Seyedeh Behnaz Varandili¹, Dragos Stoian¹, Jan Vavra¹, Kevin Rossi^1*, James R Pankhurst¹, Yannick Guntern¹, Nuria Lopez², Raffaella Buonsanti^1*

1 Laboratory of Nanochemistry for Energy (LNCE), Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne, CH-1950 Sion, Switzerland

2 Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, 43007 Tarragona, Spain

* Corresponding authors emails: kevin.rossi@epfl.ch, Raffaella.buonsanti@epfl.ch

DOI10.24435/materialscloud:3r-gn [version v1]

Publication date: Oct 22, 2021

How to cite this record

Seyedeh Behnaz Varandili, Dragos Stoian, Jan Vavra, Kevin Rossi, James R Pankhurst, Yannick Guntern, Nuria Lopez, Raffaella Buonsanti, Elucidating the structure-dependent selectivity towards methane and ethanol of CuZn in the CO2 electroreduction using tailored Cu/ZnO precatalysts, Materials Cloud Archive 2021.165 (2021), https://doi.org/10.24435/materialscloud:3r-gn

Description

Understanding the catalyst compositional and structural features that control selectivity is of uttermost importance to target desired products in chemical reactions. In this joint experimental–computational work, we leverage tailored Cu/ZnO precatalysts as a material platform to identify the intrinsic features of methane-producing and ethanol-producing CuZn catalysts in the electrochemical CO2 reduction reaction (CO2RR). Specifically, we find that Cu@ZnO nanocrystals, where a central Cu domain is decorated with ZnO domains, and ZnO@Cu nanocrystals, where a central ZnO domain is decorated with Cu domains, evolve into Cu@CuZn core@shell catalysts that are selective for methane (∼52%) and ethanol (∼39%), respectively. Operando X-ray absorption spectroscopy and various microscopy methods evidence that a higher degree of surface alloying along with a higher concentration of metallic Zn improve the ethanol selectivity. Density functional theory explains that the combination of electronic and tandem effects accounts for such selectivity. These findings mark a step ahead towards understanding structure–property relationships in bimetallic catalysts for the CO2RR and their rational tuning to increase selectivity towards target products, especially alcohols.

Materials Cloud sections using this data

Files

File name	Size	Description
pbe.inp MD5md5:0a05a6f37bbcd79a07e48839d50c2e53	1.9 KiB	cp2k.inp input file for the calculations
10001.xyz MD5md5:0ef032b777348f5631b6e5acc3369756	5.5 KiB	example position file
pbe-log.cp2k MD5md5:923ee9ba50687411c9861707932abf26	650.1 KiB	log file of the calculation
pbe-bader.inp MD5md5:0ea2d6aaa9de4ad049ba184519cd0bb7	2.0 KiB	cp2k.inp input file for the calculation with charge cube file output
README.txt MD5md5:50c9af2d04f1af080db329b6525eed15	248 Bytes	README

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External references

Keywords

CO2RR DFT CO2 Cu CuZn ERC H2020 EPFL SNSF