Size-Dependent Reactivity of Co_n^– (n = 5–25) Cluster Anions toward Carbon Dioxide

Abstract

A fundamental understanding of the reactivity evolution of nanosized clusters at an atomically precise level is pivotal to assemble desired materials with promising candidates. Benefiting from the tandem mass spectrometer coupled with a high-temperature ion-trap reactor, the reactions of mass-selected Co n – (n = 5–25) clusters with CO2 were investigated and the increased reactivity of Co20–25 – was newly discovered herein. This finding marks an important step to understand property evolution of subnanometer metal clusters (Co25 –, ∼0.8 nm) atom-by-atom. The reasons behind the increased reactivity of Co20–25 – were proposed by analyzing the reactions of smaller Co6–8 – clusters that exhibit significantly different reactivity toward CO2, in which a lower electron affinity of Co n contributes to the capture of CO2 while the flexibility of Co n – could play vital roles to stabilize reaction intermediates and suppress the barriers of O–CO rupture and CO desorption.

Observation of inserted oxocarbonyl species in the tantalum cation-mediated activation of carbon dioxide dictated by two-state reactivity

“…12,13 Infrared photodissociation spectroscopy has been widely applied to gain detailed insights into the binding behavior and mutual interactions between metal catalysts and CO 2 molecules, providing a sensitive probe for geometric characteristics as any structural rearrangements will be encoded in the vibrational spectra. 14–18 Apart from experimental investigations, there are also a considerable amount of theoretical studies focusing on transition metal-mediated reactions with CO 2 in an effort to elucidate salient features of mechanisms and kinetics. 19–23…”

Reverse water–gas shift catalyzed by RhnVO3,4− (n = 3–7) cluster anions under variable temperatures

“…CO 2 activation mediated by gas-phase clusters such as metal hydrides, metal oxides, and pure metal clusters, have been extensively studied. 12,18–35 (The results since 2020 are listed in Table 1 and those before 2020 can be found in a review paper. 35 ) CO 2 hydrogenation is usually an endothermic process ( e.g.…”