Graphene-based electrocatalysts: Hydrogen evolution reactions and overall water splitting

Recently, carbon-based materials (e.g., graphene, carbon nanotubes, carbon quantum dots) have been used as electrocatalysts to catalyze the reactions such as hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). Among them, graphene has attracted attention as an electrocatalyst, and its electrocatalytic performances have been improved by doping with metals and non-metals, surface and defect engineering, and hybrid development. In this perspective, the present paper reviewed the recent advances (2018 onwards) on the progress of graphene-based electrocatalysts for HER and overall water splitting (OWS). It is emphasizing strategies for optimizing electrocatalytic properties followed by challenges and future outlook. This review will provide the essential ideas and strategies that can help design graphene-based electrocatalysts of high performance that can be implemented for sustainable energy application.     

Facile in-situ deposition of Pt nanoparticles on nano-pore stainless steel composite electrodes for high active hydrogen evolution reaction

Hydrogen is regarded as a clean and highly efficient renewable energy. The platinum catalytic electrode is widely used in hydrogen evolution reaction (HER), but it has affected its commercial application because of its high cost. Therefore, the study on cost-effective and high-active catalysts toward HER is required to realise large-scale hydrogen production. In this work, we present a novel Pt/NPSSF catalyst prepared by a one-step in-situ deposition of Pt precursor on a nano-porous stainless-steel film (NPSSF) substrate. The prepared catalyst was evaluated in acidic and alkaline conditions for its HER activities. The preliminary results demonstrate that the Pt/NPSSF electrodes have superior catalytic activity for HER. The hydrogen overpotential of Pt/NPSSF is ?70mV (RHE) in the alkaline solution, which is lower than the Pt electrode of ?184mV. At the same time, we also obtained ?71.2 mV of overpotential for the Pt/NPSSF electrode, which is similar to the ?73mV of Pt electrode in the acid solution. The Tafel graphs plotted from the LSV curves indicate the different HER mechanism in the alkaline and acid solution. The HER kinetics of the Pt/NPSSF were studied using EIS. Comparing Pt/NPSSF to Pt electrode, the multi-pore structures of NPSSF and the Pt nanoparticles active sites decrease the charge transfer-resistance for the HER process. The facile preparation, high efficiency and low value of the Pt/NPSSF composite electrodes demonstrate the promising applications in HER.     

Study of spatial and temporal evolution of Ar and F atoms in SF6/Ar microsecond pulsed discharge by optical emission spectroscopy

The study of sulfur hexafluoride (SF₆) discharge is vital for its application in gas-insulated equipment. Direct current partial discharge (PD) may cause SF₆ decomposition, and the decomposed products of SF₆, such as F atoms, play a dominant role in the breakdown of insulation systems. In this study, the PD caused by metal protrusion defects is simulated by a needle-plate electrode using pulsed high voltage in SF₆/Ar mixtures. The spatial and temporal characteristics of SF6/Ar plasma are analyzed by measuring the emission spectra of F and Ar atoms, which are important for understanding the characteristics of PD. The spatial resolved results show that both F and Ar atom spectral intensities increase first from the plate anode to the needle and then decrease under the conditions of a background pressure of 400 Pa, peak voltage of −1000 V, frequency of 2 kHz, pulse width of 60 μs, and electrode gap of 5–9 mm. However, the distribution characteristics of F and Ar are significantly different. The temporal distribution results show that the spectral intensity of Ar decreases first and then increases slowly, while the spectral intensity of F increases slowly for the duration of the pulsed discharge at the electrode gap of 5 mm and the pulse width of 40–80 μs.     

A novel differential evolution mapping technique for generic combinatorial optimization problems

Differential evolution is primarily designed and used to solve continuous optimization problems. Therefore, it has not been widely considered as applicable for real-world problems that are characterized by permutation-based combinatorial domains. Many algorithms for solving discrete problems using differential evolution have been proposed, some of which have achieved promising results. However, to enhance their performance, they require improvements in many aspects, such as their convergence speeds, computational times and capabilities to solve large discrete problems. In this paper, we present a new mapping method that may be used with differential evolution to solve combinatorial optimization problems. This paper focuses specifically on the mapping component and its effect on the performance of differential evolution. Our method maps continuous variables to discrete ones, while at the same time, it directs the discrete solutions produced towards optimality, by using the best solution in each generation as a guide. To judge its performance, its solutions for instances of well-known discrete problems, namely: 0/1 knapsack, traveling salesman and traveling thief problems, are compared with those obtained by 8 other state-of-the-art mapping techniques. To do this, all mapping techniques are used with the same differential evolution settings. The results demonstrated that our technique significantly outperforms the other mapping methods in terms of the average error from the best-known solution for the traveling salesman problems, and achieves promising results for both the 0/1 knapsack and the traveling thief problems.     

