Intensified solar thermochemical CO₂ splitting over iron-based redox materials via perovskite-mediated dealloying-exsolution cycles

Solar thermochemical CO2-splitting (STCS) is a promising solution for solar energy harvesting and storage. However, practical solar fuel production by utilizing earth-abundant iron/iron oxides remains a great challenge because of the formation of passivation layers, resulting in slow reaction kineti...

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Main Authors: Hu, Yue, Wu, Jian, Han, Yujia, Xu, Weibin, Zhang, Li, Xia, Xue, Huang, Chuande, Zhu, Yanyan, Tian, Ming, Su, Yang, Li, Lin, Hou, Baolin, Lin, Jian, Liu, Wen, Wang, Xiaodong
Other Authors: School of Chemical and Biomedical Engineering
Format: Article
Language:English
Published: 2022
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Online Access:https://hdl.handle.net/10356/155655
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Institution: Nanyang Technological University
Language: English
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spelling sg-ntu-dr.10356-1556552023-12-29T06:51:22Z Intensified solar thermochemical CO₂ splitting over iron-based redox materials via perovskite-mediated dealloying-exsolution cycles Hu, Yue Wu, Jian Han, Yujia Xu, Weibin Zhang, Li Xia, Xue Huang, Chuande Zhu, Yanyan Tian, Ming Su, Yang Li, Lin Hou, Baolin Lin, Jian Liu, Wen Wang, Xiaodong School of Chemical and Biomedical Engineering Engineering::Chemical engineering CO₂ Splitting Iron‐Nickel Alloy Solar thermochemical CO2-splitting (STCS) is a promising solution for solar energy harvesting and storage. However, practical solar fuel production by utilizing earth-abundant iron/iron oxides remains a great challenge because of the formation of passivation layers, resulting in slow reaction kinetics and limited CO2 conversion. Here, we report a novel material consisting of an iron-nickel alloy embedded in a perovskite substrate for intensified CO production via a two-step STCS process. The novel material achieved an unprecedented CO production rate of 381 mL g−1 min−1 with 99% CO2 conversion at 850 °C, outperforming state-of-the-art materials. In situ structural analyses and density functional theory calculations show that the alloy/substrate interface is the main active site for CO2 splitting. Preferential oxidation of the FeNi alloy at the interface (as opposed to forming an FeOx passivation shell encapsulating bare metallic iron) and rapid stabilization of the iron oxide species by the robust perovskite matrix significantly promoted the conversion of CO2 to CO. Facile regeneration of the alloy/perovskite interfaces was realized by isothermal methane reduction with simultaneous production of syngas (H2/CO = 2, syngas yield > 96%). Overall, the novel perovskite-mediated dealloying-exsolution redox system facilitates highly efficient solar fuel production, with a theoretical solar-to-fuel efficiency of up to 58%, in the absence of any heat integration. Submitted/Accepted version 2022-03-11T05:27:03Z 2022-03-11T05:27:03Z 2021 Journal Article Hu, Y., Wu, J., Han, Y., Xu, W., Zhang, L., Xia, X., Huang, C., Zhu, Y., Tian, M., Su, Y., Li, L., Hou, B., Lin, J., Liu, W. & Wang, X. (2021). Intensified solar thermochemical CO₂ splitting over iron-based redox materials via perovskite-mediated dealloying-exsolution cycles. Chinese Journal of Catalysis, 42(11), 2049-2058. https://dx.doi.org/10.1016/S1872-2067(21)63857-3 1872-2067 https://hdl.handle.net/10356/155655 10.1016/S1872-2067(21)63857-3 2-s2.0-85124659015 11 42 2049 2058 en Chinese Journal of Catalysis © 2021 Dalian Institute of Chemical Physics, Chinese Academy of Sciences. All rights reserved. This paper was published by Elsevier B.V. in Chinese Journal of Catalysis and is made available with permission of Dalian Institute of Chemical Physics, Chinese Academy of Sciences. application/pdf application/pdf
institution Nanyang Technological University
building NTU Library
continent Asia
country Singapore
Singapore
content_provider NTU Library
collection DR-NTU
language English
topic Engineering::Chemical engineering
CO₂ Splitting
Iron‐Nickel Alloy
spellingShingle Engineering::Chemical engineering
CO₂ Splitting
Iron‐Nickel Alloy
Hu, Yue
Wu, Jian
Han, Yujia
Xu, Weibin
Zhang, Li
Xia, Xue
Huang, Chuande
Zhu, Yanyan
Tian, Ming
Su, Yang
Li, Lin
Hou, Baolin
Lin, Jian
Liu, Wen
Wang, Xiaodong
Intensified solar thermochemical CO₂ splitting over iron-based redox materials via perovskite-mediated dealloying-exsolution cycles
description Solar thermochemical CO2-splitting (STCS) is a promising solution for solar energy harvesting and storage. However, practical solar fuel production by utilizing earth-abundant iron/iron oxides remains a great challenge because of the formation of passivation layers, resulting in slow reaction kinetics and limited CO2 conversion. Here, we report a novel material consisting of an iron-nickel alloy embedded in a perovskite substrate for intensified CO production via a two-step STCS process. The novel material achieved an unprecedented CO production rate of 381 mL g−1 min−1 with 99% CO2 conversion at 850 °C, outperforming state-of-the-art materials. In situ structural analyses and density functional theory calculations show that the alloy/substrate interface is the main active site for CO2 splitting. Preferential oxidation of the FeNi alloy at the interface (as opposed to forming an FeOx passivation shell encapsulating bare metallic iron) and rapid stabilization of the iron oxide species by the robust perovskite matrix significantly promoted the conversion of CO2 to CO. Facile regeneration of the alloy/perovskite interfaces was realized by isothermal methane reduction with simultaneous production of syngas (H2/CO = 2, syngas yield > 96%). Overall, the novel perovskite-mediated dealloying-exsolution redox system facilitates highly efficient solar fuel production, with a theoretical solar-to-fuel efficiency of up to 58%, in the absence of any heat integration.
author2 School of Chemical and Biomedical Engineering
author_facet School of Chemical and Biomedical Engineering
Hu, Yue
Wu, Jian
Han, Yujia
Xu, Weibin
Zhang, Li
Xia, Xue
Huang, Chuande
Zhu, Yanyan
Tian, Ming
Su, Yang
Li, Lin
Hou, Baolin
Lin, Jian
Liu, Wen
Wang, Xiaodong
format Article
author Hu, Yue
Wu, Jian
Han, Yujia
Xu, Weibin
Zhang, Li
Xia, Xue
Huang, Chuande
Zhu, Yanyan
Tian, Ming
Su, Yang
Li, Lin
Hou, Baolin
Lin, Jian
Liu, Wen
Wang, Xiaodong
author_sort Hu, Yue
title Intensified solar thermochemical CO₂ splitting over iron-based redox materials via perovskite-mediated dealloying-exsolution cycles
title_short Intensified solar thermochemical CO₂ splitting over iron-based redox materials via perovskite-mediated dealloying-exsolution cycles
title_full Intensified solar thermochemical CO₂ splitting over iron-based redox materials via perovskite-mediated dealloying-exsolution cycles
title_fullStr Intensified solar thermochemical CO₂ splitting over iron-based redox materials via perovskite-mediated dealloying-exsolution cycles
title_full_unstemmed Intensified solar thermochemical CO₂ splitting over iron-based redox materials via perovskite-mediated dealloying-exsolution cycles
title_sort intensified solar thermochemical co₂ splitting over iron-based redox materials via perovskite-mediated dealloying-exsolution cycles
publishDate 2022
url https://hdl.handle.net/10356/155655
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