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Steering CO₂ electroreduction pathway toward ethanol via surface-bounded hydroxyl species-induced noncovalent interaction.

ABSTRACT: Selective electroreduction of carbon dioxide (CO₂RR) into ethanol at an industrially relevant current density is highly desired. However, it is challenging because the competing ethylene production pathway is generally more thermodynamically favored. Herein, we achieve a selective and productive ethanol production over a porous CuO catalyst that presents a high ethanol Faradaic efficiency (FE) of 44.1 ± 1.0% and an ethanol-to-ethylene ratio of 1.2 at a large ethanol partial current density of 501.0 ± 15.0 mA cm^-2, in addition to an extraordinary FE of 90.6 ± 3.4% for multicarbon products. Intriguingly, we found a volcano-shaped relationship between ethanol selectivity and nanocavity size of porous CuO catalyst in the range of 0 to 20 nm. Mechanistic studies indicate that the increased coverage of surface-bounded hydroxyl species (*OH) associated with the nanocavity size-dependent confinement effect contributes to the remarkable ethanol selectivity, which preferentially favors the *CHCOH hydrogenation to *CHCHOH (ethanol pathway) via yielding the noncovalent interaction. Our findings provide insights in favoring the ethanol formation pathway, which paves the path toward rational design of ethanol-oriented catalysts.

SUBMITTER: Zhang J

PROVIDER: S-EPMC10089218 | biostudies-literature | 2023 Mar

REPOSITORIES: biostudies-literature

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Steering CO<sub>2</sub> electroreduction pathway toward ethanol via surface-bounded hydroxyl species-induced noncovalent interaction.

Zhang Jiawei J Zeng Gangming G Zhu Shangqian S Tao Haolan H Pan Yue Y Lai Wenchuan W Bao Jun J Lian Cheng C Su Dong D Shao Minhua M Huang Hongwen H

Proceedings of the National Academy of Sciences of the United States of America 20230306 11

Selective electroreduction of carbon dioxide (CO<sub>2</sub>RR) into ethanol at an industrially relevant current density is highly desired. However, it is challenging because the competing ethylene production pathway is generally more thermodynamically favored. Herein, we achieve a selective and productive ethanol production over a porous CuO catalyst that presents a high ethanol Faradaic efficiency (FE) of 44.1 ± 1.0% and an ethanol-to-ethylene ratio of 1.2 at a large ethanol partial current de ...[more]

PMID: 36877842

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Project description:Understanding how crystallographic orientation influences the electrocatalytic performance of metal catalysts can potentially advance the design of catalysts with improved efficiency. Although single crystal electrodes are typically used for such studies, the one-at-a-time preparation procedure limits the range of secondary crystallographic orientations that can be profiled. This work employs scanning electrochemical cell microscopy (SECCM) together with co-located electron backscatter diffraction (EBSD) as a screening technique to investigate how surface crystallographic orientations on polycrystalline copper (Cu) correlate to activity under CO2 electroreduction conditions. SECCM measures spatially resolved voltammetry on polycrystalline copper covering low overpotentials of CO2 conversion to intermediates, thereby screening the different activity from low-index facets where H2 evolution is dominant to high-index facets where more reaction intermediates are expected. This approach allows the acquisition of 2500 voltammograms on approximately 60 different Cu surface facets identified with EBSD. The results show that the order of activity is (111) < (100) < (110) among the Cu primary orientations. The collection of data over a wide range of secondary orientations leads to the construction of an "electrochemical-crystallographic stereographic triangle" that provides a broad comprehension of the trends among Cu secondary surface facets rarely studied in the literature, [particularly (941) and (741)], and clearly shows that the electroreduction activity scales with the step and kink density of these surfaces. This work also reveals that the electrochemical stripping of the passive layer that is naturally formed on Cu in air is strongly grain-dependent, and the relative ease of stripping on low-index facets follows the order of (100) > (111) > (110). This allows a procedure to be implemented, whereby the oxide is removed (to an electrochemically undetectable level) prior to the kinetic analyses of electroreduction activity. SECCM screening allows for the most active surfaces to be ranked and prompts in-depth follow-up studies.

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Steering CO₂ electroreduction pathway toward ethanol via surface-bounded hydroxyl species-induced noncovalent interaction.

Publications

Steering CO<sub>2</sub> electroreduction pathway toward ethanol via surface-bounded hydroxyl species-induced noncovalent interaction.

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Steering CO2 electroreduction pathway toward ethanol via surface-bounded hydroxyl species-induced noncovalent interaction.

Publications

Steering CO<sub>2</sub> electroreduction pathway toward ethanol via surface-bounded hydroxyl species-induced noncovalent interaction.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

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Steering CO₂ electroreduction pathway toward ethanol via surface-bounded hydroxyl species-induced noncovalent interaction.