As-synthesized Polymers Research Articles

Symmetry-Engineered BINOL-Based Porous Aromatic Frameworks for H2O2 Production via Artificial Photosynthesis and In Situ Degradation of Pharmaceutical Pollutants.

Accomplishing visible light-driven H2O2 production at millimolar concentrations is practically challenging, particularly for organic semiconductors. In this context, achieving a maximum H2O2 production rate of 31.60 mmol·g-1·h-1 by using porous aromatic frameworks (PAFs) represents a significant accomplishment. We report the unusual photoactivity of tetraphenylmethane-BINOL-linked PAFs in triplet oxygen activation to facilitate the generation of reactive oxygen species (ROS), as confirmed by their optical and electrochemical responses, despite the absence of a conventional chromophoric moiety. Moreover, an in situ BINOL formation strategy was used to synthesize these PAFs during polymerization in contrast to the reported protocols involving chiral BINOLs as precursors. The as-synthesized polymers had a capsule-like morphology (for TPM-BINOL-6), high thermal stability up to 348 °C, and a high Brunauer-Emmett-Teller (BET) surface area of up to 1382 m2/g (for TPM-BINOL-4). Interestingly, they showed sunlight-driven production of H2O2 via an oxygen reduction reaction of up to 17.05 mmol·g-1·h-1 in 1:10 isopropanol in water for TPM-BINOL-6, which was quantified by titration with ceric sulfate. It also exhibited exemplary photocatalytic efficiency with an H2O2 production rate of 6.65 mmol·g-1·h-1 in seawater. Interestingly, the H2O2 production rate reached a maximum of 18.03 mmol·g-1·h-1 with an SCC efficiency of 4.5% under an AM 1.5G solar simulator and apparent quantum yield (AQY) of 15.8% (at λ = 456 nm) for TPM-BINOL-6 in ethanol:water = 1:10. Moreover, the exceptionally high H2O2 production rate of 31.60 mmol·g-1·h-1 was achieved in 1:1 ethanol in water under 50 W blue LED light. Furthermore, these PAFs generated adequate ROS, which were utilized in the photocatalytic degradation of tetracycline via the superoxide intermediate. Additionally, the as-formed H2O2 was further channelized in the pollution abatement catalytic system for the fast degradation of ciprofloxacin (within 4 h) and the reduction of toxic oxometallate Cr(VI) within 10 min, which is one of the earliest reports of utilizing photosynthesized H2O2 for environmental detoxification.

Self-healing Hydrophobic Antifouling Polymers with Fe3+-Catechol Coordination Interaction.

Hydrophobic antifouling polymers capable of self-healing performance are highly desirable for industrial applications. However, the construction of self-healing, hydrophobic antifouling polymers is challenging considering their complex fouling environments, which are humid in aqueous environment. In this work, a self-healing hydrophobic polymer containing Fe3+-catechol coordination applicable to antifouling is synthesized. The hydrophobic fluoroalkyl segments in the polymers formed unique domains dispersed in a polydimethylsiloxane matrix. The as-synthesized polymers can completely restore their tensile strength, and their self-healing efficiency is above 90% in both artificial seawater and pure water because of the dynamic Fe3+-catechol coordination interactions. The as-synthesized polymer exhibited self-healing and antifouling properties against common marine bacteria. The colony adhesion and self-healing processes of the damaged coating in artificial seawater containing marine bacteria are characterized by laser confocal microscopy. This strategy may be useful for the development of future polymeric antifouling materials.

