A review of thin film electrolytes fabricated by physical vapor deposition for solid oxide fuel cells

The ohmic resistance in solid oxide fuel cells (SOFCs) mainly comes from the electrolyte, which can be reduced by developing novel electrolyte materials with higher ionic conductivity and/or fabricating thin-film electrolytes. Among various kinds of thin-film fabrication technology, the physical vapor deposition (PVD) method can reduce the electrolyte thickness to a few micrometers and mitigate the issues associated with high-temperature sintering, which is necessary for wet ceramic methods. This review summarizes recent development progress in thin-film electrolytes fabricated by the PVD method, especially pulsed laser deposition (PLD) and magnetron sputtering. At first, the importance of the substrate surface morphology for the quality of the film is emphasized. After that, the fabrication of thin-film doped-zirconia and doped-ceria electrolytes is presented, then we provide a brief summary of the works on other types of electrolytes prepared by PVD. Finally, we have come to the summary and made perspectives.     

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.     

Bovidae-based gelatin: Extractions method,physicochemical and functional properties,applications, and future trends

Gelatin is one of the most important multifunctional biopolymers and is widely used as an essential ingredient in food, pharmaceutical, and cosmetics. Porcine gelatin is regarded as the leading source of gelatin globally then followed by bovine gelatin. Porcine sources are favored over other sources since they are less expensive. However, porcine gelatin is religiously prohibited to be consumed by Muslims and the Jewish community. It is predicted that the global demand for gelatin will increase significantly in the future. Therefore, a sustainable source of gelatin with efficient production and free of disease transmission must be developed. The highest quality of Bovidae-based gelatin (BG) was acquired through alkaline pretreatment, which displayed excellent physicochemical and rheological properties. The utilization of mammalian- and plant-based enzyme significantly increased the gelatin yield. The emulsifying and foaming properties of BG also showed good stability when incorporated into food and pharmaceutical products. Manipulation of extraction conditions has enabled the development of custom-made gelatin with desired properties. This review highlighted the various modifications of extraction and processing methods to improve the physicochemical and functional properties of Bovidae-based gelatin. An in-depth analysis of the crucial stage of collagen breakdown is also discussed, which involved acid, alkaline, and enzyme pretreatment, respectively. In addition, the unique characteristics and primary qualities of BG including protein content, amphoteric property, gel strength, emulsifying and viscosity properties, and foaming ability were presented. Finally, the applications and prospects of BG as the preferred gelatin source globally were outlined.     

Role of functionalized graphene quantum dots in hydrogen evolution reaction: A density functional theory study

Rapid advances in the field of catalysis require a microscopic understanding of the catalytic mechanisms. However, in recent times, experimental insights in this field have fallen short of expectations. Furthermore, experimental searches of novel catalytic materials are expensive and time-consuming, with no guarantees of success. As a result, density functional theory (DFT) can be quite advantageous in advancing this field because of the microscopic insights it provides and thus can guide experimental searches of novel catalysts. Several recent works have demonstrated that low-dimensional materials can be very efficient catalysts. Graphene quantum dots (GQDs) have gained much attention in past years due to their unique properties like low toxicity, chemical inertness, biocompatibility, crystallinity, etc. These properties of GQDs which are due to quantum confinement and edge effects facilitate their applications in various fields like sensing, photoelectronics, catalysis, and many more. Furthermore, the properties of GQDs can be enhanced by doping and functionalization. In order to understand the effects of functionalization by oxygen and boron based groups on the catalytic properties relevant to the hydrogen-evolution reaction (HER), we perform a systematic study of GQDs functionalized with the oxygen (O), borinic acid (BC₂O), and boronic acid (BCO₂). All calculations that included geometry optimization, electronic and adsorption mechanism, were carried out using the Gaussian16 package, employing the hybrid functional B3LYP, and the basis set 6-31G(d,p). With the variation in functionalization groups in GQDs, we observe significant changes in their electronic properties. The adsorption energy E_ads of hydrogen over O-GQD, BC₂O-GQD, and BCO₂-GQD is ?0.059 eV, ?0.031 eV and ?0.032 eV respectively. Accordingly, Gibbs free energy (ΔG) of hydrogen adsorption is extraordinarily near the ideal value (0 eV) for all the three types of functionalized GQDs. Thus, the present work suggests pathways for experimental realization of low-cost and multifunctional GQDs based catalysts for clean and renewable hydrogen energy production.     

