Microstructure induced ultra-high energy storage density coupled with rapid discharge properties in lead-free Ba0.9Ca0.1Ti0.9Zr0.1O3–SrNb2O6 ceramics

Novel lead-free (1-x)Ba_0·9Ca_0·1Ti_0·9Zr_0·1O₃-xSrNb₂O₆ ceramics were synthesized via a two-step high energy ball milling process. The evolution of microstructural properties, phase transformation, and energy storage characteristics was comprehensively investigated to assess the applicability of material in multi-layered ceramic capacitors. The substitution of SrNb₂O₆ (SNO) in Ba_0·9Ca_0·1Ti_0·9Zr_0·1O₃ (BTCZ) has resulted in substantial improvement in materials density along with a small increase in the grain size of the synthesized ceramic. A thorough microstructural investigation indicates an excellent dispersibility and compatibility between BTCZ and SNO phases. With an increase in SNO substitution, a transition from typical ferroelectric to relaxor ferroelectric has been observed, which has led to a significantly slimmer ferroelectric loop along with frequency dispersive dielectric properties. The optimized composition (i.e., x = 0.10) exhibits an ultra-high recoverable energy density of 2.68 J/cm³ along with a moderately high energy efficiency of 83.4%. Further, SNO substituted samples have also shown an enhancement in breakdown strength. The improvement in energy storage performance and breakdown strength of SNO substituted BTCZ composites are mainly attributed to relatively homogeneous grain morphology, optimum grain size, microstructural density, and improved grain boundary interface.     

Reconstructed Water Oxidation Electrocatalysts: The Impact of Surface Dynamics on Intrinsic Activities

Electroreduction of small molecules such as H₂O, CO₂, and N₂ for producing clean fuels or valuable chemicals provides a sustainable approach to meet the increasing global energy demands and to alleviate the concern on climate change resulting from fossil fuel consumption. On the path to implement this purpose, however, several scientific hurdles remain, one of which is the low energy efficiency due to the sluggish kinetics of the paired oxygen evolution reaction (OER). In response, it is highly desirable to synthesize high-performance and cost-effective OER electrocatalysts. Recent advances have witnessed surface reconstruction engineering as a salient tool to significantly improve the catalytic performance of OER electrocatalysts. In this review, recent progress on the reconstructed OER electrocatalysts and future opportunities are discussed. A brief introduction of the fundamentals of OER and the experimental approaches for generating and characterizing the reconstructed active sites in OER nanocatalysts are given first, followed by an expanded discussion of recent advances on the reconstructed OER electrocatalysts with improved activities, with a particular emphasis on understanding the correlation between surface dynamics and activities. Finally, a prospect for clean future energy communities harnessing surface reconstruction-promoted electrochemical water oxidation will be provided.     

Non-Platinum Group Metal Electrocatalysts toward Efficient Hydrogen Oxidation Reaction

Developing non-platinum group metal (non-PGM) electrocatalysts for the hydrogen oxidation reaction (HOR) represents the efforts towards the more economical use of hydrogen fuel cells and hydrogen energy, which has attracted tremendous attention recently. However, non-PGM electrocatalysts for the HOR are still in their early development stages as compared with the significant advances in those for the oxygen reduction reaction and hydrogen evolution reaction. Herein, this paper summarizes the recent progresses and highlights the key challenges for the rational design of non-PGM electrocatalysts, aiming to promote the development of non-PGM HOR electrocatalysts. Fundamental understandings of the HOR mechanism are firstly reviewed, where theoretical interpretations on the low HOR kinetics in alkaline media, including the hydrogen binding energy theory, the bifunctional mechanism, and the water molecule reorganization, are particularly discussed. Subsequently, progresses of typical non-PGM HOR electrocatalysts in acid and alkaline media are summarized separately. For the HOR under alkaline conditions, the superiorities and challenges of Ni-based catalysts are discussed with a particular focus as they are the most promising non-PGM electrocatalysts. Finally, this paper highlights the challenges and provide perspectives on the future development directions of non-PGM HOR electrocatalysts.     

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.     

Development and characterisation of microporous biomimetic scaffolds loaded with magnetic nanoparticles as bone repairing material

Fine-tuning of the scaffolds structural features for bone tissue engineering can be an efficient approach to regulate the specific response of the osteoblasts. Here, we loaded magnetic nanoparticles aka superparamagnetic iron oxide nanoparticles (SPIONs) into 3D composite scaffolds based on biological macromolecules (chitosan, collagen, hyaluronic acid) and calcium phosphates for potential applications in bone regeneration, using a biomimetic approach. We assessed the effects of organic (chitosan/collagen/hyaluronic acid) and inorganic (calcium phosphates, SPIONs) phase over the final features of the magnetic scaffolds (MS). Mechanical properties, magnetic susceptibility and biological fluids retention are strongly dependent on the final composition of MS and within the recommended range for application in bone regeneration. The MS architecture/pore size can be made bespoken through changes of the final organic/inorganic ratio. The scaffolds undertake mild degradation as the presence of inorganic components hinders the enzyme catalytic activity. In vitro studies indicated that osteoblasts (SaOS-2) on MS9 had similar cell behaviour activity in comparison with the TCP control. In vivo data showed an evident development of integration and resorption of the MS composites with low inflammation activity. Current findings suggest that the combination of SPIONs into 3D composite scaffolds can be a promising toolkit for bone regeneration.     

