Dataset Information

Enhanced CH₃OH selectivity in CO₂ hydrogenation using Cu-based catalysts generated via SOMC from Ga^III single-sites.

ABSTRACT: Small and narrowly distributed nanoparticles of copper alloyed with gallium supported on silica containing residual Ga^III sites can be obtained via surface organometallic chemistry in a two-step process: (i) formation of isolated Ga^III surface sites on SiO₂ and (ii) subsequent grafting of a Cu^I precursor, [Cu(O ^t Bu)]₄, followed by a treatment under H₂ to generate CuGa _x alloys. This material is highly active and selective for CO₂ hydrogenation to CH₃OH. In situ X-ray absorption spectroscopy shows that gallium is oxidized under reaction conditions while copper remains as Cu⁰. This CuGa material only stabilizes methoxy surface species while no formate is detected according to ex situ infrared and solid-state nuclear magnetic resonance spectroscopy.

SUBMITTER: Lam E

PROVIDER: S-EPMC8159433 | biostudies-literature | 2020 Feb

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Enhanced CH3OH selectivity in CO2 hydrogenation using Cu-based catalysts generated via SOMC from GaIII single-sites.

Lam Erwin E Noh Gina G Chan Ka Wing KW Larmier Kim K Lebedev Dmitry D Searles Keith K Wolf Patrick P Safonova Olga V OV Copéret Christophe C

Chemical science 20200226 29

Small and narrowly distributed nanoparticles of copper alloyed with gallium supported on silica containing residual GaIII sites can be obtained via surface organometallic chemistry in a two-step process: (i) formation of isolated GaIII surface sites on SiO2 and (ii) subsequent grafting of a CuI precursor, [Cu(O t Bu)]4, followed by a treatment under H2 to generate CuGa x alloys. This mate ...[more]

PMID: 34094136

Similar Datasets

Project description:To address the challenge of selectivity toward single products in Cu-catalyzed electrochemical CO2 reduction, one strategy is to incorporate a second metal with the goal of tuning catalytic activity via synergy effects. In particular, catalysts based on Cu modified with post-transition metals (Sn or In) are known to reduce CO2 selectively to either CO or HCOO- depending on their composition. However, it remains unclear exactly which factors induce this switch in reaction pathways and whether these two related bimetal combinations follow similar general structure-activity trends. To investigate these questions systematically, Cu-In and Cu-Sn bimetallic catalysts were synthesized across a range of composition ratios and studied in detail. Compositional and morphological control was achieved via a simple electrochemical synthesis approach. A combination of operando and quasi-in situ spectroscopic techniques, including X-ray photoelectron, X-ray absorption, and Raman spectroscopy, was used to observe the dynamic behaviors of the catalysts' surface structure, composition, speciation, and local environment during CO2 electrolysis. The two systems exhibited similar selectivity dependency on their surface composition. Cu-rich catalysts produce mainly CO, while Cu-poor catalysts were found to mainly produce HCOO-. Despite these similarities, the speciation of Sn and In at the surface differed from each other and was found to be strongly dependent on the applied potential and the catalyst composition. For Cu-rich compositions optimized for CO production (Cu85In15 and Cu85Sn15), indium was present predominantly in the reduced metallic form (In0), whereas tin mainly existed as an oxidized species (Sn2/4+). Meanwhile, for the HCOO--selective compositions (Cu25In75 and Cu40Sn60), the indium exclusively exhibited In0 regardless of the applied potential, while the tin was reduced to metallic (Sn0) only at the most negative applied potential, which corresponds to the best HCOO- selectivity. Furthermore, while Cu40Sn60 enhances HCOO- selectivity by inhibiting H2 evolution, Cu25In75 improves the HCOO- selectivity at the expense of CO production. Due to these differences, we contend that identical mechanisms cannot be used to explain the behavior of these two bimetallic systems (Cu-In and Cu-Sn). Operando surface-enhanced Raman spectroscopy measurements provide direct evidence of the local alkalization and its impact on the dynamic transformation of oxidized Cu surface species (Cu2O/CuO) into a mixture of Cu(OH)2 and basic Cu carbonates [Cux(OH)y(CO3)y] rather than metallic Cu under CO2 electrolysis. This study provides unique insights into the origin of the switch in selectivity between CO and HCOO- pathways at Cu bimetallic catalysts and the nature of surface-active sites and key intermediates for both pathways.

Dataset Information

Enhanced CH₃OH selectivity in CO₂ hydrogenation using Cu-based catalysts generated via SOMC from Ga^III single-sites.

Publications

Enhanced CH<sub>3</sub>OH selectivity in CO<sub>2</sub> hydrogenation using Cu-based catalysts generated <i>via</i> SOMC from Ga<sup>III</sup> single-sites.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets