to transformthe methane oxidation to methanol

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  Studies revealed that even in the absence of steam or carbon dioxide, Cu/ZnO catalyst was irreversibly deactivateddue to the reduction of CuO catalyst to Cu 2 Kinetic studies, besides investigations about the adsorption of isotopic-labeled species on the surface of different catalysts could beuseful to understand the methanol formation from the CO 3.2. For instance, identifying the nature of ac- tive sites or the methanol precursor (i.e., CO or CO 2 O 3 via the syngas route has many issues that are currently the From a mechanical perspective, the methanol synthesis over Cu–ZnO/Al adsorbed in the catalyst surface [38–40] . The combination of these adsorbed molecules provides the adsorbed format (H 2 COO ads ) [38–40] .

3.3. Cu–Zn/Al

  They concluded that Cu(I) ions are formed throughoutthe process and are stabilized by promoters (i.e., ZnO, CsCO 2 O 3 catalyst: Synetix process for methanol production anol under pressure of 50 to 100 bar and temperatures in the range of 513 to 533 K ( Scheme 2 ) [10] . Forat a CO:H 2 molar ratio equal to 3:1, methanol synthesis requires a these reasons, the price of liquid methanol (i.e., produced via the syngas 2:1 molar proportion between CO and H 2 (see Scheme 3 ) [46] .

3 Undeniably, such development could be an achievement that could

  First, it is important to highlight that although methanol synthesis notably expand the production of methanol-derivatives and influencefrom syngas is exothermic, the overall enthalpy of the reactions 1 to 3 the planet's economy [48] . (iii) Solid-catalyzed processes in the liquid phase; Despite large capital investment to build industrial plants, the syn- (iv) Homogeneous catalytic processes in the liquid phase, in the gas route constitutes the most important process to convert methane presence of soluble catalysts;to clean fuels, such as methanol [49] .

4.2. Activation of C–H bonds by enzymatic complexes

  Arutyunov et al.assessed the technological prospects and applications of the direct con- version of methane to methanol via free-catalyst reactions in the gasphase and concluded that these technologies can be useful if employed at least for low-scale and local applications, mainly if natural gas isabundant and located in remote sites, where storage and transportation challenges exist [79] . However, poor selectivity (ca. 2%) was ob- tained due to methane combustion, in addition to the strong interactionof methanol and the zeolite, which leads to the formation Si–OCH cations of α-sites are activated by nitrous oxide generating adsorbed oxidant species (i.e., Fe As can be seen, the Fe Fe-ZSM-5 catalyst), based on kinetic dependences data measured at 433 K ( Scheme 9 ) [102] .

13 C CP/MAS NMR (i.e., Solid-state Cross-

  [102] . assessed the activity of Co–ZSM-5 solid catalysts on reactions of partial oxidation of methane.

13 C CP/

76 Scheme 9. Equations of reaction CH 4 + N 2 O + α sites over Fe-ZSM-5 catalyst

  However, poor selectivity (ca. 2%) was ob- tained due to methane combustion, in addition to the strong interactionof methanol and the zeolite, which leads to the formation Si–OCH cations of α-sites are activated by nitrous oxide generating adsorbed oxidant species (i.e., Fe As can be seen, the Fe Fe-ZSM-5 catalyst), based on kinetic dependences data measured at 433 K ( Scheme 9 ) [102] . An outstanding result was obtained by comparing the activity of all these different molybdenum based catalysts with data obtained froman empty reactor; none of the reactions performed in the presence of catalysts assessed by them reached the conversion and methanol selec-tivity achieved in reactions made with an empty reactor ( Table 9 ) [109] .

2 O 3 (MoO 3 ) 3 , which resulted in 869 g methanol/kg cat h [105]

  flow reactor was less effective that in an empty reactorChun and Anthony also assessed the participation of the reactor's wall in the reaction of methane oxidation to methanol [115] . evaluated the activity of supported silica vanadium ox- ides in the methane oxidation by nitric oxide and oxygen mixturesunder room pressure, and verified that an increase of NO concentration to 1.5% sharply improved the methanol and formaldehyde combinedselectivity ( Fig. 16 ) [118] .

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