Single-atom Sn-Zn pairs in CuO catalyst promote dimethyldichlorosilane synthesis

Abstract

Single-atom catalysts are of great interest because they can maximize the atom-utilization efficiency and generate unique catalytic properties; however, much attention has been paid to single-site active components, rarely to catalyst promoters. Promoters can significantly affect the activity and selectivity of a catalyst, even at their low concentrations in catalysts. In this work, we designed and synthesized CuO catalysts with atomically dispersed co-promoters of Sn and Zn. When used as the catalyst in the Rochow reaction for the synthesis of dimethyldichlorosilane, this catalyst exhibited much-enhanced activity, selectivity and stability compared with the conventional CuO catalysts with promoters in the form of nanoparticles. Density functional theory calculations demonstrate that single-atomic Sn substitution in the CuO surface can enrich surface Cu vacancies and promote dispersion of Zn to its atomic levels. Sn and Zn single sites as the co-promoters cooperatively generate electronic interaction with the CuO support, which further facilitates the adsorption of the reactant molecules on the surface, thereby leading to the superior catalytic performance.

Surface Coordination Chemistry of Atomically Dispersed Metal Catalysts

“…For instance, metal cations on oxide supports can work synergistically with the dispersed catalytic metal centers to promote catalysis, suggesting the positive impact of having more than single metal atoms in catalysis. Apart from the randomly distributed isolated atoms, the presence of paired catalytic atoms, or several atoms close to each other but without metal–metal bonding, was also occasionally observed in ADCs . Grafting pre-established organometallics with paired metal centers is one of the effective strategies to create ADCs with paired metals (Figure a). − However, this method requires the precise synthesis of dinuclear precursors and careful control over the deposition surface and conditions.…”

Isolating Single and Few Atoms for Enhanced Catalysis

“…However, it remains a significant challenge to synthesize dual atoms due to the aggregation tendency of metal atoms during the preparation process. Recently, some researchers turn attention to the development of synthesis strategies for DACs, including wet chemical adsorption, [ 74–76 ] photochemical reduction, [ 77 ] self‐assembly, [ 77,78 ] pyrolysis process, [ 78–81 ] ALD, [ 31,61,71,82 ] heteroatom modulator, [ 83 ] etc. In this section, some commonly used synthesis methods for DACs involving oxides, graphene, nitrogen‐doped carbon materials, and MOFs stabilized dual atoms are introduced.…”

“…Su and co‐workers designed and synthesized the atomically dispersed Sn and Zn on CuO by using the impregnated method, aiming to investigate the role of promoters. [ 76 ] Specifically, Sn 1 /CuO was added in 100 mL of ethanol to obtain a suspension. Then, the water solution of ZnCl 2 was slowly added into Sn 1 /CuO suspension with stirring for 150 min.…”

X-ray Diffraction Phase Analysis of Changes in the Lattice of Pervouralsk Quartzite upon Heating

“…The authors in articles [22][23][24][25] carried out studies for materials based on Si. Thus, In [22] reported a general bottom-up synthesis of CuO-based trimetallic oxide mesocrystals using a simple precipitation method followed by a hydrothermal treatment and a topotactic transformation via calcination.…”

“…Thus, In [22] reported a general bottom-up synthesis of CuO-based trimetallic oxide mesocrystals using a simple precipitation method followed by a hydrothermal treatment and a topotactic transformation via calcination. In [23], CuO catalysts with atomically dispersed co-promoters of Sn and Zn were designed and synthesized. Paper [24] demonstrates a practical route for designing sophisticated architectural structures that combine several structural functions within one catalyst system and their catalysis applications.…”