vacancies and the formation of a heterostructure, the improved separation and transportation rates of charge carriers are realized. In addition, the MIL-101-NH2/BiVO4 composite is favorable for Cr(VI) photocatalytic removal (91.2%). Moreover, FNBV-3 (Fe/Bi = 0.25) also exhibited an excellent reusability after five cycles.

Spatial Relation Controllable Di-Defects Synergy Boosts Electrocatalytic Hydrogen Evolution Reaction over VSe2 Nanoflakes in All pH Electrolytes.

Defect engineering of transition metal dichalcogenides (TMDCs) is important for improving electrocatalytic hydrogen evolution reaction (HER) performance. Herein, a facile and scalable atomic-level di-defect strategy over thermodynamically stable VSe2 nanoflakes, yielding attractive improvements in the electrocatalytic HER performance over a wide electrolyte pH range is reported. The di-defect configuration with controllable spatial relation between single-atom (SA) V defects and single Se vacancy defects effectively triggers the electrocatalytic HER activity of the inert VSe2 basal plane. When employed as a cathode, this di-defects decorated VSe2 electrocatalyst requires overpotentials of 67.2, 72.3, and 122.3 mV to reach a HER current density of 10 mA cm-2 under acidic, alkaline, and neutral conditions, respectively, which are superior to most previously reported non-noble metal HER electrocatalysts. Theoretical calculations reveal that the reactive microenvironment consists of two adjacent SA Mo atoms with two surrounding symmetric Se vacancies, yielding optimal water dissociation and hydrogen desorption kinetics. This study provides a scalable strategy for improving the electrocatalytic activity of other TMDCs with inert atoms in the basal plane.

Cation-Modulated HER and OER Activities of Hierarchical VOOH Hollow Architectures for High-Efficiency and Stable Overall Water Splitting.

Atom-scale modulation of electronic regulation in nonprecious-based electrocatalysts is promising for efficient catalytic activities. Here, hierarchically hollow VOOH nanostructures are rationally constructed by partial iron substitution and systematically investigated for electrocatalytic water splitting. Benefiting from the hierarchically stable scaffold configuration, highly electrochemically active surface area, the synergistic effect of the active metal atoms, and optimal adsorption energies, the 3% Fe (mole ratio) substituted electrocatalyst (VOOH-3Fe) exhibits a low overpotential of 90 and 195 mV at 10 mA cm-2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline media, respectively, superior than the other samples with a different substituted ratio. To the best of current knowledge, 195 mV overpotential at 10 mA cm-2 is the best value reported for V or Fe (oxy)hydroxide-based OER catalysts. Moreover, the electrolytic cell employing the VOOH-3Fe electrode as both the cathode and anode exhibits a cell voltage of 0.30 V at 10 mA cm-2 with a remarkable stability over 60 h. This work heralds a new pathway to design efficient bifunctional catalysts toward overall water splitting.

Synthesis of 1H-indole-3-sulfonates via palladium-catalyzed tandem reactions of 2-alkynyl arylazides with sulfonic acids.

An efficient method for the synthesis of 1H-indole-3-sulfonates via palladium-catalyzed tandem reactions of 2-alkynyl arylazides with sulfonic acids has been developed. The desired products were obtained in good to excellent yields under mild reaction conditions. The reactions were shown to proceed very fast, in most cases, within 10 min.

Synthesis of Gemini-type imidazoline quaternary ammonium salt using by-product fatty acid as corrosion inhibitor for Q235 steel.

Gemini-type imidazoline quaternary ammonium salt is a new type of environmentally friendly corrosion inhibitor has been widely used in engineering materials. However, most of them are hazardous/toxic compounds derived from petroleum-based products, which did harm to environment. In this work, an environmentally friendly Gemini-shaped imidazoline quaternary ammonium salt corrosion inhibitor (G211) was synthesized using cheap fatty acid recycled from dimer acid industry as feedstock. The corrosion inhibition effects of G211 on Q235 steel in 1 M HCl solution were investigated through weight loss experiments, potential polarization curves, and alternating current impedance spectroscopy experiments. The results show that the inhibition rate of G211 as a mixed-type inhibitor is up to 94.4% and the concentration drop as low as 500 ppm at 25 â„ƒ. The adsorption of G211 on Q235 surface follows Langmuir adsorption isothermal curve. The chemical composition of the Q235 steel surface was analyzed through scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Furthermore, the possible corrosion inhibition mechanism of G211 on the surface of Q235 steel is proposed. This article not only presents an outstanding solution for safeguarding Q235 steel against corrosion but also introduces a feasible method for high-value utilization of monomer acid (MA).

Integration of N- and P- elements in sodium alginate aerogels for efficient flame retardant and thermal insulating properties.

