Hydrogen sulfide gas detection by Au-decorated ZnO nanotube: a computational study and comparison to experimental observations

Based on the experimental reports, Au-decoration on the ZnO nanostructures dramatically increases the electronic sensitivity to H₂S gas. In the current study, we computationally scrutinized the mechanism of Au-decoration on a ZnO nanotube (ZON) and the influence on its sensing behavior toward H₂S gas. The intrinsic ZON weakly interacted with the H₂S gas with an adsorption energy of ?11.2 kcal/mol. The interaction showed no effect on the HOMO–LUMO gap and conductivity of ZON. The predicted response of intrinsic ZON toward H₂S gas is 6.3, which increases to 78.1 by the Au-decoration at 298 K. The corresponding experimental values are about 5.0 and 80.0, indicating excellent agreement with our findings. We showed that the Au atom catalyzes the reaction 3O₂?+?2H₂S?→?2SO₂?+?2H₂O. Our calculated energy barrier (at 298 K) is about 12.3 kcal/mol for this reaction. The gap and electrical conductance Au-ZON largely changed by this reaction are attributed to the electron donation and back-donation processes. The obtained recovery time is about 1.35 ms for desorption of generated gases from the surface of the Au-ZON sensor.     

Facile high yield synthesis of MgCo2O4 and investigation of its role as anode material for lithium ion batteries

In this article, we have reported a one-step scalable synthesis of MgCo₂O₄ nanostructures as efficient anode material for Li-ion batteries and investigated the role of post-synthesis calcination temperature (400, 600 and 800 °C) on its physiochemical properties and electrochemical performances. The XRD pattern of the calcinated sample at 400 °C (MC 400) indicates a pure phase of MgCo₂O₄. However, on increasing the calcination temperature to 600 °C (MC 600), an additional phase corresponding to MgO was detected and the corresponding XRD peak intensity further increased on increasing the calcination temperature to 800 °C (MC 800 °C). This was accompanied by a morphological transformation from flake and rod-like nanostructures, to an agglomerated dense flake-like morphology. Electrochemical studies revealed that the calcination temperature plays an important role in determining the electrochemical performance of the MgCo₂O₄ as anode material. In a half cell, the MC 600 showed the best electrochemical performance with high discharge capacity of 980 mA h g⁻¹ (2nd discharge at 60 mA g⁻¹) and a reversible discharge capacity of 886 mA h g⁻¹ at the end of 50 cycles with high coulombic efficiency of 98%. Long term stability was carried out at 0.5C which showed a capacity retention of 358 mA h g⁻¹ at the end of 500 cycles. The superior electrochemical performance of the MC600 can be attributed to the presence of the small amount of MgO, which is believed to provide the anode materials better structural stability during cycling. The claim was further supported by ex-situ TEM analysis of the anode material of a cycled cell (50 cycles).     

Combating Biofilm Associated Infection In Vivo: Integration of Quorum Sensing Inhibition and Photodynamic Treatment based on Multidrug Delivered Hollow Carbon Nitride Sphere

Recently, quorum sensing (QS) inhibitors (QSIs) have been combined with antibiotics to enhance antibiofilm efficacy in vitro and in vivo. However, targeting QS signals alone is not enough to prevent bacterial infections. Drug resistance and recurrence of biofilms makes it difficult to eradicate. Herein, photodynamic therapy (PDT) is selected to unite QSIs and antibiotics. A synergistically antibiofilm system, which combines QSIs, antibiotics, and PDT based on hollow carbon nitride spheres (HCNSs) is envisaged. First, HCNS provides the multidrug delivering ability, enabling QSIs and antibiotics to be released in sequence. Subsequently, multistage releases sensitize bacteria effectively, potentiating the chemotherapeutic effects of the antibiotics. Finally, the integration of QSIs and PDT not only minimizes the possibility of drug resistance, but also overcomes the problem of limited mass and extension of PDT. Even after 48 h of incubation, the bacterial biofilm is obviously inhibited. And its biofilm disperse efficiency exceeds 48% (compared with QSI‐potentiated chemotherapy group) and 40% (compared with PDT group). Besides, the inhibition of the QS system influences phenotypes related to virulence factor production and surface hydrophobicity, which weaken biofilm invasion and formation. Eventually, this system is applied to disperse bacterial biofilm in vivo. Overall, PDT and QS modulation are devoted to eradicate drug resistance and recurrence of the biofilm.     

