Catalytic effects of graphene structures on Pt/graphene catalysts.

Pt/C catalysts have been considered the ideal cathodic catalyst for proton exchange membrane fuel cells (PEMFCs) due to their superior oxygen reduction reaction (ORR) catalytic activity at low temperatures. However, oxidation and corrosion of the carbon black support at the cathode result in the agglomeration of Pt particles, which reduces the active sites in the Pt/C catalyst. Graphene supports have shown great promise to address this issue, and therefore, finding out the main structural features of the graphene support is of great significance for guiding the rational construction of graphene-based Pt (Pt/graphene) catalysts for optimized ORR catalysts. In order to systematically study the influence of the structural features of the graphene support on the electro-catalytic properties of Pt/graphene catalysts, we prepared porous nitrogen-doped reduced graphene oxide (P-NRGO), nitrogen-doped reduced graphene oxide (NRGO), treated P-NRGO (TP-NRGO) and reduced graphene oxide (RGO) with different nitrogen species contents (7.76, 7.54, 3.24, and 0.14 at%), oxygen species contents (18.68, 18.12, 6.34 and 21.12 at%), specific surface areas (370.4, 70.6, 347.7 and 276.2 m2 g-1) and pore volumes (1.366, 0.1424, 1.3299 and 1.0414 cm3 g-1). The ORR activity of the four Pt/graphene catalysts when listed in the order of their half-wave potentials (E 1/2) and peak power densities was found to be as Pt/P-NRGO > Pt/NRGO > Pt/TP-NRGO > Pt/RGO. The long-term durability of Pt/P-NRGO for the operation of H2-air PEMFCs is better than that of commercial Pt/C catalysts. The excellent ORR catalytic performance of Pt/P-NRGO compared to that of the other three Pt/graphene catalysts is ascribed to the high nitrogen species content of P-NRGO that can facilitate the uniform dispersion of Pt particles and provide accessible active sites for ORR. The results indicate that the specific surface area (SSA) and heteroatom dopants have strong influence on the Pt particle size, and that the nitrogen species of graphene supports play a more important role than the oxygen species, specific surface area and pore volume for the Pt/graphene catalysts in providing accessible active sites.

NiCo2 O4 Nanowires Immobilized on Nitrogen-Doped Ti3 C2 Tx for High-Performance Wearable Magnesium-Air Batteries.

Flexible magnesium (Mg)-air batteries provide an ideal platform for developing efficient energy-storage devices toward wearable electronics and bio-integrated power sources. However, high-capacity bio-adaptable Mg-air batteries still face the challenges in low discharge potential and inefficient oxygen electrodes, with poor kinetics property toward oxygen reduction reaction (ORR). Herein, spinel nickel cobalt oxides (NiCo2 O4 ) nanowires immobilized on nitrogen-doped Ti3 C2 Tx (NiCo2 O4 /N-Ti3 C2 Tx ) are reported via surface chemical-bonded effect as oxygen electrodes, wherein surface-doped pyridinic-N-C and Co-pyridinic-N moieties accounted for efficient ORR owing to increased interlayer spacing and changed surrounding environment around Co metals in NiCo2 O4 . Importantly, in polyethylene glycol (PVA)-NaCl neutral gel electrolytes, the NiCo2 O4 /N-Ti3 C2 Tx -assembled quasi-solid wearable Mg-air batteries delivered high open-circuit potential of 1.5 V, good flexibility under various bent angles, high power density of 9.8 mW cm-2 , and stable discharge duration to 12 h without obvious voltage drop at 5 mA cm-2 , which can power a blue flexible light-emitting diode (LED) array and red smart rollable wearable device. The present study stimulates studies to investigate Mg-air batteries involving human-body adaptable neutral electrolytes, which will facilitate the application of Mg-air batteries in portable, flexible, and wearable power sources for electronic devices.

Freeing Fluoride Termination of Ti3C2Tx via Electrochemical Etching for High-Performance Capacitive Deionization.

Ti3C2Tx MXene is a promising Faradic capacitive deionization (CDI) electrode for high salt removal in future desalination, whereas the surface termination group of fluoride (-F) significantly impedes ion access to Ti3C2 and charge-transfer efficiency. Herein, we propose an electrochemically etched strategy to synthesize -F-free Ti3C2Tx through three-electrode cyclic voltammetry scanning within a narrowed potential window in an alkaline electrolyte. The resulting assembly of an asymmetric electrochemical-etched Ti3C2Tx//activated carbon CDI device can deliver an excellent salt removal capacity of 20.27 mg·g-1 with an adsorption rate of 1.01 mg g-1 min-1 owing to the enhanced hydrophilicity and ion transport. The tiny CDI device is demonstrated, which can generate an electric current during the electrosorption of salt ions, thus facilitating the powering of a red light-emitting diode. This study opens a new avenue for the surface chemistry of Ti3C2Tx and is expected to achieve future applications in desalination and renewable energy.

