Direct Cation Stabilization Effects of CO Dimerization for Boosting C2 Pathways of CO2 Reduction on Noble Metal Surfaces

Hon Ho Wong; Mingzi Sun; Tong Wu; Lu Lu; Qiuyang Lu; Baian Chen; Cheuk Hei Chan; Bolong Huang

doi:10.1002/aesr.202400110

Direct Cation Stabilization Effects of CO Dimerization for Boosting C₂ Pathways of CO₂ Reduction on Noble Metal Surfaces

Hon Ho Wong
, Mingzi Sun
, Tong Wu
, Lu Lu
, Qiuyang Lu
, Baian Chen
, Cheuk Hei Chan
, Bolong Huang^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

3 Citations (Scopus)

11 Downloads (CityUHK Scholars)

Abstract

The carbon dioxide reduction reaction (CO₂RR) is one of the most promising solutions for realizing carbon neutralization via converting the emitted CO₂ into value-added chemicals. The CC coupling step for CO dimerization is the rate-determining step for C₂ pathways, which have not been thoroughly investigated. Herein, the direct cation stabilization effects on CO dimerization for *OCCO formation on the representative Cu(100) and Pt(100) surfaces are investigated. Density functional theory calculations show that the presence of alkali metal ions plays a vital role in promoting the coupling of *CO monomers on both metal surfaces, where Cu shows a stronger stabilization effect. More importantly, a strong linear correlation (R² ≈ 0.9) between the dimer stabilization energy and the reaction energy is revealed for the first time, which is a promising indicator for the selectivity of C₂ pathways. Further investigations on electronic structures reveal that the promoting effect on *OCCO formation is strongly related to the negative charges of the molecules, in which the negative charge accumulation is favored by the directional electron transfer due to the chemisorption of *OCCO on Cu(100) surface. This work offers insights into the understanding of CC coupling reactions for CO₂RR mechanisms. © 2024 The Authors. Advanced Energy and Sustainability Research published by Wiley-VCH GmbH.

Original language	English
Article number	2400110
Journal	Advanced Energy and Sustainability Research
Volume	5
Issue number	8
Online published	12 May 2024
DOIs	https://doi.org/10.1002/aesr.202400110
Publication status	Published - Aug 2024
Externally published	Yes

Funding

The authors gratefully acknowledge the support from the National Key R&D Program of China (grant no. 2021YFA1501101), Research Grant Council of Hong Kong (grant no. 15304023), National Natural Science Foundation of China/Research Grant Council of Hong Kong Joint Research Scheme (grant no. N_PolyU502/21), National Natural Science Foundation of China/Research Grants Council of Hong Kong Collaborative Research Scheme (grant no. CRS_PolyU504/22), the funding for Projects of Strategic Importance of The Hong Kong Polytechnic University (Project Code: 1-ZE2V), Shenzhen Fundamental Research Scheme-General Program (grant no. JCYJ20220531090807017), Natural Science Foundation of Guangdong Province (grant no. 2023A1515012219), and Departmental General Research Fund (Project Code: ZVUL) from The Hong Kong Polytechnic University. The authors also thank the support from Research Centre for Carbon-Strategic Catalysis (RC-CSC), Research Institute for Smart Energy (RISE), and Research Institute for Intelligent Wearable Systems (RI-IWEAR) of the Hong Kong Polytechnic University.

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 13 Climate Action

Research Keywords

alkali metal cations
cation effect
CO dimerization
CO2 reduction reaction
stabilization effects

Publisher's Copyright Statement

This full text is made available under CC-BY 4.0. https://creativecommons.org/licenses/by/4.0/

RGC Funding Information

RGC-funded

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Cite this

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title = "Direct Cation Stabilization Effects of CO Dimerization for Boosting C2 Pathways of CO2 Reduction on Noble Metal Surfaces",

