Direct solid-state nucleation and charge-transport dynamics of alkali metal-intercalated M₂Mo₆S₆ (M = K, Rb, Cs) nanorods

Abstract

Microwave-assisted solid-state heating has been employed to induce anisotropic nucleation of M2Mo6S6 (M = K, Rb, Cs) nanorods without a template for the first time, and interfacial charge-transport properties of these rods are evaluated.

Multi-dimensional designer catalysts for negative emissions science (NES): bridging the gap between synthesis, simulations, and analysis

“…We have this potential testbed in 2D cross-dimensional heterostructures ( vide infra ). However, we must establish surface structure–reactivity relationships taking into account the surface and bulk composition which can help accelerate discovery and design ( Perryman et al., 2020a ; Ortiz-Rodríguez et al., 2020 ). Where 2D vdW structures are posited to afford bidentate coordination environments ( Figure 1 A) for catalytically important intermediate species in the CO2RR as an alternative to potentially less favorable monodentate structures ( Figure 1 B), it has been shown that the ternary composition of 3D chalcogenides like Chevrel phases affords a similar level of control over adsorbate binding ( Liu et al., 2010 ; Liu and Liu, 2015 ).…”

“…Beyond simply controlling local coordination via compositional modification in flexible 3D chalcogenide frameworks, it is also understood—albeit underexplored—that even morphological changes in 3D systems can introduce profound changes in locally observed electric fields for CO 2 reduction intermediates ( Gao et al., 2012 , 2020 ). This strongly motivates the exploration of additional synthetic techniques that will enable control over particle morphology on well-defined chalcogenide compositions ( Perryman et al., 2020a ), similar to the established hydrothermal and solvothermal routes that have been employed for metal oxide nanoparticle catalysts for thermal CO 2 reduction ( Jiang et al., 2020a ; Liang et al., 2014 ).…”

“…2D photocatalysts (aka 2-periodic) based on metal chalcogenides (e.g. MoS 2 , SnS 2 , WSe 2 , Bi 2 S 3 , Chevrel phases, to mention a few) ( Rahman et al., 2016 ; Degrauw et al., 2017 ; Ortiz-Rodríguez et al., 2020 ; Perryman et al., 2020a , 2020b ; Perryman and Velázquez, 2021 ; Hill and Hill, 2019 , 2021 ; Strange et al., 2020 ; Hill et al., 2020 ; Tolbert and Hill, 2021 ) and 2D metal halide perovskites ( Amerling et al., 2020 , 2021 ; Wu et al., 2021 ; Yuan et al., 2021 ; Pareja-Rivera et al., 2021 ) are well-suited materials for the reduction of CO 2 due to their strong light-matter interactions. Although many low-dimensional photocatalysts have a high density of electronically active sites for CO 2 binding, these same sites can act as recombination centers that detrimentally affect CO 2 conversion efficiencies.…”

“…Additionally, the 2D heterostructure arrangements should provide high current densities (>200 mA/cm 2 ) given the high electron mobility (200–1,500 S cm −1 ) of the individual building blocks ( Ogle et al., 2021 ; Ortiz-Rodríguez et al., 2020 ; Perryman et al., 2020a , 2020b ; Perryman and Velázquez, 2021 ). An important research direction will be to model the catalytic activity of 2DMOFs, Chevrel phases, and 2DMHPs, their active sites, and selectivity toward reducing CO 2 into high value-added molecules.…”

Charge Transport Dynamics in Microwave Synthesized One-Dimensional Molybdenum Chalcogenides

“…Previously reported results of computational surface energy modeling for K2Mo6S6 <010>, <110>, and <001> surfaces 8. …”