Flexible Supercapacitor with Wide Electrochemical Stable Window Based on Hydrogel Electrolyte.

Hydrogel electrolyte can endow supercapacitors with excellent flexibility, which has developed rapidly in recent years. However, the water-rich structures of hydrogel electrolyte are easy to freeze at subfreezing and dry at high temperatures, which will affect its energy storage characteristics. The low energy density of micro supercapacitors also hinders their development. Herein, a strategy is proposed to reduce the free water activity in the hydrogel to improve the operating voltage and the energy density of the device, which is achieved through the synergistic effect of the hydrogel skeleton, N, N'-dimethylformamide (DMF), NaClO4 and water. High concentrations of DMF and NaClO4 are introduced into sodium alginate/polyacrylamide (SA/PAAM) hydrogel through solvent exchange to obtain SA/PAAM/DMF/NaClO4 hydrogel electrolyte, which exhibited a high ionic conductivity of 82.1 mS cm-1, a high breaking strength of 563.2 kPa, and a wide voltage stability window of 3.5 V. The supercapacitor devices are assembled by the process of direct adhesion of the hydrogel electrolyte and  laser induced graphene (LIG). The micro-supercapacitor exhibited an operating voltage of 2.0 V, with a specific capacitance of 2.41 mF cm-2 and a high energy density of 1.34 µWh cm-2, and it also exhibit a high cycle stability, good flexibility, and integration performance.

Preparation and rebinding properties of protein-imprinted polysiloxane using mesoporous calcium silicate grafted non-woven polypropylene as matrix.

Calcium silicate particle containing mesoporous SiO2 (CaSiO3@SiO2) was grafted on the surface of non-woven polypropylene. The PP non-woven grafted calcium silicate containing mesoporous SiO2 (PP-g-CaSiO3@SiO2) was used as the matrix to prepare bovine serum albumin (BSA) molecularly imprinted polysiloxane (MIP) by using silanes as the functional monomers and BSA as the template. PP non-woven grafted BSA-imprinted polysiloxane (PP-g-CaSiO3@SiO2 MIP) was characterized by scanning electron microscope (SEM), Fourier transform infrared spectometry (FTIR) and drilling string compensator (DSC). Influence factors on the rebinding capacity of the MIP were investigated, such as grafting degree, the pH in treating CaSiO3 and the type and proportion of silanes. The rebinding properties of BSA on PP-g-CaSiO3@SiO2 and MIP were investigated under different conditions. The results indicated that the rebinding capacity of MIP for BSA reached 56.32 mg/g, which was 2.65 times of NIP. The non-woven polypropylene grafted BSA-imprinted polysiloxane could recognize the template protein and the selectivity factor (ß) was above 2.4 when using ovalbumin, hemoglobin and γ-globulin as control proteins. The PP-g-CaSiO3@SiO2 MIP has favorable reusability.

Fabrication of Hydrophilic and Hydrophobic Sites on Polypropylene Nonwoven for Oil Spill Cleanup: Two Dilemmas Affecting Oil Sorption.

This article mainly deals with the following dilemmas, which affect oil sorption and sorbent preparation: (1) hydrophobization could facilitate oil sorption but has adverse impacts on emulsion sorption; (2) micropores of conventional oil sorbent do not exhibit effective emulsion sorption. To solve the above contradictions, hydrophilic and hydrophobic sites were fabricated onto polypropylene (PP) nonwoven through electron beam radiation and subsequent ring-opening reaction. Further, a similar structure without a hydrophilic site was constructed as comparison to verify the dilemmas. An oil sorption and emulsion adsorption experiment revealed that the PP nonwoven with specific hydrophilic and hydrophobic sites is more suitable for oil cleanup. The hydrophobic site preserved its hydrophobicity and sorption capacity, and the hydrophilic site on PP surface effectively increased the affinity between the hydrophilic interface of emulsion and sorbent. The overlapped and intertwined structures could provide spaces large enough to accommodate oil and emulsion. In addition, the oil and emulsion sorption behaviors were systematically analyzed. The PP nonwoven fabricated in this study may find practical application in the cleanup of oil spills and the removal of organic pollutants from water surfaces.

