Optimization of Mg-Al Layered Double Hydroxide Film Preparation and Corrosion Resistance Study on AZ91D Mg Alloy by Multivariate Polynomial Regression Fitting.

Layered double hydroxide (LDH) films have received extensive attention for their unique physical barrier function and ion exchange properties, which make them promising candidates for corrosion protection of magnesium alloys. In this paper, we used the multiple polynomial regression fitting method to establish a regression equation for the electrochemical corrosion resistance with the reaction temperature (T), pH, and reaction time (t) of the Mg-Al LDH film on the AZ91D magnesium alloy. The goodness of fit, confidence, and residual analyses confirmed the high accuracy of the model equation. According to the calculation using the fmincon function, the best corrosion resistance of the prepared samples could be achieved when the parameters are T = 135 °C, pH = 12.0, and t = 15 h. Then, the experimental results showed that the corrosion current density (Icorr) of the obtained LDH film under the above conditions could be 1.07 × 10-7 A/cm2, approximately 3 orders of magnitude lower than the magnesium alloy substrate, after immersion in a 3.5 wt % NaCl solution for 180 h, the surface structure of the LDH film did not change significantly, and the Icorr was still 2 orders of magnitude higher than that of the magnesium alloy substrate. Hence, a synergistic effect equation for the reaction temperature, pH, and reaction time on the corrosion resistance of the LDH film on a magnesium alloy surface prepared by the hydrothermal method was obtained. Moreover, using this equation, we obtained an LDH film with good corrosion resistance and durability, providing theoretical guidance for optimizing the process of preparing the LDH film by the hydrothermal method in practical applications.

Preparation of S-C3N4/AgCdS Z-Scheme Heterojunction Photocatalyst and Its Effectively Improved Photocatalytic Performance.

In this study, S-doped graphitic carbon nitride (S-C3N4) was prepared using the high-temperature polymerization method, and then S-C3N4/AgCdS heterojunction photocatalyst was obtained using the chemical deposition method through loading Ag-doped CdS nanoparticles (AgCdS NPs) on the surface of S-C3N4. Experimental results show that the AgCdS NPs were evenly dispersed on the surface of S-C3N4, indicating that a good heterojunction structure was formed. Compared to S-C3N4, CdS, AgCdS and S-C3N4/CdS, the photocatalytic performance of S-C3N4/AgCdS has been significantly improved, and exhibits excellent photocatalytic degradation performance of Rhodamine B and methyl orange. The doping of Ag in collaboration with the construction of a Z-scheme heterojunction system promoted the effective separation and transport of the photogenerated carriers in S-C3N4/AgCdS, significantly accelerated its photocatalytic reaction process, and thus improved its photocatalytic performance.

First-Principles Study of Atomic Diffusion by Vacancy Defect of the L12-Al3M (M = Sc, Zr, Er, Y) Phase.

Atomic diffusion by the vacancy defect of L12-Al3M (M = Sc, Zr, Er, Y) was investigated based on a first-principles calculation. The point defect formation energies were firstly evaluated. Then, the migration energy for different diffusion paths was obtained by the climbing-image nudged elastic band (CI-NEB) method. The results showed that Al atomic and M atomic diffusions through nearest-neighbor jump (NNJ) mediated by Al vacancy (VAl) were, respectively, the preferred diffusion paths in Al3M phases under both Al-rich and M-rich conditions. The other mechanisms, such as six-jump cycle (6JC) and next-nearest-neighbor jump (NNNJ), were energetically inhibited. The order of activation barriers for NNJ(Al-VAl) was Al3Zr < Al3Y < Al3Er < Al3Sc. The Al3Sc phase had high stability with a high self-diffusion activation barrier, while the Al3Zr and Al3Y phases were relatively unstable with a low self-diffusion activation energy. Moreover, the atomic-diffusion behavior between the core and shell layers of L12-Al3M was also further investigated. Zr atoms were prone to diffusion into the Al3Y core layer, resulting in no stable core-shelled Al3(Y,Zr), which well agreed with experimental observation.

Highly Soluble Dimethoxymethyl Tetrathiafulvalene with Excellent Stability for Non-Aqueous Redox Flow Batteries.

