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Surface hydrophobicity is an important factor in controlling the catalytic activity of heterogeneous catalysts in various reactions, particularly liquid-phase reactions using water as the (co)solvent. In this study, the surface hydrophobicity of Fe-ZSM-5 was successfully controlled using a simple coating method in which furfuryl alcohol was used as the carbon precursor. Various techniques, such as N2 physisorption, temperature-programmed desorption of ammonia, and contact angle measurements of water droplets, were used to characterize the catalysts. Fe-ZSM-5 catalysts with different degrees of hydrophobicity were used for the aqueous-phase selective oxidation of methane with H2O2. The positive effect of the surface carbon coating on the catalytic performance was confirmed when the carbon content was not sufficiently high to block the pores. [ABSTRACT FROM AUTHOR]

Methane is an abundant and relatively clean fossil fuel resource; therefore, its utilization as a chemical feedstock has a major impact on the chemical industry. However, its inert nature makes direct conversion into value-added products difficult under mild conditions. Compared to the gas-phase selective oxidation of methane, there have been several recent advances in the liquid-phase conversion of methane. This review categorizes the reports on the liquid-phase selective oxidation of methane according to the solvent and oxidant used. The advantages and disadvantages of each approach are discussed. High yields of methyl bisulfate as a methanol precursor can be achieved using SO3 in sulfuric acid; however, more attention should be paid to the separation process and overall economic analysis. However, the aqueous-phase selective oxidation of methane with in situ generated H2O2 is quite promising from an environmental point of view, provided that an economical reducing agent can be used. Based on the current state-of-the-art on this topic, directions for future research are proposed. [ABSTRACT FROM AUTHOR]

The dry reforming of methane (DRM) is a promising method for controlling greenhouse gas emissions by converting CO2 and CH4 into syngas, a mixture of CO and H2. Ni-based catalysts have been intensively investigated for their use in the DRM. However, they are limited by the formation of carbonaceous materials on their surfaces. In this review, we explore carbon-induced catalyst deactivation mechanisms and summarize the recent research progress in controlling and mitigating carbon deposition by developing coke-resistant Ni-based catalysts. This review emphasizes the significance of support, alloy, and catalyst structural strategies, and the importance of comprehending the interactions between catalyst components to achieve improved catalytic performance and stability. [ABSTRACT FROM AUTHOR]

The direct oxidation of methane to methanol is considered challenging due to the intrinsically low reactivity of the C–H bond of methane and the formation of a large number of unstable intermediates (methanol, formaldehyde, and formic acid) relative to the yield of methane. However, promising advances have recently been reported in this area based on the use of electrochemical systems that differ from traditional thermal catalysis. In this review, the recent advances in direct and indirect electrochemical methane conversion with homogeneous catalysts are reviewed and discussed, especially under low-temperature conditions. Finally, the limitations of the current electrochemical methane conversion technology and future research directions are discussed. [ABSTRACT FROM AUTHOR]

Photoelectrochemical (PEC) H2 production from water using solar energy is an ideal and environmentally friendly process. CuInS2 is a p-type semiconductor that offers many advantages for PEC H2 production. Therefore, this review summarizes studies on CuInS2-based PEC cells designed for H2 production. The theoretical background of PEC H2 evolution and properties of the CuInS2 semiconductor are initially explored. Subsequently, certain important strategies that have been executed to improve the activity and charge-separation characteristics of CuInS2 photoelectrodes are examined; these include CuInS2 synthesis methods, nanostructure development, heterojunction construction, and cocatalyst design. This review helps enhance the understanding of state-of-the-art CuInS2-based photocathodes to enable the development of superior equivalents for efficient PEC H2 production. [ABSTRACT FROM AUTHOR]

Ammonia decomposition is a key step in hydrogen production and is considered a promising practical intercontinental hydrogen carrier. In this study, 1 wt.% Ru/SiO2 catalysts were prepared via wet impregnation and subjected to calcination in air at different temperatures to control the particle size of Ru. Furthermore, silica supports with different surface areas were prepared after calcination at different temperatures and utilized to support a change in the Ru particle size distribution of Ru/SiO2. N2 physisorption and transmission electron microscopy were used to probe the textural properties and Ru particle size distribution of the catalysts, respectively. These results show that the Ru/SiO2 catalyst with a high-surface area achieved the highest ammonia conversion among catalysts at 400 °C. Notably, this is closely related to the Ru particle sizes ranging between 5 and 6 nm, which supports the notion that ammonia decomposition is a structure-sensitive reaction. [ABSTRACT FROM AUTHOR]

