Atomic-level insights into the modification mechanism of Fe (III) ion on smithsonite (1 0 1) surface from DFT calculation

Fe(III) ion can strongly inhibit the sulphidation amine flotation of smithsonite. However, its modification mechanism on smithsonite surface is still obscure. In this work, a systematic study of the modification of Fe(III) ion on smithsonite (1 0 1) surface was performed using DFT calculation. The optimal number of H₂O ligands for Fe(III) ion hydrates in aqueous conditions was probed, and [Fe(OH)₂(H₂O)₄]⁺ and [Fe(OH)₄]^? were identified as the major modification species, then their adsorption and bonding mechanisms were further revealed by analyzing the frontier orbitals, density of state, Mulliken population, and electron density. The calculated adsorption structures were consistent with the former experiment, and we found the O site that bonded to the C atom on smithsonite surface was the most favorable position for [Fe(OH)₂(H₂O)₄]⁺ and [Fe(OH)₄]^? adsorptions. Besides, their adsorption mechanisms on smithsonite surface were principally due to the combined effect of FeO bond and hydrogen bonding. Simultaneously, hydrogen bonding greatly enhanced the stability of the adsorption structures. Moreover, the dominant orbital contribution for the bonding of FeO was primarily due to the orbital hybridization between Fe 3d and O 2p orbitals. This work can help in deeper understanding of the depression of Fe(III) ion on the sulphidation amine flotation of smithsonite.     

Manufacturing catalyst-coated membranes by ultrasonic spray deposition for PEMFC: Identification of key parameters and their impact on PEMFC performance

This study deals with the manufacturing of catalyst-coated membranes (CCMs) for newcomers in the field of coating. Although there are many studies on electrode ink composition for improving the performance of proton-exchange membrane fuel cells (PEMFCs), there are few papers dealing with electrode coating itself. Usually, it is a know-how that often remains secret and constitutes the added value of scientific teams or the business of industrialists. In this paper, we identify and clarify the role of key parameters to improve coating quality and also to correlate coating quality with fuel cell performance via polarization curves and electrochemical active surface area measurements. We found that the coating configurations can affect the performance of lab-made CCMs in PEMFCs. After the repeatability of the performance obtained by our coating method has been proved, we show that: (i) edge effects, due to mask shadowing - cannot be neglected when the active surface area is low, (ii) a heterogeneous thickness electrode produces performance lower than a homogeneous thickness electrode, and (iii) the origin and storage of platinum on carbon powders are a very important source of variability in the obtained results.     

Integrating coral-like morphology into cyano-containing carbon nitride towards efficient photocatalytic H2 evolution and Cr(Ⅵ) reduction

The incomplete polymerization of graphite carbon nitride (g-C₃N₄) due to the kinetic problems resulted in its high recombination rate of photo-generated electron-hole pairs. Hence, cyano-containing carbon nitride with coral-like morphology (CCCN) was prepared by the molten salt method with heptazine-based melem as precursor, which presented excellent separation rate of photo-generated electron-hole pairs. SEM exhibited that CCCN owned coral-like morphology which exposed ample active sites and enhanced the capture ability of visible light while FT-IR and XPS demonstrated that cyano groups appearing in coral-like carbon nitride enhanced the separation rate of photo-induced charge carriers. The synergistic effect of coral-like morphology and cyano groups endowed CCCN-15% with superior performance of both the photocatalytic H₂ evolution (4207 μmol h^?1 g^?1) and Cr (Ⅵ) reduction (k = 0.059 min^?1), approximately 16.8 and 6.0 times that of g-C₃N₄, which was comparable among the similar materials. Density functional theory calculation (DFT) revealed that cyano groups decreased the bandgap and strengthened the activation degree of reaction substrate, which enhanced the thermodynamic driving force and the interaction between catalyst and substrate. This work provided a potential strategy for both the renewable energy generation and environmental restoration.     