Crystallization behavior and density functional theory study of solution combustion synthesized silicon doped calcium phosphates

The influence of heat-treatment temperatures (700 °C, 900°C, 1200 °C) on the phase, physical properties, crystallization rate, and in vitro properties of the solution combustion synthesized silicon-doped calcium phosphates (CaPs) were investigated. The thermodynamic aspects (enthalpy, entropy, and free energy) of the synthesis process and the crystallographic properties of the final samples were first predicted and then confirmed using density functional theory (DFT). Results demonstrated that the crystallization rate was controlled by the fuel(s) type (glycine, citric acid, and urea) and the amounts of Si⁴⁺ ions (0, 0.1, 0.4 mol). The highest calculated crystallization rate values of the un-doped, 0.1, and 0.4 mol Si-doped samples were 64%, 22%, 38%, respectively. The obtained results from the DFT simulation revealed that crystal growth in the direction of c-axis of hydroxyapatite (HAp) structure could change the stability of (001) surface of (HAp). Also, the computational data confirmed the adsorption of Si–OH groups on the (001) surface of HAp during the SCS process with an adsorption energy of 1.53 eV. AFM results in line with DFT simulation showed that the observed change in the surface roughness of Si-doped CaPs from 2 to 8 nm could be related to the doping of Si⁴⁺ ions onto the surface of CaPs. Besides, the theoretical and experimental investigation showed that crystal growth and doping of Si⁴⁺ ions could decrease the activation energy of oxygen reduction reaction (ORR). Furthermore, the results showed that the crystallized HAp structure could have great potential to efficiently reduce oxidative stress in human body.     

Western Canadian dairy farmers' perspectives on the provision of outdoor access for dairy cows and on the perceptions of other stakeholders

The provision of pasture and outdoor access for dairy cattle differs around the globe. For example, in Ireland, New Zealand, and Australia, dairy farms are largely pasture based, whereas dairy farms in the United States and Canada are largely confinement based. There is a high level of public support for pasture and outdoor access for dairy cows, and the available evidence shows that dairy cattle are highly motivated to access pasture, especially at night. The decision as to whether to provide outdoor access is typically made by farmers, but little is known about dairy farmers' perspectives on this topic. We investigated perspectives of Western Canadian dairy farmers on outdoor access, as well as how they believe different stakeholders (i.e., the dairy industry, the dairy cows, and the general public) regard outdoor access for dairy cows. Data were collected via (1) 11 focus group discussions with a total of 50 Western Canadian dairy farmers, and (2) semi-structured individual interviews with an additional 6 dairy farmers of Hutterite colonies. Data were analyzed using template analysis. Although most participants in this study did not provide outdoor access on their farms, or only provided outdoor access to certain cow groups, participants generally mentioned that they enjoyed seeing cows on pasture or outdoors. However, participants shared that the Canadian supply management system (including processors) required a consistent flow of production, which was thought to be easier and more economically realized with indoor housing of lactating cows. Participants believed that pasture or outdoor access for dairy cows was desired by the public. Some participants believed that dairy cows prefer to spend time outside under favorable weather conditions, but others felt that cows preferred to stay indoors in modern, ventilated freestall barns. The results of this study describe the perspectives of dairy farmers regarding the views of dairy industry stakeholders as they relate to outdoor access, helping to inform conversations around the provision of outdoor access for dairy cattle.     

Understanding enhancing mechanism of Pr6O11 and Pr(OH)3 in methanol electrooxidation

The presence of oxygen vacancies and hydroxyl groups are both favorable for the methanol electrooxidation on Pt-based catalysts.Understanding and differentiating the enhancing mechanism between oxygen vacancies and hydroxyl groups for high activity of Pt catalysts in methanol oxidation reaction(MOR)is essential but still challenging.Herein,we developed two kinds of co-catalyst for Pt/CNTs,Pr₆O₁₁is rich in oxygen vacancies but contains substantially no hydroxyl groups,while Pr(OH)₃ possesses abundant hydroxyl groups without oxygen vacancies.After a seque nce of designed experiments,it can be found that both oxygen vacancies and hydroxyl groups can improve the performance of Pt/CNTs electrocatalysts,but the enhancing mechanism and improving degree of oxygen vacancies and hydroxyl groups for the MOR are different.Since the oxygen vacancies are more conducive to increasing the intrinsic activity of the Pt catalyst,and the hydroxyl groups play a decisive role in dehydrogenation and deproto nation of methanol,the co-catalysts with both oxygen vacancies and hydroxyl groups mixed with Pt/CNTs have higher catalytic performance.Therefore,hydroxyl-rich Pr₆O₁₁·xH₂O was prepared and used as MOR electrocatalyst after mixed with Pt/CNTs.Benefiting from the synergistic effect of oxygen vacancies and hydroxyl groups,the Pr₆O₁₁·xH₂O/Pt/CNTs shows a high peak current density of 741 mA/mg,which is three times higher than that of Pt/CNTs.These new discoveries serve as a promising strategy for the rational design of MOR catalysts with low cost and high activity.     

