Numerical study on laminar burning velocity of ammonia flame with methanol addition

The combustion characteristics of ammonia/methanol mixtures were investigated numerically in this study. Methanol has a dramatic promotive effect on the laminar burning velocity (LBV) of ammonia. Three mechanisms from literature and another four self-developed mechanisms constructed in this study were evaluated using the measured laminar burning velocities of ammonia/methanol mixtures from Wang et al. (Combust.Flame. 2021). Generally, none of the selected mechanisms can precisely predict the measured laminar burning velocities at all conditions. Aiming to develop a simplified and reliable mechanism for ammonia/methanol mixtures, the constructed mechanism utilized NUI Galway mechanism (Combust.Flame. 2016) as methanol sub-mechanism and the Otomo mechanism (Int. J. Hydrogen. Energy. 2018) as ammonia sub-mechanism was optimized and reduced. The reduced mechanism entitled ‘DNO-NH3’, can accurately reproduce the measured laminar burning velocities of ammonia/methanol mixtures under all conditions. A reaction path analysis of the ammonia/methanol mixtures based on the DNO-NH3 mechanism shows that methanol is not directly involved in ammonia oxidation, instead, the produced methyl radicals from methanol oxidization contribute to the dehydrogenation of ammonia. Besides, NO_x emission analysis demonstrates that 60% methanol addition results in the highest NO_x emissions. The most important reactions dominating the NO_x consumption and production are identified in this study.     

Completely eliminating the metal barrier cracks on Nafion for suppressing methanol crossover with anodic aluminum oxide substrates

Methanol crossover is one of the main challenges for direct methanol fuel cells (DMFCs). Depositing a metal barrier on Nafion can reduce the crossover but usually faces the metal cracking issues. This study presents a new composite membrane in which an anodic aluminum oxide (AAO) substrate is impregnated with a Nafion solution and then coated with a layer of Au. The AAO/Nafion/Au composite membrane shows an ideal metal crack-free surface. Higher and more stable voltage has been achieved for the cell with the membrane, indicating an effectively suppressed methanol-crossover. Results reveal that there is a tradeoff between suppressing the methanol crossover and increasing the ion transmission. By optimizing the membrane, it can not only suppress the methanol crossover but also enhance the output performance of DMFCs. The current density and power density of the cells can be enhanced by 59% and 52.85%, respectively, compared to the cell with a commercial Nafion 117. Overall, this work provides a new approach to designing crack-free membranes for DMFCs.     

Imidazolium functionalized poly(vinyl alcohol) membranes for direct methanol alkaline fuel cell applications

In this study, imidazolium functionalized poly(vinyl alcohol) (PVA) was synthesized by acetalization and direct quaternization reaction. Afterwards, composite anion exchange membranes based on imidazolium‐ and quaternary ammonium‐ functionalized PVA were used for direct methanol alkaline fuel cell applications. ¹H NMR and Fourier transform infrared spectroscopy data indicated that imidazole functionalized PVA was successfully synthesized. Inductively coupled plasma mass spectrometry data demonstrated that the imidazolium structure was efficiently obtained by direct quaternization of the imidazole group. Composite anion exchange membranes were fabricated by application of the functionalized PVA solution on the surface of porous polycarbonate (PC) membranes. Fuel cell related properties of all prepared membranes were investigated systematically. The imidazolium functionalized composite membrane (PVA‐Im/PC) exhibited higher ionic conductivity (7.8 mS cm^?1 at 30 °C) despite a lower water uptake and ion exchange capacity value compared to that of quaternary ammonium. In addition, PVA‐Im/PC showed the lowest methanol permeation rate and the highest membrane selectivity as well as high alkaline and oxidative stability. Dynamic mechanical analysis results reveal that both composite membranes were mechanically resistant up to 10⁷ Pa at 140 °C. The superior performance of imidazolium functionalized PVA composite membrane compared to quaternary ammonium functionalized membrane makes it a promising candidate for direct methanol alkaline fuel cell applications. © 2020 Society of Chemical Industry     

Hybrid sonochemic urea-nitrate combustion preparation of CuO/ZnO/Al2O3 nanocatalyst used in fuel cell-grade hydrogen production from methanol: Effect of sonication and fuel/nitrate ratio

Fuel cell-grade hydrogen production has been studied via steam reforming of methanol (SRM) over a series of CuO/ZnO/Al₂O₃ nanocatalysts fabricated by the combustion method. The effect of sonication and urea/nitrate ratio on the characteristics and catalytic properties of the prepared catalysts has been investigated. The synthesized catalysts were characterized by x-ray diffraction (XRD), field emission scanning electron microscope (FESEM), Particle Size Distribution (PSD), energy dispersive x-ray (EDX), Brunauer-Emmett-Teller (BET) and FTIR analyses XRD patterns showed positive influence of urea/nitrate ratio on CuO and ZnO crystallite sizes. The ultrasonic mixing of primary gel compared with conventional mixing led to lower crystallite size. FESEM images showed that the sample mixed by sonication with a urea/nitrate ratio of 1 had more homogeneous morphology with narrow particle size distribution. EDX results proved the presence of all metals on the surface of the nanocatalysts and better consistence between the gel and surface composition of elements in samples prepared by sonication. Catalytic performance showed that sonication during the mixing of primary gel dramatically increased the methanol conversion. It was also proved that increasing the amount of urea led to lower catalytic activity. The ultrasound-treated nanocatalyst with urea/nitrate?=?1 was the best sample in terms of activity and selectivity. It was stable in the SRM for 1200?min without considerable change in methanol conversion and product selectivity.     