Influencing Factors for Organic Spill Recovery Performance with a Novel Polypropylene-Methacrylate Sorbent.

Insoluble organic matter released to the water body through accidental spillage imposes serious damage on the environment. Polypropylene (PP) fiber and methacrylate resin, however, end up in certain morphology or low sorption capacity after a single use. In this study, a novel sorbent was prepared by radiation-induced graft polymerization of butyl methacrylate (BMA) onto PP fiber matrix to retain the advantages of both PP fibers and methacrylate resins to overcome the shortcomings of each used alone. The different parameters including irradiation power, irradiation time and monomer concentration that effect the grafting degree of grafted fiber were studied. The resulting grafted fibers (PP-g-BMA) were evaluated in this study in terms of sorption capacity, retention behaviors and reusability properties. The investigation revealed that the homopolymerization rate, organic matter temperature and pH values of organic-over-water aqueous solution are the most important factors in the sorption performance of polypropylene grafted fiber sorbent.

Adsorption of bisphenol A based on synergy between hydrogen bonding and hydrophobic interaction.

The study mainly investigated the synergetic adsorption of hydrogen bonding and hydrophobic interaction. To simplify the adsorption driving forces and binding sites, the hydrophilic and hydrophobic microdomain was introduced onto polypropylene (PP) nonwoven. The amphiphilic structure was constructed for the adsorption of bisphenol A (BPA). A solvent shielding experiment was conducted to calculate the contributions of diverse interactions. Also, a specific structure without hydrophilic microdomain was constructed as comparison to determine the adsorption rate and quantify the diffusion behaviors. On the basis of double-exponential model, the adsorption process can be distinctly divided into three stages, namely film diffusion stage, intralayer diffusion stage, and dynamic equilibrium stage. The adsorption rate was dramatically improved due to the influence of hydrophilic microdomain and participation of hydrogen bonding adsorption. Discussions on adsorption priority were also proposed. The results of surface energy heterogeneity revealed that the hydrophilic microdomain or the hydrogen bonding site was occupied preferentially.

Integration of adsorption, reduction, and filtration in PANI/PVDF nanofiber composite membrane for removal of Cr(VI).

Here, polyaniline/polyvinylidene fluoride (PANI/PVDF) nanofiber composite membrane was fabricated using electrostatic spinning technology to remove hexavalent chromium Cr(VI). The employment of PANI not only extremely enhanced the hydrophilic property of the nanofiber membrane, but also facilitated the transfer of Cr2O72- from water to the membrane. The PANI/PVDF membrane had an extremely excellent performance in getting rid of Cr(VI) and a quite large flux (250 L/m2 h). The maximum adsorption quantity of the membrane could reach 334.5 mg/g in which adsorption played 52.12% part and reduction played 47.87% part. The removal rate could reach nearly 100% immediately in the permeate solution under filtration while it needed 240 min to reach 100% only by static adsorption. Therefore, the interception of the membrane and the adsorption reduction of PANI had synergistic effect on removal of Cr(VI). Furthermore, the removal rate of Cr(VI) could still reach 95.97% after reused 8 times. The membrane showed a very good reusability and application prospect.

Tailoring Surface Engineering with Expanded Precursor Libraries via Rapid Mussel-Inspired Chemistry.

Mussel-inspired coating is a substrate-independent surface modification technology. However, its application is limited by time-consuming, tailoring specific functions require tedious secondary reaction. To overcome those drawbacks, a strategy for the rapid fabrication of diverse coatings by expanding the library of precursors using oxidation coupled with polyamine was proposed. Based on DFT simulations of the reaction pathways, a method was developed to achieve rapid deposition of coatings by coupling oxidation and polyamines, which simultaneously accelerated the oxidation of precursors and polymer chain growth. The feasibility and generalizability of the strategy was validated by the rapid coating of 10 catechol derivatives and polyamines on various substrates. The surface properties of the substrates such as functional group densities, Zeta potential and contact angles can be easily tuned. The tailored surface engineering application of the strategy was demonstrated by the heavy metal adsorbents and superwetting materials prepared through the delicate combination of different building blocks. Our strategy was flexible in terms of diverse surface engineering design which greatly enriched the connotation of mussel-inspired technique.

