Scaling analysis of hydrogen flow with carbon dioxide cushion gas in subsurface heterogeneous porous media

Subsurface hydrogen (H₂) storage in geological formations is of growing interest for decarbonization. However, there is a knowledge gap in understanding the multiphase flow involved in this process, which can have a significant impact on the recovery performance of H₂. Therefore, a full-compositional modeling study was conducted to analyze potential issues and to understand the fundamental hydrodynamic mechanisms of H₂ storage. We performed a range of 2D vertical simulations at the decametre scale with a very fine cell size (0.1 m) to observe the detailed flow behaviour of H₂ with carbon dioxide (CO₂) as cushion gas in various flow regimes. Issues such as viscous instability, capillary bypassing, gas trapping and gravity segregation are analysed here. To generalize our calculations, we have validated and applied the scaling theory in the context of subsurface H₂ storage. Since this study is focused on the hydrodynamic behaviour, three dimensionless groups, including aspect factor, capillary/viscous ratio and gravity/viscous ratio were identified to correlate recovery performance between various scales in a fixed heterogeneous system. It was found that H₂ could infiltrate the cushion gas in the proximity of the injectors, meaning that CO₂ is not displaced away from the injectors in a piston-like fashion. As a result, the purity of the back produced H₂ is much degraded, particularly in a viscous-dominated scenario. On the other hand, the injected H₂ mostly accumulates at the top forming a highly restricted mixing zone with CO₂ in the gravity-dominated case. The recovery performance is therefore much improved in this case. Although the gas distribution can be significantly altered by capillary forces leading to bypassed zones, the recovery performance of H₂ is hardly influenced. This is because the back-produced H₂ recovery is not dependent on the sweep efficiency of the gas. H₂ can be back produced following the same paths which were formed during injection.     

Iron-based sulfur and nitrogen dual doped porous carbon as durable electrocatalysts for oxygen reduction reaction

The widespread use of fuel cell technology is hampered by the use of expensive and scarce platinum metal in electrodes which is required to facilitate the sluggish oxygen reduction reaction (ORR). In this work, a viable synthetic approach was developed to prepare iron-based sulfur and nitrogen dual doped porous carbon (Fe@SNDC) for use in ORR. Benzimidazole, a commercially available monomer, was used as a precursor for N doped carbon and calcined with potassium thiocyanate at different temperatures to tune the pore size, nitrogen content and different types of nitrogen functionality such as pyridinic, pyrrolic and graphitic. The Fe@SNDC–950 with high surface area, optimum N content of about 5 at% and high amount of pyridinic and graphitic N displayed an onset potential and half-wave potential of 0.98 and 0.83 V vs RHE, respectively, in 0.1 M KOH solution. The catalyst also exhibits similar oxygen reduction reaction performance compared to Pt/C (20 wt%) in acidic media. Furthermore, when compared to commercially available Pt/C (20 wt%), Fe@SNDC–950 showed enhanced durability over 6 h and poison tolerance in case of methanol crossover with the concentration up to 3.0 M in oxygen saturated alkaline electrolyte. Our study demonstrates that the presence of N and S along with Fe-N moieties synergistically served as ORR active sites while the high surface area with accessible pores allowed for efficient mass transfer and interaction of oxygen molecules to the active sites contributing to the ORR activity of the catalyst.     

毫米波三维异质异构集成技术的进展与应用

三维异质异构集成技术是实现电子信息系统向着微型化、高效能、高整合、低功耗及低成本方向发展的最重要方法,也是决定信息化平台中微电子和微纳系统领域未来发展的一项核心高技术。文章详细介绍了毫米波频段三维异质异构集成技术的优势、近年来的发展趋势以及面临的挑战。利用硅基MEMS 光敏复合薄膜多层布线工艺可实现异质芯片的低损耗互连,同时三维集成高性能封装滤波器、高辐射效率封装天线等无源元件,还能很好地处理布线间的电磁兼容和芯片间的屏蔽问题。最后介绍了一款新型毫米波三维异质异构集成雷达及其在远距离生命体征探测方面的应用。     

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.     

Understanding on the hydrogen detection of plasma sprayed tin oxide/tungsten oxide (SnO2/WO3) sensor

The plasma spray technique was well proven in producing metal oxide based gas sensors in the last two decades using different powder feedstocks. However, limited research was made to fabricate hydrogen gas sensor from tin oxide layer coated over tungsten oxide layer. This paper attempts to interpret the hydrogen gas sensing performances of plasma sprayed coating derived by depositing tin oxide layer over tungsten oxide (SnO₂/WO₃) layer. Plasma sprayed SnO₂/WO₃ sensor showed maximum response of 90% at 150 °C in contrast to stand-alone WO₃ (89% at 350 °C) and stand-alone SnO₂ (89% at 250 °C). The lower operating temperature of SnO₂/WO₃ sensor without compromising gas response was attributed to the WO₃–SnO₂ hetero-junction. SnO₂/WO₃ sensor showed selective sensing towards hydrogen with respect to carbon monoxide and methane gases. This sensor also possessed repeatable characteristics after 39 days from the initial measurement. In a nut-shell, plasma spayed SnO₂/WO₃ sensor showed stability of base resistance, repeatability after successive response and recovery cycles, selective sensing towards 500 ppm H₂ with significant magnitude of gas response of 90%, response time of 35 s and recovery time of 269 s at a temperature of 150 °C.     

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.     

The role of microbial electrogenesis in regulating methane and nitrous oxide emissions from constructed wetland-microbial fuel cell

This study assesses a sustainable solution to greenhouse gases (GHGs) mitigation using constructed wetland-microbial fuel cells (CW-MFC). Roots of wetland plant Acorus Calamus L. are placed in biological anode to better enable anode microorganisms to obtain rhizosphere secretion for power improvement. Three selected cathode materials have a large difference in GHG emissions, and among them, carbon fiber felt (CFF) shows the lowest emissions of methane and nitrous oxide, which are 0.77 ± 0.04 mg/(m²·h) and 130.78 ± 13.08 μg/(m²·h), respectively. The CFF CW-MFC achieves the maximum power density of 2.99 W/m³. As the influent pH value is adjusted from acidic to alkaline, the GHGs emissions are reduced. The addition of Ni inhibits GHGs emission but decreases the electricity, the power density is reduced to 1.09 W/m³, and the methane and nitrous oxide emission fluxes decline to 0.20 ± 0.04 mg/(m²·h) and 15.49 ± 1.86 μg/(m²·h), respectively. Low C/N ratio reduces methane emission, while high C/N ratio effectively inhibits nitrous oxide emission. At the influent pH 8 and C/N = 5:1, the methane emission flux is approximately 10.60 ± 0.27 mg/(m²·h), and the nitrous oxide emission flux is only 10.90 ± 1.10 μg/(m²·h). Based on the above experimental results by controlling variable factors, it is proposed that CW-MFC offers an environment-friendly solution to regulate GHG emissions.     

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.