Gas-phase reactions driven by polarized metal–metal bonding in atomic clusters

Abstract

Multimetallic catalysts exhibit great potentials in the activation and catalytic transformation of small molecules. The polarized metal-metal bonds have been gradually recognized to account for the reactivity of multimetallic catalysts...

Conversion of Carbon Dioxide into a Series of CBxOy– Compounds Mediated by LaB3,4O2– Anions: Synergy of the Electron Transfer and Lewis Pair Mechanisms to Construct B–C Bonds

“…The other possible isomers of LaB 3 O 3 – are given in Figure S12a. This mechanism for forming CO is similar to those reported in most of the CO 2 reduction reactions, , that is, the CO bond is directly cleaved in one step after CO 2 adsorption.…”

Thermal Reactions of NiAl3O6+ and Al4O6+ with Methane: Reactivity Enhancement by Doping

“…Atomic clusters, with the advantage that their compositions could be precisely defined, have been proved as effective models for the catalytic active sites of practical importance, permitting clarification of the specific role each atom played during chemical reactions at the microscopic level. − Available gas phase studies about the reactivity of heteronuclear cluster systems containing aluminum oxides toward methane conversion have shown the crucial role of the doping effect on cluster reactivity and product selectivity. While the pristine Al 3 O 4 + and Al 2 O 4 – exhibit inertness toward CH 4 at room temperature, the cluster doping with single noble metal (NM) atoms of Rh (RhAl 3 O 4 + and RhAl 2 O 4 – ) could not only bring about methane activation but also transform methane into syngas (CO + H 2 ) driven by the high electron-withdrawing capability of Rh to induce the four C–H bonds cleaved. , Distinctly, the Al 2 O 4 – cluster doping with a single Pt atom that has one less valence electron than Rh only selectively activates two C–H bonds and finally converts CH 4 into formaldehyde (CH 2 O) with 100% product selectivity .…”

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

“…In real-life catalytic reactions, the confined active sites involved in the cleavage and formation of chemical bonds on heterogeneous catalysts are generally composed of a limited number of atoms. The reactivity study of isolated atomic clusters [10][11][12][13][14][15][16][17] that compositionally and chemically resemble these active sites is an intriguing strategy to understand the nature of active sites and the mechanisms that govern chemical reactions such as CO 2 hydrogenation. CO 2 activation mediated by gas-phase clusters such as metal hydrides, metal oxides, and pure metal clusters, have been extensively studied.…”