Highly sulfonated hyper-cross-linked polymers as promising adsorbents for efficient and selective removal of ciprofloxacin from water

This study aims at the development of novel and highly sulfonated hyper-cross-linked polymers (sHCPs) using facile and one-step synthetic approach, and verification of the potential applicability of the as-synthesized polymers in the adsorptive removal of various antibiotic pollutants under environmentally relevant conditions. The sHCPs synthesized in this work were capable of highly efficient removal of antibiotic pollutants at relatively high (30 mg/L) and low (50 µg/L) initial concentrations, both from a simple as well as complex water matrices. The rate of ciprofloxacin removal and the adsorption capacity observed for the most efficient adsorbent (qe = 757.7 mg/g) were found to be approximately twice higher than that established for other previously reported sulfonated polymers prepared via post-synthetic sulfonation (qe = 476.9 mg/g), and commercial polymer-based adsorbents (e.g. Amberlyst-15, qe = 438.5 mg/g). The highest adsorption capacity was observed at pH close to neutral for polar antibiotic pollutants that contain protonated functional groups and exist in cationic or zwitterion form (e.g. ciprofloxacin and tetracycline). The reported results clearly imply that highly sulfonated hyper-cross-linked polymers are promising candidates for potential practical application for the elimination of organic pollutants from aqueous media, being capable of selective removal of various antibiotics via ionic interaction even in the presence of a great excess of other cations, anions and organic matter naturally existing in environmentally relevant water samples (e.g. river water).

Spirobifluorene-BINOL-based microporous polymer nanoreactor for efficient 1H-tetrazole synthesis and iodine adsorption with facile charge transfer.

Porous polymeric nanoreactors capable of multitasking are attractive and require a judicious design strategy. Herein, we describe an unusual approach for the synthesis of a porous polymer SBF-BINOL-6 by in situ formation of the BINOL entity taking substituted naphthols and spirobifluorene as co-monomers with high yield (81%). The as-synthesized polymer exhibited nanotube and nanosphere-like morphology, thermal endurance up to 372 °C and a BET surface area as high as 590 m2 g-1. The polymer endowed efficient loading of silver nanoparticles to generate Ag@SBF6, as confirmed from X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy. Ag@SBF6 was effectively used as a heterogeneous catalyst towards the [3 + 2] dipolar cycloaddition reaction for the synthesis of biologically important 5-substituted 1H-tetrazoles with yields in the range of 75-99% and recyclability for at least seven times without a significant decline in its catalytic efficiency. Additionally, a superior host-guest interaction by the polymer offered iodine adsorption in the vapour phase with a high uptake capacity of up to 4.0 g g-1. Interestingly, the iodine-loaded polymer, I2@SBF6, demonstrated iodine-promoted increased conductivity (1.3 × 10-3 S cm-1) through facile charge transfer interactions.

Synthesis and investigation of the structure, thermal, optical, and electrical properties of poly (indol-thiazolo-thiadiazole) derivatives at room temperature

This research work is intended for the novel synthesis and study of structural, thermal, optical, electrical, and dielectric properties of semiconductor poly (2-amino-5-(1H-indolyl)-5H-thiazolo[4,3-b]-1,3,4-thiadiazole) (PAITTD) and its N-substituted indole derivatives with a side chain containing chlorobenzoyl (PACBITTD) and bromobenzene sulphonyl (PABBSITTD). The characterization techniques such as H1NMR, FTIR, SEM, and TGA/DSC ensured the structural and thermal properties of the as-synthesized polymers. In addition, the molecular weight of the PAITTD, PACBITTID, and PABBSITTD was calculated via H1NMR technique. The optical band gap as obtained from the absorbance study was found to be in the range of 1.5 eV to 2.58 Ev. Moreover, the ground-state geometries and the absorption wavelengths for the studied compounds were investigated by DFT and TD-DFT, where the theoretical results show coincidence with these of the experimental where the calculated (λmax) values are approximately near to the experimental (λmax) values for the PAITTD, PACBITTID, and PABBSITTD. The impedance ac conductivity and dielectric properties of the PAITTD, PACBITTID, and PABBSITTD were performed in the frequency ranges from 20 Hz to 10 MHz at room temperature, where their values were 3.0 × 10−7, 8.7 × 10−7, and 2.6 × 10−6, respectively. The Nyquist plot confirmed the presence of both grain and grain boundary effects for conducting PAITTD, PACBITTID, and PABBSITTD, and Double relaxation behavior was also observed. The variation of ac conductivity with frequency obeys the modification of Jonscher’s universal power law (JUPL). Based on the optical and electrical properties, synthetic PAITTD, PACBITTID, and PABBSITTD are promising materials in the design of optoelectronic semiconductor devices.