Superhydrophilic and oleophobic sponges prepared based on Mussel-Inspired chemistry for efficient oil-water separation.

Superhydrophilic/oleophobic materials are considered to be the best materials for achieving oil-water separation, but their preparation is difficult and the existing methods are not universal. In this paper, a two-step modification strategy was used to prepare superhydrophilic/oleophobic sponges by adjusting the polar and nonpolar components of the materials using mussel-inspired chemistry. While remaining superhydrophilic, the modified sponge surface has a maximum contact angle of 135° with different oils in air. The modified sponge exhibited superoleophobicity in water, and the contact angle of oil could reach more than 150°. In addition, the modified sponges were also reusable, chemically stable, and mechanically durable. Its oil-water separation flux was up to 24900 Lm-2 h-1 bar-1 , and the separation efficiency was above 97 %. We believe that this method will provide an environmentally friendly and efficient way to prepare the superhydrophilic/oleophobic materials.

Preparation of CdTe/CdS/SiO2 core/multishell structured composite nanoparticles.

Novel CdTe/CdS/SiO2 core/multishell fluorescent composite nanoparticles were prepared by reverse microemulsion method in this paper. Water-soluble CdTe/CdS core/shell quantum dots (QDs) were synthesized with 3-mercaptopropionic acid as the stabilizers and thiourea as the sulphur source in aqueous solution. CdTe/CdS/SiO2 fluorescent nanoparticles were obtained by hydrolysis of tetraethyl orthosilicate (TEOS) at room temperature in cyclohexane solution when polyethylene glycol tert-octylphenyl ether (Triton X-100) as the surfactant and n-hexanol as the co-surfactant. The resultant core/multishell fluorescent composite nanoparticles were inert and chemically stable in harsh environments because of the silica layer. In this paper, the diameter of these particles was about 64 nm, and the maximum emission was about 678 nm. The coating of silica could provide a great convenience for the biological functionalization of the surface of luminescent QDs and be useful to label biological molecules in vitro and vivo in the biological analyses.

Tailored Sky-Parking Architectures of 3D Graphene Oxide Towards Highly-Efficient Water Purification.

The widespread use of chemicals has brought serious water pollution threatening human health and environment, which requires green, fast, and low-cost purification urgently. Here, we build up a novel material family of sky-parking-like 3D structured graphene oxides (SP-GOs) with adjustable interlayer-space of 0.8-1.7 nm via the insertion of different sized diamine compounds as support pillars between GO layers. The assembled 3D SP-GOs exhibit superior adsorption capacity and short removal time for various aromatic organic compounds in water, achieving record-breaking maximum adsorption capacity of 535.79 mg g-1 toward the most common water-pollutant bisphenol A (BPA) at ambient conditions as well as significantly improved removal of other organic pollutants including sulfapyridine, carbamazepine, ketoprofen and 2-naphthol. The construction of SP-GO provides a simple approach for evolving the GO material from 2D to 3D and a new avenue for the decontamination of pollutants in environmental remediation.

A novel hollow microsphere composite MnOx/PAA: effective catalyst for ozone decomposition at high humidity.

