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.     

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.     

Hydrogen production performance of a photovoltaic thermal system coupled with a proton exchange membrane electrolysis cell

As one of the cleanest energies, hydrogen has attracted much attention over the past decade. Hydrogen can be produced using water electrolysis in a Proton Exchange Membrane Electrolysis Cell (PEMEC). In the present study, the performance of the PEMEC, powered by the Photovoltaic-Thermal (PVT) system, is scrutinized. It is considered that the PVT system provides the required electrical power of the PEMEC and preheats the feedwater. A comprehensive numerical model of the coupled PVT-PEMEC system is developed. The model is used to investigate the effect of various operating parameters, including solar radiation intensity, inlet feedwater temperature, and feedwater mass flow rate, on the hydrogen production and operating voltage of the PEMEC at various Exchange Current Densities (ECDs). Furthermore, the effect of integration of Phase Change Material (PCM) and Thermoelectric Generator (TEG) on the hydrogen production of the system is evaluated. According to the obtained results, the PVT-TEG-PEMEC system outperforms other systems in hydrogen production. However, integration of the PVT-PEMEC system with PCM has a negligible effect on its hydrogen production.     

A survey on tracking control of unmanned underwater vehicles: Experiments-based approach

This paper aims to provide a review of the conceptual design and theoretical framework of the main control schemes proposed in the literature for unmanned underwater vehicles (UUVs). Additionally, the objective of the paper is not only to present an overview of the recent control architectures validated on UUVs but also to give detailed experimental-based comparative studies of the proposed control schemes. To this end, the main control schemes, including proportional–integral–derivative (PID) based, sliding mode control (SMC) based, adaptive based, observation-based, model predictive control (MPC) based, combined control techniques, are revisited in order to consolidate the principal efforts made in the last two decades by the automatic control community in the field. Besides implementing some key tracking control schemes from the classification mentioned above on Leonard UUV, several real-time experimental scenarios are tested, under different operating conditions, to evaluate and compare the efficiency of the selected tracking control schemes. Furthermore, we point out potential investigation gaps and future research trends at the end of this survey.     

Effects of alkali metal ion on imprinting GRIN microstructure in GeS2-Ga2S3-MCl (M=Na,K, Cs) glasses for visible to mid-infrared microgratings

Gradient refractive index (GRIN) micro-optics present unique opportunities for control of the chromatic properties, new degrees of freedom for optical design as well as the potential for use in new optical system applications. GRIN microgratings were imprinted in GeS₂-Ga₂S₃-MCl (M = Na, K, Cs) chalcohalide glasses by microthermal poling, and the effects of the type and concentration of alkali cations on their performance were investigated. Two effective imprinting formation regions of the GRIN microstructure based on the poling saturation voltage (U_s) and glass composition are observed at fixed poling time and temperature. The U_s increases from 140 to 750 and 2600 V in accordance with the activation energy (E_a) of alkali ions (Na⁺ to K⁺ and Cs⁺) increasing from 45.15 to 58.62 and 92.58 kJ/mol for studied samples. The saturated numbers of diffraction order (N_s) of the gratings in these samples are 7, 9 and 6, respectively, the highest number being provided by the K⁺-containing sample. This is in accordance with imprinting-induced phase differences (0.14λ, 0.19λ and 0.09λ) measured in the fabricated samples containing Na⁺, K⁺ and Cs⁺ ions. Furthermore, the U_s of samples decreases from 1500 to 300 V with four concentrations of K⁺ from 10 to 30%, associated with their E_a of K⁺ decreasing from 69.62 to 53.46 kJ/mol, while N_s increases from 8 to 14, which is attributed to the increase of the phase difference in the GRIN structures. The controllable GRIN microstructures are realized by adjusting the type and concentration of alkali cations in chalcohalide glasses, which is expected to drive the design of broadband GRIN microgratings.