Low-Valence Znδ+ (0<δ<2) Single-Atom Material as Highly Efficient Electrocatalyst for CO2 Reduction

Simin Li; Siqi Zhao; Xiuyuan Lu; Marcel Ceccato; Xin-Ming Hu; Alberto Roldan; Jacopo Catalano; Min Liu; Troels Skrydstrup; Kim Daasbjerg

doi:10.1002/anie.202107550

Low-Valence Zn^δ+ (0<δ<2) Single-Atom Material as Highly Efficient Electrocatalyst for CO₂ Reduction

Simin Li, Siqi Zhao, Xiuyuan Lu, Marcel Ceccato, Xin-Ming Hu^*, Alberto Roldan, Jacopo Catalano, Min Liu^*, Troels Skrydstrup, Kim Daasbjerg^*

^*Corresponding author for this work

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

130 Citations (Scopus)

Abstract

A nitrogen-stabilized single-atom catalyst containing low-valence zinc atoms (Zn^δ+-NC) is reported. It contains saturated four-coordinate (Zn-N₄) and unsaturated three-coordinate (Zn-N₃) sites. The latter makes Zn a low-valence state, as deduced from X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, electron paramagnetic resonance, and density functional theory. Zn^δ+-NC catalyzes electrochemical reduction of CO₂ to CO with near-unity selectivity in water at an overpotential as low as 310 mV. A current density up to 1 A cm⁻² can be achieved together with high CO selectivity of >95 % using Zn^δ+-NC in a flow cell. Calculations suggest that the unsaturated Zn-N₃ could dramatically reduce the energy barrier by stabilizing the COOH* intermediate owing to the electron-rich environment of Zn. This work sheds light on the relationship among coordination number, valence state, and catalytic performance and achieves high current densities relevant for industrial applications.

Original language	English
Journal	Angewandte Chemie International Edition
Volume	60
Issue	42
Pages (from-to)	22826-22832
Number of pages	7
ISSN	1433-7851
DOIs	https://doi.org/10.1002/anie.202107550
Publication status	Published - Oct 2021

Keywords

CO2 reduction
ELECTROREDUCTION
METAL
SITES
coordination environment
electrocatalysis at scale
low valence
zinc single atoms

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title = "Low-Valence Znδ+ (0<δ<2) Single-Atom Material as Highly Efficient Electrocatalyst for CO2 Reduction",

abstract = "A nitrogen-stabilized single-atom catalyst containing low-valence zinc atoms (Znδ+-NC) is reported. It contains saturated four-coordinate (Zn-N4) and unsaturated three-coordinate (Zn-N3) sites. The latter makes Zn a low-valence state, as deduced from X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, electron paramagnetic resonance, and density functional theory. Znδ+-NC catalyzes electrochemical reduction of CO2 to CO with near-unity selectivity in water at an overpotential as low as 310 mV. A current density up to 1 A cm−2 can be achieved together with high CO selectivity of >95 % using Znδ+-NC in a flow cell. Calculations suggest that the unsaturated Zn-N3 could dramatically reduce the energy barrier by stabilizing the COOH* intermediate owing to the electron-rich environment of Zn. This work sheds light on the relationship among coordination number, valence state, and catalytic performance and achieves high current densities relevant for industrial applications.",

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author = "Simin Li and Siqi Zhao and Xiuyuan Lu and Marcel Ceccato and Xin-Ming Hu and Alberto Roldan and Jacopo Catalano and Min Liu and Troels Skrydstrup and Kim Daasbjerg",

year = "2021",

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pages = "22826--22832",

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Low-Valence Zn^δ+ (0<δ<2) Single-Atom Material as Highly Efficient Electrocatalyst for CO₂ Reduction. / Li, Simin; Zhao, Siqi; Lu, Xiuyuan et al.
In: Angewandte Chemie International Edition, Vol. 60, No. 42, 10.2021, p. 22826-22832.

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

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AU - Li, Simin

AU - Zhao, Siqi

AU - Lu, Xiuyuan

AU - Ceccato, Marcel

AU - Hu, Xin-Ming

AU - Roldan, Alberto

AU - Catalano, Jacopo

AU - Liu, Min

AU - Skrydstrup, Troels

AU - Daasbjerg, Kim

PY - 2021/10

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N2 - A nitrogen-stabilized single-atom catalyst containing low-valence zinc atoms (Znδ+-NC) is reported. It contains saturated four-coordinate (Zn-N4) and unsaturated three-coordinate (Zn-N3) sites. The latter makes Zn a low-valence state, as deduced from X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, electron paramagnetic resonance, and density functional theory. Znδ+-NC catalyzes electrochemical reduction of CO2 to CO with near-unity selectivity in water at an overpotential as low as 310 mV. A current density up to 1 A cm−2 can be achieved together with high CO selectivity of >95 % using Znδ+-NC in a flow cell. Calculations suggest that the unsaturated Zn-N3 could dramatically reduce the energy barrier by stabilizing the COOH* intermediate owing to the electron-rich environment of Zn. This work sheds light on the relationship among coordination number, valence state, and catalytic performance and achieves high current densities relevant for industrial applications.

AB - A nitrogen-stabilized single-atom catalyst containing low-valence zinc atoms (Znδ+-NC) is reported. It contains saturated four-coordinate (Zn-N4) and unsaturated three-coordinate (Zn-N3) sites. The latter makes Zn a low-valence state, as deduced from X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, electron paramagnetic resonance, and density functional theory. Znδ+-NC catalyzes electrochemical reduction of CO2 to CO with near-unity selectivity in water at an overpotential as low as 310 mV. A current density up to 1 A cm−2 can be achieved together with high CO selectivity of >95 % using Znδ+-NC in a flow cell. Calculations suggest that the unsaturated Zn-N3 could dramatically reduce the energy barrier by stabilizing the COOH* intermediate owing to the electron-rich environment of Zn. This work sheds light on the relationship among coordination number, valence state, and catalytic performance and achieves high current densities relevant for industrial applications.

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Low-Valence Zn^δ+ (0<δ<2) Single-Atom Material as Highly Efficient Electrocatalyst for CO₂ Reduction

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