Enhanced oxygen evolution reaction kinetics through biochar-based nickel-iron phosphides nanocages in water electrolysis for hydrogen production

Highly-efficient and stable non-noble metal electrocatalysts for overcoming the sluggish kinetics of oxygen evolution reaction (OER) is urgent for water electrolysis. Biomass-derived biochar has been considered as promising carbon material because of its advantages such as low-cost, renewable, simple preparation, rich structure, and easy to obtain heteroatom by in-situ doping. Herein, Ni₂P–Fe₂P bimetallic phosphide spherical nanocages encapsulated in N/P-doped pine needles biochar is prepared via a simple two-step pyrolysis method. Benefiting from the maximum synergistic effects of bimetallic phosphide and biochar, high conductivity of biochar encapsulation, highly exposed active sites of Ni₂P–Fe₂P spherical nanocages, rapid mass transfer in porous channels with large specific surface area, and the promotion in adsorption of reaction intermediates by high-level heteroatom doping, the (Ni_0.75Fe_0.25)₂P@NP/C demonstrates excellent OER activity with an overpotential of 250 mV and a Tafel slope of 48 mV/dec at 10 mA/cm² in 1 M KOH. Also it exhibits a long-term durability in 10 h electrolysis and its activity even improves during the electrocatalytic process. The present work provides a favorable strategy for the inexpensive synthesis of biochar-based transition metal electrocatalysts toward OER, and improves the water electrolysis for hydrogen production.     

Analysis of surface and interior degradation of gas diffusion layer with accelerated stress tests for polymer electrolyte membrane fuel cell

The effects of surface and interior degradation of the gas diffusion layer (GDL) on the performance and durability of polymer electrolyte membrane fuel cells (PEMFCs) have been investigated using three freeze-thaw accelerated stress tests (ASTs). Three ASTs (ex-situ, in-situ, and new methods) are designed from freezing ?30 °C to thawing 80 °C by immersing, supplying, and bubbling, respectively. The ex-situ method is designed for surface degradation of the GDL. Change of surface morphology from hydrophobic to hydrophilic by surface degradation of GDL causes low capillary pressure which decreased PEMFC performance. The in-situ method is designed for the interior degradation of the GDL. A decrease in the ratio of the porosity to tortuosity by interior degradation of the GDL deteriorates PEMFC performance. Moreover, the new method showed combined effects for both surface and interior degradation of the GDL. It was identified that the main factor that deteriorated the fuel cell performance was the increase in mass transport resistance by interior degradation of GDL. In conclusion, this study aims to investigate the causes of degraded GDL on the PEMFC performance into the surface and interior degradation and provide the design guideline of high-durability GDL for the PEMFC.     

Enhancing sustainable bioelectricity generation using facile synthesis of nanostructures of bimetallic Co–Ni at the combined support of halloysite nanotubes and reduced graphene oxide as novel oxygen reduction reaction electrocatalyst in single-chambered microbial fuel cells

The present study aims to utilize the high surface area of the nanotube structure of halloysite (HNTs), an aluminosilicate clay, and conductivity of reduced graphene oxide (rGO) as support material for the deposition of nickel (Ni) and cobalt (Co) nanoparticles. With that aim, a novel bimetallic cathode electrocatalyst, Co–Ni @ HNTs-rGO (Catalyst H₃), is developed. This catalyst is characterized by X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and Transmission Electron Microscopy (TEM). Catalyst H₃ demonstrates outstanding oxygen reduction reaction (ORR) activity, electrochemical stability, electrocatalytic performance, and lowest resistance in comparison to the other developed catalysts and conventional Pt/C. Catalyst H₃ is used in single-chambered MFCs (microbial fuel cells), where the anode is filled with molasses-laden wastewater. The attained maximum power density in MFC (catalyst H₃) is 455 ± 9 mW/m², which is higher than other catalysts. All the results indicate towards its potential use in MFC application.     

