Mechanistic Insight into Acceptorless Dehydrogenation of Methanol to Syngas Catalyzed by MACHO-Type Ruthenium and Manganese Complexes: A DFT Study.

The acceptorless dehydrogenation of methanol to produce carbon monoxide (CO) and dihydrogen (H2) mediated by MACHO-type 1-Ru and 1-Mn complexes was theoretically investigated via density functional theory calculations. The 1-Ru-catalyzed process involves the formation of active species 4-Ru through a methanol-bridged H2 release pathway. Methanol dehydrogenation by 4-Ru yields formaldehyde and 1-Ru, followed by H2 release to regenerate 4-Ru (rate-determining step, ΔG‡ = 32.5 kcal/mol). Formaldehyde further reacts with methanol via nucleophilic attack of the MeO- ligand in the Ru complex (ΔG‡ = 9.6 kcal/mol), which is more favorable than the traditional methanol-to-formaldehyde nucleophilic attack (ΔG‡ = 33.8 kcal/mol) due to the higher nucleophilicity of MeO-. CO is ultimately produced through the methyl formate decarbonylation reaction. Accelerated H2 release in the early reaction stage compared to CO results from the initial methanol dehydrogenation and condensation of formaldehyde with methanol. In contrast, CO generation occurs later via methyl formate decarbonylation. The 1-Mn-catalyzed reaction has reduced efficiency compared to 1-Ru for the higher Gibbs energy barrier (ΔG‡ = 34.1 kcal/mol) of the rate-determining step. Excess NaOtBu promotes the reaction of CO and methanol, forming methyl formate, significantly reducing the CO/H2 ratio as the catalyst amount decreases. These findings deepen our understanding of the methanol-to-syngas transformation and can drive progress in this field.

Recent Advances on Tuning the Interlayer Coupling and Properties in van der Waals Heterostructures.

2D van der Waals (vdW) heterostructures are receiving increasing research attention due to the theoretically amazing properties and unprecedented application potential. However, the as-synthesized heterostructures are generally underperforming due to the weak interlayer coupling, which inspires the researchers to find ways to modulate the interlayer coupling and properties, realizing the tailored performance for actual applications. There have been a lot of publications regarding the controllable regulation of the structures and properties of 2D vdW heterostructures in the past few years, while a review work summarizing the current advances is not yet available, though it is significant. This paper conducts a state-of-the-art review regarding the current research progress of performance modulation of vdW heterostructures by different techniques. First, the general synthesis methods of vdW heterostructures are summarized. Then, different performance modulation techniques, that is, mechanical-based, external fields-assisted, and particle beam irradiation-based methods, are discussed and compared in detail. Some of the newly proposed concepts are described. Thereafter, applications of vdW heterostructures with tailored properties are reviewed for the application prospects of the topic around this area. Moreover, the future research challenges and prospects are discussed, aiming at triggering more research interest and device applications around this topic.