Ozone air pollution poses a serious threat to human health and ecological environment. Manganese oxide (MnOx) is a popular material for ozone decomposition with excellent catalytic performance. However, the catalytic activity may be reduced under high-humidity conditions because of oxygen vacancy of MnOx from the water evaporation. In this paper, a new type of MnOx/poly(acrylic acid-co-divinylbenzene) (PAA) catalyst with MnOx supported on hollow PAA was successfully prepared, which greatly improved the ozone decomposition efficiency under high humidity. It was shown that when the acrylic acid (AA) content was more than 50%, the PAA polymer layer was hydrophilic and the ozone decomposition efficiency would keep high activity for both the low- and high-humidity conditions. The best performance of ozone decomposition was identified for the methanol reduction and AA content of 60%, in which the efficiencies reached 94.5% and 85% at 50% and 90% humidity levels, respectively. It is the synergetic effect of the hydrophilic PAA support and hollow structure that retains and improves the decomposition activity, which can absorb the water vapor molecules and increase the ozone retention time. Therefore, the hollow microsphere catalyst prepared in this paper has great potential in solving the problem of ozone air pollution.

Polypropylene fiber grafted calcium alginate with mesoporous silica for adsorption of Bisphenol A and Pb2.

Polypropylene grafted calcium alginate with mesoporous silica (PP-g-CaAlg@SiO2) for adsorbing Bisphenol A (BPA) and Pb2+ was prepared by calcium chloride (CaCl2) crosslinking and hydrochloric acid solution treatment. The PP-g-CaAlg@SiO2 was characterized by SEM, TEM, BET, XRD, FTIR and TG. PP-g-CaAlg@SiO2 exhibited excellent adsorption capacity for BPA and Pb2+, because the formation of reticulated nanorod structure increased its specific surface area. Subsequently, the adsorption behaviours of BPA and Pb2+, including adsorption isotherms and adsorption kinetics, were investigated. Afterward, isothermal titration calorimetry (ITC) and molecular dynamics (MD) simulation were performed to explore the adsorption mechanism. The results indicated that hydrogen bonding played the leading role in the adsorption of BPA, while the bonding of Pb2+ to carboxyl group binding sites was the focus of Pb2+ adsorption. In addition, the adsorption capacity of PP-g-CaAlg@SiO2 was stable over 10 cycles.

Utilization of recycled polypropylene-acrylate grafted nonwoven for the removal of oil from water.

To solve water pollution caused by oil spillage, a new sorbent was prepared by radiation-induced graft polymerization. Acrylate monomer was introduced to polypropylene nonwoven and hydrophobic groups were introduced by the grafting method. The grafting degree of sorbent was determined as a function of monomer concentration and solvent solubility for monomer. Fourier transform-infrared spectra and static contact angle measurements were used to characterize the chemical changes of the polypropylene nonwoven surface. The grafted sorbent showed a fast sorption rate and a maximum sorption capacity of 13.56 g/g for diesel oil, while the original polypropylene nonwoven was only 7.48 g/g. In addition, retention measurement and the reusability test were conducted to evaluate the suitability of the polypropylene-acrylate grafted nonwoven for the treatment of oil spillage.

Enhancing oil-sorption performance of polypropylene fiber by surface modification via UV-induced graft polymerization of butyl acrylate.

In order to improve oil sorption performances, polypropylene (PP) fiber was modified through graft polymerization with butyl acrylate (BA) initiated by ultraviolet (UV) radiation in isopropanol/water mixture solution. Fourier transform infrared (FT-IR) spectra, scanning electron microscopy (SEM) and specific surface area were used to characterize the chemical and morphological changes of the PP fiber surface. Static contact angle (CA) measurements showed that the hydrophilicity of original PP fiber was enhanced after graft polymerization. The grafted fiber exhibited an excellent oil-sorption, oil-retention performance, fast saturation-sorption rate and superior reusability of oil. When the grafting degree was 15.55%, the maximum oil-sorption capacity reached 18.35 g/g, while the oil-sorption capacity of original PP fiber was only 11.54 g/g. After the tenth cycle of reuse, the grafted fiber sorbent assembly only lost 30% of its virgin sorption capacity.

Temperature-controlled ultra-high hydrogen evolution photocatalytic activity of cadmium sulfide without cocatalysts.

