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

doi:10.1016/S1872-2067(21)63857-3

Abstract

Abstract:

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 FeO_x 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.

Key words: CO₂ splitting, Iron-nickel alloy, Perovskite, Methane, Solar-to-fuel efficiency

Yue Hu, Jian Wu, Yujia Han, Weibin Xu, Li Zhang, Xue Xia, Chuande Huang, Yanyan Zhu, Ming Tian, Yang Su, Lin Li, Baolin Hou, Jian Lin, Wen Liu, Xiaodong Wang. Intensified solar thermochemical CO₂ splitting over iron-based redox materials via perovskite-mediated dealloying-exsolution cycles[J]. Chinese Journal of Catalysis, 2021, 42(11): 2049-2058.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63857-3

https://www.cjcatal.com/EN/Y2021/V42/I11/2049

Figures/Tables 8

Fig. 1. Schematic of CO2 splitting process. (a) Traditional two-step STCS process with temperature swing; (b) isothermal two-step STCS process utilizing CH4 as reducing gas; (c) CO2 splitting over metallic Fe induces formation of FeOx passivation layer. Note: ox and red are abbreviations for oxidation and reduction; Tred and Tox represent the reduction and oxidation temperature.

Fig. 2. Local structure and elemental distribution analysis. (a) HRTEM image of a typical particle of FeNi-LFA catalyst. (b) Enlarged view of zone 1 in image (a). La (c), Ni (d), Fe (e), Al (f) and O (g) EDS maps of the same region of image (a). (h) EDS line-scan taken across the particle, as indicated by red dashed arrow in image (a). White dashed circles in (c) represent the areas with relatively low concentration of La.

Fig. 3. CO2 splitting performance. Gas composition during CO2 pulse reaction over FeNi-LFA (a) and corresponding CO2 conversion and CO yield in the reaction (b). (c) Transient CO evolution rate during CO2 splitting half-cycle of two-step STCS process. Pulse reaction conditions: 64 μmol CO2 g-1 of FeNi-LFA was injected in each pulse reaction at 850 °C. STCS reaction conditions: 385 mL CO2 min-1 g-1 (STP) of FeNi-LFA at 850 °C during CO2 splitting half-cycle. The dashed line in (c) gives the average CO productivity during 10 sequential redox cycles.

Fig. 4. CO2 splitting and methane partial oxidation performance over FeNi-LFA under optimized redox conditions. Reaction conditions: 850 °C, total flow = 150 mL min-1 g-1, PCO2 = 0.05, PCH4 = 0.05.

Fig. 5. In-situ structural analysis. (a) In situ XRD measurement under CO2 and CH4 atmosphere at 850 °C. (b1-b6) Representative HAADF image of fresh FeNi-LFA and corresponding element maps of Fe, Ni, La, O and Al. (b7) Line-scan results along the red dashed arrow in image (b1). (c1-c6) HAADF image of FeNi-LFA after CO2 treatment at 850 °C and corresponding element maps of Fe, Ni, La, O and Al. (c7) Line-scan results along the red dashed arrow in image (c1). White dashed area in (b2) contains relatively low iron concentration. White dash arrowed and area in (c2) show the iron migration direction.

Fig. 6. Structural analysis of FeNi-LFA after CO2 splitting. (a) Room temperature 57Fe Mössbauer spectra. The spectrum of LaFeO3 is added as a reference. Representative HAADF image (b1) and corresponding element maps of La (b2), Fe (b3), Ni (b4), Al (b5) and O (b6). White dashed areas in (b2) and (b3) show the LaFeO3 layer.

Fig. 7. Schematic of heat flows for the two-step solar thermochemical CO2 splitting. Note: T0 is ambient temperature and TR is the reaction temperature.

Fig. 8. DFT calculation results. (a) CO2 splitting (CO2 (g) → CO*+O*) on FeNi alloy and FeNi/La2O3 interface, (b) CH4 dissociation (CH4 (g) → CH3*+H*) on Ni and Ni/LaFeO3 interface. Inset: top views of the reaction intermediates: Ni (green), La (blue), Fe (purple), O of redox material (red), C (gray), O of CO2 (pink), and H (orange).

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

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