Non-aqueous redox flow batteries (RFBs) are highly attractive for grid-scale energy storage applications because of their independent design of energy and power, high energy density and efficiency, easy maintenance, and potentially low cost. In order to develop active molecules with large solubility, excellent electrochemical stability, and high redox potential for a non-aqueous RFB catholyte, herein, two flexible methoxymethyl groups had been attached to a famous redox-active tetrathiafulvalene (TTF) core. The strong intermolecular packing of the rigid TTF unit was effectively depressed, leading to a dramatically improved solubility of up to 3.1 M in conventional carbonate solvents. The performance of the obtained dimethoxymethyl TTF (DMM-TTF) was studied in a semi-solid RFB system with Li foil as the counter electrode. When using porous Celgard as the separator, the hybrid RFB with 0.1 M DMM-TTF had two high discharge plateaus at 3.20 and 3.52 V and a low capacity retention of 30.7% after 100 cycles at 5 mA cm-2. Replacing Celgard with a permselective membrane, the capacity retention was increased to 85.4%. Further increasing the concentration of DMM-TTF to 1.0 M and current density to 20 mA cm-2, the hybrid RFB exhibited a high volumetric discharge capacity of 48.5 A h L-1 and an energy density of 154 W h L-1. The capacity was maintained at 72.2% after 100 cycles (10.7 days). The great redox stability of DMM-TTF was revealed by UV-vis and 1H NMR tests and verified by density functional theory calculations. Therefore, the methoxymethyl group is an excellent group to increase the solubility while maintaining the redox capability of TTF for high-performance non-aqueous RFBs.

Corrosion resistance and mechanisms of Nd(NO3)3 and polyvinyl alcohol organic-inorganic hybrid material incorporated MAO coatings on AZ31 Mg alloy.

This work reports the design and preparation of novel organic (polyvinyl alcohol, PVA)-inorganic (neodymium nitrate, Nd(NO3)3) hybrid coatings on micro-arc oxidation (MAO) coating for magnesium (Mg) alloy corrosion protection. X-ray diffractometer, X-ray photoelectron spectroscopy, fourier transform infrared spectroscopy, field emission scanning electron microscope, Energy Dispersive X-ray spectrometer and surface roughness were applied to characterize the chemical composition and surface morphology of the coatings. The corrosion resistance of the coatings was evaluated by electrochemical and salt spray tests. The results suggested that the formation of PVA-Nd3+ and PVA-Mg2+ complexes promoted the enrichment of Nd3+ on the surface, and thereby improved the sealing quality and compactness of the coating. Interestingly, when the coating was damaged, the Nd3+ ions were transformed to their carbonates and covered the active sites, and thus exhibiting self-healing function. Further, the corrosion resistance of PVA-Nd3+ modified MAO composite coating on AZ31 Mg alloy was improved.

Intrinsic Mechanism Analyses of Significantly Enhanced Photoelectrochemical Performance of the Bi2MoO6/BiVO4 System.

In this paper, the electrodeposition and hydrothermal methods were used to prepare the Bi2MoO6/BiVO4 photoelectrode, and the intrinsic mechanism of significantly enhanced photoelectrochemical performance of the prepared Bi2MoO6/BiVO4 heterojunction system was studied. Work functions of Bi2MoO6 and BiVO4 were analyzed using a scanning Kelvin probe, and the direction of the heterojunction electric field and the transfer direction of photogenerated carriers were finally determined by the relative positions of the energy bands and the Fermi levels of Bi2MoO6 and BiVO4. A type II Bi2MoO6/BiVO4 heterojunction system was finally confirmed to be formed. Formation of the type II Bi2MoO6/BiVO4 heterojunction system reduces the recombination efficiency of photogenerated electrons and holes and thus improves the photoelectrochemical performance. The photogenerated current density of the Bi2MoO6/BiVO4 photoelectrode reaches 1.47 mA·cm-2, which is 4.9 times that of pure BiVO4 and thousands of times that of Bi2MoO6. The successful application of a scanning Kelvin probe in the verification of the heterojunction type provides theoretical and technical bases for the design and construction of efficient heterojunctions.