Synthesizing a multifunctional polymer to construct the catalytically NO-generating coating for improving corrosion resistance and biocompatibility of the magnesium alloy stent materials

Owing to its excellent mechanical properties and biodegradability, magnesium-based alloys have become the research focus of biodegradable cardiovascular materials. However, the in vivo rapid degradation and poor surface endothelial regeneration and repair ability still restrict their clinical applications in the field of vascular stent materials. Nitric oxide (NO), as an endogenous gas signaling molecule, has multiple effects such as anticoagulation, promoting endothelialization, and anti-restenosis, showing a great potential for improving the performances of the cardiovascular materials and devices. In the present study, based on six-arm polyethylene glycol (PEG), a novel anticoagulant polymer (PEG-Hep-SeCA) with the catalytic release of NO was synthesized by successively introducing heparin and selenocystamine, followed by the immobilization of the as-synthesized polymer on the Zn2+-loaded polydopamine coating modified magnesium alloy surface to enhance the anti-corrosion and biocompatibility. The results demonstrated that the PEG-Hep-SeCA polymer coating was uniform and dense, which could not only obviously enhance the anticorrosion and the hydrophilicity of the magnesium alloy, but also selectively promote the bovine serum albumin (BSA) adsorption, thereby significantly improving the endothelial cells (ECs) growth and hemocompatibility. Additionally, the as-prepared polymer coating could effectively catalyze the release of NO from endogenous NO donors, which can further ameliorate the hemocompatibility and ECs growth, as well as enhance the expression of vascular endothelial cell growth factor (VEGF) and NO of the ECs. Therefore, this study opens a new way to construct the multifunctional coating with the ability of catalytic releasing NO on the surfaces of the magnesium-based alloys to simultaneously reduce the corrosion speed, improve the hemocompatibility, and accelerate the reendothelialization.

In-situ self-crosslinking strategy for autonomous self-healing materials

Autonomous self-healing anticorrosion protective coatings from intrinsic polymers is a great challenge. In this work, in-situ self-crosslinking strategy was demonstrated for constructing self-healing anticorrosion polymers. The as-synthesized polymers had tunable catechol content and mechanical properties. The specimens could be repaired in an Fe3+ solution owing to the formation of dynamic catechol-Fe3+ coordination crosslinking sites. Moreover, when scratched, the prepared polymers exhibited a self-healing anticorrosion performance, as evidenced by salt immersion and electrochemical impedance spectroscopy. An in-situ self-crosslinking mechanism was proposed, which was derived from the dynamic coordination of catechol groups in the polymer chains and Fe3+ produced from the metal substrate. This intrinsic self-healing anticorrosion polymer are highly potential for anticorrosion applications in harsh environments.

Triphenylamine–Anthracene-Based Conjugated Microporous Polymers for the Detection and Photocatalytic Degradation of Organic Micropollutants

