Designing Poly(3,4-ethylenedioxythiophene) Polystyrene Sulfonate/Graphene Oxide/Graphene Nanosheet/Polyethylene Glycol Phase-Change Composites with Superior Thermal Management for Photo-thermoelectric Generators.

Recently, growing interest in self-powered devices has led to the invention of new energy conversion devices. Photo-thermoelectric generators (PTEGs) have rapidly developed for their ability to harvest both light and thermal energy, but these devices are overly dependent on the continuity of energy input and cannot sustain output in an emergency situation. In the current study, poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS)/graphene oxide (GO)/graphene nanosheets (GNPs)/polyethylene glycol (PEG) phase-change composites (PCCs) were prepared with freeze-drying and vacuum-filling processes to acquire materials suitable for imparting energy storage characteristics to PTEGs. The melting and crystallization enthalpies of the PCCs fabricated based on the PEDOT:PSS/GO/GNP aerogels can reach 211.5 and 207.6 J g-1, respectively, which increase by nearly 5% compared with pure PEG, and the growth rate of thermal conductivity of the composites is as high as 262.7% (1.12 W m-1 K-1). Meanwhile, the excellent photothermal properties and high-temperature shape stability that pure PEG does not possess can also be imparted to PCCs by the aerogels. The PTEG assembled with PCCs and thermoelectric components can achieve a continuous output of over 1500 s after 300 s of light irradiation. After integrating the output of the device during the lamp on/off period, it is found that the total output of the device during the light-off period (8.4 V and 9.6 mW) can far exceed its total output during the light-on period (2.7 V and 4.4 mW). This work provides guidance for modulating the performance of PCCs and giving PTEGs the ability to operate under emergency or extremely harsh conditions and the prepared PTEGs are highly promising for practical use.

Biomimetic Polylactic Acid Electrospun Fibers Grafted with Polyethyleneimine for Highly Efficient Methyl Orange and Cr(VI) Removal.

The rapid growth of industrialization has resulted in the release of large quantities of pollutants into the environment, especially dyes and heavy metals, which are environmentally hazardous for humans and animals. It is considered as the most promising and environmentally friendly route to develop green materials by using the green modification method, which has no negative impact on the environment. In this work, the green material of polylactic acid (PLA) was used as the substrate material, and a novel modification method of polydopamine (PDA)-assisted polyethyleneimine (PEI) grafting was developed. The electrospun PLA fibers are mainly composed of stereocomplex crystallites, which were achieved via the electrospinning of poly(l-lactic acid) and poly(d-lactic acid). The water-soluble PEI was grafted onto the PDA-modified PLA fibers through the glutaraldehyde-assisted cross-linking reaction. The prepared composite fibers can be degraded, which is environmentally friendly and meets the requirements of sustainable development. The potential application of such PLA composite fibers in wastewater treatment was intensively evaluated. The results show that at appropriate fabrication conditions (PDA concentration of 3 g·L-1 and a PEI molecular weight of 70,000 g·mol-1), the composite fibers exhibit the maximum adsorption capacities of 612 and 398.41 mg·g-1 for methyl orange (MO) and hexavalent chromium [Cr(VI)], respectively. Simultaneously, about 64.79% of Cr(VI) adsorbed on the composite fibers was reduced to Cr(III). The above results show that the PLA composite fibers have a good development prospect in the field of wastewater treatment.

Constructing A/B-Side Heterogeneous Asynchronous Structure with Ag2Se Layers and Bushy-like PPy toward High-Performance Flexible Photo-Thermoelectric Generators.