Surface fluorine preservation dependence of Ti3C2Tx MXene for high electrochemical properties in ionic liquid electrolytes.

We identified the contribution of -CF3 terminations to the Ti3C2Tx surface structure when ethanol and water were used as solvents during delamination through experimental and computational studies. Ethanol-treated -CF3-terminated Ti3C2Tx achieves better prevention of nanoflake aggregation, hydrophobicity, and small size, enabling enhanced capacitive properties in ionic liquid compared to water-treated Ti3C2Tx in aqueous and ionic liquid electrolytes.

Pseudocapacitive Charge Storage in MXene-V2O5 for Asymmetric Flexible Energy Storage Devices.

Pseudocapacitive asymmetric supercapacitors are promising candidates for achieving high energy density in flexible energy storage devices. However, seeking suitable positive electrode materials that are compatible with negative electrode materials remains a considerable challenge. In the current study, a pseudocapacitive Ti3C2Tx MXene used as negative electrodes is rationally compatible with redox-type V2O5 as positive electrodes, resulting in the assembly of an all-pseudocapacitive Ti3C2Tx MXene//V2O5 asymmetric flexible energy storage device. The solid-state asymmetric device can deliver an energy density of 8.33 mW h cm-3 at a current density of 0.5 A g-1. Moreover, it can operate in an expanded voltage window of 1.5 V, with dominant surface-capacitive charge-storage mechanisms. Additionally, the device can power a yellow light-emitting diode for up to 7 s, indicating the potential of the device for use in practical applications. This study demonstrates the possibility of using other two-dimensional transition-metal carbide nanosheets for high-energy density flexible energy storage devices.

The effect of hydrothermal temperature on the properties of SBA-15 materials.

In present work, ordered mesoporous material SBA-15 was synthesized by using poly (alkylene oxide) block copolymer (Pluronic P123) as template and ethylsilicate as silica source in weak acid environment in a wide range of temperature. The focus of synthesis research was high hydrothermal temperature. The obtained products were characterized by various techniques, including XRD, N2 sorption isotherms, FTIR spectroscopy and thermogravimetric. The effect of hydrothermal temperature on the specific surface area, pore volume and pore size of SBA-15 products was investigated systematically. As the hydrothermal temperature increases from the 100-120 °C, the specific surface area and the pore volume of the mesoporous molecular sieve increase greatly. When the hydrothermal temperature increase further, the pore volume of the mesoporous molecular sieve increase continually. But the specific surface area decrease significantly. When the hydrothermal temperature is too high (over 140 °C), the order degree begins to decrease, So the specific surface area and pore volume decrease significantly because the pores structure have significant destruction and collapse. Mechanism and structural characteristics of P123 block copolymer could explain in detail the effect of hydrothermal temperature on the property and structure of mesoporous molecular sieve SBA-15.

Structural and Binding Properties on Aß Mature Fibrils Due to the Histidine Tautomeric Effect.

Many studies have focused on histidine behaviors in misfolding diseases. However, histidine behaviors on mature fibrils are still unknown. In the current study, we investigated mature fibrils with various histidine states to understand the structural properties of the histidine tautomeric effect on mature fibrils. Our results show that substituting chain 1 with different histidine states affects Aß structural properties in A2, D7-G9, H14-Q15, S26-N27, and G33-G37 regions. The binding free energies with substituted fibrils were influenced not only along the axial direction, but also between duplex fibrils. Our results suggest that substituted (εδδ) preferentially disturbed the stability among the current mature fibrils. Further, H-bonded network differences indicate that twisted morphologies in mature fibrils are derived from the position and orientation of the imidazole ring in histidines. Our current study helps to elucidate histidine behaviors on mature fibrils, which will present opportunities to understand the misfolding mechanisms.

Surface Functional Groups and Electrochemical Behavior in Dimethyl Sulfoxide-Delaminated Ti3 C2 Tx MXene.

Functional groups in two-dimensional (2D) Ti3 C2 Tx MXene are an important factor influencing electrochemical performance in many applications involving energy storage, electrochemical sensors, and water purification. However, after dimethyl sulfoxide (DMSO) delamination, the effect of surface functionalities in Ti3 C2 Tx is still unclear and there are no systematic reports on its capacitive behavior. Experiments and theoretical calculations confirm the relationship between different surface functionalities, the DMSO delamination effect, and the electrochemical behavior of the DMSO-delaminated Ti3 C2 Tx . The dominant -O and -OH terminations are attributed for surfaces delaminated by using HF [Ti3 C2 Tx (HF)] and LiF/HCl [Ti3 C2 Tx (LiF/HCl)], respectively. Theoretical results are also in agreement with experimental results in that -OH terminations are essential for the formation of a free-standing film. Compared to non-delaminated Ti3 C2 Tx (HF) (similar O/F ratios of 1.37 and 1.42), there is a significant DMSO delamination effect for Ti3 C2 Tx (LiF/HCl) because of different O/F ratios of 2.9 and 3.6. Additionally, the delaminated Ti3 C2 Tx (LiF/HCl) electrodes deliver a higher capacitance of 508 F cm-3 than that of 333 F cm-3 for the delaminated Ti3 C2 Tx (HF), although it exhibited lower equivalent series resistance, lower interlayer spacing, and slightly lower specific surface area. This study provides direct and systematic experimental evidence for different functional groups in Ti3 C2 Tx MXene based on the DMSO delamination effect.

