Copper/alkaline earth metal oxide interfaces for electrochemical CO2-to-alcohol conversion by selective hydrogenation

Aoni Xu; Sung Fu Hung; Ang Cao; Zhenbin Wang; Naiwrit Karmodak; Jianan Erick Huang; Yu Yan; Armin Sedighian Rasouli; Adnan Ozden; Feng Yi Wu; Zih Yi Lin; Hsin Jung Tsai; Tsung Ju Lee; Fengwang Li; Mingchuan Luo; Yuhang Wang; Xue Wang; Jehad Abed; Ziyun Wang; Dae Hyun Nam; Yuguang C. Li; Alexander H. Ip; David Sinton; Chaofang Dong; Edward H. Sargent

doi:10.1038/s41929-022-00880-6

Copper/alkaline earth metal oxide interfaces for electrochemical CO₂-to-alcohol conversion by selective hydrogenation

Aoni Xu, Sung Fu Hung, Ang Cao, Zhenbin Wang, Naiwrit Karmodak, Jianan Erick Huang, Yu Yan, Armin Sedighian Rasouli, Adnan Ozden, Feng Yi Wu, Zih Yi Lin, Hsin Jung Tsai, Tsung Ju Lee, Fengwang Li, Mingchuan Luo, Yuhang Wang, Xue Wang, Jehad Abed, Ziyun Wang, Dae Hyun NamYuguang C. Li, Alexander H. Ip, David Sinton, Chaofang Dong^*, Edward H. Sargent^*

^*此作品的通信作者

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研究成果: Article › 同行評審

20 引文斯高帕斯（Scopus）

摘要

Multicarbon alcohols produced by electrochemical CO₂ reduction (CO₂RR) are attractive alternatives to fossil fuels; however, the selectivity towards alcohols in CO₂RR remains low, a result of competing hydrocarbon (that is, ethylene) production. Here we report on Cu catalysts decorated with different alkaline earth metal oxides (MOs). We found that BaO delivers a Faradaic efficiency of 61% towards C₂₊ alcohols. At an industry-relevant current density of 400 mA cm⁻², the ratio of alcohols to hydrocarbon reached 3:1. Mechanistic studies, including in operando X-ray absorption spectroscopy, in situ Raman spectroscopy and density functional theory calculations, suggested that the increased selectivity towards alcohols originates from sites at the MO/Cu interface. Furthermore, computational studies indicated that the incorporation of MOs favours a hydroxy-containing C₂ intermediate (*HCCHOH) over the hydrocarbon intermediate (*HCC) at interfacial Cu sites on the path to alcohol products. We also propose that the relative bond strengths of Cu–COH and C–OH correlate with the selectivity for alcohol over hydrocarbon. [Figure not available: see fulltext.]

原文	English
頁（從 - 到）	1081-1088
頁數	8
期刊	Nature Catalysis
卷	5
發行號	12
DOIs	https://doi.org/10.1038/s41929-022-00880-6
出版狀態	Published - 12月 2022

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10.1038/s41929-022-00880-6

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Xu, A., Hung, S. F., Cao, A., Wang, Z., Karmodak, N., Huang, J. E., Yan, Y., Sedighian Rasouli, A., Ozden, A., Wu, F. Y., Lin, Z. Y., Tsai, H. J., Lee, T. J., Li, F., Luo, M., Wang, Y., Wang, X., Abed, J., Wang, Z., ... Sargent, E. H. (2022). Copper/alkaline earth metal oxide interfaces for electrochemical CO₂-to-alcohol conversion by selective hydrogenation. Nature Catalysis, 5(12), 1081-1088. https://doi.org/10.1038/s41929-022-00880-6

@article{ef3f9e19aba3489c9039a795d5a269ed,

title = "Copper/alkaline earth metal oxide interfaces for electrochemical CO2-to-alcohol conversion by selective hydrogenation",

abstract = "Multicarbon alcohols produced by electrochemical CO2 reduction (CO2RR) are attractive alternatives to fossil fuels; however, the selectivity towards alcohols in CO2RR remains low, a result of competing hydrocarbon (that is, ethylene) production. Here we report on Cu catalysts decorated with different alkaline earth metal oxides (MOs). We found that BaO delivers a Faradaic efficiency of 61% towards C2+ alcohols. At an industry-relevant current density of 400 mA cm−2, the ratio of alcohols to hydrocarbon reached 3:1. Mechanistic studies, including in operando X-ray absorption spectroscopy, in situ Raman spectroscopy and density functional theory calculations, suggested that the increased selectivity towards alcohols originates from sites at the MO/Cu interface. Furthermore, computational studies indicated that the incorporation of MOs favours a hydroxy-containing C2 intermediate (*HCCHOH) over the hydrocarbon intermediate (*HCC) at interfacial Cu sites on the path to alcohol products. We also propose that the relative bond strengths of Cu–COH and C–OH correlate with the selectivity for alcohol over hydrocarbon. [Figure not available: see fulltext.]",

author = "Aoni Xu and Hung, {Sung Fu} and Ang Cao and Zhenbin Wang and Naiwrit Karmodak and Huang, {Jianan Erick} and Yu Yan and {Sedighian Rasouli}, Armin and Adnan Ozden and Wu, {Feng Yi} and Lin, {Zih Yi} and Tsai, {Hsin Jung} and Lee, {Tsung Ju} and Fengwang Li and Mingchuan Luo and Yuhang Wang and Xue Wang and Jehad Abed and Ziyun Wang and Nam, {Dae Hyun} and Li, {Yuguang C.} and Ip, {Alexander H.} and David Sinton and Chaofang Dong and Sargent, {Edward H.}",

