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Methanol serves as a versatile building‐block for various commodity chemicals, and the development of industrially promising strategies for its conversion remains the ultimate goal in methanol chemistry. In this study, we design a dual Cu−Cs catalytic system that enables a one‐step direct conversion of methanol and methyl acetate/ethanol into high value‐added esters/aldehydes, with customized chain length and saturation by leveraging the proximity and distribution of Cu−Cs sites. Cu−Cs at a millimeter‐scale intimacy triggers methanol dehydrogenation and condensation, involving proton transfer, aldol formation, and aldol condensation, to obtain unsaturated esters and aldehydes with selectivities of 76.3 % and 31.1 %, respectively. Cu−Cs at a micrometer‐scale intimacy significantly promotes mass transfer of intermediates across catalyst interfaces and their subsequent hydrogenation to saturated esters and aldehydes with selectivities of 67.6 % and 93.1 %, respectively. Conversely, Cu−Cs at a nanometer‐scale intimacy alters reaction pathway with a similar energy barrier for the rate‐determining step, but blocks the acidic‐basic sites and diverts the reaction to byproducts. More importantly, an unprecedented quadruple tandem catalytic production of methyl methacrylate (MMA) is achieved by further tailoring Cu and Cs distribution across the reaction bed in the configuration of Cu−Cs||Cs, outperforming the existing industrial processes and saving at least 15 % of production costs. [ABSTRACT FROM AUTHOR]

Cu‐CHA is the state‐of‐the‐art catalyst for the Selective Catalytic Reduction (SCR) of NOx in vehicle applications. Although extensively studied, diverse mechanistic proposals still stand in terms of the nature of active Cu‐ions and reaction pathways in SCR working conditions. Herein we address the redox mechanism underlying Low‐Temperature (LT) SCR on Cu‐CHA by an integration of chemical‐trapping techniques, transient‐response methods, operando UV/Vis‐NIR spectroscopy with modelling tools based on transient kinetic analysis and density functional theory calculations. We show that the rates of the Reduction Half‐Cycle (RHC) of LT‐SCR display a quadratic dependence on CuII, thus questioning mechanisms based on isolated CuII‐ions. We propose, instead, a CuII‐pair mediated LT‐RHC pathway, in which NO oxidative activation to mobile nitrite‐precursor intermediates accounts for CuII reduction. These results highlight the role of dinuclear Cu complexes not only in the oxidation part of LT‐SCR, but also in the RHC reaction cascade. [ABSTRACT FROM AUTHOR]

Based on detailed in situ attenuated total-reflection-surface-enhanced IR reflection absorption spectroscopy (ATR-SEIRAS) studies of the methanol oxidation reaction (MOR) on Ru/Pt thin film and commercial Johnson-Matthey PtRu/C, a revised MOR enhancement mechanism is proposed in which CO on Pt sites is irrelevant but instead Pt-Ru boundary sites catalyze the oxygen insertion reaction that leads to the formation of formate and enhances the direct reaction pathway. [ABSTRACT FROM AUTHOR]