Novel graphitic sheets with ripple-like folds as an NCA cathode coating layer for high-energy-density lithium-ion batteries.

In this work, novel graphitic sheets with ripple-like folds (GSRFs) are synthesized from cheap resin via a facile route. The obtained GSRFs are used as a cladding layer for LiNi0.8Co0.15Al0.05O2 (NCA) particles to construct a GSRF@NCA composite cathode. Electrochemical testing for GSFR@NCA exhibits better cycling and C-rate performance than those of original NCA. Moreover, the capacity retention (85%) of the full-cell (GSFR@NCA versus graphite) is much higher than that (79%) of the full-cell (NCA versus graphite) after 400 cycles. Most importantly, this approach allows the preparation of GSFR@NCA with highly promising applications as a cathode for high-energy-density lithium-ion batteries, since in this contribution just simple equipment and a precursor with low cost are involved.

The excited-state relaxation mechanism of potential UVA-activated phototherapeutic molecules: trajectory surface hopping simulations of both 4-thiothymine and 2,4-dithiothymine.

Recent experimental investigations of the photochemical properties of a series of sulfur-substituted pyrimidine derivatives provide insights into the phototherapeutic potential of these nucleobase variants. Herein we elucidate the triplet formation mechanism of two prospective UVA-activated phototherapeutic molecules, 4-thiothymine and 2,4-dithiothymine, upon photo-excitation by applying the trajectory surface hopping dynamics at the LR-TDDFT level. Our simulations reasonably reproduce the experimental time constants and demonstrate the preferred triplet formation pathway which starts from the S1(nSπ*) state for both molecules. It is found that deactivation of the first bright state to the S1(nSπ*) state proceeds through a mechanism involving elongation of the C5-C6 and C4-S8 bond-lengths and C2-pyramidalization in 4-thiothymine and involving elongation of the C5-C6 and C2-S7 bond-lengths in 2,4-dithiothymine. The intersystem crossing of 2,4-dithiothymine occurs either at geometries characterized by elongated C5-C6 and C2-S7 bond-lengths or at geometries showing elongated C5-C6 and C4-S8 bond-lengths as seen in 4-thiothymine. The solvents are found to affect the S2 state decay of 4-thiothymine, leading to a competing pathway between S2→ S1 and S2→ T3. This study provides a molecular-level understanding of the underlying excited-state relaxation of the two UVA-activated thiopyrimidines, which may be linked to their potential applications in pharmacological science and also prove helpful for designing more effective phototherapeutic agents.

In vitro degradation and cytocompatibility of a low temperature in-situ grown self-healing Mg-Al LDH coating on MAO-coated magnesium alloy AZ31.

Basically, Mg-Al layered double hydroxide (LDH) coatings are prepared on the surface of micro-arc oxidation (MAO) coated magnesium (Mg) alloys at a high temperature or a low pH value. This scenario leads to the growth rate of LDH coating inferior to the dissolution rate of the MAO coating. This in turn results in limited corrosion resistance of the composite coating. In this study, a Mg-Al LDH coating on MAO-coated Mg alloy AZ31 is prepared through a water bath with a higher pH (13.76) at a lower temperature (60 °C). FE-SEM, EDS, XRD, XPS, and FT-IR are applied to analyze the surface morphology, chemical compositions, and growth process. Electrochemical polarization, electrochemical impedance spectroscopy (EIS) and hydrogen evolution tests are employed to evaluate the corrosion resistance of the samples. The results disclose that the MAO coating is completely covered by the nanosheet-structured LDH coating with a thickness of approximately 3.8 µm. The corrosion current density of the MAO-LDH composite coating is decreased four orders of magnitude in comparison to its substrate; the presence of a wide passivation region in anodic polarization branch demonstrates its strong self-healing ability, indicating the hybrid coating possesses excellent corrosion resistance. The formation mechanism of the LDH coating on the MAO-coated Mg alloy is proposed. Furthermore, the cytocompatibility is assessed via an indirect extraction test for MC3T3-E1 pre-osteoblasts, which indicates an acceptable cytocompatibility of osteoblasts for the composite coating.

