Activation and Transformation of Ethane by Au₂VO₃⁺ Clusters with Closed‐Shell Electronic Structures

Abstract

The study of chemical reactions between gold-containing heteronuclear oxide clusters and small molecules can provide molecular level mechanisms to understand the excellent activity of gold supported by metal oxides. While the promotion role of gold in alkane transformation was identified in the clusters with atomic oxygen radicals (O(-.)), the role of gold in the systems without O(-.) is not clear. By employing mass spectrometry and quantum chemistry calculations, the reactivity of Au2 VO3(+) clusters with closed-shell electronic structures toward ethane was explored. Both the dehydrogenation and ethene elimination channels were identified. It is gold rather than oxygen species initiating the C-H activation. The Au-Au dimer formed during the reactions plays important roles in ethane transformation. The reactivity comparison between Au2 VO3(+) and bare Au2(+) demonstrates that Au2 VO3(+) not only retains the property of bare Au2(+) that transforming ethane to dihydrogen, but also exhibits new functions in converting ethane to ethene, which reveals the importance of the composite system. This study provides a further understanding of the reactivity of metal oxide supported gold in alkane activation and transformation.

Reactivity of Tantalum Carbide Cluster Anions TaCn– (n = 1–4) with Dinitrogen

“…After confining the cluster ions in the trap for about 0.9 ms, the reactant gas molecules (N 2 ) were delivered through a third pulsed valve to interact with the clusters. It has been demonstrated that the ions were thermalized to room temperature (298 K) before reactions. − After interacting for about 7 ms, the reactant and product ions ejected from the LIT were transferred into the TOF-MS for mass and intensity measurements.…”

Consecutive H2 Oxidation Mediated by Au2VO4+ Clusters

“…Furthermore, another isomer 1 IS6 with a closed-shell electronic structure and separate gold atoms was also determined as candidates for the ground-state structures of Au 2 VO 4 + since it has close energy to 3 IS1. The previous study has determined the ground-state structure of Au 2 VO 3 + cluster ( 1 IS4, Figure b), which has a closed-shell electronic structure with two terminal gold atoms and one terminal oxygen atom (O t ). The gold atoms terminally bonded with bridging oxygen atoms are separated from each other.…”

“…Density functional theory (DFT) calculations using the Gaussian 09 program were carried out to investigate the mechanistic details of catalytic H 2 oxidation mediated by Au 2 VO x + clusters ( x = 2–4). The TPSS functional has been proved to perform well for the Au–V–O system; , thus, the results by TPSS were given throughout this work. The TZVP basis set for V, O, H atoms and a D95 V basis set combined with the Stuttgart/Dresden relativistic effective core potential (denoted as SDD in Gaussian software) for the Au atom were used in all the calculations.…”

H2 Oxidation Mediated by Au1-Doped Vanadium Oxide Cluster Cation AuV2O5+: A Comparative Study with AuCe2O4+

“…The DFT calculations with the Gaussian 09 program were employed to study the structures of AuV 2 O 5 + cluster and the reaction mechanism with H 2 . The TPSS functional has been proved to perform well for the Au–V–O system; ,− thus, the results by TPSS were given throughout this work. The TZVP basis set for V, O, H atoms and a D95V basis set combined with the Stuttgart/Dresden relativistic effective core potential (denoted as SDD in Gaussian software) for the Au atom were used in all the calculations.…”