Comparative Spectroscopic Study Revealing Why the CO2 Electroreduction Selectivity Switches from CO to HCOO– at Cu–Sn- and Cu–In-Based Catalysts

El-Nagar, Gumaa A. and Yang, Fan and Stojkovikj, Sasho and Mebs, Stefan and Gupta, Siddharth and Ahmet, Ibbi Y. and Dau, Holger and Mayer, Matthew T. (2022) Comparative Spectroscopic Study Revealing Why the CO2 Electroreduction Selectivity Switches from CO to HCOO– at Cu–Sn- and Cu–In-Based Catalysts. ACS Catalysis, 12 (24). pp. 15576-15589. ISSN 2155-5435

Text el-nagar-et-al-2022-comparative-spectroscopic-study-revealing-why-the-co2-electroreduction-selectivity-switches-from-co.pdf - Published Version Download (980kB)

Abstract

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.

KEYWORDS: CO2 electroreduction, Cu nanostructures, in situ spectroscopy, bimetallic catalysts, electrodeposition

Item Type:	Article
Impact Factor Value:	12.9
Subjects:	Engineering and Technology > Chemical engineering Natural sciences > Chemical sciences Natural sciences > Earth and related environmental sciences Engineering and Technology > Environmental engineering Engineering and Technology > Materials engineering Natural sciences > Other natural sciences
Divisions:	Faculty of Technology
Depositing User:	Saso Stojkovik
Date Deposited:	27 Feb 2024 11:53
Last Modified:	27 Feb 2024 11:53
URI:	https://eprints.ugd.edu.mk/id/eprint/33769

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