The enthusiasm for environmental energy harvesting has triggered a boom in research on photo-thermoelectric generators (PTEGs), and the relevant applications are mainly focused on self-energy supply sensors owing to the limitations of their output performances. For this purpose, high-output hierarchical heterogeneous PTEGs were constructed by assembling separately optimized thermoelectric (TE) and photothermal (PT) layers. The pressure and temperature conditions of Ag2Se films during the pressing process were first explored, and the sample with the optimal performance and least defects was selected as the TE layer. At the same time, different morphologies of polypyrrole (PPy) PT layers were electrochemically synthesized. It is found that the three-dimensional structure of Bushy-PPy could effectively improve the light absorption and thus enhance the PT conversion performance. The final assembled PTEG can produce an output voltage of -9.03 mV and an output power of 3.53 µW under the irradiation of a near-infrared light source of 300 mW cm-2 without a cooling source, and it can also achieve considerable output power under visible light irradiation of different intensities. Combining its high retentions of electrical conductivity (99%) and output performance (97%) after 1000 bending-tension cycles, it is proven to be a promising next-generation wearable flexible energy harvesting device.

Polydopamine-assisted polyethylenimine grafting melamine foam and the application in wastewater purification.

Melamine foam (MF) is a widely used commercial product and exhibits wide applications in many fields ranging from building, transportation to daily chemical product. Recent researches confirm that the special three-dimensional (3D) framework structure of MF can be an ideal substrate to prepare functional materials. In this work, the water-soluble polyethylenimine (PEI) was grafted onto the framework of MF to develop the water purification material toward heavy metal ions removal. The grafting of PEI on MF was achieved with the aids of polydopamine (PDA) coating and epoxy chloropropane (ECH) cross-linking successively. The 3D framework of MF could be well reserved and PEI was homogeneously grafted onto the framework surface. The adsorption capacity of the adsorbent was dependent upon the molecular wight of PEI. Lower PEI molecular weight endowed the adsorbent with better adsorption ability. The maximum adsorption capacity reached 328.95 mg/g, and the adsorbent exhibited extremely high adsorption stability with increasing cycling measurement numbers. Further results showed that the adsorbent also exhibited high reduction ability and induced about 62.5% toxic Cr(VI) to be reduced. This work confirms that the PEI-modified MF sample is a promising adsorbent in the removal of heavy metal ions and it can be used in wastewater treatment.

Chitosan-assisted MOFs dispersion via covalent bonding interaction toward highly efficient removal of heavy metal ions from wastewater.

Metal organic frameworks (MOFs) have been considered to be robust adsorbent for the removing heavy metal ions from wastewater due to their unique properties such as large active sites, high specific surface area and high porosity, etc., however, their practical engineering application faces the problem of serious agglomeration. In this work, a new strategy of chitosan (CS) assisting MOF dispersion was proposed to develop the new generation of MOF-based adsorbents, namely, CS grafted UiO-66-NH2 composite materials (CGUNCM). The UiO-66-NH2 was selected and it was grafted onto the main chains of CS through covalent bonding interaction with the aid of glutaraldehyde, which was totally different from the common method that grafting molecular chains on the surface of MOFs resulting in the dramatic reduction of active adsorption sites. The results show that grafting MOFs onto CS main chains not only greatly improves the dispersion of MOFs but also reserves the morphology of MOFs as much as possible. The adsorption performances toward Cu(II) and Pb(II) were intensively studied by varying adsorbate concentration, ionic strength, the contact time, adsorption temperature and pH value of solution. The results show that the composite adsorbent exhibits high adsorption efficiency and the adsorption equilibrium can be reached within 45 min, and the maximum adsorption capacity toward Cu(II) and Pb(II) achieve 364.96 mg/g and 555.56 mg/g, respectively. Furthermore, the composite adsorbent shows good reusability. This work provides a new method of fabricating the MOF-based adsorbent and paves the way for the practical application of such adsorbents in wastewater treatment.

Freely switchable super-hydrophobicity and super-hydrophilicity of sponge-like poly(vinylidene fluoride) porous fibers for highly efficient oil/water separation.