Photocatalytic water spitting is one way of hydrogen production from energy conservation and emission reduction. However, the activities of most photocatalytic materials need to be enhanced by cocatalysts. In this study, we explored to control the photocatalytic hydrogen evolution (PHE) ability of cadmium sulfide (CdS) without any cocatalysts by temperature and largely improve its photocatalytic ability. It was experimentally found the activity of CdS without cocatalysts under heating conditions (<100 °C) was much higher than that at room temperature, and increased first and then decreased, with a maximum at 50 °C (169716 umol/h, 68.2 % , λ = 450 nm). Therefore, it is convenient to control the hydrogen production activity of CdS by temperature. The large increment of photocatalytic activity was realized because the temperature complemented the shortcomings of semiconductors in light absorption, and together with light radiation, increased the electron migration rate and density, quantity of surface adsorbed H3O+ and number of active sites, prolonged the living of electrons, and reduced the overpotential of water splitting and the reverse reactions. Heating brings the above advantages, but also exacerbates the recombination of electron-hole pairs. Therefore, the activity shows an extreme value along with the temperature rise. This work experimentally proves temperature control is one of the most efficient and simple ways to largely enhance the PHE ability.

Near infrared spectroscopy combined with chemometrics for quantitative analysis of corn oil in edible blend oil.

In this study, near infrared (NIR) spectroscopy combined with chemometrics was used for the quantitative analysis of corn oil in binary to hexanary edible blend oil. Sesame oil, soybean oil, rice oil, sunflower oil and peanut oil were mixed with corn oil subsequently to form binary, ternary, quaternary, quinary and hexanary blend oil datasets. NIR spectra for the five order blend oil datasets were measured in a transmittance mode in the range of 12000-4000 cm-1. Partial least square (PLS) was used to build models for the five datasets. Six spectral preprocessing methods and their combinations were investigated to improve the prediction performance. Furthermore, the optimal preprocessing-PLS models were further optimized by uninformative variable elimination (UVE), Monte Carlo uninformative variable elimination (MCUVE) and randomization test (RT) variable selection methods. The optimal models acquire root mean square error of prediction (RMSEP) of 1.7299, 2.2089, 2.3742, 2.5608 and 2.6858 for binary, ternary, quaternary, quinary and hexanary blend oil datasets, respectively. The determination coefficients of prediction set (R2P) and residual predictive deviations (RPDs) for the five datasets are all above 0.93 and 3. Results show that the prediction accuracy is gradually decreased with the increasing of mixture order of blend oil. However, with proper spectral preprocessing and variable selection, the optimal models present good prediction accuracy even for the higher order blend oil. It demonstrates that NIR technology is feasible for determining the pure oil contents in binary to hexanary blend oil.

Synthesis of a new ion-imprinted polymer for selective Cr(VI) adsorption from aqueous solutions effectively and rapidly.

Removing hexavalent chromium (Cr(VI)) from aqueous solution is strategically important. A novel and selective adsorbent was synthesized using a high electron beam irradiation pre-grafting and post-surface ion imprinting method using Cr(VI) and polypropylene (PP) fibers as the template and substrates, respectively. The results obtained using Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TG) indicated that the prepared sorbent was successfully synthesized. At the same time, the adsorption performances were studied through batch experiments. The results exhibited rapid adsorption kinetics, a wide working pH range, and excellent selectivity and regeneration. The equilibrium adsorption was achieved within 30 min, the maximum sorption capacity of Cr(VI)-IIPs was 156.5 mg g-1 and partition coefficients (PC) was 0.591 mg g-1 uM-1 at 400 mg L-1 initial concentration and 298 K. The relative selectivity coefficients of the ion-imprinted polymer (IIP) for Cr2O72-/HPO42- and Cr2O72-/NO3- were 36.7 and 39.9, respectively. In addition, the prepared sorbent has a negligible loss in adsorption capacity after five cycles. IIP has good application prospects in the selective removal of Cr(VI) ions.