Synthesis of Ni@NiSn Composite with High Lithium-Ion Diffusion Coefficient for Fast-Charging Lithium-Ion Batteries.

To solve the problems of fast-charging of lithium-ion batteries in essence, development of new electrode materials with higher lithium-ion diffusion coefficients is the key. In this work, a novel flower-like Ni@SnNi structure is synthesized via a two-step process design, which consists of the fabrication of Ni cores by spray pyrolysis followed by the formation of SnNi shells via a simple oxidation-reduction reaction. The obtained Ni@SnNi composite exhibits an initial capacity of ≈693 mA h g-1 and a reversible capacity of ≈570 mA h g-1 after 300 charge/discharge cycles at 0.5 C, and maintains 450 mA h g-1 even at a high rate of 3 C. Further, it is proved that a Ni@SnNi composite possesses high lithium-ion diffusion coefficient (≈10-8), which is much higher than those (≈10-10) reported previously, which can be mainly attributed to the unique flower-like Ni@SnNi structure. In addition, the full cell performance (Ni@SnNi-9h/graphite vs LiCoO2) with a capacity ratio of 1.13 (anode/cathode) is also tested. It is found that even at 2 C rate charging/discharging, the capacity retention at 100 cycles is still close to 89%. It means that Ni@SnNi-9h is a promising anode additive for lithium-ion batteries with high energy density and power density.

Titania/Electro-Reduced Graphene Oxide Nanohybrid as an Efficient Electrochemical Sensor for the Determination of Allura Red.

Titania/electro-reduced graphene oxide nanohybrids (TiO2/ErGO) were synthesized by the hydrolysis of titanium sulfate in graphene oxide suspension and in situ electrochemical reduction. It provides a facile and efficient method to obtain nanohybrids with TiO2 nanoparticles (TiO2 NPs) uniformly coated by graphene nanoflakes. TiO2/ErGO nanohybrids were characterized by transmission electron microscopy, X-ray diffraction, cyclic voltammogram, and electrochemical impedance spectroscopy in detail. Compared with pure ErGO and TiO2 NPs, TiO2/ErGO nanohybrids greatly enhanced the electrocatalytic activity and voltammetric response of Allura Red. In the concentration range of 0.5-5.0 µM, the anodic peak currents of Allura Red were linearly correlated to their concentrations. However, the linear relationship was changed to the semi-logarithmic relationship at a higher concentration region (5.0-800 µM). The detection limit (LOD) was 0.05 µM at a signal-to-noise ratio of 3. The superior sensing performances of the proposed sensor can be ascribed to the synergistic effect between TiO2 NPs and ErGO, which provides a favorable microenvironment for the electrochemical oxidation of Allura Red. The proposed TiO2/ErGO/GCE showed good reproducibility and stability both in determination and in storage, and it can accurately detect the concentration of Allura Red in milk drinks, providing an efficient platform for the sensitive determination of Allura Red with high reliability, simplicity, and rapidness.

Towards emerging EEG applications: a novel printable flexible Ag/AgCl dry electrode array for robust recording of EEG signals at forehead sites.

OBJECTIVES: With the rapid development of EEG-based wearable healthcare devices and brain-computer interfaces, reliable and user-friendly EEG sensors for EEG recording, especially at forehead sites, are highly desirable and challenging. However, existing EEG sensors cannot meet the requirements, since wet electrodes require tedious setup and conductive pastes or gels, and most dry electrodes show unacceptable high contact impedance. In addition, the existing electrodes cannot absorb sweat effectively; sweat would cause cross-interferences, and even short circuits, between adjacent electrodes, especially in the moving scenarios, or a hot and humid environment. To resolve these problems, a novel printable flexible Ag/AgCl dry electrode array was developed for EEG acquisition at forehead sites, mainly consisting of screen printing the Ag/AgCl coating, conductive sweat-absorbable sponges and flexible tines. APPROACH: A systematic method was also established to evaluate the flexible dry electrode array. MAIN RESULTS: The experimental results show the flexible dry electrode array has reproducible electrode potential, relatively low electrode-skin impedance, and good stability. Moreover, the EEG signals can be effectively captured with a high quality that is comparable to that of wet electrodes. SIGNIFICANCE: All the results confirmed the feasibility of forehead EEG recording in real-world scenarios using the proposed flexible dry electrode array, with a rapid and facile operation as well as the advantages of self-application, user-friendliness and wearer comfort.