Highly efficient oil/water separation ability is a prerequisite for the actual application of the membranes in oily sewage treatment, which is closely related to the surface feature and the porous structure of the membranes. In this work, the electrospun poly(vinylidene fluoride) (PVDF) porous fibers were firstly fabricated through blend-electrospinning with poly(vinyl pyrrolidone) (PVP) and then treating in distilled water. The results showed that the fibers exhibited the sponge-like porous structure, and a few PVP was reserved in the fibers due to the relatively good interaction between PVDF and PVP. The fibrous membrane exhibited high porosity, super-wettability with freely switchable super-lipophilicity and super-hydrophilicity. The oil adsorption capacities as well as the oil and water fluxes were measured, and the oil adsorption capacities were varied in the range of 22.7-76.0 g/g, and oil and water fluxes were 54,737.3 and 56,869.9 L/(m2h), respectively. Specifically, the PVDF porous fibrous membranes showed excellent separation abilities and they could highly efficiently separate oil from oil-in-water emulsions or separate water from water-in-oil emulsions, accompanied with the extremely high water or oil flux. This work confirms that the PVDF membranes composed of the porous fibers can be used in wastewater treatment.

Electrospun stereocomplex polylactide porous fibers toward highly efficient oil/water separation.

The urgent needs for water protection are not only developing the highly efficient wastewater treatment technologies but also designing the eco-friendly materials. In this work, the eco-friendly composite fibers composed of poly(L-lactide) (PLLA), poly(D-lactide) (PDLA) and maghemite nanoparticles γ-Fe2O3 nanoparticles were fabricated through electrospinning technology. Through regulating the processing parameters and introducing additional annealing treatment, nanoscale porous structure and the stereocomplex crystallites (SCs) are simultaneously constructed in the composite electrospun fibers. Physicochemical performances measurements exhibited that the fiber membranes had excellent lipophilicity, good mechanical performances, and high hydrolysis resistance, and all of which endowed the fiber membranes with high oil adsorption capacities, and the maximum oil adsorption capacities achieved 148.9 g/g at 23 °C and 114.8 g/g at 60 °C. Further results showed that the fiber membranes had good oil/water separation ability. The gravity-driven oil flux was 6824.4 L/m2h2, and the water rejection ratio was nearly 100% during separating oil/water mixture. Specifically, the fiber membranes showed good stability during the cycling measurements. It is evidently confirmed that the composite PLLA-based fiber membranes with porous structure and SCs can be used in wastewater treatment, especially in some rigorous circumstances.

Achieving high performance poly(vinylidene fluoride) dielectric composites via in situ polymerization of polypyrrole nanoparticles on hydroxylated BaTiO3 particles.

Polymer dielectric composites have widespread applications in many fields ranging from energy storage, microelectronic devices, and sensors to power driven systems, etc. and attract much attention of researchers. However, it is still challenging to prepare advanced polymer dielectric composites with a high dielectric constant (ε'), low dielectric loss (tan δ) and simultaneously high breakdown strength (E bd). In this work, conductive polypyrrole (PPy) nanoparticles were in situ synthesized in a reaction system containing the common barium titanate (BaTiO3, BT) or hydroxylated BaTiO3 (BTOH) particles, and then the PPy@BT and PPy@BTOH composite particles were incorporated into poly(vinylidene fluoride) (PVDF) to prepare the composites. The morphologies and microstructures of the PPy@BT and PPy@BTOH composite particles and the corresponding PVDF composites were comparatively investigated. The results showed that the PPy@BTOH composite particles had a 'mulberry'-like morphology with a rough surface and the self-assembled structure could be maintained in the PVDF composites, which was apparently different from the PVDF/PPy@BT composites, in which most of the PPy nanoparticles dissociatively dispersed in the PVDF matrix. Electrical conductivity measurements showed that at high particle content (≥20 wt%), the PPy@BTOH composite particles endowed the composites with lower electrical conductivity compared with the PPy@BT composite particles. Dielectric property measurements showed that the 'mulberry'-like PPy@BTOH composite particles endowed the PVDF composites with extremely high ε', ultralow tan δ and high E bd compared with the PVDF/PPy@BT composites with dissociatively dispersed PPy nanoparticles and BaTiO3 particles. The polarization and loss mechanisms of the composites were then proposed based on the morphologies and the microstructures of the composites. This work provides an alternative way to fabricate functional dielectric particles through trace functional groups inducing in situ polymerization of conductive polymers, and these particles can be used to fabricate advanced dielectric composites.