Carbon vacancies improved photocatalytic hydrogen generation of g-C3N4 photocatalyst via magnesium vapor etching

Vacancies engineering was widely reported as the promising strategy for the improvement of the photocatalytic performance of semiconductor photocatalysts. In current work, carbon vacancies are constructed successfully in graphitic carbon nitride (g-C₃N₄) photocatalyst via magnesium vapor etching. Experimental results show that the formed carbon vacancies in g-C₃N₄ photocatalyst can significantly improve the photocatalytic H₂ generation performance. XRD, FTIR, SEM/TEM, XPS and PL characterization data are employed to evidence the construction of carbon vacancies, which are revealed to be the reason for the enhancement of photocatalytic H₂ evolution. This work develops an alternative route to construct carbon vacancies in g-C₃N₄ materials and gives an insight into the influence of vacancies on the photocatalytic performance of photocatalysts.     

Investigation of the versatility of SPES membranes customized with sulfonated molybdenum disulfide nanosheets for DMFC applications

Sulfonated poly(ether sulfone) (SPES) based proton exchange membranes (PEMs) are fabricated using sulfonated molybdenum disulfide (S-MoS₂) nanosheets via facile solution casting method. SPES (DS = 30%) and S-MoS₂ are synthesized and sulfonation is evidently observed in FTIR and XRD analysis. The anchoring of sulfonic acid group on exfoliated molybdenum disulfide (E-MoS₂) and elemental composition of S-MoS₂ are confirmed by XPS spectrum. Physico-chemical characteristics such as ion-exchange capacity (IEC), water uptake, swelling ratio and oxidation stability are found to be increases after the addition of S-MoS₂ into SPES matrix. Increment in S-MoS₂ content in SPES matrix decreases the surface contact angle due to the increase in hydrophilicity. Further, the dispersing ability of S-MoS₂ in SPES matrix is evidently shown by an increase in surface roughness, tensile strength and thermal stability of the SPES/S-MoS₂ nanocomposite membranes. On the whole, SPES/S-MoS₂-1 membrane showed the highest proton conductivity of 5.98 × 10⁻³ Scm⁻¹, selectivity of 19.6 × 10⁴ Scm⁻³s, peak power density of 28.28 mWcm⁻² and lesser methanol permeability of 3.05 × 10⁻⁸ cm²s⁻¹. The strong interfacial interaction between SPES and S-MoS₂ in nanocomposite membranes create strong hydrogen bond network to facilitate the proton conduction pathway via both vehicle and Grotthuss type mechanisms. Overall results suggested that the SPES/S-MoS₂ nanocomposite membranes are superior and appropriate alternative for commercially high-cost Nafion® membranes for use in renewable direct methanol fuel cell (DMFC) devices.     

Self-supported Ni2P nanotubes coated with FeP nanoparticles electrocatalyst (FeP@Ni2P/NF) for oxygen evolution reaction

