Dataset Information

Cu-Sn Aerogels for Electrochemical CO₂ Reduction with High CO Selectivity.

ABSTRACT: This work reports the synthesis of Cu_xSn_y alloy aerogels for electrochemical CO₂ reduction catalysts. An in situ reduction and the subsequent freeze-drying process can successfully give CnxSny aerogels with tuneable Sn contents, and such aerogels are composed of three-dimensional architectures made from inter-connected fine nanoparticles with pores as the channels. Density functional theory (DFT) calculations show that the introduction of Sn in Cu aerogels inhibits H₂ evolution reaction (HER) activity, while the accelerated CO desorption on the catalyst surface is found at the same time. The porous structure of aerogel also favors exposing more active sites. Counting these together, with the optimized composition of Cu₉₅Sn₅ aerogel, the high selectivity of CO can be achieved with a faradaic efficiency of over 90% in a wide potential range (-0.7 V to -1.0 V vs. RHE).

SUBMITTER: Pan Y

PROVIDER: S-EPMC9919718 | biostudies-literature | 2023 Jan

REPOSITORIES: biostudies-literature

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Cu-Sn Aerogels for Electrochemical CO2 Reduction with High CO Selectivity.

Pan Yexin Y Wu Muchen M Ye Ziran Z Tang Haibin H Hong Zhanglian Z Zhi Mingjia M

Molecules (Basel, Switzerland) 20230119 3

This work reports the synthesis of CuxSny alloy aerogels for electrochemical CO2 reduction catalysts. An in situ reduction and the subsequent freeze-drying process can successfully give CnxSny aerogels with tuneable Sn contents, and such aerogels are composed of three-dimensional architectures made from inter-connected fine nanoparticles with pores as the channels. Density functional theory (DFT) calculations show that the introduction of Sn in Cu aerogels inhibi ...[more]

PMID: 36770699

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Project description:The electrochemical CO2 reduction reaction (CO2RR) holds enormous potential as a carbon-neutral route to the sustainable production of fuels and platform chemicals. The durability for long-term operation is currently inadequate for commercialization, however, and the underlying deactivation process remains elusive. A fundamental understanding of the degradation mechanism of electrocatalysts, which can dictate the overall device performance, is needed. In this work, we report the structural dynamics and degradation pathway of Cu oxide nanoparticles (CuOx NPs) during the CO2RR by using in situ small-angle X-ray scattering (SAXS) and X-ray absorption spectroscopy (XAS). The in situ SAXS reveals a reduction in the size of NPs when subjected to a potential at which no reaction products are detected. At potentials where the CO2RR starts to occur, CuOx NPs are agglomerated through a particle migration and coalescence process in the early stage of the reaction, followed by Ostwald ripening (OR) as the dominant degradation mechanism for the remainder of the reaction. As the applied potential becomes more negative, the OR process becomes more dominant, and for the most negative applied potential, OR dominates for the entire reaction time. The morphological changes are linked to a gradual decrease in the formation rate for multicarbon products (C2H4 and ethanol). Other reaction parameters, including reaction intermediates and local high pH, induce changes in the agglomeration process and final morphology of the CuOx NPs electrode, supported by post-mortem ex situ microscopic analysis. The in situ XAS analysis suggests that the CuOx NPs reduced into the metallic state before the structural transformation was observed. The introduction of high surface area carbon supports with ionomer coating mitigates the degree of structural transformation and detachment of the CuOx NPs electrode. These findings show the dynamic nature of Cu nanocatalysts during the CO2RR and can serve as a rational guideline toward a stable catalyst system under electrochemical conditions.

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

Cu-Sn Aerogels for Electrochemical CO₂ Reduction with High CO Selectivity.

Publications

Cu-Sn Aerogels for Electrochemical CO<sub>2</sub> Reduction with High CO Selectivity.

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