Triphenylamine (TPA)–anthracene (AN)-based conjugated microporous polymers (CMPs), namely PTPA-AN-9,10 and PTPA-AN-2,6, were synthesized by the Suzuki–Miyaura cross-coupling reaction of tris(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-amine with 9,10-dibromoanthracene and 2,6-dibromoanthracene, respectively. The as-synthesized polymers exhibited cauliflower-like nanoscale morphology , high Brunauer–Emmett–Teller surface area of 362 m2/g, and thermal stability up to 458 °C in the case of PTPA-AN-2,6. Interestingly, PTPA-AN-9,10 showed bright cyan fluorescence in tetrahydrofuran dispersion and exhibited fluorescence-based sensing of various nitroaromatics, where 2,4,6-trinitrophenol exhibited the lowest limit of detection of 34 μM and the highest Stern–Volmer constant (KSV) of 5.8 × 103 L mol–1. On the other hand, PTPA-AN-2,6 showed efficient photocatalytic reduction of various nitroaromatic micropollutants such as p-nitrophenol (p-NP) (k = 0.164 min–1 and turnover frequency (TOF) = 0.769 h–1) and degradation of Congo red from water with ultrafast kinetics (k = 0.047 min–1 and TOF = 0.024 h–1) which are much better than most of the previously reported CMPs. These polymers were recovered using simple filtration and were recycled four to five times without losing their catalytic efficiency significantly for p-NP reduction as well as dye degradation. In general, TPA-based CMPs have been used as efficient multitasking materials for the sensing of nitroaromatic micropollutants and photocatalytic degradation of Congo red dye as well as p-NP to its value-added product p-aminophenol.

Copper(II)-Incorporated Porphyrin-Based Porous Organic Polymer for a Nonenzymatic Electrochemical Glucose Sensor.

To date, the fabrication of multifunctional nanoplatforms based on a porous organic polymer for electrochemical sensing of biorelevant molecules has received considerable attention in the search for a more active, robust, and sensitive electrocatalyst. Here, in this report, we have developed a new porous organic polymer based on porphyrin (TEG-POR) from a polycondensation reaction between a triethylene glycol-linked dialdehyde and pyrrole. The Cu(II) complex of the polymer Cu-TEG-POR shows high sensitivity and a low detection limit for glucose electro-oxidation in an alkaline medium. The characterization of the as-synthesized polymer was done by thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, and 13C CP-MAS solid-state NMR. The N2 adsorption/desorption isotherm was carried out at 77 K to analyze the porous property. TEG-POR and Cu-TEG-POR both show excellent thermal stability. The Cu-TEG-POR-modified GC electrode shows a low detection limit (LOD) value of 0.9 μM and a wide linear range (0.001-1.3 mM) with a sensitivity of 415.8 μA mM-1 cm-2 toward electrochemical glucose sensing. The interference of the modified electrode from ascorbic acid, dopamine, NaCl, uric acid, fructose, sucrose, and cysteine was insignificant. Cu-TEG-POR exhibits acceptable recovery for blood glucose detection (97.25-104%), suggesting its scope in the future for selective and sensitive nonenzymatic glucose detection in human blood.

Dual-Ligand Strategy Employing Rigid 2,5-Thiophenedicarboxylate and 1,10-Phenanthroline as Coligands for Solvothermal Synthesis of Eight Lanthanide(III) Coordination Polymers: Structural Diversity, DFT Study, and Exploration of the Luminescent Tb(III) Coordination Polymer as an Efficient Chemical Sensor for Nitroaromatic Compounds.

Lanthanide coordination polymers (Ln-CPs) are potential chemosensors when fabricated to depict a detectable change in optical properties on interaction with target analytes. This work investigates the interaction of nitroaromatic compounds with Ln-CPs leading to induced changes in fluorescence emission intensity, a crucial strategy to develop a selective and sensitive system for the sensing of nitroaromatics. Approaching toward this objective, solvothermal reactions of 2,5-thiophenedicarboxylic (2,5-TDC) acid, 1,10-phenanthroline (1,10-Phen), and Ln(NO3)3·xH2O are carried out to assemble eight Ln(III) coordination polymers [Ln2(2,5-TDC)3(1,10-Phen)2(H2O)2] [Ln = Pr (1), Nd (2)], {[Tb(2,5-TDC)1.5(1,10-Phen)(H2O)]·DMF} (3), and [Ln(2,5-TDC)1.5(1,10-Phen)]·xH2O (Ln = Tb (4), Dy (5), Ho (6), Er (7), and Yb (8)); x = 0 for CP 4, 5, 6, and 8 and x = 1 for CP 7 with two different space groups and dimensions. The as-synthesized polymers 1-8 are characterized by powder X-ray crystallography, infrared spectroscopy, and thermogravimetric analysis. The structure-corroborated density functional theory (DFT) studies are done on the selected CPs to investigate the interactions between different structural motifs of the assembled CPs. The luminescence properties of CP 4 are explored in detail and are found to be highly sensitive for the detection of p-nitrotoluene as indicated by the most intensive fluorescence quenching with the lowest limit of detection (0.88 ppm) and high quenching constant (4.3 × 104 M-1). Other nitro compounds (viz., o-nitrobenzaldehyde, m-nitroaniline, picric acid, m-dinitrobenzene, p-nitrophenol, and p-nitroaniline) are also screened for potential sensing by CP 4.