In this study, a Cu-promoted Fe/ZSM-5 catalyst was examined to reveal the effects of Cu species in selective oxidation of methane into methane oxygenates using H2O2 in water. Cu/ZSM-5, Cu-Fe/ZSM-5, and Fe/ZSM-5 catalysts were prepared using wet impregnation, solid-state ion exchange, and ion-exchange methods. Various techniques, including nitrogen physisorption, temperature-programmed reduction with H2, UV-vis spectroscopy, and FT-IR spectroscopy after NO adsorption, were utilized to characterize the catalysts. The promotional effect of Cu on the Cu-Fe/ZSM-5 catalyst in terms of methanol selectivity was confirmed. The preparation method has a considerable influence on the catalyst performance, and the ion-exchange method is the most effective. However, leaching of the Cu species was observed during this reaction, which can affect the quantification of formic acid by 1H-NMR. The homogeneous Cu species increase hydrogen peroxide decomposition and CO2 selectivity, which is undesirable for this reaction. [ABSTRACT FROM AUTHOR]

Methane is an abundant resource and its direct conversion into value-added chemicals has been an attractive subject for its efficient utilization. This method can be more efficient than the present energy-intensive indirect conversion of methane via syngas, a mixture of CO and H2. Among the various approaches for direct methane conversion, the selective oxidation of methane into methane oxygenates (e.g., methanol and formaldehyde) is particularly promising because it can proceed at low temperatures. Nevertheless, due to low product yields this method is challenging. Compared with the liquid-phase partial oxidation of methane, which frequently demands for strong oxidizing agents in protic solvents, gas-phase selective methane oxidation has some merits, such as the possibility of using oxygen as an oxidant and the ease of scale-up owing to the use of heterogeneous catalysts. Herein, we summarize recent advances in the gas-phase partial oxidation of methane into methane oxygenates, focusing mainly on its conversion into formaldehyde and methanol. [ABSTRACT FROM AUTHOR]

CO2 methanation is a promising reaction for utilizing CO2 using hydrogen generated by renewable energy. In this study, CO and CO2 methanation were examined over ceria-supported cobalt catalysts with low cobalt contents. The catalysts were prepared using a wet impregnation and co-precipitation method and pretreated at different temperatures. These preparation variables affected the catalytic performance as well as the physicochemical properties. These properties were characterized using various techniques including N2 physisorption, X-ray diffraction, H2 chemisorption, temperature-programmed reduction with H2, and temperature-programmed desorption after CO2 chemisorption. Among the prepared catalysts, the ceria-supported cobalt catalyst that was prepared using a wet impregnation method calcined in air at 500 °C, and reduced in H2 at 500 °C, showed the best catalytic performance. It is closely related to the large catalytically active surface area, large surface area, and large number of basic sites. The in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) study revealed the presence of carbonate, bicarbonate, formate, and CO on metallic cobalt. [ABSTRACT FROM AUTHOR]

Methane has been reported to be directly converted into value-added products through various methods. Among them, photoelectrochemical (PEC) methane conversion is considered an eco-friendly method because it utilizes solar light and is able to control the selectivity to different products by means of application of an external bias. Recently, some PEC methane conversion systems have been reported, but their performance efficiencies are relatively lower than those of other existing thermal, photocatalytic, and electrochemical systems. The detailed mechanism of methane activation is not clear at this stage. In this review, various catalytic materials and their roles in the reaction pathways are summarized and discussed. Furthermore, promising semiconductor materials, co-catalysts, and oxidants have also been proposed. Finally, direct and indirect pathways in the design of the PEC methane conversion system have been discussed. [ABSTRACT FROM AUTHOR]

