Spin-state regulating of cobalt assisted by iron doping and coordination for enhanced oxygen evolution reaction

Customizing catalysts from the electronic structure, such as spin state, is an effective but challenging strategy for oxygen evolution reaction (OER). Herein, an ultrafine Co–Fe material highly dispersed on nitrogen carbide matrix is fabricated by coordination polymer and self-templating method to scrutinize the impact of spin state of Co on OER through Fe doping. The optimized catalyst shows boosted OER performance, which only requires overpotential of 333 mV at 10 mA cm^?2, outperforming other control samples and commercial RuO₂. The elevated local spin states of Co by Fe doping lead to charge transfer acceleration and fast generation of oxygenated intermediates, which is proved to account for the OER elevation. In addition, the long-term stability of Co–Fe material is guaranteed by the strong coordination of Co/Fe to the melamine-formaldehyde resin, which is used to adsorb metal ions, contributing to the high dispersion of active sites during the OER process.     

Simply constructed highly dispersed cobalt nanoparticles in diverse N-doped graphitic carbon with remarkable performances for water electrolysis

Metal/carbon composite materials are highly promising electrocatalysts for water electrolysis. In this work, three composites of metal cobalt nanoparticles highly dispersed in N-doped carbon materials were facilely constructed by pyrolysis of different phenylenediamine based Schiff base-Co complexes (PDBs). Interestingly, the composites derived from PDBs based on different phenylenediamine exhibited different morphologies. The superior case is that rodlike composite catalyst was derived from o-phenylenediamine based PDBs. The obtained catalyst exhibited remarkable performances for both cathodic hydrogen evolution reaction (HER) and anodic oxygen evolution reaction (OER), as well as overall water electrolysis. Only 172 and 289 mV of overpotentials and 1.57 V of cell voltage were exhibited at 10 mA cm^?2 for HER, OER and water splitting in 1.0 M KOH, respectively. The catalyst also displayed robust stability and high Faraday efficiency, and thus are potential high-performance catalyst for commercial water electrolysis.     

Electrochemical performance of in situ LiFePO4 modified by N-doped graphene for Li-ion batteries

LiFePO₄ modified by N-doped graphene (NG) with a three-dimensional conductive network structure was synthesized via a one-step in situ hydrothermal method. The effects of N amount of NG on the phase structure, morphology, and electrochemical properties of LiFePO₄ are investigated in this study. X-ray diffraction (XRD) results show that doping suitable N amounts in NG do not alter the crystal structure of LiFePO_4, and scanning electron microscopy (SEM) images show that NG can slightly reduce the particle size of LiFePO₄. The high-resolution transmission electron microscopy (HRTEM) results show that the LiFePO₄ particles are well covered and connected by NG. The electrochemical performance confirms that LiFePO₄ modified by 20% N-doped graphene (named LFP/NG-4) displays a perfect specific capacity of 166.6 mAh·g^?1 at a rate of 0.2C and can reach 125 mAh·g^?1 at a rate of 5 C. Electrochemical impedance spectroscopy (EIS) results illustrate that the charge transfer resistance value of the LFP/NG-4 composite is only 58.6 Ω, which is very low compared with LiFePO₄. Cyclic voltammetry (CV) tests indicate that the addition of 20% N-doped graphene can effectively reduce electrode polarization and improve reversibility. The LFP/NG-4 composite with a three-dimensional conductive network structure can be regarded as a promising cathode material for Li-ion batteries.     

Ag nanoparticles-polypyrrole-carbon black/mesoporous TiO2 novel nanocomposite as ultrafast visible-light-driven photocatalyst

Effective design and fabrication of novel visible light-oriented photocatalysts is an existing challenging task that requires further dedicated efforts, and it has been always a main concern among the scientific community. This study deals with the design and fabrication of an extremely active and ultrafast ternary photocatalyst based on Ag nanoparticles, polypyrrole doped carbon black (PPy-C) and mesoporous TiO₂ (m-TiO₂). Sol-gel methodology along with sonication and photodeposition routes have been employed for the successful creation of the ternary framework. Ternary photocatalyst composed of uniform spherical titania nanoparticles (10–15 nm in size) perfectly intermingled with the polymeric linkage of PPy-C. Fruitful creation of unique trio photocatalyst between AgNPs, PPy-C and m-TiO₂ was confirmed by XPS and XRD. FTIR analysis further supports the development of nanocomposite photocatalyst. TEM analysis showed uniform spherical m-TiO₂ nanoparticles (10–15 nm in size) covered by PPy-C with compact nodes like appearance interlocked very well among each other. The newly developed Ag@PPy-C/m-TiO₂ ternary photocatalyst exhibited band gap energy in desired visible range of spectra. The photocatalytic efficiency for all created photocatalysts has been evaluated taking Imidacloprid (insecticide derivative) and methylene blue (MB) dye as target pollutants. The novel Ag@PPy-C/m-TiO₂ photocatalyst produced astonishing results with ultrafast removal of both Imidacloprid as well MB dye under visible light irradiation. The newly created ultrafast Ag@PPy-C/m-TiO₂ photocatalyst has removed 96.0% of the insecticide Imidacloprid in only 25 min with almost ? 2.65 times more efficient than bare m-TiO₂ towards the removal of insecticide derivative. The present report offers a highly encouraging and vastly talented Ag@PPy-C/m-TiO₂ ternary photocatalyst, enabling the ideal management of extremely lethal and notorious chemicals.     