Lanthanide coordination polymers functionalized by 5-nitroisophthalic acid: Synthesis, structure-DFT correlation and photoluminescent sensor of Cd2+ ion

Lanthanide coordination polymers (LnCPs) are influential chemosensors when designed to undergo a detectable change in optical properties upon interacting with target analytes. This work reports interaction of metal ions with LnCPs leading to elicit changes in fluorescence emission intensity, an essential step en route to developing sensitive and selective systems for metal-ion sensing. Towards this goal, solvothermal reaction of 5- Nitroisophthalic Acid (5-NIAH2) and Ln (NO3)3⋅xH2O produced seven Ln-coordination polymers {[Nd (5-NIA) (5-NIAH) (H2O)2]⋅CH3CN}n (1), {[Sm (5-NIA) (5-NIAH) (H2O)2]⋅CH3CN⋅H2O}n (2), {[Gd (5-NIA) (5-NIAH) (H2O)2]⋅(H2O)2}n (3), {[Tb (5-NIA) (5-NIAH) (H2O)2]⋅CH3CN)}n (4), [Dy (5-NIA) (5-NIAH) (H2O)2]n (5), [Ho(5-NIA) (5-NIAH) (H2O)2]n (6) and [Er2 (5-NIA)3(H2O)3(CH3CN)]n (7) with two-dimensional structures. The as-synthesized polymers are characterized by powder X-ray crystallography, infrared spectroscopy, thermogravimetric analysis, photoluminescence and DFT studies. The luminescence properties of [Tb (5-NIA) (5-NIAH) (H2O)2]⋅CH3CN)}n (4) is investigated. The CP-4 is highly sensitive for the detection of Cd2+ exhibiting most intensive fluorescence quenching with the lowest limit of detection. Other metal ions, including Co2+, Fe3+, Fe2+ and Pb2+ are also detected demonstrating the range of sensing capabilities.

Single crystal structure features of a new tri-hetero metallic polymer, a catalyst for mild homogeneous peroxidative oxidation of cyclohexane

This work reports the synthesis of a new water-soluble tri-hetero metallic polymer formulated as [Cu0.152 Mn0.848 (μ-dipic)2{Na2 (μ-H2O)4}]n·nH2O (1) where dipic2− ​= ​pyridine 2,6-dicarboxylato. Elemental analysis, fourier transformed-infrared (FT-IR) spectroscopy, thermogravimetric analyses (TGA), differential thermal analysis (DTA), vibration sample magnetometer (VSM), and single-crystal X-ray diffraction (SC-XRD) analysis were used for characterization of polymer 1. According to crystal structure analysis, polymer 1 belongs to a monoclinic system with space group C2/m, while cations of Cu2+ and Mn2+ occupy 15.2% and 84.8% of octahedral sites, respectively. The divalent ions of Mn2+ and Cu2+ show coordination number six, which have significantly distorted octahedral geometry. The as-synthesized polymer presents a 3D network extended by monomeric [Mn/Cu(dipic)2]2– units and polymeric{[Na2(μ-H2O)4]2+}n chains with extensive hydrogen bonding between crystal water molecules and adjacent layers. Polymer 1 was used as homogeneous catalyst for the mild oxidation of cyclohexane to the corresponding products (alcohol and ketone) in the presence of hydrogen peroxide as an environmentally friendly oxidant. To obtain the highest catalytic performance, various reaction parameters such as temperature, reaction time, the molar ratio of nitric acid to the catalyst, and the molar ratio of oxidant to the catalyst, were optimized. As a result, polymer 1 exhibited the maximum catalytic performance with a total product yield of 39.2% under optimized conditions. The mechanism of cyclohexane oxidation catalyzed by polymer 1 was also discussed.

