The absence of intrinsic protons in proton-conducting oxides (PCO) is a significant challenge that limits the proton conductivity of proton-conducting perovskites, such as Y-doped BaMO3 (M = Zr, Ce), in proton ceramic fuel cells exhibit low conductivity (10-3 to 10-2 S cm-1 at 600 °C). Herein, we introduce a photo-assisted synthesis method for incorporating protons into Al-doped ceria (AlxCe1-xO2-δ, x = 0.2; M-ACO), leveraging the open cubic fluorite structure and photo-activated radical reactions. Specifically, photon-generated hydroxyl reactive <InlineEquation ID="IEq1"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="42004_2025_1488_Article_IEq1.gif" Format="GIF" Height="19" Rendition="HTML" Resolution="72" Type="Linedraw" Width="45" /> </InlineMediaObject> <EquationSource Format="TEX">$\left({{{\rm{OH}}}}^{{{\bullet }}}\right)$</EquationSource> <EquationSource Format="MATHML"><math> <mfenced close=")" open="("> <mrow> <msup> <mrow> <mi mathvariant="normal">OH</mi> </mrow> <mrow> <mo>∙</mo> </mrow> </msup> </mrow> </mfenced> </math></EquationSource> </InlineEquation> and superoxide (<InlineEquation ID="IEq2"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="42004_2025_1488_Article_IEq2.gif" Format="GIF" Height="20" Rendition="HTML" Resolution="72" Type="Linedraw" Width="31" /> </InlineMediaObject> <EquationSource Format="TEX">${{{\rm{O}}}}_{2}^{{{\bullet }}-}$</EquationSource> <EquationSource Format="MATHML"><math> <msubsup> <mrow> <mi mathvariant="normal">O</mi> </mrow> <mrow> <mn>2</mn> </mrow> <mrow> <mo>∙</mo> <mo>−</mo> </mrow> </msubsup> </math></EquationSource> </InlineEquation>) Radicals are generated and interact with the ACO crystal lattice, facilitating proton incorporation and resulting in the synthesis of native-proton-type PCO. This process results in a protonated (H-ACO) with a high proton conductivity of 0.14 S cm-1 and exceptional power density of 922 mW cm-2 at 500 °C. This versatile synthesis methodology offers broader development of advanced PCO for energy-related applications.

Photo-assisted synthesis of protonated oxides for fuel cells

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2025年4月22日

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Atif Nazar,
Bushra Bibi,
Chenjie Lou,
Fan Yang,
Fan Qi,
Yifu Jing,
Shukui Li,
Rizwan Raza,
Muhammad Yousaf,
Muhammad Afzal,
Kashif Nazar,
Mingxue Tang,
Liangdong Fan,
Bin Zhu

摘要

The absence of intrinsic protons in proton-conducting oxides (PCO) is a significant challenge that limits the proton conductivity of proton-conducting perovskites, such as Y-doped BaMO₃ (M = Zr, Ce), in proton ceramic fuel cells exhibit low conductivity (10^-3 to 10^-2 S cm^-1 at 600 °C). Herein, we introduce a photo-assisted synthesis method for incorporating protons into Al-doped ceria (Al_xCe_1-xO_2-δ, x = 0.2; M-ACO), leveraging the open cubic fluorite structure and photo-activated radical reactions. Specifically, photon-generated hydroxyl reactive $\left({{{\rm{OH}}}}^{{{\bullet }}}\right)$ $({OH}^{∙})$ and superoxide ( ${{{\rm{O}}}}_{2}^{{{\bullet }}-}$ $O_{2}^{∙ -}$ ) Radicals are generated and interact with the ACO crystal lattice, facilitating proton incorporation and resulting in the synthesis of native-proton-type PCO. This process results in a protonated (H-ACO) with a high proton conductivity of 0.14 S cm^-1 and exceptional power density of 922 mW cm^-2 at 500 °C. This versatile synthesis methodology offers broader development of advanced PCO for energy-related applications.