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.     

Co?N graphene encapsulated cobalt catalyst for H2O2 decomposition under acidic conditions

Hydrogen peroxide (H₂O₂) has been listed as one of the 100 most important chemicals in the world. However, huge amount of residual H₂O₂ is hard to timely decomposed into O₂ and H₂O under acidic condition, easily resulting in explosion hazard. Here, we reported a core–shell structure catalyst, that is graphene with Co N structure encapsulated Co nanoparticles. Co N graphene shell serves as the active site for the H₂O₂ decomposition, and Co core further enhance this decomposition. Benefiting from it, the H₂O₂ decomposition were close to 100% after 6 cycles without pH adjustment, which increased 6 orders of magnitude compared with no catalyst. At the same time, the O₂ generation reached 99.67% in 2 h with little metal leaching, and ·OH has been greatly inhibited to only 0.08%. This work can cleanly remove H₂O₂ with little deep oxidation and protect the process of H₂O₂ utilization to achieve a safer world.     

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.     

Fe3O4-carbon spheres core–shell supported palladium nanoparticles: A robust and recyclable catalyst for suzuki coupling reaction

Suzuki-Miyaura (S-M) is regarded the most powerful way for synthesis biaryls, triaryls, or incorporating of substituted aryl moieties in organic preparation by the cross-coupling of aryl boronic acid with aryl halides using the Pd catalyst. This work reports the combining of the hydrothermal and microwave-assisted protocol to convert the glucose to magnetic carbon spheres (Fe₃O₄-CSPs) decorated with Pd nanoparticles (NPs) as the catalyst for Suzuki-Miyaura cross-coupling reactions. The physicochemical properties in the produced composite were examined using FESEM, HRTEM, nitrogen isotherms, Raman spectroscopy, FTIR, XPS, and XRD. The as-fabricated composite Pd/Fe₃O₄-CSPs is mostly spherical with a core–shell structure and possesses a great surface area of 253.2 m²·g^-1. Its catalytic performance demonstrates that the composite has excellent stability and high tolerance Suzuki-Miyaura cross-coupling reactions in 30 min at 80 ℃. Both activated and deactivated aryl halides provided excellent yield. The as-fabricated catalyst was recycled for up to four catalytic cycles without a substantial decline in performance. Moreover, this research offers a facile roadmap for synthesizing Pd/Fe₃O₄-CSPs composites and promoting the practical implementation of Pd/Fe₃O₄-CSPs catalysts for organic transformation processes.     

羟基磷灰石作为催化材料的研究进展

羟基磷灰石(HAP)由于具有无毒性、生物相容性、热稳定性、吸附性、离子交换性、结构稳定性等,因而被广泛应用到催化剂的制备中。作为一种新型催化材料,HAP的特殊晶体结构对一些反应表现出催化活性,并且经过改性、负载等方法处理过后的HAP催化剂显示出独特的催化优势。基于近年来HAP在催化邻域的发展,综述了HAP作为催化材料在降解污染物、制氢、药物合成、还原氮氧化物等反应中的不同应用,并对未来的研究方向进行了展望。     

Ir(III) and Ru(II) Complexes in Photoredox Catalysis and Photodynamic Therapy: A New Paradigm towards Anticancer Applications

Individually, photoredox catalysis (PC) and photodynamic therapy (PDT) are well-established concepts that have experienced a remarkable resurgence in recent years, leading to significant progress in organic synthesis for PC and clinical approval of anticancer drugs for PDT. But, very recently, new photoredox catalyst systems based on Ir(III) and Ru(II) complexes have garnered significant interest because they can simultaneously be used as PDT agents apart from their demonstrated PC activity. This highlight discusses the unique PC behavior of emerging Ir(III)- and Ru(II)-based systems while also examining their potential PDT activity in cancer treatment.     

Helices on Interdomain Interface Couple Catalysis in the ATPPase Domain with Allostery in Plasmodium falciparum GMP Synthetase

GMP synthetase catalyses the conversion of XMP to GMP through a series of reactions that include hydrolysis of Gln to generate ammonia in the glutamine amidotransferase (GATase) domain, activation of XMP to adenyl-XMP intermediate in the ATP pyrophosphatase (ATPPase) domain and reaction of ammonia with the intermediate to generate GMP. The functioning of GMP synthetases entails bidirectional domain crosstalk, which leads to allosteric activation of the GATase domain, synchronization of catalytic events and tunnelling of ammonia. Herein, we have taken recourse to the analysis of structures of GMP synthetases, site-directed mutagenesis and steady-state and transient kinetics on the Plasmodium falciparum enzyme to decipher the molecular basis of catalysis in the ATPPase domain and domain crosstalk. Our results suggest an arrangement at the interdomain interface, of helices with residues that play roles in ATPPase catalysis as well as domain crosstalk enabling the coupling of ATPPase catalysis with GATase activation. Overall, the study enhances our understanding of GMP synthetases, which are drug targets in many infectious pathogens.     

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.