Regulating donor-acceptor interactions in triazine-based conjugated polymers for boosted photocatalytic hydrogen production

The donor-acceptor (D-A) interactions between the triazine ring unit and adjacent substituents is one of the decisive factors that affect the performance of triazine-based conjugated polymer photocatalysts. Herein, we design and synthesize novel conjugated polymers by introducing electron-drawing 1,3,4-oxadiazole units into 1,3,5-triazine-based π-conjugated skeletons for photocatalytic hydrogen production. Compared with the bulk polymer, the modified photocatalysts show extended visible light harvesting and boosted charge separation. Notably, under the irradiation of full-spectrum solar light, as-synthesized polymer with bi-1,3,4-oxadiazole linkage (denoted as TCP-BOXD) shows a highly improved hydrogen-evolving rate up to 3000 μmol g−1 h−1. Furthermore, DFT calculation reveals that N atoms in the introduced 1,3,4-oxadiazole unit, coupled with those in the triazine ring, act as synergistic bi-active sites for superior photocatalytic hydrogen production. Our findings may help the rational design and controllable synthesis of novel triazine-based conjugated polymers for photocatalysis.

Photocatalytic hydrogen production of Melon/Azodiphenylamine polymers

Hydrogen is one of the most attractive energy sources at present for its excellent properties, such as high energy density, clean and non-pollution energy. Photocatalytic hydrogen evolution is one of the ideal strategies to obtain hydrogen energy. This work aimed to improve the visible-light absorption ability of the structure similar to g-C3N4 by anchoring azo groups into the structure. By this, the photocatalytic hydrogen production rate of the resulting product was improved apparently. We use melamine as starting material to prepare Melon, which was further reacted with KOH, PCl5 and 4, 4-Diaminoazobenzene to get the target Melon/4, 4-Diaminoazobenzene polymer. The condition influencing on the reaction was investigated, such as reaction temperature, the ratio of reactants and concentration of KOH solution. The structure of the as-synthesized polymer was determined IR, XRD, SEM, TGA and EIS. At the same time, its photocatalytic property was investigated.

Preparation of melamine-functionalized porous organic polymer and its adsorption properties for methyl orange

首先以对三联苯(TP)和对苯二甲酰氯(TC)为单体合成了酮基聚合物前体(TP-TC),而后基于席夫碱反应将三聚氰胺(MA)与之交联得到胺功能化的多孔有机聚合物TP-TC-MA。通过扫描电镜(SEM)、透射电镜(TEM)、傅里叶变换红外光谱(FT-IR)、X射线衍射(XRD)、氮气吸附-脱附(BET)以及零电荷点(pHpzc)的测定等手段对合成的多孔有机聚合物进行表征。以染料废水中典型的阴离子染料甲基橙为研究对象,研究了TP-TC-MA对其吸附行为,并探讨了吸附机制。利用紫外-可见分光光度计(UV-Vis)得出目标污染物的紫外吸收光谱标准曲线,标准曲线拟合相关系数(R2)为0.999。结果表明,TP-TC-MA由于具有高比表面积(708.5 m2/g)和总孔体积(0.556 cm3/g)以及丰富的含氮基团,对阴离子染料甲基橙表现出优异的吸附性能。TP-TC-MA对水中甲基橙的吸附动力学符合准二级动力学方程,吸附平衡数据可以采用Langmuir等温吸附模型描述。经由Langmuir等温吸附模型计算得到的理论最大吸附容量为156.3 mg/g。选择性实验结果表明,TP-TC-MA对阴离子染料甲基橙具有更强的吸附作用,吸附作用机理可归结为静电相互作用、氢键和π-π相互作用等。在重复使用5次之后,TP-TC-MA对甲基橙仍保持90%以上的去除率,表明材料具有良好的稳定性和重复利用性,在染料废水处理中具有很好的应用前景。