In the field of building energy conservation, the development of biodegradable biomass aerogels with excellent mechanical performance, flame retardancy and thermal insulation properties is of particular importance. Here, a directional freeze-drying method was used for fabricating composite sodium alginate (SA) aerogels containing functionalized ammonium polyphosphate (APP) flame retardant. In particular, APP was coated with melamine (MEL) and phytic acid (PA) by a supramolecular assembly process. Through optimizing the flame retardant addition, the SA-20 AMP sample exhibited excellent flame retardant and thermal insulation properties, with the limiting oxygen index of 38.2 % and the UL-94 rating of V-0. Such aerogels with anisotropic morphology demonstrated a low thermal conductivity of 0.0288 (W/m·K) in the radial direction (perpendicular to the lamellar structure). In addition, as-obtained aerogels displayed remarkable water stability and mechanical properties, indicating significant potential for practical applications.

Preparation and Properties of Epoxy Adhesives with Fast Curing at Room Temperature and Low-Temperature Resistance.

Developing a highly efficient multifunctional epoxy adhesive is still an enormous challenge, which can rapidly cure at room temperature and has excellent low-temperature resistance performance and is crucial for the epoxy adhesive and electrical sealing fields during severe cold seasons. Herein, diglycidyl phthalate (DP) was synthesized with phthalic anhydride (PA) and epichlorohydrin (ECH) to enhance the curing rate and low-temperature resistance of bisphenol A diglycidyl ether (DGEBA) adhesive. The modified DP/DGEBA adhesives were systematically analyzed by gel time, mechanical properties, and aging resistance (time, temperature, and dry/wet treatment). The results showed that DP with highly active ester groups significantly accelerates the curing speed of DP/DGEBA. DP's rigid aromatic ring-benzene ring and flexible group-ester group gave the adhesive better low-temperature resistance. When the addition of DP was 10 wt % (based on the mass of DGEBA), the gel time of DP/DGEBA epoxy adhesives was reduced by 58 min compared to unmodified DGEBA epoxy adhesive, and after aging at low temperature (-20 °C) for 7 days, the tensile shear strengths of polyvinyl chloride (PVC) and aluminum plate increased by 76.2 and 80.6%, respectively. The results of non-isothermal curing kinetics and dynamic mechanical analysis suggested that when the amount of DP was 10 wt %, the reaction activation energy of DP/DGEBA epoxy adhesive decreased by 4.0%, and the cross-linking density increased by 8.9%. Moreover, the toughness of the modified adhesive was also improved. This study opens up a feasible way for the development of a low temperature-resistant epoxy adhesive cured rapidly at room temperature in practical application.

Developing novel imidazoline-modified glucose derivatives as eco-friendly corrosion inhibitors for Q235 steel.

Many natural compounds and imidazoline derivatives have been previously evaluated as eco-friendly corrosion inhibitors for application in the food, pharmaceutical and chemical industries. Herein, a novel alkyl glycoside cationic imaginary ammonium salt (FATG) was designed via the grafting of imidazoline molecules into the skeleton of a glucose derivative, and its effects on the electrochemical corrosion behavior of Q235 steel in 1 M HCl were systemically investigated by electrochemical impedance spectroscopy (EIS), potentiodynamic polarization curves (PDP), and gravimetric measurements. The results indicated that its maximum inhibition efficiency (IE) was 96.81% at a concentration as low as 500 ppm. The adsorption of FATG on the Q235 steel surface followed the Langmuir adsorption isotherm. The scanning electron microscopy (SEM) and diffraction X-ray (XRD) results suggested the formation of inhibitor film on the metal surface, which significantly impeded the corrosion of Q235 steel. Additionally, FATG showed a high biodegradability efficiency (98.4%), which had great potential as a green corrosion inhibitor based on concepts of greenness and biocompatibility.

Recyclable TPA-Modified MIL-88-Supported Ionic Pt as a Highly Efficient Catalyst for Alkene Hydrosilylation.

The hydrosilylation reaction driven by a homogeneous catalyst has been widely used in the industrial synthesis of functionalized silicone compounds. However, the homogeneous catalyst for hydrosilylation has the shortcomings of nonrecyclability, undesirable side reactions, and high cost. In this work, a highly efficient heterogeneous catalyst was prepared by loading Pt ions on MIL-88 modified with trimethoxy[3-(phenylamino)propyl]silane. In comparison with previous research studies, the resulting catalyst can exhibit high catalytic activity and excellent stability during the hydrosilylation reaction, which was attributed to the presence of a pyrrolic nitrogen structure between TPA-MIL-88 and the Pt ion. Besides them, 1.2%Pt/TPA-MIL-88 showed the highest catalytic activity and can be reused five times without significant deactivation. Importantly, 1.2%Pt/TPA-MIL-88 also achieved satisfactory results when it was used to catalyze the hydrosilylation reaction for other olefins, implying great potential for application in the silicone industry.

