Dataset Information

Operando NRIXS and XAFS Investigation of Segregation Phenomena in Fe-Cu and Fe-Ag Nanoparticle Catalysts during CO₂ Electroreduction.

ABSTRACT: Operando nuclear resonant inelastic X-ray scattering (NRIXS) and X-ray absorption fine-structure spectroscopy (XAFS) measurements were used to gain insight into the structure and surface composition of FeCu and FeAg nanoparticles (NPs) during the electrochemical CO₂ reduction (CO₂ RR) and to extract correlations with their catalytic activity and selectivity. The formation of a core-shell structure during CO₂ RR for FeAg NPs was inferred from the analysis of the operando NRIXS data (phonon density of states, PDOS) and XAFS measurements. Electrochemical analysis of the FeAg NPs revealed a faradaic selectivity of 36?% for CO in 0.1?M KHCO₃ at -1.1?V vs. RHE, similar to that of pure Ag NPs. In contrast, a predominant selectivity towards H₂ evolution is obtained in the case of the FeCu NPs, analogous to the results obtained for pure Fe NPs, although small Cu NPs have also been shown to favor H₂ production.

SUBMITTER: Kunze S

PROVIDER: S-EPMC7756314 | biostudies-literature | 2020 Dec

REPOSITORIES: biostudies-literature

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Operando NRIXS and XAFS Investigation of Segregation Phenomena in Fe-Cu and Fe-Ag Nanoparticle Catalysts during CO2 Electroreduction.

Kunze Sebastian S Grosse Philipp P Bernal Lopez Miguel M Sinev Ilya I Zegkinoglou Ioannis I Mistry Hemma H Timoshenko Janis J Hu Michael Y MY Zhao Jiyong J Alp Ercan E EE Chee See Wee SW Roldan Cuenya Beatriz B

Angewandte Chemie (International ed. in English) 20201006 50

Operando nuclear resonant inelastic X-ray scattering (NRIXS) and X-ray absorption fine-structure spectroscopy (XAFS) measurements were used to gain insight into the structure and surface composition of FeCu and FeAg nanoparticles (NPs) during the electrochemical CO2 reduction (CO2 RR) and to extract correlations with their catalytic activity and selectivity. The formation of a core-shell structure during CO2 RR for FeAg NPs was inferred from the analysis of the o ...[more]

PMID: 32833290

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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.

Dataset Information

Operando NRIXS and XAFS Investigation of Segregation Phenomena in Fe-Cu and Fe-Ag Nanoparticle Catalysts during CO₂ Electroreduction.

Publications

Operando NRIXS and XAFS Investigation of Segregation Phenomena in Fe-Cu and Fe-Ag Nanoparticle Catalysts during CO<sub>2</sub> Electroreduction.

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