Efficient and Selective CO2 Reduction to Formate on Pd-Doped Pb3(CO3)2(OH)2: Dynamic Catalyst Reconstruction and Accelerated CO2 Protonation

Wenjing Huang; Yijin Wang; Jiawei Liu; Yu Wang; Daobin Liu; Jingfeng Dong; Ning Jia; Lan Yang; Chuntai Liu; Zheng Liu; Bin Liu; Qingyu Yan

doi:10.1002/smll.202107885

Efficient and Selective CO₂ Reduction to Formate on Pd-Doped Pb₃(CO₃)₂(OH)₂: Dynamic Catalyst Reconstruction and Accelerated CO₂ Protonation

Wenjing Huang, Yijin Wang, Jiawei Liu, Yu Wang, Daobin Liu, Jingfeng Dong, Ning Jia, Lan Yang, Chuntai Liu, Zheng Liu^*, Bin Liu^*, Qingyu Yan^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

32 Citations (Scopus)

Abstract

Exploring catalyst reconstruction under the electrochemical condition is critical to understanding the catalyst structure–activity relationship as well as to design effective electrocatalysts. Herein, a PbF₂ nanocluster is synthesized and its self-reconstruction under the CO₂ reduction condition is investigated. F⁻ leaching, CO₂-saturated environment, and application of a cathodic potential induce self-reconstruction of PbF₂ to Pb₃(CO₃)₂(OH)₂, which effectively catalyze the CO₂ reduction to formate. The in situ formed Pb₃(CO₃)₂(OH)₂ discloses >80% formate Faradaic efficiencies (FEs) across a broad range of potentials and achieves a maximum formate FE of ≈90.1% at −1.2 V versus reversible hydrogen electrode (RHE). Kinetic studies show that the CO₂ reduction reaction (CO₂RR) on the Pb₃(CO₃)₂(OH)₂ is rate-limited at the CO₂ protonation step, in which proton is supplied by bicarbonate (HCO₃⁻) in the electrolyte. To improve the CO₂RR kinetics, the Pb₃(CO₃)₂(OH)₂ is further doped with Pd (4 wt%) to enhance its HCO₃⁻ adsorption, which leads to accelerated protonation of CO₂. Therefore, the Pd-Pb₃(CO₃)₂(OH)₂ (4 wt%) reveals higher formate FEs of >90% from −0.8 to −1.2 V versus RHE and reaches a maximum formate FE of 96.5% at −1.2 V versus RHE with a current density of ≈13 mA cm⁻².

Original language	English
Article number	2107885
Journal	Small
Volume	18
Issue number	16
DOIs	https://doi.org/10.1002/smll.202107885
Publication status	Published - Apr 21 2022
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2022 Wiley-VCH GmbH.

ASJC Scopus Subject Areas

Biotechnology
General Chemistry
Biomaterials
General Materials Science
Engineering (miscellaneous)

Keywords

CO reduction reaction
formate
Pb (CO ) (OH)
rate-determining step
self-reconstruction

Access to Document

10.1002/smll.202107885

Cite this

@article{6cf76e2768d5444fb36ecaa08ecd55fe,

title = "Efficient and Selective CO2 Reduction to Formate on Pd-Doped Pb3(CO3)2(OH)2: Dynamic Catalyst Reconstruction and Accelerated CO2 Protonation",

abstract = "Exploring catalyst reconstruction under the electrochemical condition is critical to understanding the catalyst structure–activity relationship as well as to design effective electrocatalysts. Herein, a PbF2 nanocluster is synthesized and its self-reconstruction under the CO2 reduction condition is investigated. F− leaching, CO2-saturated environment, and application of a cathodic potential induce self-reconstruction of PbF2 to Pb3(CO3)2(OH)2, which effectively catalyze the CO2 reduction to formate. The in situ formed Pb3(CO3)2(OH)2 discloses >80% formate Faradaic efficiencies (FEs) across a broad range of potentials and achieves a maximum formate FE of ≈90.1% at −1.2 V versus reversible hydrogen electrode (RHE). Kinetic studies show that the CO2 reduction reaction (CO2RR) on the Pb3(CO3)2(OH)2 is rate-limited at the CO2 protonation step, in which proton is supplied by bicarbonate (HCO3−) in the electrolyte. To improve the CO2RR kinetics, the Pb3(CO3)2(OH)2 is further doped with Pd (4 wt%) to enhance its HCO3− adsorption, which leads to accelerated protonation of CO2. Therefore, the Pd-Pb3(CO3)2(OH)2 (4 wt%) reveals higher formate FEs of >90% from −0.8 to −1.2 V versus RHE and reaches a maximum formate FE of 96.5% at −1.2 V versus RHE with a current density of ≈13 mA cm−2.",