A novel remediation method of cadmium (Cd) contaminated soil: Dynamic equilibrium of Cd2+ rapid release from soil to water and selective adsorption by PP-g-AA fibers-ball at low concentration.

The acid-extractable fraction Cd(II) in soil accumulates easily in organisms, migrates and transforms in the ecological environment, which has posed potential health risks to human. This study found that the acid-extractable fraction Cd(II) in soil could be released rapidly into water at very low Cd2+ concentration. Carboxylated polypropylene (PP-g-AA) fibers-ball with high selectivity as adsorbent was used in the Cd(II) contaminated soil-water system. It could remove promptly trace Cd2+ from water even in the presence of interfering metal ions. Moreover, Cd(II) desorbed from soil to water could be continuously adsorbed by PP-g-AA fibers-ball, which kept the Cd2+ concentration always at a low level. This forms a dynamic equilibrium of rapid release- selective adsorption toward the acid-extractable fraction Cd(II) in the soil-water system. Here, the migratory pathway for the acid-extractable fraction Cd(II) to be released from contaminated soil to water and adsorbed simultaneously on the surface of PP-g-AA fibers-ball was established. This work offers a novel protocol that can remove more than 90% of the acid-extractable fraction Cd(II) from contaminated soil within 12 h, thereby contributes better to mitigate the risk of Cd(II) from soil to the food chain without changing the physical and chemical properties of soil.

Caffeic acid polymer rapidly modified sponge with excellent anti-oil-adhesion property and efficient separation of oil-in-water emulsions.

The efficient treatment of high stability emulsion with small diameter and the prevention of oil contamination of materials are serious issues in the process of emulsion separation. In order to address those issues, we reported a fast and versatile hydrophilic surface coating technology that uses oxidants and diamines to synergistically promote the polymerization of caffeic acid (CA). It was found that amino groups can not only accelerate the polymerization of CA, but also promote the deposition of polymers on the sponge surface. Using silica nanoparticles to improve the roughness, superhydrophilic melamine sponge could be prepared, which exhibited excellent superhydrophlic-underwater superolephobic and anti-oil-adhesion properties. DFT simulation was employed to explore the potential mechanism of the anti-oil adhesion ability. In addition, combined with the mechanical compression strategy, the sponge exhibited a high efficiency of 99.10% with a permeation flux of 19080 ±â€¯700 Lm-2 h-1 in emulsion separation just under the action of gravity. Moreover, based on the interaction between the surfactant and the surface of the material, the separation mechanism was discussed. Overall, this work provided an advanced method for the preparation of superhydrophilic sponge with anti-oil-fouling performance, which showed great potential in dealing with practically challenging emulsified wastewater.

Functional group-rich hyperbranched magnetic material for simultaneous efficient removal of heavy metal ions from aqueous solution.

In order to achieve the purpose of simultaneous removal of coexisting heavy metal ions, in this work, functionalized magnetic mesoprous nanomaterials (Fe3O4-HBPA-ASA) with high density and multiple adsorption sites were designed and prepared. The obtained Fe3O4-HBPA-ASA was characterized by SEM, FTIR, VSM, TGA and zeta potential. Cu(II), Pb(II) and Cd(II) were chosen as the model heavy metal ions, the adsorption experiments showed that Fe3O4-HBPA-ASA showed hightheoretical adsorption capacitiesin individual system, and the maximum adsorption capacity was 136.66 mg/g, 88.36 mg/g and 165.46 mg/g, respectively. In the binary and ternary systems, the competitive adsorption leads to a decrease in the adsorption capacity of Cu(II), Pb(II) and Cd(II). However, in the ternary system with a concentration lower than 15 mg/L, the simultaneous removal rate was still higher than 90%. The adsorption isotherms and kineticswere well fitted by Langmuir and pseudo-second-order models, respectively. The XPS and density functional theory (DFT) analysis have confirmed that the adsorption of metal ions was related to various types of functional groups on the surface of Fe3O4-HBPA-ASA, while the adsorption mechanisms of Cu(II), Cd(II) and Pb(II) were different.