Recent Advances in the Synthesis, Characterization and Application of Zn⁺‐containing Heterogeneous Catalysts

Abstract

Monovalent Zn+ (3d104s1) systems possess a special electronic structure that can be exploited in heterogeneous catalysis and photocatalysis, though it remains challenge to synthesize Zn+‐containing materials. By careful design, Zn+‐related species can be synthesized in zeolite and layered double hydroxide systems, which in turn exhibit excellent catalytic potential in methane, CO and CO2 activation. Furthermore, by utilizing advanced characterization tools, including electron spin resonance, X‐ray absorption fine structure and density functional theory calculations, the formation mechanism of the Zn+ species and their structure‐performance relationships can be understood. Such advanced characterization tools guide the rational design of high‐performance Zn+‐containing catalysts for efficient energy conversion.

Nature and Topology of Metal–Oxygen Binding Sites in Zeolite Materials:17O High‐Resolution EPR Spectroscopy of Metal‐Loaded ZSM‐5

“…These values are in good agreement with the Mulliken spin population analysis (Supporting Information, Table S7). Exploiting the presence of sufficiently abundant magnetically active isotopes— 65 Zn (abundance 4.11 %), 111 Cd and 113 Cd (abundance 12.75 % and 12.26 %, respectively)—an experimentally derived spin density on the Zn and Cd atoms of the order of ρ Zn(total) =77 % and ρ Cd(total) =84 % is estimated, in reasonable agreement with the computed values (81–86 %, Table ) and the spin delocalization over the binding oxygens. It thus emerges that the metal–oxygen bond displays a non‐negligible covalent character with an approximately 10 % participation of the oxygens valence orbitals to the SOMO.…”

“…Zn + and Cd + metal ions, characterized by a n s 1 electron configuration, have recently emerged as promising catalytic active centers in the context of small‐molecule activation . Taking advantage of the simplicity of their electronic configuration, in this contribution, we use these chemical species as paramagnetic probes to unravel the nature of the chemical bond and the topology of metal binding sites in zeolites by monitoring the extent of the delocalization of their unpaired electron onto a 17 O‐enriched ZSM‐5 zeolite framework.…”

Von Sonnenlicht zu Brennstoffen: aktuelle Fortschritte der C1‐Solarchemie

“…Die katalytische Leistung von Siliciumdioxid konnte durch Einführen bestimmter Metallkationen, wie Al, Mg und Zr, mit geringer Konzentration erhçht werden. [189,190] Auch die direkte Umwandlung von CH 4 in nützliche Verbindungen fürd ie Synthese,w ie Olefine und Arene,g ewinnt zunehmend an Aufmerksamkeit. [186] Ga 2 O 3 ist sehr beständig gegen Photoreduktion, was zu einer ausgezeichneten Leistung für NOCM unter UV-Lichtanregung nahe Raumtemperatur führt.…”

“…[183][184][185] Hochdispergiertes Titanoxid und Ceroxid auf Siliciumdioxid zeigten ebenfalls eine hohe AktivitätfürNOCM. [186] [189,190] Auch die direkte Umwandlung von CH 4 in nützliche Verbindungen fürd ie Synthese,w ie Olefine und Arene,g ewinnt zunehmend an Aufmerksamkeit. Die Arbeitsgruppe von Li synthetisierte Si-dotierte GaN-Nanodraht-Halbleiter-Photokatalysatoren mit einer 97 %-m-Ebene,d ie unter UV-Lichtanregung bei Raumtemperatur Methan direkt in Benzol und Wasserstoff umwandeln kçnnen.…”

Zn+–O– Dual-Spin Surface State Formation by Modification of ZnO Nanoparticles with Diboron Compounds

“…Zn + (3d 10 4s 1 ) systems possess special electronic structure that has been reported and studied in ZnO relate chemistry. 13 Monovalent zinc ions have been prepared under extremely harsh physical conditions, such as -irradiation, 14 electron impact ionization, 15 glow discharge 16 and laser vaporization. 17 In 2004, the Carmona group reported a landmark discovery of the dimetallic sandwich compound decamethyldizincocene (Zn 2 (η5-C 5 Me 5 ) 2 ), containing a central subvalent Zn-Zn bond with both Zn atoms formally in the +1 oxidation state.…”