Lithiation MXene Derivative Skeletons for Wide-Temperature Lithium Metal Anodes

Lithium (Li) metal, as an appealing candidate for the next-generation of high-energy-density batteries, is plagued by its safety issue mainly caused by uncontrolled dendrite growth and infinite volume expansion. Developing new materials that can improve the performance of Li-metal anode is one of the urgent tasks. Herein, a new MXene derivative containing pure rutile TiO₂ and N-doped carbon prepared by heat-treating MXene under a mixing gas, exhibiting high chemical activity in molten Li, is reported. The lithiation MXene derivative with a hybrid of LiTiO₂-Li₃N-C and Li offers outstanding electrochemical properties. The symmetrical cell assembling lithiation MXene derivative hybrid anode exhibits an ultra-long cycle lifespan of 2000 h with an overpotential of ≈30 mV at 1 mA cm⁻², which overwhelms Li-based anodes reported so far. Additionally, long-term operations of 34, 350, and 500 h at 10 mA cm⁻² can be achieved in symmetrical cells at temperatures of −10, 25, and 50 °C, respectively. Both experimental tests and density functional theory calculations confirm that the LiTiO₂-Li₃N-C skeleton serves as a promising host for Li infusion by alleviating volume variation. Simultaneously, the superlithiophilic interphase of Li₃N guides Li deposition along the LiTiO₂-Li₃N-C skeleton to avoid dendrite growth.     

Predicting the mechanical properties of Cu–Al2O3 nanocomposites using machine learning and finite element simulation of indentation experiments

Micromechanics model, finite element (FE) simulation of microindentation and machine learning were deployed to predict the mechanical properties of Cu–Al₂O₃ nanocomposites. The micromechanical model was developed based on the rule of mixture and grain and grain boundary sizes evolution to predict the elastic modulus of the produced nanocomposites. Then, a FE model was developed to simulate the microindentation test. The input for the FE model was the elastic modulus that was computed using the micromechanics model and wide range of yield and tangent stresses values. Finally, the output load-displacement response from the FE model, the elastic modulus, the yield and tangent strengths used for the FE simulations, and the residual indentation depth were used to train the machine learning model (Random vector functional link network) for the prediction of the yield and tangent stresses of the produced nanocomposites. Cu–Al₂O₃ nanocomposites with different Al₂O₃ concentration were manufactured using insitu chemical method to validate the proposed model. After training the model, the microindentation experimental load-displacement curve for Cu–Al₂O₃ nanocomposites was fed to the machine learning model and the mechanical properties were obtained. The obtained mechanical properties were in very good agreement with the experimental ones achieving 0.99 coefficient of determination R2 for the yield strength.     

Enhancing the Photovoltaic Performance of Ladder-Type Heteroheptacene-based Nonfullerene Acceptors by Incorporating Halogen Atoms on Their Ending Groups

Ending group halogenation is an effective strategy for modulating the energy levels, bandgaps, and intermolecular interactions of nonfullerene acceptors. Understanding the influence of different halogen atoms on the acceptor properties is of great importance for designing high-performance nonfullerene acceptors. Here, three acceptor–donor–acceptor (A-D-A) type nonfullerene acceptors (M5, M6, and M7), which are constructed by using a ladder-type heteroheptacene core without the traditional sp³ carbon-bonded side chains as the electron-rich core, and 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile without or with halogen atoms as the ending groups. The nonfullerene acceptors with chlorinated (M6) and brominated (M7) ending groups exhibit broadened absorption spectra, down-shifted energy levels, and enhanced molecular ordering compared to the counterpart without any halogenated ending groups (M5). Among the nonfullerene acceptors, M6 has the strongest intermolecular π π interaction with its shortest π π interaction distance and the longest coherent length which are beneficial for enhancing the charge transport and therefore boosting the photovoltaic performance. An excellent power conversion efficiency of 15.45% is achieved for the best-performing polymer solar cell based on M6. These results suggest that the halogenated ending groups are essential for high-performance heteroheptacene-based nonfullerene acceptors considering their simultaneous enhancements in both the light-harvesting and the charge transport.