Revamping SiO2 Spheres by Core–Shell Porosity Endowment to Construct a Mazelike Nanoreactor for Enhanced Catalysis in CO2 Hydrogenation to Methanol

Beyond the catalytic activity of nanocatalysts, the support with architectural design and explicit boundary could also promote the overall performance through improving the diffusion process, highlighting additional support for the morphology-dependent activity. To delineate this, herein, a novel mazelike-reactor framework, namely multi-voids mesoporous silica sphere (MVmSiO₂), is carved through a top-down approach by endowing core-shell porosity premade Stöber SiO₂ spheres. The precisely-engineered MVmSiO₂ with peripheral one-dimensional pores in the shell and interconnecting compartmented voids in the core region is simulated to prove combined hierarchical and structural superiority over its analogous counterparts. Supported with CuZn-based alloys, mazelike MVmSiO₂ nanoreactor experimentally demonstrated its expected workability in model gas-phase CO₂ hydrogenation reaction where enhanced CO₂ activity, good methanol yield, and more importantly, a prolonged stable performance are realized. While tuning the nanoreactor composition besides morphology optimization could further increase the catalytic performance, it is accentuated that the morphological architecture of support further boosts the reaction performance apart from comprehensive compositional optimization. In addition to the found morphological restraints and size-confinement effects imposed by MVmSiO₂, active sites of catalysts are also investigated by exploring the size difference of the confined CuZn alloy nanoparticles in CO₂ hydrogenation employing both in-situ experimental characterizations and density functional theory calculations.     

Nickel-decorated MoS2/MXene nanosheets composites for electrocatalytic oxidation of methanol

Nickel incorporated on MoS₂/MXene composites (NiMoS₂/MXene) via a wet impregnation method is used as an anode electrode material for methanol electro-oxidation. X-ray diffraction, X-ray photoelectron spectra, and scanning electron microscopy equipped with energy-dispersive X-ray spectroscopy techniques were used for the confirmation of MoS₂/MXene formation. Textural properties of catalysts were obtained in N₂ adsorption-desorption analysis. Electrochemical measurements in 0.1 M KOH demonstrated the better electrocatalytic activity of NiMoS₂/MXene catalysts. The NiMoS₂/MXene system exhibited enhanced electrocatalytic activity for methanol oxidation due to low onset potential offered by Ni, high tolerance toward CO poisoning by MoS₂, and high conductivity and high mechanical stability of MXene. NiMoS₂-3/MXene catalysts exhibited high current density, electrochemical active surface area, long-term stability, and low Rct value. Based on the electrochemical results, NiMoS₂/MXene catalysts is a highly electroactive anode material. Hence can be utilized in fuel cell applications such as Direct Methanol Fuel Cell (DMFC).     

Controllable electrodeposition synthesis of Pd/TMxOy-rGO/CFP composite electrode for highly efficient methanol electro-oxidation

A novel and high-efficiency Pd/TM_xO_y-rGO/CFP (TM_xO_y = Co₃O₄, Mn₃O₄, Ni(OH)₂) electrocatalyst for directly integrated membrane electrode was synthesized by controllable cyclic voltammetry electrodeposition combined with hydrothermal process. The results showed excellent performance towards methanol oxidation reduction. The Pd/Co₃O₄-rGO/CFP as-prepared catalyst has the best electrocatalytic activity, and mass activity is 5181 mA·mg⁻¹_Pd, which is about 40 times and 4.3 times that of the commercial Pd/C and Pt/C catalyst (JM). It can be attributed that the small size of Pd nanoparticle, uniformity of distribution, and the synergistic interaction between transition metal oxide on the support surface and Pd nanoparticles. The prepared Pd/TM_xO_y-rGO/CFP composite electrode is a promising catalyst for integrated membrane electrode assembly of proton exchange membrane fuel cells in the future.     

Porous Ni2P nanoflower supported on nickel foam as an efficient three-dimensional electrode for urea electro-oxidation in alkaline medium

Porous Ni₂P nanoflower supported on nickel foam (Ni₂P@Ni foam) electrodes are synthesized via a simple hydrothermal growth strategy accompanied with further phosphating treatment. The prepared electrodes are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and transmission electron microscopy (TEM). Electro-catalytic performances towards urea electro-oxidation are tested by cyclic voltammetry (CV), chronoamperometry (CA) coupled with electrochemical impedance spectroscopy (EIS). By phosphating Ni(OH)₂ precursor, the final obtained Ni₂P@Ni foam electrode presents a porous Ni₂P nanoflower structure within abundant porosity, and so exposes a large amount of electro-catalytic active sites and electronic transmission channels to accelerate the interfacial reaction. Compared with Ni(OH)₂@Ni foam precursor, the Ni₂P@Ni foam catalyst exhibits more excellent electro-catalytic activity as well as lower onset oxidation potential. Remarkably, the Ni₂P@Ni foam catalyst reaches a peak current density of 750 mA cm^?2 with an onset oxidation potential of 0.24 V (vs. Ag/AgCl) accompanied by an excellent stability in 0.60 M urea with 5.00 M KOH solutions. Benefiting from the unique porous nanosheet structure, the as-synthesized Ni₂P@Ni foam catalyst performs a highly enhanced catalytic behavior for alkaline urea electro-oxidation, indicating that the material can be hopefully applied in direct urea fuel cells.