abstract = "The carbon dioxide reduction reaction (CO2RR) is one of the most promising solutions for realizing carbon neutralization via converting the emitted CO2 into value-added chemicals. The CC coupling step for CO dimerization is the rate-determining step for C2 pathways, which have not been thoroughly investigated. Herein, the direct cation stabilization effects on CO dimerization for *OCCO formation on the representative Cu(100) and Pt(100) surfaces are investigated. Density functional theory calculations show that the presence of alkali metal ions plays a vital role in promoting the coupling of *CO monomers on both metal surfaces, where Cu shows a stronger stabilization effect. More importantly, a strong linear correlation (R2 ≈ 0.9) between the dimer stabilization energy and the reaction energy is revealed for the first time, which is a promising indicator for the selectivity of C2 pathways. Further investigations on electronic structures reveal that the promoting effect on *OCCO formation is strongly related to the negative charges of the molecules, in which the negative charge accumulation is favored by the directional electron transfer due to the chemisorption of *OCCO on Cu(100) surface. This work offers insights into the understanding of CC coupling reactions for CO2RR mechanisms. {\textcopyright} 2024 The Authors. Advanced Energy and Sustainability Research published by Wiley-VCH GmbH.",

keywords = "alkali metal cations, cation effect, CO dimerization, CO2 reduction reaction, stabilization effects",

author = "Wong, \{Hon Ho\} and Mingzi Sun and Tong Wu and Lu Lu and Qiuyang Lu and Baian Chen and \{Hei Chan\}, Cheuk and Bolong Huang",

year = "2024",

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T1 - Direct Cation Stabilization Effects of CO Dimerization for Boosting C2 Pathways of CO2 Reduction on Noble Metal Surfaces

AU - Wong, Hon Ho

AU - Sun, Mingzi

AU - Wu, Tong

AU - Lu, Lu

AU - Lu, Qiuyang

AU - Chen, Baian

AU - Hei Chan, Cheuk

AU - Huang, Bolong

PY - 2024/8

Y1 - 2024/8

N2 - The carbon dioxide reduction reaction (CO2RR) is one of the most promising solutions for realizing carbon neutralization via converting the emitted CO2 into value-added chemicals. The CC coupling step for CO dimerization is the rate-determining step for C2 pathways, which have not been thoroughly investigated. Herein, the direct cation stabilization effects on CO dimerization for *OCCO formation on the representative Cu(100) and Pt(100) surfaces are investigated. Density functional theory calculations show that the presence of alkali metal ions plays a vital role in promoting the coupling of *CO monomers on both metal surfaces, where Cu shows a stronger stabilization effect. More importantly, a strong linear correlation (R2 ≈ 0.9) between the dimer stabilization energy and the reaction energy is revealed for the first time, which is a promising indicator for the selectivity of C2 pathways. Further investigations on electronic structures reveal that the promoting effect on *OCCO formation is strongly related to the negative charges of the molecules, in which the negative charge accumulation is favored by the directional electron transfer due to the chemisorption of *OCCO on Cu(100) surface. This work offers insights into the understanding of CC coupling reactions for CO2RR mechanisms. © 2024 The Authors. Advanced Energy and Sustainability Research published by Wiley-VCH GmbH.

AB - The carbon dioxide reduction reaction (CO2RR) is one of the most promising solutions for realizing carbon neutralization via converting the emitted CO2 into value-added chemicals. The CC coupling step for CO dimerization is the rate-determining step for C2 pathways, which have not been thoroughly investigated. Herein, the direct cation stabilization effects on CO dimerization for *OCCO formation on the representative Cu(100) and Pt(100) surfaces are investigated. Density functional theory calculations show that the presence of alkali metal ions plays a vital role in promoting the coupling of *CO monomers on both metal surfaces, where Cu shows a stronger stabilization effect. More importantly, a strong linear correlation (R2 ≈ 0.9) between the dimer stabilization energy and the reaction energy is revealed for the first time, which is a promising indicator for the selectivity of C2 pathways. Further investigations on electronic structures reveal that the promoting effect on *OCCO formation is strongly related to the negative charges of the molecules, in which the negative charge accumulation is favored by the directional electron transfer due to the chemisorption of *OCCO on Cu(100) surface. This work offers insights into the understanding of CC coupling reactions for CO2RR mechanisms. © 2024 The Authors. Advanced Energy and Sustainability Research published by Wiley-VCH GmbH.

KW - alkali metal cations

KW - cation effect

KW - CO dimerization

KW - CO2 reduction reaction

KW - stabilization effects

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U2 - 10.1002/aesr.202400110

DO - 10.1002/aesr.202400110

M3 - RGC 21 - Publication in refereed journal

SN - 2699-9412

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JO - Advanced Energy and Sustainability Research

JF - Advanced Energy and Sustainability Research

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