Sensitive Voltammetric Sensor for Tryptophan Detection by Using Polyvinylpyrrolidone Functionalized Graphene/GCE.

In this paper, an electrochemical method for the measurement of tryptophan (Trp) was developed based on a glassy carbon electrode modified with polyvinylpyrrolidonefunctionalized graphene (PVP-GR)/glassy carbon electrode (GCE). In 0.1 M phosphate buffer solution (PBS, pH = 2.2), compared with bare GCE, PVP/GCE, and GR/GCE, the oxidation peak current of Trp increased dramatically at PVP-GR/GCE. The oxidation mechanism of Trp on the PVP-GR/GCE was discussed and the experimental conditions were optimized. Under the best experimental conditions, the oxidation peak current of Trp was proportional to its concentration in the range of 0.06 µM-10.0 µM and 10.0-100.0 µM, and the limit of detection (LOD) was 0.01 µM (S/N = 3). The target modified electrode with excellent repeatability, stability and selectivity, was successfully applied to detectTrp in drugs and biological samples.

Broadband Plasmonic Enhancement of High-Efficiency Dye-Sensitized Solar Cells by Incorporating Au@Ag@SiO2 Core-Shell Nanocuboids.

The introduction of plasmonic additives is a promising approach to boost the efficiency of the dye-sensitized solar cell (DSSC) since they may improve the light harvesting of a solar cell. Herein, we design broadband and strong plasmonic absorption Au@Ag@SiO2 nanocuboids (GSS NCs) as nanophotonic inclusions to achieve plasmon-enhanced DSSCs. These multiple-resonance absorptions arising from GSS NCs can be readily adjusted by altering their structures to complementarily match the absorption spectra of the dyes, especially in weak absorption zones. By subtly regulating the position of nanophotonic inclusions in the photoanodes, not only the plasmonic near-field enhancement but also far-field light scattering could be adequately developed to promote the light harvest and thus the efficiency of DSSCs. The resulting solar cells yield an average efficiency of 10.34%, with a champion value of 10.58%. The electromagnetic simulations are consistent with the experimental observations, further corroborating the synergistic effect of plasmonic improvement in these DSSCs.

Arylene Ethynylene-Functionalized Bithiazole-Based Zinc Polymers for Ultraefficient Photocatalytic Activity.

Polymers 4 containing poly(arylene ethynylene) were synthesized and characterized systematically. Among them, 4c exhibited a remarkable H2 evolution rate (14.32 mmol h-1 g-1) with visible-light irradiation, lasting 72 h in different water qualities; the corresponding apparent quantum yield was 11.6% at 450 nm.

Biodegradable Polylactide/TiO2 Composite Fiber Scaffolds with Superhydrophobic and Superadhesive Porous Surfaces for Water Immobilization, Antibacterial Performance, and Deodorization.

In this short communication, TiO2-nanoparticle-functionalized biodegradable polylactide (PLA) nonwoven scaffolds with a superhydrophobic and superadhesive surface are reported regarding their water immobilization, antibacterial performance, and deodorization. With numerous regular oriented pores on their surface, the as-fabricated electrospun porous PLA/TiO2 composite fibers possessed diameters in the range from 5 µm down to 400 nm, and the lengths were even found to be up to the meters range. The PLA/TiO2 composite fiber surface was demonstrated to be both superhydrophobic and superadhesive. The size of the pores on the fiber surface was observed to have a length of 200 ± 100 nm and a width of 150 ± 50 nm using field-emission scanning electron microscopy and transmission electron microscopy. The powerful adhesive force of the PLA/TiO2 composite fibers toward water droplets was likely a result of van der Waals forces and accumulated negative pressure forces. Such a fascinating porous surface (functionalized with TiO2 nanoparticles) of the PLA/TiO2 composite fiber scaffold endowed it with multiple useful functions, including water immobilization, antibacterial performance, and deodorization.