Toward nanograined gadolinia doped ceria via two-step sintering at ultralow temperature and its electrical conductivity

Highly dense (>98%) and nanograined (∼60 nm) gadolinia doped ceria are obtained from ultrafine powders by adopting two-step sintering (TSS) procedure at an ultralow temperature of 750 °C with a dwell time of 20 h, which is the lowest sintering temperature for ceria family without sintering aids up to now. Electrochemical impedance spectroscopy investigations suggest that the electrical conductivities of densified electrolytes are closely related to sintering temperature and grain size, and GDC900-750 exhibits the highest total electrical conductivity of 3.640 S m⁻¹ at 700 °C in air. Fitting calculation indicates partial grain-size dependence of oxygen vacancy association enthalpy and grain-size independence of oxygen ion migration enthalpy. Grain boundary maturity influences on grain boundary conductivity to some extent, and younger grain boundary endues the densified electrolytes with higher grain boundary conductivity.     

Effect of Co addition on microstructural and mechanical properties of WC–B4C–SiC composites

In this study, the effect of Co addition on microstructural and mechanical properties of WC-B₄C–SiC composites sintered by spark plasma sintering (SPS) method was investigated. For this purpose, three batches of WC-B₄C–SiC with different contents of Co (10 vol%, 15 vol%, and 20 Vol %) were sintered at 1400 °C. The results of X-ray diffraction (XRD) analysis of the samples indicated the formation of W₂B₅, W₃CoB₃ as well as the remained C phases and unreacted SiC phase. It was observed that by increasing the Co content, the amount of W₂B₅ phase reduces and W₃CoB₃ and C contents increase. Therefore, W₂B₅ peaks were not detected in the sample containing 20vol% Co. Relative density values above 97% were obtained for all the composites. However, a decrease was observed in relative density by increasing the Co content in the composites. The highest flexural strength (510 ± 42 MPa), fracture toughness (10.34 ± 0.82 MPa m^1/2), and hardness (20.63 ± 0.75 GPa) were also obtained for the sample containing 10vol% Co compared to the other samples. In addition, Transgranular fracture of SiC as well as pulling out of W₃CoB₃ and W₂B₅ particles were observed in the fracture surface micrographs of the samples. The presence of micro-cracks in the SiC grains, fracture of W₃CoB₃ grains, and crack deflection was reported as dominant toughening mechanisms.     

Effect of Y concentration and film thickness on microstructure and electrical properties of HfO2 based thin films

In this work, we introduced a simple solution processing method to prepare yttrium (Y) doped hafnium oxide (HfO₂) based dielectric films. The films had high densities, low surface roughness, maximum permittivity of about 32, leakage current < 1.0 × 10^?7 A/cm² at 2 MV/cm, and breakdown field >5.0 MV/cm. In addition to dielectric performance, we investigated the influence of YO_1.5 fraction on the electronic structure between Y doped HfO₂ thin films and silicon (Si) substrates. The valence band electronic structure, energy gap and conduction band structure changed linearly with YO_1.5 fraction. Given this cost-effective deposition technique and excellent dielectric performance, solution-processed Y doped HfO₂ based thin films have the potential for insulator applications.     

Synthesis and characterization of transition metal mixed oxide doped graphene embedded durable electrocatalyst for hydrogen evolution reaction

A promising electrocatalyst containing variable percentage of V₂O₅–TiO₂ mixed oxide in graphene oxide support was prepared by embedding the catalyst on Cu substrate through facile electroless Ni–Co–P plating for hydrogen evolution reaction. The solvothermal decomposition method was opted for tuning the crystalline characteristics of prepared material. The optimized mixed oxide was well characterized, active sites centres were identified and explained by X-ray diffraction, high resolution tunnelling electron microscopy, scanning electron microscopy coupled with energy dispersive X-ray and X-ray photon spectroscopy analysis. The structural and electronic characteristics of material was done by fourier transform infrared spectroscopy and the electrochemical behaviour of the prepared material was evaluated by using Tafel plot, electrochemical impedance analysis, linear sweep voltammetry, open circuit analysis and chronoamperometry measurements. The results show the enhanced catalytic activity of Ni–Co–P than pure Ni–P plate, due to synergic effect. Moreover, the prepared mixed oxide incorporated Ni–Co–P plate has a high activity towards HER with low over potential of 101 mV, low Tafel slope of 36 mVdec^?1, high exchange current density of 9.90 × 10^?2 Acm^?2.     

Kinetics and mechanistic studies of methane dry reforming over Ca promoted 1Co–1Ce/AC-N catalyst

The mechanism and kinetic features of dry reforming with methane (DRM) over Ca promoted 1Co–1Ce/AC-N catalyst was investigated. The mechanistic pathway studies have conducted by FTIR and XPS analysis, structure-activity correlations demonstrated the CH₄ and CO₂ could adsorb on catalyst active sites and generate intermediate CH_x, OH and CH_xO, continue to generate CO and H₂ and then desorbed from active sites. Moreover, CH₄ could also oxidized by Ce⁴⁺ and CO₂ reduced by Ce³⁺, the same content of Ce⁴⁺ and Ce³⁺ on promoted catalyst greatly improved the reaction rate. The kinetic of dry reforming with methane was examined for temperature between 650 and 850 at 800 °C. The research was carried out by changing the CH₄/CO₂ ratios between 0.3 and 3.0. The obtained experiment data were fitted by three typical kinetic models (Power Law, Eley-Rideal and Langmuir-Hinshelwood), the fitting results demonstrated that the best prediction of reforming rates can provided by Langmuir-Hinshelwood model for the reaction temperatures between 650 and 800 °C. Moreover, activation energies of methane and carbon dioxide consumption were ?117 and ?47 kJ/mol, indicating that much higher energy barrier is needed for methane activation compared to carbon dioxide.