Bimetallic phosphides have been widely investigated as electrocatalysts for oxygen evolution reaction (OER) due to their efficient activity and environmental friendliness. While the reasonable design and controllable synthesis of bimetallic phosphide with typical nanostructure is still a great challenge. Hence, we put forward a novel and straightforward way for constructing FeP nanoparticles coated Ni₂P ultrathin nanotube arrays on the surface of Ni foil (FeP@Ni₂P/NF), which is synthesized through two steps of electrodeposition and subsequent in-situ phosphorization process. The obtained FeP@Ni₂P/NF shows excellent electrochemical activity for OER, and it only needs potential of 1.52 V vs. RHE to reach the current density of 50 mA cm⁻² in an alkaline media. The excellent electrocatalytic activity of FeP@Ni₂P/NF mainly benefits from: (i) the synergistic effect between FeP and Ni₂P promoting electron transfer; (ii) the formation of the unique 3D ultrathin nanotube arrays increasing the quantity of active sites and avoiding the agglomeration of catalysts during testing. In addition, the influence of reaction condition on the electrochemical activity for OER has also been investigated through altering the phosphorization temperature of precursor.     

One-step synthesis of CuCo2O4-Sm0.2Ce0.8O1.9 nanofibers as high performance composite cathodes of intermediate-temperature solid oxide fuel cells

One-dimensional nanostructured CuCo₂O₄-Sm_0.2Ce_0.8O_1.9 (SDC) nanofibers are prepared by the electrospinning method and one step sintering as a cathode with low polarization resistance for intermediate temperature solid oxide fuel cells (IT-SOFC). The CuCo₂O₄-SDC nanofibers cathodes form a porous network structure and have large triple-phase boundaries. Correspondingly, the electrochemical performance of the CuCo₂O₄-SDC nanofibers composite cathodes shows significantly improve, achieving the polarization resistance of 0.061 Ω cm² and the maximum power densities of 976 mW·cm⁻² at 750 °C. Thus, these results suggest that CuCo₂O₄-SDC nanofiber could be a highly active cathode material for IT-SOFCs.     

Semiconductor Fe-doped SrTiO3-δ perovskite electrolyte for low-temperature solid oxide fuel cell (LT-SOFC) operating below 520 °C

High-temperature operation of solid oxide fuel cells causes several degradation and material issues. Lowering the operating temperature results in reduced fuel cell performance primarily due to the limited ionic conductivity of the electrolyte. Here we introduce the Fe-doped SrTiO_3-δ (SFT) pure perovskite material as an electrolyte, which shows good ionic conduction even at lower temperatures, but has low electronic conduction avoiding short-circuiting. Fuel cell fabricated using this electrolyte exhibits a maximum power density of 540 mW/cm² at 520 °C with Ni-NCAL electrodes. It was found that the Fe-doping into the SrTiO_3-δ facilitates the creation of oxygen vacancies enhancing ionic conductivity and transport of oxygen ions. Such high performance can be attributed to band-bending at the interface of electrolyte/electrode, which suppresses electron flow, but enhances ionic flow.     

Catalytic dehydrogenation of formic acid-triethanolamine mixture using copper nanoparticles

In a bid to complement the lost reserves from fossils, recent advances in research are tailored towards producing hydrogen as an alternative source of fuel which is aimed at fostering a globally sustainable and reliable energy-economy. In this work, hydrogen was produced from formic acid (FA) using a new technology that involves the use of copper nanoparticles (CuNPs) supported on triethanolamine. The CuNP-catalysts of variant concentrations (i.e. 0.6–1.2 M) were synthesized using the conventional chemical deposition method. Also, a novel approach that bothers on the application of the Differential Method of Analysis (DMA) was used in determining the kinetic parameters for the FA-dehydrogenation. Based on the results, the volume of H₂ produced varied with time, pH, concentration and catalyst-size. At 6 h, the 1 M CuNPs gave the highest volume (815 mL) of hydrogen with corresponding pH, particle size and approximate conversion of 3.19, 1.5 nm and 100% respectively, whereas, over extended periods i.e. over 6 h, the approximate volume-conversions of FA increased insignificantly for all catalysts. According to the investigation, the optimum CuNP-catalyst concentration required to produce 815 mL H₂ in 6 h is 1 M. The decomposition was a first-order-type with a rate constant (k-value) of 1.0041 s⁻¹.