Selective Enrichment of Clenbuterol onto Molecularly Imprinted Polymer Microspheres with Tailor-made Structure and Oxygen Functionalities.

The noxious clenbuterol misapplied as the feed additive has posed an enormous threat to humans who actively rely on the food chains with high potential of contamination by clenbuterol, such as pork and beef. It is, therefore, highly desirable to develop novel materials and strategies for dealing with the clenbuterol. Herein, functional polymer microspheres prepared by Pickering emulsion polymerization were explored for the selective enrichment of the clenbuterol, and their structure and oxygen functionalities could be tailor-made by a molecular imprinting process. The clenbuterol imprinting was adequately demonstrated to not only increase the particle size (~52 nm vs. ~42 nm) and create cavities for the accommodation of the clenbuterol molecules, but also reduce the oxygen functionalities of the resulting molecularly imprinted polymer microspheres (MIPMs) by approximately 4 at.%, which is believed to correlate with the high specificity of the MIPMs. Various characterization methods were employed to evidence these findings, including scanning electron microscopy, BET measurements, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and elemental mapping examination. More importantly, the MIPMs showed a markedly superior enrichment capability towards clenbuterol to the counterpart, that is, non-molecularly imprinted polymer microspheres (NIPMs). Compared to the NIPMs without specificity for clenbuterol, the MIPMs exhibited an impressive selectivity to clenbuterol, with the relative selectivity coefficient (k') values largely exceeding 1, thus corroborating that the useful molecular imprinting led to the generation of the binding sites complementary to the clenbuterol molecule in the size and functionalities. The MIPMs were also employed as the stationary phase to fabricate molecularly imprinting solid-phase extraction column, and the spike recovery was demonstrated to be not significantly decreased even after nine cycles. Furthermore, the reliability of the method was also evidenced through the comparison of the MIPMs prepared from different batches.

A minireview of hydroamination catalysis: alkene and alkyne substrate selective, metal complex design.

Organic compounds that contain nitrogen are very important intermediates in pharmaceutical and chemical industry. Hydroamination is the reaction that can form C-N bond with high atom economy. The research progress in metals catalyzed hydroamination of alkenes and alkynes from the perspective of reaction mechanism is categorized and summarized.

Recent advances in two-dimensional transition metal dichalcogenides for biological sensing.

Layered transition metal dichalcogenides (TMDs) are important members in the family of two-dimensional (2D) materials. The large surface-to-volume ratio, combined with the fascinating tunable electronic and optical properties, low toxicity, unique van der Waals layered structure, and engineerable surface structure, renders 2D TMDs highly valuable for next-generation biosensing applications. Herein, the recent progress in the development of 2D TMDs-based biosensors is comprehensively reviewed, with special focus on the implementation of the structural, electronic and optical properties of 2D TMDs in the realization of high-performance biosensors with different configurations for a wide spectrum of bioanalytes and bio-species. In addition, the comparison on biosensing performances with graphene as the currently most studied 2D candidate is critically discussed. Finally, future perspectives are provided along the development progress of 2D TMDs-based biosensors which are currently undergoing an intense study. This work will lead researchers to explore more novel sensing candidates within the category of TMDs with exotic chemical composition, structure, morphologies, dimensionalities, and properties.

Liquid Phase Exfoliated Hexagonal Boron Nitride/Graphene Heterostructure Based Electrode Toward Asymmetric Supercapacitor Application.

In this paper, owing to the electrostatic interaction between graphene and h-BN, a facile liquid phase exfoliation method was carried out to fabricate h-BN/graphene based van der Waals heterostructure nanocomposites without additional chemical cross-linkers. The physicochemical properties of as-prepared composites were characterized by several electron microscopic and spectroscopic measurements. The h-BN/graphene heterostructure composites were employed to use as the anodes of asymmetric supercapacitor, and exhibited exceptional capacitive performance due to their synergistic effects. It is expected that the as-prepared h-BN/graphene materials can boost scalable heterostructure electrodes in supercapacitors, and our liquid phase exfoliation method can be used for the construction of the other energy storage and electronics.