Metal-promoted Mo₆S₈ clusters: a platform for probing ensemble effects on the electrochemical conversion of CO₂ and CO to methanol

Abstract

Presented herein is an investigation of a promising ternary metal sulfide catalyst that is capable of electrochemically converting CO2 to liquid and gas fuels such as methanol and hydrogen.

A Synergistic Approach to Unraveling the Thermodynamic Stability of Binary and Ternary Chevrel Phase Sulfides

“…1−12 Chevrel phases (CPs) constitute a fascinating subset of the chalcogenide family with highly flexible compositions of the general formula M y Mo 6 X 8 (M = alkali, alkaline earth, transition, or post-transition metal, y = 0−4, X = S, Se, Te) and equally flexiblealbeit composition-dependentsynthetic accessibility. Successful synthesis of these materials has been reported via traditional solid-state methods, 5,13,14 rapid microwave-assisted methods, 7,15 self-propagating combustion methods, 16 and thin-film conversion methods, 17 among others. Although these materials have been extensively characterized as multivalent ion intercalation cathodes during reversible battery cycling, 1−3,10,11,18−23 alternative applications for this chalcogenide family are abundant.…”

“…The immense body of work demonstrating binary and ternary chalcogenides for a wide variety of applications, along with their conspicuous compositional and structural tunability, make them especially attractive solid-state inorganic frameworks to develop formalisms for material properties that transcend specific crystal structures and compositions. − Chevrel phases (CPs) constitute a fascinating subset of the chalcogenide family with highly flexible compositions of the general formula M y Mo 6 X 8 (M = alkali, alkaline earth, transition, or post-transition metal, y = 0–4, X = S, Se, Te) and equally flexiblealbeit composition-dependentsynthetic accessibility. Successful synthesis of these materials has been reported via traditional solid-state methods, ,, rapid microwave-assisted methods, , self-propagating combustion methods, and thin-film conversion methods, among others. Although these materials have been extensively characterized as multivalent ion intercalation cathodes during reversible battery cycling, − ,,,− alternative applications for this chalcogenide family are abundant.…”

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

“…CO 2 reduction to higher alcohols and hydrocarbons). CO 2 reduction represents a vast field of research that has recently expanded into the realm of metal chalcogenides ( Perryman et al., 2020b ; Abbasi et al., 2017 ; Asadi et al., 2016 ). Much promise has been attributed to singular metal-chalcogenide-based electrocatalysts for CO 2 reduction due to their ability to break pernicious intermediate scaling relations that plague non-copper monometallic surfaces ( Chan et al., 2014 ; Hong et al., 2016 ).…”

“…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.…”