keywords = "CO reduction reaction, formate, Pb (CO ) (OH), rate-determining step, self-reconstruction",

author = "Wenjing Huang and Yijin Wang and Jiawei Liu and Yu Wang and Daobin Liu and Jingfeng Dong and Ning Jia and Lan Yang and Chuntai Liu and Zheng Liu and Bin Liu and Qingyu Yan",

note = "Publisher Copyright: {\textcopyright} 2022 Wiley-VCH GmbH.",

year = "2022",

month = apr,

day = "21",

doi = "10.1002/smll.202107885",

language = "English",

volume = "18",

journal = "Small",

issn = "1613-6810",

publisher = "Wiley-VCH Verlag",

number = "16",

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TY - JOUR

T1 - Efficient and Selective CO2 Reduction to Formate on Pd-Doped Pb3(CO3)2(OH)2

T2 - Dynamic Catalyst Reconstruction and Accelerated CO2 Protonation

AU - Huang, Wenjing

AU - Wang, Yijin

AU - Liu, Jiawei

AU - Wang, Yu

AU - Liu, Daobin

AU - Dong, Jingfeng

AU - Jia, Ning

AU - Yang, Lan

AU - Liu, Chuntai

AU - Liu, Zheng

AU - Liu, Bin

AU - Yan, Qingyu

PY - 2022/4/21

Y1 - 2022/4/21

N2 - Exploring catalyst reconstruction under the electrochemical condition is critical to understanding the catalyst structure–activity relationship as well as to design effective electrocatalysts. Herein, a PbF2 nanocluster is synthesized and its self-reconstruction under the CO2 reduction condition is investigated. F− leaching, CO2-saturated environment, and application of a cathodic potential induce self-reconstruction of PbF2 to Pb3(CO3)2(OH)2, which effectively catalyze the CO2 reduction to formate. The in situ formed Pb3(CO3)2(OH)2 discloses >80% formate Faradaic efficiencies (FEs) across a broad range of potentials and achieves a maximum formate FE of ≈90.1% at −1.2 V versus reversible hydrogen electrode (RHE). Kinetic studies show that the CO2 reduction reaction (CO2RR) on the Pb3(CO3)2(OH)2 is rate-limited at the CO2 protonation step, in which proton is supplied by bicarbonate (HCO3−) in the electrolyte. To improve the CO2RR kinetics, the Pb3(CO3)2(OH)2 is further doped with Pd (4 wt%) to enhance its HCO3− adsorption, which leads to accelerated protonation of CO2. Therefore, the Pd-Pb3(CO3)2(OH)2 (4 wt%) reveals higher formate FEs of >90% from −0.8 to −1.2 V versus RHE and reaches a maximum formate FE of 96.5% at −1.2 V versus RHE with a current density of ≈13 mA cm−2.

AB - Exploring catalyst reconstruction under the electrochemical condition is critical to understanding the catalyst structure–activity relationship as well as to design effective electrocatalysts. Herein, a PbF2 nanocluster is synthesized and its self-reconstruction under the CO2 reduction condition is investigated. F− leaching, CO2-saturated environment, and application of a cathodic potential induce self-reconstruction of PbF2 to Pb3(CO3)2(OH)2, which effectively catalyze the CO2 reduction to formate. The in situ formed Pb3(CO3)2(OH)2 discloses >80% formate Faradaic efficiencies (FEs) across a broad range of potentials and achieves a maximum formate FE of ≈90.1% at −1.2 V versus reversible hydrogen electrode (RHE). Kinetic studies show that the CO2 reduction reaction (CO2RR) on the Pb3(CO3)2(OH)2 is rate-limited at the CO2 protonation step, in which proton is supplied by bicarbonate (HCO3−) in the electrolyte. To improve the CO2RR kinetics, the Pb3(CO3)2(OH)2 is further doped with Pd (4 wt%) to enhance its HCO3− adsorption, which leads to accelerated protonation of CO2. Therefore, the Pd-Pb3(CO3)2(OH)2 (4 wt%) reveals higher formate FEs of >90% from −0.8 to −1.2 V versus RHE and reaches a maximum formate FE of 96.5% at −1.2 V versus RHE with a current density of ≈13 mA cm−2.

KW - CO reduction reaction

KW - formate

KW - Pb (CO ) (OH)

KW - rate-determining step

KW - self-reconstruction

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