A Study on Dual-Load-Zone Model of Overlying Strata and Evolution Law of Mining Stress

The changeable structure and movement law of overlying strata are the main contributor to the change of mining stress. Starting from the relevant theory of key stratum and particularly based on the theory of mine ground pressure and strata control, this research proposed a new solution to mining stress problems by establishing a dual-load-zone stratum structural model. Elastic foundation beam theory was used to solve the stress of overlying strata of the dual-load-zones with superposition method, which revised the traditional calculation method of mining stress. The abnormal increase of lead abutment pressure in the mining area was explained effectively, through which the evolution law of mining stress in the case of hard rock was obtained. The results indicate that mining stress experiences a drastic change within the range of 50 m ahead of the coal wall due to the collapse of main roof; under the influence of main key stratum and inferior key strata, the influence range of lead abutment pressure is extended up to approximately 120 m in the working face; this remarkable increase can be attributed to the excessive length of sagging zone. Results from both the dual-load-zone model experiment and field measurement demonstrate high consistency. The model can predict the influence range of abutment pressure effectively and thus guide the safety production of mining.     

HVOF制备MCrAlY涂层过程中WC杂质颗粒的演变遗传行为研究

在热喷涂工业生产过程中,喷涂制备不同材料体系的涂层之前需要对送粉路径(送粉罐、送粉盘、搅拌器、送粉管路、送粉针)进行清理,但由于送粉路径内部结构复杂且存在静电吸附效应,使得残留于喷涂系统的粉末无法被完全去除,通常以微量杂质颗粒的形式被带入新涂层,进而影响新涂层的性能。为此,本文研究了在单晶基材表面采用高速火焰(HVOF)喷涂制备MCrAlY涂层过程中,送粉路径残留的WC杂质颗粒(WC-10Co4Cr)在涂层及涂层与基材界面处的遗传演变行为,分别采用SEM、EDS分析了WC杂质在喷涂态、热处理态涂层中的微观组织和相组成。研究结果表明,WC杂质颗粒确实存在于MCrAlY涂层中,并在后期热处理及氧化试验中进一步分解而固溶于涂层中,甚至扩散至单晶基材内部引起含W碳化物的生成,影响涂层及单晶基材的显微组织,改变局部的成分均匀性。同时,本文还采用ThermoCalc软件进行了热力学计算模拟,辅助分析了WC分解及W与C元素在显微组织中的遗传特性。对于WC类粉末和MCrAlY粉末共用的HVOF喷涂设备,建议给MCrAlY粉末配备单独的送粉路径,以确保涂层的纯净度与质量。     

Microstructure and damage evolution of SiCf/PyC/SiC and SiCf/BN/SiC mini-composites: A synchrotron X-ray computed microtomography study

SiC_f/PyC/SiC and SiC_f/BN/SiC mini-composites comprising single tow SiC fibre-reinforced SiC with chemical vapor deposited PyC or BN interface layers are fabricated. The microstructure evolutions of the mini-composite samples as the oxidation temperature increases (oxidation at 1000, 1200, 1400, and 1600?°C in air for 2?h) are observed by scanning electron microscopy, energy dispersive spectrometry, and X-ray diffraction characterization methods. The damage evolution for each component of the as-fabricated SiC_f/SiC composites (SiC fibre, PyC/BN interface, SiC matrix, and mesophase) is mapped as a three-dimensional (3D) image and quantified with X-ray computed tomography. The mechanical performance of the composites is investigated via tensile tests.The results reveal that tensile failure occurs after the delamination and fibre pull-out in the SiC_f/PyC/SiC composites due to the volatilization of the PyC interface at high temperatures in the air environment. Meanwhile, the gaps between the fibres and matrix lead to rapid oxidation and crack propagation from the SiC matrix to SiC fibre, resulting in the failure of the SiC_f/PyC/SiC composites as the oxidation temperature increases to 1600?°C. On the other hand, the oxidation products of B₂O₃ molten compounds (reacted from the BN interface) fill up the fracture, cracks, and voids in the SiC matrix, providing excellent strength retention at elevated oxidation temperatures. Moreover, under the protection of B₂O₃, the SiC_f/BN/SiC mini-composites show a nearly intact microstructure of the SiC fibre, a low void growth rate from the matrix to fibre, and inhibition of new void formation and the SiO₂ grain growth from room to high temperatures. This work provides guidance for predicting the service life of SiC_f/PyC/SiC and SiC_f/BN/SiC composite materials, and is fundamental for establishing multiscale damage models on a local scale.     

Cofactors as Molecular Fossils To Trace the Origin and Evolution of Proteins

Due to their early origin and extreme conservation, cofactors are valuable molecular fossils for tracing the origin and evolution of proteins. First, as the order of protein folds binding with cofactors roughly coincides with protein-fold chronology, cofactors are considered to have facilitated the origin of primitive proteins by selecting them from pools of random amino acid sequences. Second, in the subsequent evolution of proteins, cofactors still played an important role. More interestingly, as metallic cofactors evolved with geochemical variations, some geochemical events left imprints in the chronology of protein architecture; this provides further evidence supporting the coevolution of biochemistry and geochemistry. In this paper, we attempt to review the molecular fossils used in tracing the origin and evolution of proteins, with a special focus on cofactors.