Development of titanium bipolar plates fabricated by additive manufacturing for PEM fuel cells in electric vehicles

Bipolar plates (BPs) are one of the main parts of proton exchange membrane (PEM) fuel cell stacks, which constitute a significant percentage of a PEM fuel cell system in terms of cost, weight, and structural strength. Although frequently used graphite BPs have low density, high conductivity, and high corrosion resistance, machining the desired flow channels on these plates is challenging. On the other hand, BPs made of various materials rather than graphite can be also fabricated by additive manufacturing methods. These methods can be considered as a reasonable alternative to conventional machining for the fabrication of graphite BPs in PEM fuel cells regarding material cost, fabrication of flow channels, and some post-processes in which the large-scale manufacturing of graphite BPs is more complex. This study offers a comparison of formed stainless-steel, additive manufactured titanium and machined composite graphite plates having the same flow-field geometry as a bipolar plate. In addition, titanium BPs are coated with gold and their performances are compared. Among the cells tested, the highest peak power of 639 mWcm^?2 is measured from the cell with 450 nm gold coated titanium BP, whereas those of the cell with conventional graphite and stainless-steel BP are only around 322 mWcm^?2 and 173 mWcm^?2, respectively. Moreover, a new titanium bipolar plate design providing high specific power density is also presented.     

An active balancer with rapid bidirectional charge shuttling and adaptive equalization current control for lithium-ion battery strings

This article proposes an active balancer, which features bidirectional charge shuttling and adaptive equalization current control, to fast counterbalance the state of charge (SOC) of cells in a lithium-ion battery (LIB) string. The power circuit consists of certain bidirectional buck-boost converters to transfer energy among the different cells back and forth. Owing to the characterization of the open-circuit voltage (OCV) vs SOC in LIB being relatively smooth near the SOC middle range, the SOC-inspected balance strategy can achieve more precise and efficient equilibrium than the voltage-based control. Accordingly, a compensated OCV-based SOC estimation is put forward to take into account the discrepancy of SOC estimation. Besides, the varied-duty-cycle (VDC) and curve-fitting modulation (CFM) methods are devised herein to tackle the problems of slow equalization rate and low balance efficacy, which arise from the diminution in balancing current as the SOC difference between the cells decreases in the later duration of equalization especially. The proposed strategies have taken the battery nonlinear characteristic and circuit parameter nonideality into account and can adaptively modulate the duty cycle with the SOC difference to keep balancing current constant throughout the balancing cycle. Simulated and experimental results are given to demonstrate the feasibility and effectiveness of the same prototype constructed. Compared with the fixed duty cycle and the VDC methods, the proposed CFM has the best balancing efficiency of 81.4%, and the balance time is shortened by 27.1% and 18.6%, respectively.     

Electromagnetic transients in the control system of output parameters of a solar power plant in Tajikistan Central Asia region

At present, as the demand for electricity increases in all sectors, there is an urgent need to introduce alternative renewable energy sources into modern energy systems. Renewable energy sources, which consist of solar (photovoltaic, PV), wind and hydro power, are key alternative sources of “green energy’’ energies, but it can also be used to produce “green” hydrogen. Thanks to scientific and technological progress, the cost of photovoltaic solar radiation converters is constantly decreasing at a high rate, which makes it possible to build solar power plants of sufficiently large capacity. In the coming decades, solar energy will become an incentive for the economic development of countries that have the maximum “solar” resource. The Republic of Tajikistan is one of these countries with a high potential for solar energy.The article presents an analysis of the resources and potential of solar energy in the Republic of Tajikistan. The study of electromagnetic transients in networks with photovoltaic solar power plants is performed. The main equations, simulation model and calculations of transients are presented, taking into account changes in voltage on DC buses. An algorithm for controlling the system of automatic control of output parameters is proposed. The analysis of dynamic and static modes in parallel operation of a solar power plant with the grid is carried out. A block diagram and computer model is constructed in the MATLAB package together with Simulink and Power System Blockset.