Cellulose-based polypropoxy ether carboxylates as highly compatible, effective, and migration-resistant plasticizers for poly (lactic acid).

The utilization of cellulose for enhancing the strength, the PLA has received significant attention, however, poor interfacial compatibility of solid cellulose with PLA matrix still hinders their broader application. Herein, highly compatible cellulose-based polypropoxy ether carboxylates (CPPEC) were firstly manufactured via propoxylation of cellulose and following esterification with acetic acid, butyric acid, as well as oleic acid, respectively. Liquid CPPEC delivered excellent performances to PLA, especially, the values of elongation at break and low-temperature resistance of PLA blended with cellulose-based polypropoxy ether acetate (PLA/CPPEA) were respectively increased by 630.9 % and 146.3 % compared with those of neat PLA due to the synergistic effect of propyl and methyl groups in CPPEC with PLA matrix. Additionally, migration resistance of PLA/CPPEA increased 14.3 and 11.2 times, respectively, compared with those of PLA specimens blended with epoxidized soybean oil and dioctyl phthalate. All findings suggest that the CPPEC is suitable for large-scale application in the PLA industry.

Facile construction of a sulfur vacancy defect-decorated CoSx@In2S3 core/shell heterojunction for efficient visible-light-driven photocatalytic hydrogen evolution.

Photoinduced electron-separation and -transport processes are two independent crucial factors for determining the efficiency of photocatalytic hydrogen production. Herein, a sulfur vacancy defect-decorated CoSx@In2S3 (CoSx@VS-In2S3) core/shell heterojunction photocatalyst was synthesized via an in situ sulfidation method followed by a liquid-phase corrosion process. Photocatalytic hydrogen evolution experiments showed that the CoSx@VS-In2S3 nanohybrids delivered an attractive photocatalytic activity of 4.136 mmol h-1 g-1 under visible-light irradiation, which was 8.23 times higher than that of the pristine In2S3 samples. As expected, VS could enhance the charge-separation efficiency of In2S3 through rearranging the electrons of the In2S3 basal plane, in addition to improving the electron-transfer efficiency, as visually verified by transient absorption spectroscopy. Mechanism studies based on density functional theory calculations confirmed that the In atoms adjacent to VS played a key role in the translation, rotation, and transformation of electrons for water reduction. This scalable strategy focused on defect engineering paves a new avenue for the design and assembly of 2D core/shell heterostructures for efficient and robust water-splitting photocatalysts.

Integration of Phosphotungstic Acid into Zeolitic Imidazole Framework-67 for Efficient Methylene Blue Adsorption.

To enhance the dye adsorption capacity of zeolitic imidazolate framework-67 (ZIF-67), phosphotungstic acid (HPW) was integrated into ZIF-67 to prepare composite adsorbents. Characterization results demonstrated that the electronegative HPW was uniformly and tightly deposited on the electropositive ZIF-67. Methylene blue (MB) was selected as a model contaminant to evaluate the adsorption performance of hybrid adsorbents. Results showed that HPW@ZIF-67 had excellent adsorption capacity toward cationic MB. The optimal ZIF-67-0.2 HPW sample with a HPW dosage of 9.9 wt % presented an adsorption capacity of 446.4 mg g-1. ZIF-67-0.2 HPW displayed good reusability, and the adsorption data can be well described by pseudo-second order and Langmuir isotherm models. The adsorption mechanism was ascribed to the preferred electrostatic attraction and π-π stacking between MB and composite adsorbents. This work provides a route to enhance organic dye removal efficiency of ZIF materials through regulation of surface charge property and sheds light on the development of ZIF-based adsorbents.

Construction of MIL-125-NH2@BiVO4 Composites for Efficient Photocatalytic Dye Degradation.

The design and construction of a photocatalyst with a heterostructure are a feasible and effective way to enhance the catalytic performance. Herein, a specially designed composite based on MIL-125-NH2 and BiVO4 was prepared and used for wastewater treatment. In the hybrid MIL-125-NH2@BiVO4, MIL-125-NH2 was uniformly dispersed on the BiVO4 surface. There is a high affinity between MIL-125-NH2 and BiVO4 due to the lattice defects. Under visible light irradiation, the catalytic activity of the as-prepared composite was evaluated by the degradation of various dyes such as malachite green, crystal violet, methylene blue, and Congo red. Nearly 98.7, 99.1, and 41.0% of the initial MG, MB and Cr(VI) were respectively removed over the optical sample of BVTN-5, demonstrating that the hybrid holds great promise for practical applications. Moreover, the composites can be recycled and reused with good stability after five consecutive cycles. The mechanism was proposed and discussed in detail. This work will shed light on the construction of MOF-based composites for efficient photocatalysis.