Enhanced methanol oxidation on PtNi nanoparticles supported on silane-modified reduced graphene oxide

Developing low cost, highly efficient, and long-term stability electrocatalysts are critical for direct oxidation methanol fuel cell. Despite huge efforts, designing low-cost electrocatalysts with high activity and long-term durability remains a significant technical challenge. Here, we prepared a new kind of platinum-nickel catalyst supported on silane-modified graphene oxide (NH₂-rGO) by a two-step method at room temperature. Powder X-ray diffraction, UV–vis spectroscopy, Raman, FTIR spectroscopy and X-ray photoelectron spectroscopy results confirm that GO was successfully modified with 3-aminopropyltriethoxysilane (APTES), which helps to uniformly disperse PtNi nanoparticles. Cyclic voltammetry, chronoamperometry, CO-stripping and rotating disk electrode (RDE) results imply that PtNi/NH₂-rGO catalyst has significantly higher catalytic activity, enhance the CO toxicity resistance, higher stability and much faster kinetics of methanol oxidation than commercial Pt/C under alkaline conditions.     

Ir-Pt/C composite with high metal loading as a high-performance anti-reversal anode catalyst for proton exchange membrane fuel cells

Voltage reversal induced by hydrogen starvation can severely corrode the anode catalyst support and deteriorate the performance of proton exchange membrane fuel cells. A material-based strategy is the inclusion of an oxygen evolution reaction catalyst (e.g., IrO₂) in the anode to promote water electrolysis over harmful carbon corrosion. In this work, an Ir-Pt/C composite catalyst with high metal loading is prepared. The membrane-electrode-assembly (MEA) with 80 wt% Ir-Pt(1:2)/C shows a first reversal time (FRT) of up to 20 hours, which is about ten times that of MEA with 50 wt% Ir-Pt(1:2)/C does. Furthermore, the MEA with 80 wt% Ir-Pt(1:2)/C exhibits a minimum cell voltage loss of 6 mV@1 A/cm² when the FRT is terminated in 2 hours, in which the MEA with 50 wt% Ir-Pt(1:2)/C exhibits a voltage loss of 105 mV@1 A/cm². Further physicochemical and electrochemical characterizations demonstrate that the destruction of anode catalyst layer caused by the voltage reversal process is alleviated by the use of the composite catalyst with high metal loading. Hence, our results reveal that the combination of OER catalyst on the Pt/C with high metal loading is a promising approach to alleviate the degradation of anode catalyst layer during the voltage reversal process for PEMFCs.     

Completely eliminating the metal barrier cracks on Nafion for suppressing methanol crossover with anodic aluminum oxide substrates

Methanol crossover is one of the main challenges for direct methanol fuel cells (DMFCs). Depositing a metal barrier on Nafion can reduce the crossover but usually faces the metal cracking issues. This study presents a new composite membrane in which an anodic aluminum oxide (AAO) substrate is impregnated with a Nafion solution and then coated with a layer of Au. The AAO/Nafion/Au composite membrane shows an ideal metal crack-free surface. Higher and more stable voltage has been achieved for the cell with the membrane, indicating an effectively suppressed methanol-crossover. Results reveal that there is a tradeoff between suppressing the methanol crossover and increasing the ion transmission. By optimizing the membrane, it can not only suppress the methanol crossover but also enhance the output performance of DMFCs. The current density and power density of the cells can be enhanced by 59% and 52.85%, respectively, compared to the cell with a commercial Nafion 117. Overall, this work provides a new approach to designing crack-free membranes for DMFCs.     

Swapping catalytic active sites from cationic Ni to anionic F in Fe–F–Ni3S2 enables more efficient alkaline oxygen evolution reaction and urea oxidation reaction

Electrolysis of water for producing hydrogen instead of traditional fossil fuels is one of the most promising methods to alleviate environmental pollution and energy crisis. In this work, Fe and F ion co-doped Ni₃S₂ nanoarrays grown on Ni foam substrate were prepared by typical hydrothermal and sulfuration processes for the first time. Density functional theory (DFT) calculation demonstrate that the adsorption energy of the material to water is greatly enhanced due to the doping of F and Fe, which is conducive to the formation of intermediate species and the improvement of electrochemical performance of the electrode. The adsorption energy of anions (F and S) and cations (Fe and Ni) to water in each material was also calculated, and the results showed that F ion showed the most optimal adsorption energy of water, which proved that the doping of F and Fe was beneficial to improve the electrochemical performance of the electrode. It is worth noting that the surface of Fe–F–Ni₃S₂ material will undergo reconstruction during the process of water oxidation reaction and urea oxidation reaction, and amorphous oxides or hydroxides in situ would be formed on the surface of electrode, which are the real active species.     

High H2 selectivity with low coke formation for methanol steam reforming over Cu/Y1.5Ce0.84Ru0.04O4 catalyst in a microchannel plate reactor

The synthesized novel metal oxides Y_xCe_yRu_zO₄ (x = 1.5, y = 0.84, z = 0.04) which was produced by the sol-gel method was used as a support for Cu active metal on the surface of a microchannel plate reactor in the methanol steam reforming (MSR) process. The prepared catalysts were characterized by X-ray powder diffraction (XRD), BET surface area analysis (S_BET), energy-dispersive X-ray analysis (EDX), field-emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), temperature-programmed desorption (NH₃-TPD), and temperature-programmed reduction (H₂-TPR). High methanol conversion (99.5%) and H₂ selectivity (98.7%) and low CO selectivity (1.4%) were achieved for Cu/Y_xCe_yRu_zO₄ coated microchannel reactor at 250 °C. FE-SEM images and TGA curve of the spent catalyst displayed no coke formation on the surface of the catalyst after 32 h on stream at 300 °C. The low reduction temperature of Cu, high BET surface area, and high pore volume of the catalyst are considered imperative factors that cause a better dispersion of copper on the Y_1.5Ce_0.84Ru_0.04O₄ support.