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      Methane Oxidation over the Zeolites-Based Catalysts

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      Catalysts
      MDPI AG

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          Abstract

          Zeolites have ordered pore structures, good spatial constraints, and superior hydrothermal stability. In addition, the active metal elements inside and outside the zeolite framework provide the porous material with adjustable acid–base property and good redox performance. Thus, zeolites-based catalysts are more and more widely used in chemical industries. Combining the advantages of zeolites and active metal components, the zeolites-based materials are used to catalyze the oxidation of methane to produce various products, such as carbon dioxide, methanol, formaldehyde, formic acid, acetic acid, and etc. This multifunction, high selectivity, and good activity are the key factors that enable the zeolites-based catalysts to be used for methane activation and conversion. In this review article, we briefly introduce and discuss the effect of zeolite materials on the activation of C–H bonds in methane and the reaction mechanisms of complete methane oxidation and selective methane oxidation. Pd/zeolite is used for the complete oxidation of methane to carbon dioxide and water, and Fe- and Cu-zeolite catalysts are used for the partial oxidation of methane to methanol, formaldehyde, formic acid, and etc. The prospects and challenges of zeolite-based catalysts in the future research work and practical applications are also envisioned. We hope that the outcome of this review can stimulate more researchers to develop more effective zeolite-based catalysts for the complete or selective oxidation of methane.

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          Most cited references118

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          Direct Conversion of Methane to Value-Added Chemicals over Heterogeneous Catalysts: Challenges and Prospects.

          The quest for an efficient process to convert methane efficiently to fuels and high value-added chemicals such as olefins and aromatics is motivated by their increasing demands and recently discovered large reserves and resources of methane. Direct conversion to these chemicals can be realized either oxidatively via oxidative coupling of methane (OCM) or nonoxidatively via methane dehydroaromatization (MDA), which have been under intensive investigation for decades. While industrial applications are still limited by their low yield (selectivity) and stability issues, innovations in new catalysts and concepts are needed. The newly emerging strategy using iron single sites to catalyze methane conversion to olefins, aromatics, and hydrogen (MTOAH) attracted much attention when it was reported. Because the challenge lies in controlled dehydrogenation of the highly stable CH4 and selective C-C coupling, we focus mainly on the fundamentals of C-H activation and analyze the reaction pathways toward selective routes of OCM, MDA, and MTOAH. With this, we intend to provide some insights into their reaction mechanisms and implications for future development of highly selective catalysts for direct conversion of methane to high value-added chemicals.
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            Selective anaerobic oxidation of methane enables direct synthesis of methanol.

            Direct functionalization of methane in natural gas remains a key challenge. We present a direct stepwise method for converting methane into methanol with high selectivity (~97%) over a copper-containing zeolite, based on partial oxidation with water. The activation in helium at 673 kelvin (K), followed by consecutive catalyst exposures to 7 bars of methane and then water at 473 K, consistently produced 0.204 mole of CH3OH per mole of copper in zeolite. Isotopic labeling confirmed water as the source of oxygen to regenerate the zeolite active centers and renders methanol desorption energetically favorable. On the basis of in situ x-ray absorption spectroscopy, infrared spectroscopy, and density functional theory calculations, we propose a mechanism involving methane oxidation at Cu(II) oxide active centers, followed by Cu(I) reoxidation by water with concurrent formation of hydrogen.
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              Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts

              An efficient and direct method of catalytic conversion of methane to liquid methanol and other oxygenates would be of considerable practical value. However, it remains an unsolved problem in catalysis, as typically it involves expensive or corrosive oxidants or reaction media that are not amenable to commercialization. Although methane can be directly converted to methanol using molecular oxygen under mild conditions in the gas phase, the process is either stoichiometric (and therefore requires a water extraction step) or is too slow and low-yielding to be practical. Methane could, in principle, also be transformed through direct oxidative carbonylation to acetic acid, which is commercially obtained through methane steam reforming, methanol synthesis, and subsequent methanol carbonylation on homogeneous catalysts. However, an effective catalyst for the direct carbonylation of methane to acetic acid, which might enable the economical small-scale utilization of natural gas that is currently flared or stranded, has not yet been reported. Here we show that mononuclear rhodium species, anchored on a zeolite or titanium dioxide support suspended in aqueous solution, catalyse the direct conversion of methane to methanol and acetic acid, using oxygen and carbon monoxide under mild conditions. We find that the two products form through independent pathways, which allows us to tune the conversion: three-hour-long batch-reactor tests conducted at 150 degrees Celsius, using either the zeolite-supported or the titanium-dioxide-supported catalyst, yield around 22,000 micromoles of acetic acid per gram of catalyst, or around 230 micromoles of methanol per gram of catalyst, respectively, with selectivities of 60–100 per cent. We anticipate that these unusually high activities, despite still being too low for commercial application, may guide the development of optimized catalysts and practical processes for the direct conversion of methane to methanol, acetic acid and other useful chemicals.
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                Author and article information

                Journal
                CATACJ
                Catalysts
                Catalysts
                MDPI AG
                2073-4344
                March 2023
                March 16 2023
                : 13
                : 3
                : 604
                Article
                10.3390/catal13030604
                63934494-8a59-48c2-9d7d-8e185bc4b87b
                © 2023

                https://creativecommons.org/licenses/by/4.0/

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