Neutral pH Gel Electrolytes for V2O5·0.5H2O-Based Energy Storage Devices.

Gel electrolytes are considered to be promising candidates for the use in supercapacitors. It is worthy to systematically evaluate the internal electrochemical mechanisms with a variety of cations (poly(vinyl alcohol) (PVA)-based Li+, Na+, and K+) toward redox-type electrode. Herein, we describe a quasi-solid-state PVA-KCl gel electrolyte for V2O5·0.5H2O-based redox-type capacitors, effectively avoiding electrochemical oxidation and structural breakdown of layered V2O5·0.5H2O during 10 000 charge-discharge cycles (98% capacitance retention at 400 mV s-1). With the gel electrolyte, symmetric V2O5·0.5H2O-reduced graphene oxide (V2O5·0.5H2O-rGO) devices exhibited a volumetric capacitance of 136 mF cm-3, which was much higher than that of 68 mF cm-3 for PVA-NaCl and 45 mF cm-3 for PVA-LiCl. Additionally, hybrid full cells of activated carbon cloth//V2O5·0.5H2O-rGO delivered an energy density of 102 µWh cm-3 and a power density of 73.38 mW cm-3 over a wide potential window of 2 V. The present study provides direct experimental evidence for the contribution of PVA-KCl gel electrolytes toward quick redox reactions for redox-type capacitors, which is also helpful for the development of neutral pH gel electrolytes for energy storage devices.

Dendritic Ni(Cu)-polypyrrole hybrid films for a pseudo-capacitor.

Dendritic Ni(Cu)-polypyrrole hybrid films are fabricated for a pseudo-capacitor in a unique morphology using two simple methods: electro-deposition and electrochemical de-alloying. Three-dimensional structures of porous dendrites are prepared by electro-deposition within the hydrogen evolution reaction (HER) at a high cathodic potential; the high-surface-area structure provides sufficient redox reactions between the electrodes and the electrolyte. The dependence of the active-layer thickness on the super-capacitor performance is also investigated, and the 60 µm-thick Ni(Cu)PPy hybrid electrode presents the highest performance of 659.52 F g(-1) at the scan rate of 5 mV s(-1). In the thicker layers, the specific capacitance became smaller due to the diffusion limitation of the ions in an electrolyte. The polypyrrole-hybridization on the porous dendritic Ni(Cu) electrode provides superior specific capacitance and excellent cycling stability due to the improvement in electric conductivity by the addition of conducting polypyrrole in the matrices of the dendritic nano-porous Ni(Cu) layer and the synergistic effect of composite materials.

Surfactant Effects on the Morphology and Pseudocapacitive Behavior of V2 O5 ⋠H2 O.

To overcome the drawback of low electrical conductivity within supercapacitor applications, several surfactants are used for nanoscale V2 O5 to enhance the specific surface area. Polyethylene glycol 6000 (PEG-6000), sodium dodecylbenzene sulfonate (SDBS), and Pluronic P-123 (P123) controllers, if used as soft templates, easily form large specific surface area crystals. However, the specific mechanism through which this occurs and the influence of these surfactants is not clear for V2 O5 ⋅H2 O. In the present study, we aimed to investigate the mechanism of crystal growth through hydrothermal processes and the pseudocapacitive behavior of these crystals formed by using diverse surfactants, including PEG-6000, SDBS, and P123. Our results show that different surfactants can dramatically influence the morphology and capacitive behavior of V2 O5 ⋅H2 O powders. Linear nanowires, flower-like flakes, and curly bundled nanowires can be obtained because of electrostatic interactions in the presence of PEG-6000, SDBS, and P123, respectively. Furthermore, the electrochemical performance of these powders shows that the nanowires, which are electrodes mediated by PEG-6000, exhibit the highest capacitance of 349 F g(-1) at a scan rate of 5 mV s(-1) of all the surfactants studied. However, a symmetric P123 electrode comprising curly bundled nanowires with numerous nanopores showed an excellent and stable specific capacitance of 127 F g(-1) after 200 cycles. This work is beneficial to understanding the fundamental role of the surfactant in the assisted growth of V2 O5 ⋅H2 O and the resulting electrochemical properties of the pseudocapacitors, which could be useful for the future design of appropriate materials.