note = "Publisher Copyright: {\textcopyright} 2022, The Author(s), under exclusive licence to Springer Nature Limited.",

year = "2022",

month = dec,

doi = "10.1038/s41929-022-00880-6",

language = "English",

volume = "5",

pages = "1081--1088",

journal = "Nature Catalysis",

issn = "2520-1158",

publisher = "Nature Publishing Group",

number = "12",

}

Xu, A, Hung, SF, Cao, A, Wang, Z, Karmodak, N, Huang, JE, Yan, Y, Sedighian Rasouli, A, Ozden, A, Wu, FY, Lin, ZY, Tsai, HJ, Lee, TJ, Li, F, Luo, M, Wang, Y, Wang, X, Abed, J, Wang, Z, Nam, DH, Li, YC, Ip, AH, Sinton, D, Dong, C & Sargent, EH 2022, 'Copper/alkaline earth metal oxide interfaces for electrochemical CO₂-to-alcohol conversion by selective hydrogenation', Nature Catalysis, 卷 5, 編號 12, 頁 1081-1088. https://doi.org/10.1038/s41929-022-00880-6

TY - JOUR

T1 - Copper/alkaline earth metal oxide interfaces for electrochemical CO2-to-alcohol conversion by selective hydrogenation

AU - Xu, Aoni

AU - Hung, Sung Fu

AU - Cao, Ang

AU - Wang, Zhenbin

AU - Karmodak, Naiwrit

AU - Huang, Jianan Erick

AU - Yan, Yu

AU - Sedighian Rasouli, Armin

AU - Ozden, Adnan

AU - Wu, Feng Yi

AU - Lin, Zih Yi

AU - Tsai, Hsin Jung

AU - Lee, Tsung Ju

AU - Li, Fengwang

AU - Luo, Mingchuan

AU - Wang, Yuhang

AU - Wang, Xue

AU - Abed, Jehad

AU - Wang, Ziyun

AU - Nam, Dae Hyun

AU - Li, Yuguang C.

AU - Ip, Alexander H.

AU - Sinton, David

AU - Dong, Chaofang

AU - Sargent, Edward H.

PY - 2022/12

Y1 - 2022/12

N2 - Multicarbon alcohols produced by electrochemical CO2 reduction (CO2RR) are attractive alternatives to fossil fuels; however, the selectivity towards alcohols in CO2RR remains low, a result of competing hydrocarbon (that is, ethylene) production. Here we report on Cu catalysts decorated with different alkaline earth metal oxides (MOs). We found that BaO delivers a Faradaic efficiency of 61% towards C2+ alcohols. At an industry-relevant current density of 400 mA cm−2, the ratio of alcohols to hydrocarbon reached 3:1. Mechanistic studies, including in operando X-ray absorption spectroscopy, in situ Raman spectroscopy and density functional theory calculations, suggested that the increased selectivity towards alcohols originates from sites at the MO/Cu interface. Furthermore, computational studies indicated that the incorporation of MOs favours a hydroxy-containing C2 intermediate (*HCCHOH) over the hydrocarbon intermediate (*HCC) at interfacial Cu sites on the path to alcohol products. We also propose that the relative bond strengths of Cu–COH and C–OH correlate with the selectivity for alcohol over hydrocarbon. [Figure not available: see fulltext.]

AB - Multicarbon alcohols produced by electrochemical CO2 reduction (CO2RR) are attractive alternatives to fossil fuels; however, the selectivity towards alcohols in CO2RR remains low, a result of competing hydrocarbon (that is, ethylene) production. Here we report on Cu catalysts decorated with different alkaline earth metal oxides (MOs). We found that BaO delivers a Faradaic efficiency of 61% towards C2+ alcohols. At an industry-relevant current density of 400 mA cm−2, the ratio of alcohols to hydrocarbon reached 3:1. Mechanistic studies, including in operando X-ray absorption spectroscopy, in situ Raman spectroscopy and density functional theory calculations, suggested that the increased selectivity towards alcohols originates from sites at the MO/Cu interface. Furthermore, computational studies indicated that the incorporation of MOs favours a hydroxy-containing C2 intermediate (*HCCHOH) over the hydrocarbon intermediate (*HCC) at interfacial Cu sites on the path to alcohol products. We also propose that the relative bond strengths of Cu–COH and C–OH correlate with the selectivity for alcohol over hydrocarbon. [Figure not available: see fulltext.]

UR - http://www.scopus.com/inward/record.url?scp=85142421885&partnerID=8YFLogxK

U2 - 10.1038/s41929-022-00880-6

DO - 10.1038/s41929-022-00880-6

M3 - Article

AN - SCOPUS:85142421885

SN - 2520-1158

VL - 5

SP - 1081

EP - 1088

JO - Nature Catalysis

JF - Nature Catalysis

IS - 12

ER -

Copper/alkaline earth metal oxide interfaces for electrochemical CO2-to-alcohol conversion by selective hydrogenation

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Copper/alkaline earth metal oxide interfaces for electrochemical CO₂-to-alcohol conversion by selective hydrogenation