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IR spectroscopic characterization of the co-adsorption of CO₂ and H₂ onto cationic Cu_n⁺ clusters.

ABSTRACT: To understand elementary reaction steps in the hydrogenation of CO₂ over copper-based catalysts, we experimentally study the adsorption of CO₂ and H₂ onto cationic Cu_n⁺ clusters. For this, we react Cu_n⁺ clusters formed by laser ablation with a mixture of H₂ and CO₂ in a flow tube-type reaction channel and characterize the products formed by IR multiple-photon dissociation spectroscopy employing the IR free-electron laser FELICE. We analyze the spectra by comparing them to literature spectra of Cu_n⁺ clusters reacted with H₂ and with new spectra of Cu_n⁺ clusters reacted with CO₂. The latter indicate that CO₂ is physisorbed in an end-on configuration when reacted with the clusters alone. Although the spectra for the co-adsorption products evidence H₂ dissociation, no signs for CO₂ activation or reduction are observed. This lack of reactivity for CO₂ is rationalized by density functional theory calculations, which indicate that CO₂ dissociation is hindered by a large reaction barrier. CO₂ reduction to formate should energetically be possible, but the lack of formate observation is attributed to kinetic hindering.

SUBMITTER: Lushchikova OV

PROVIDER: S-EPMC8653698 | biostudies-literature |

REPOSITORIES: biostudies-literature

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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.

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IR spectroscopic characterization of the co-adsorption of CO₂ and H₂ onto cationic Cu_n⁺ clusters.

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IR spectroscopic characterization of the co-adsorption of CO2 and H2 onto cationic Cun+ clusters.

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IR spectroscopic characterization of the co-adsorption of CO₂ and H₂ onto cationic Cu_n⁺ clusters.