Synergetic Effect of Side-Chain Engineering of Polymer Donors and Conformation Tuning of Small-Molecule Acceptors on Molecular Properties, Morphology, and Photovoltaic Performance

It is demonstrated that the side-chain engineering of polymer donors and molecular conformation of small-molecule acceptors (SMAs) plays a crucial role in the morphology and photovoltaic performance of polymer solar cells (PSCs). However, the synergetic effect of these two aspects has been rarely reported. Herein, two wide-band gap donor–acceptor (D–A) copolymers (PST-TTC and PSPT-TTC) featuring the same main-chain backbone but different conjugated side chains were developed and combined with three low-band gap symmetric SMAs (ITIC, DTCFO-ICCl, and Y6) with various molecular conformations (S-shape, C-shape, and U-shape) to investigate the synergetic effect of side-chain engineering of polymer donors and conformation manipulation of SMAs on molecular properties, device physics, film morphology, and photovoltaic performance. The results indicate that PST-TTC with an alkylthiothiophene side chain exhibits a broader absorption spectrum, a smaller optical band gap (1.95 vs 1.99 eV), and a deeper-lying highest occupied molecular orbital (HOMO) level (−5.39 vs −5.36 eV) as compared to PSPT-TTC with an alkylthiophenylthiophene side chain. The PSCs were constructed according to the different donor/acceptor combinations based on the two as-synthesized polymers and three selected SMAs. After optimization, PST-TTC paired with S-shaped ITIC provides a power conversion efficiency (PCE) of 10.10% and the PCE can be further improved up to 10.60% when C-shaped DTCFO-ICCl was used to replace ITIC as the acceptor. However, the device performance becomes worse, accompanied with a sharply reduced PCE of 7.36% after the substitution of ITIC for U-shaped Y6. On the contrary, when the paired donor was changed to PSPT-TTC, the PSPT-TTC:Y6-based PSC achieves a remarkably increased PCE of up to 11.46%. These delicate observations suggest that the polymer donor with different conjugated side chains should collaborate with symmetric SMAs possessing various molecular conformations to realize superior morphology and device performance.

Universal Self-Healing Poly(dimethylsiloxane) Polymer Crosslinked Predominantly by Physical Entanglements.

Harsh conditions are inevitable for long-term use of self-healing polymers. However, the majority of reported self-healing materials cannot remain stable under harsh conditions due to the presence of vulnerable dynamic crosslinking sites. Herein, a universal self-healing poly(dimethylsiloxane) (PDMS) polymer is reported. In our design, the PDMS polymer chains are crosslinked predominantly through physical entanglements. Owing to the invulnerable nature of the entanglement junctions and high mobility of polymer chains, the as-synthesized polymer exhibits autonomous self-healing capabilities not only under ambient conditions but also in a variety of harsh environments, including aqueous solutions, organic solvents, and extreme conditions (strong acid/alkali, redox agents, freezing temperature). Moreover, this polymer can be easily integrated with a eutectic gallium-indium (EGaIn) alloy to achieve layer-by-layer self-healing electronic skin sensors, which realize the combination of excellent electrical conductivity, long-term sensing stability, and universal self-healing capability.

Synthesis of the hyper-branched polyamides and their effective utilization in adsorption and equilibrium isothermal study for cadmium ion uptake

This report deals with the simple development of a method for the uptake of cadmium ions by polymer adsorbent from the main sources of cadmium like water. The monomer is synthesized by reacting 2,4,6-trichloro-1,3,5-triazine with N(4-aminophenyl)acetamide. The adsorbents synthesis is completed by reacting a synthesized monomer with 1,3,5-tribenzoylchloride, terephthaloyl chloride, and isophthaloyl chloride. The as-synthesized polymer exhibits high molecular mass with narrow molecular weight distribution and good thermal stability. The metal ion adsorption study is established by using atomic absorption spectroscopy at optimized parameters, showing excellent adsorption capacity of polymer adsorbent. Further, the isothermal equilibrium adsorption study reveals the monolayer adoption of the metal ion by the Langmuir model with experimental and theoretical parameters, optimized by the linear regression analysis using the curve fitting tool in MATLAB software.

Sulfur-doped triazine-conjugated microporous polymers for achieving the robust visible-light-driven hydrogen evolution

Conjugated microporous polymers (CMPs) have emerged in recent years as prospective materials for photocatalytic hydrogen production. The most common synthesis method for triazine is ionothermal synthesis at high temperatures (>350 °C), which also requires a large amount of ZnCl2, in which CF3SO3H-catalyzed method was invented to synthesize triphenyl triazine at room temperature. Herein, we reported the synthesis and characterization of two triazine-based conjugated micropores polymers photocatalysts at low temperature via polymerization of triphenyl triazine (TPT) with TPT and pyrene (Py). The TPT-based CMPs show excellent photocatalytic performance and a hydrogen evolution rate of 108.1 and 116.5 µmol h−1 under visible light for Py-TPT-CMP and TPT-TPT-CMP, respectively, but with low photocatalytic stability. In general, organic polymers add a small amount of platinum to efficiently produce H2 with high photocatalyst stability. To provide a new opportunity to overcome the low stability, a sulfur doping method using readily available sulfur (S8) has been proposed which was used here for the first time to achieve a highly photocatalyst stability development without the use of noble metals. The as-synthesized polymers after sulfur doped exhibit an enhanced photocatalytic stability which can keep the hydrogen production for a long period of time without loss in the photocatalytic efficiency. Furthermore, our triazine-based CMP materials have interest apparent quantum yield (AQY) values particularly for Py-TPT-CMP and TPT-TPT-CMP which exhibit AQY of 41.9 and 32.38%, respectively at 420 nm, these values are compatible with the highest AQY of organic photocatalysts up to date. This study makes a significant contribution forward for photocatalysis with polymers because it provides excellent HERs and AQYs for the sulfur-doped triazine-based CMPs with high thermal, chemical, and photo stabilities. As well as, this work could give researchers in the field a different opinion on the effect of sulfur-doping.

A Terpyridine-Fe2+-Based Coordination Polymer Film for On-Chip Micro-Supercapacitor with AC Line-Filtering Performance.

The preparation of redox-active, ultrathin polymer films as the electrode materials represents a major challenge for miniaturized flexible electronics. Herein, we demonstrated a liquid–liquid interfacial polymerization approach to a coordination polymer films with ultrathin thickness from tri(terpyridine)-based building block and iron atoms. The as-synthesized polymer films exhibit flexible properties, good redox-active and narrow bandgap. After directly transferred to silicon wafers, the on-chip micro-supercapacitors of TpPB-Fe-MSC achieved the high specific capacitances of 1.25 mF cm−2 at 50 mV s−1 and volumetric energy density of 5.8 mWh cm−3, which are superior to most of semiconductive polymer-based micro-supercapacitor (MSC) devices. In addition, as-fabricated on-chip MSCs exhibit typical alternating current (AC) line-filtering performance (−71.3° at 120 Hz) and a short resistance–capacitance (RC) time (0.06 ms) with the electrolytes of PVA/LiCl. This study provides a simple interfacial approach to redox-active polymer films for microsized energy storage devices.