Liquid-phase selective oxidation of methane into methane oxygenates, including methanol and formic acid, with molecular oxygen was investigated using Fe-zeolites and Pd/activated carbon in the presence of molecular hydrogen as a reducing agent. Various Fe-zeolites such as Fe-ZSM-5, Fe-mordenite, Fe-β, Fe-Y, and Fe-ferrierite were prepared by ion-exchange and compared for this reaction. Among them, Fe-ZSM-5 was selected for further study because this catalyst showed high activity in the selective oxidation of methane with relatively less leaching. Further, the effect of reaction temperature, pH, and the amount of catalyst was examined, and detailed investigations revealed that the leached Fe species, which were facilitated in the presence of acid, were mainly responsible for methane oxidation under the given reaction conditions. [ABSTRACT FROM AUTHOR]

In this study, unique core-shell aluminate spinel supports, Al@MAl2O4 (M = Zn, Mg, or Mn), were obtained by simple hydrothermal surface oxidation and were applied to the preparation of supported Ni catalysts for CO2 methanation. For comparison, CO methanation was also evaluated using the same catalysts. The prepared catalysts were characterized with a variety of techniques, including N2 physisorption, CO2 chemisorption, H2 chemisorption, temperature-programmed reduction with H2, temperature-programmed desorption of CO2, X-ray diffraction, high-resolution transmission electron microscopy, and in-situ diffuse reflectance infrared Fourier transform spectroscopy. The combination of supports with core-shell spinel structures and Ni doping with a deposition–precipitation method created outstanding catalytic performance of the Ni catalysts supported on Al@MgAl2O4 and Al@MnAl2O4 due to improved dispersion of Ni nanoparticles and creation of moderate basic sites with suitable strength. Good stability of Ni/Al@MnAl2O4 catalyst was also confirmed in the study. [ABSTRACT FROM AUTHOR]

The oxidative coupling of methane (OCM) is operated at high temperatures and is a highly exothermic reaction; thus, hotspots form on the catalyst surface during reaction unless the produced heat is removed. It is crucial to control the heat formed because surface hotspots can degrade catalytic performance. Herein, we report the preparation of Mn2O3-Na2WO4/SiC catalysts using SiC, which has high thermal conductivity and good stability at high temperatures, and the catalyst was applied to the OCM. Two Mn2O3-Na2WO4/SiC catalysts were prepared by wet-impregnation on SiC supports having different particle sizes. For comparison, the Mn2O3-Na2WO4/SiO2 catalyst was also prepared by the same method. The catalysts were analyzed by nitrogen adsorption–desorption, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The transformation of SiC into α-cristobalite was observed for the Mn2O3-Na2WO4/SiC catalysts. Because SiC was completely converted into α-cristobalite for the nano-sized SiC-supported Mn2O3-Na2WO4 catalyst, the catalytic performance for the OCM reaction of Mn2O3-Na2WO4/n-SiC was similar to that of Mn2O3-Na2WO4/SiO2. However, only the surface layer of SiC was transformed into α-cristobalite for the micro-sized SiC (m-SiC) in Mn2O3-Na2WO4/m-SiC, resulting in a SiC@α-cristobalite core–shell structure. The Mn2O3-Na2WO4/m-SiC showed higher methane conversion and C2+ yield at 800 and 850 °C than Mn2O3-Na2WO4/SiO2. [ABSTRACT FROM AUTHOR]

We investigated the influence of the reduction method on the preferential oxidation of CO in H2 (CO-PROX) over Au/La2O3/Al2O3 catalysts. An Au/La2O3/Al2O3 sample, prepared using deposition–precipitation with urea, was reduced by chemical reduction with NaBH4 or glycerol. Several techniques, such as diffuse-reflectance infrared Fourier-transform spectroscopy after CO adsorption (CO-DRIFTS), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) were used to characterize the catalysts. Additionally, the catalysts were examined by in situ DRIFTS during methanol decomposition. The results reveal that the reduction method affects the average particle size and electronic state of gold, as well as the characteristics of the CO–Au0 interactions. The best CO-PROX performance was observed for the catalyst chemically reduced using NaBH4 with a NaBH4/Au molar ratio of 35. This catalyst contained gold particles with size of ~4 nm, for which the XPS binding energy was lower than that of metallic gold. [ABSTRACT FROM AUTHOR]