Preparation of aramid-based epoxy resin from low-grade aramid.

Low-grade aramid fibers, an unavoidable by-product in the industrialized process of aramid fiber production, are difficult to utilize and harmful to the environment. In this study, low-grade aramid fibers were recycled to assemble a high-quality epoxy resin through an epoxidation modification. Triggered by the epichlorohydrin, the molecular configuration of the low-grade aramid fibers was altered through crosslinking and chain-extension processes. bisphenol-A epoxy resin (E-51) with 5% aramid-based epoxy resin cured product exhibited improved mechanical and thermal properties, outperforming pure E-51 and pure aramid. This improvement is caused by the increased percentage of epoxide groups and flexible ether bonds. This work opens up new possibilities to maximize the reclamation of low-grade aramid fibers, which currently poses an obstacle in waste recycling.

Study on the Synthesis of Castor Oil-Based Plasticizer and the Properties of Plasticized Nitrile Rubber.

A series of new environment-friendly plasticizers was synthesized from castor oil and used to plasticize nitrile rubber (NBR). The test results showed that tensile strength, elongation at break, and tear strength of NBR vulcanizates plasticized by castor oil-based plasticizers were found to be better than that of dioctyl phthalate (DOP). The aging test taken demonstrated that the castor oil-based plasticizers could improve the hot air and oil aging resistance of NBR vulcanizates. The thermal stability test illustrated that castor oil-based plasticizers enhanced the thermal stability of NBR vulcanizates, and the initial decomposition temperatures (T10%) were about 100 °C higher than that of DOP. In general, the studies manifested that EACO and EBCO can replace DOP to plasticize NBR and are used in fields that require high mechanical properties, aging resistance, and thermal stability. This study emphasizes the effects of sustainable, cost-effective, and high-efficiency plasticizers on NBR.

Synthesis and properties of castor oil based plasticizers.

A series of environment-friendly plasticizers has been synthesized from castor oil through a mild esterification/epoxidation reaction. The modified epoxy acetylated castor oil (EACO) can plastify poly(vinyl chloride) (PVC) efficiently, even better than the commercial plasticizers dioctyl terephthalate (DOTP) and epoxidized soybean oil (ESO), in terms of in tensile strength, migration stability, solvent extraction stability and thermal stability. Specifically, the tensile strength and elongation at break of a PVC sample plastified by epoxy acetylated castor oil (EACO) were 18.5 and 10.0% higher than that of DOTP, and 13.9 and 23.8% higher than that of ESO, respectively. Volatility, migration, solvent extraction and thermal stability tests indicated that the presence of carbon-carbon double bonds and hydroxy groups reduce the compatibility of a plasticizer with PVC while the presence of epoxy groups and ester bonds can improve the plasticizing effect of the plasticizer on PVC. In addition, alkyl groups can improve the plasticizing effect on PVC while benzene rings increase the rigidity of the PVC. The design strategy based on castor oil highlights a sustainable avenue for preparing cost-effective and high-efficiency plasticizers.

Role of the Oxethyl Unit in the Structure of Vegetable Oil-Based Plasticizer for PVC: An Efficient Strategy to Enhance Compatibility and Plasticization.

Developing vegetable oil-derived primary plasticizers for poly(vinyl chloride) (PVC) is still a challenge because of their insufficient compatibility. As described in this work, we report the synthesis of plasticizers through the esterification of polyethylene glycol methyl ether and dimer acid, in which dimer acid is renewable material prepared via a two-step reaction (1) the hydrolysis of fatty acids from soybean oil at 70 °C and (2) subsequent Diels-Alder reaction at 250 °C. The resulting plasticizers, dimer acid-derived polyethylene glycol methyl ether esters (DA-2n, 2n = 2, 4, 6 or 8 referring to the number of oxethyl units per molecule), were blended with PVC. It was found that the tensile properties, transparency, and thermal stability of plasticized PVC (PVC-DA-2n) increased significantly with an increase in the number of oxyethyl units. Fourier-transform infrared spectroscopy analysis revealed that its good compatibility can be attributed to the strong interaction between oxyethyl units and PVC. As the number of the oxyethyl units of plasticizer increased, the glass transition temperature (Tg) of the corresponding plasticized PVC samples decreased from 62.3 (PVC-DA-2) to 35.4 °C (PVC-DA-8). Owing to the excellent plasticization of DA-8, the performances of PVC-DA-8 were comparable or better than that of the PVC plasticized using commercial dioctyl terephthalate (DOTP). The simple but efficient method of this study provides a new avenue for the preparation of vegetable oil-based plasticizers for PVC.