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 af dette arbejde

Publikation: Bidrag til tidsskrift/Konferencebidrag i tidsskrift /Bidrag til avis › Tidsskriftartikel › Forskning › peer review

185 Citationer (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.

Originalsprog	Engelsk
Tidsskrift	Angewandte Chemie International Edition
Vol/bind	60
Nummer	42
Sider (fra-til)	22826-22832
Antal sider	7
ISSN	1433-7851
DOI	https://doi.org/10.1002/anie.202107550
Status	Udgivet - 11 okt. 2021

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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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T1 - Low-Valence Znδ+ (0<δ<2) Single-Atom Material as Highly Efficient Electrocatalyst for CO2 Reduction

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 - 2021/10/11

Y1 - 2021/10/11

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.

KW - CO2 reduction

KW - ELECTROREDUCTION

KW - METAL

KW - SITES

KW - coordination environment

KW - electrocatalysis at scale

KW - low valence

KW - zinc single atoms

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U2 - 10.1002/anie.202107550

DO - 10.1002/anie.202107550

M3 - Journal article

C2 - 34396665

SN - 1433-7851

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JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

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