Research progress of H2 and CO electrochemical oxidation mechanisms in metal and doped ceria system

doi:10.16085/j.issn.1000-6613.2024-0510

Abstract

Abstract:

The application of metal-rare earth doped ceria anode is one of the most important strategies for the moderate and low temperature solid oxide fuel cells (SOFC). The mixed ionic and electronic conductor (MIEC) characteristic of doped ceria expands the reaction interface and complicates the reaction mechanism. This article reviewed the electrochemical oxidation mechanism of H₂ and CO in metal and doped ceria system. It was pointed out that the Ni/YSZ-like H spillover mechanism was dominant in the H₂ electrochemistry. For the CO electrochemistry, combined with the predominant Marse-van Krevelen (MvK) type mechanism in the CO catalytic reaction and the reverse process of the CO₂ electrochemical reduction reaction, it was predicted that the charge transfer step mainly occurred in the oxygen vacancy formation and the CO₂ formation reactions. In the MIEC type reaction mechanism, the main difference in the H₂ oxidation reaction pathways was the difference of H₂ dissociation adsorption site. The CO oxidation reaction pathway can be categorized into two modes based on the adsorption site: directly reacting with CeO₂ lattice oxygen to generate CO₂ or generating carbonate intermediates, and the charge transfer step involved carbonate formation and CO₂ formation reactions. In summary, H₂ electrochemical oxidation was dominated by H spillover, while the dominant reaction mechanism of CO electrochemical oxidation was still unclear and required further study. This article was instructive for clarifying the reaction mechanisms of Ni/YSZ and MIEC types in H₂ and CO, as well as H₂/CO hybrid fuel systems.

Key words: solid oxide fuel cells, electrochemistry, oxidation, reaction mechanism, mixed ionic and electronic conductor, ceria-based oxides, catalysis

摘要：

应用金属-稀土元素掺杂氧化铈阳极是固体氧化物燃料电池（SOFC）中低温化的重要策略之一。掺杂氧化铈自身的混合离子电子导体（MIEC）特性拓展了反应界面，也使得反应机理更为复杂。本文综述了金属-掺杂氧化铈体系H₂和CO的电化学氧化反应机理，指出在H₂电化学反应中类Ni/YSZ型H溢出机理占主导地位；对于CO电化学反应，结合在CO催化反应中主要的Marse-van Krevelen（MvK）机制和CO₂电化学还原反应逆过程，预测其电荷转移步骤主要发生在氧空位形成和CO₂形成反应。在MIEC型反应机理中，H₂氧化反应路径的主要区别在于H₂解离吸附位点的不同；而CO氧化反应路径根据吸附位点可分为与CeO₂晶格氧反应直接生成CO₂或者生成碳酸盐中间体，电荷转移步骤为碳酸盐形成和CO₂形成反应。综上，H₂电化学氧化以H溢出为主，CO电化学氧化的主导反应机理尚不明确，亟待深入研究。本文工作对明晰H₂和CO乃至H₂/CO混合燃料体系类Ni/YSZ型和MIEC型反应机理具有一定的指导意义。

关键词: 固体氧化物燃料电池, 电化学, 氧化, 反应机理, 混合离子电子导体, Ce基氧化物, 催化

CLC Number:

TK91

LIN Meijie, MI Shuodong, BAO Cheng. Research progress of H₂ and CO electrochemical oxidation mechanisms in metal and doped ceria system[J]. Chemical Industry and Engineering Progress, 2024, 43(S1): 209-224.

林梅洁, 米烁东, 包成. 金属-掺杂氧化铈体系H₂/CO电化学反应机理研究进展[J]. 化工进展, 2024, 43(S1): 209-224.

Figures/Tables 12

双羟基路径(DH)^[54-55]	均相解离路径^[55]	非均相路径（在PDC、NDC、SDC和GDC上掺杂金属参与的过程）^[54-55]	非均相路径（在含有氧空位的GDC上，O空位参与的过程）^[55]
$H_{2} (g) \overset{}{\to} H_{2} (C e_{s u r f})$	$H_{2} (g) + *^{C e} \overset{}{\to} H_{2}^{C e}$	$H_{2} (g) + *^{D M} \overset{}{\to} H_{2}^{D M}$	$H_{2} (g) + *^{D M} \overset{}{\to} H_{2}^{D M}$
$H_{2} (C e_{s u r f}) + 2 (O) \overset{}{\to} 2 H (O)$	$H_{2}^{C e} + 2 O^{} \overset{}{\to} 2 H^{O} + ^{C e}$	$H_{2}^{D M} + *^{O} \overset{}{\to} H^{O} + H^{D M}$	$H_{2}^{D M} + ^{V_{O}^{• •}} + ^{O} \overset{}{\to} *^{D M} + H^{V_{O}^{• •}} + H^{O}$
$H (O) + O^{2 -} (S D C) \overset{}{\to} O H^{-} (S D C) + e^{-}$	$2 H^{O} \overset{}{\to} H_{2} O^{V_{O}^{\cdot \cdot}} + *^{O}$	$H^{O} + H^{D M} \overset{}{\to} H_{2} O^{V_{O}^{• •}} + *^{D M}$	$H^{V_{O}^{• •}} + ^{O_{S}} \overset{}{\to} ^{V_{O}^{• •}} + H^{O_{_{S}}}$
$H (O) + O H^{-} (S D C) \overset{}{\to} H_{2} O (S D C) + e^{-}$	$H_{2} O^{V_{O}^{• •}} \overset{}{\to} H_{2} O (g) + V_{O}^{• •}$	$H_{2} O^{V_{O}^{• •}} \overset{}{\to} H_{2} O (g) + V_{O}^{• •}$	$H^{O} + H^{O_{S}} \overset{}{\to} H_{2} O^{V_{O}^{\cdot \cdot}} + *^{O_{S}}$
$H_{2} O (S D C) \overset{}{\to} (S D C) + H_{2} O (g)$			$H_{2} O^{V_{O}^{• •}} \overset{}{\to} H_{2} O (g) + V_{O}^{• •}$

双羟基路径(DH)^[54-55]	均相解离路径^[55]	非均相路径（在PDC、NDC、SDC和GDC上掺杂金属参与的过程）^[54-55]	非均相路径（在含有氧空位的GDC上，O空位参与的过程）^[55]
$H_{2} (g) \overset{}{\to} H_{2} (C e_{s u r f})$	$H_{2} (g) + *^{C e} \overset{}{\to} H_{2}^{C e}$	$H_{2} (g) + *^{D M} \overset{}{\to} H_{2}^{D M}$	$H_{2} (g) + *^{D M} \overset{}{\to} H_{2}^{D M}$
$H_{2} (C e_{s u r f}) + 2 (O) \overset{}{\to} 2 H (O)$	$H_{2}^{C e} + 2 O^{} \overset{}{\to} 2 H^{O} + ^{C e}$	$H_{2}^{D M} + *^{O} \overset{}{\to} H^{O} + H^{D M}$	$H_{2}^{D M} + ^{V_{O}^{• •}} + ^{O} \overset{}{\to} *^{D M} + H^{V_{O}^{• •}} + H^{O}$
$H (O) + O^{2 -} (S D C) \overset{}{\to} O H^{-} (S D C) + e^{-}$	$2 H^{O} \overset{}{\to} H_{2} O^{V_{O}^{\cdot \cdot}} + *^{O}$	$H^{O} + H^{D M} \overset{}{\to} H_{2} O^{V_{O}^{• •}} + *^{D M}$	$H^{V_{O}^{• •}} + ^{O_{S}} \overset{}{\to} ^{V_{O}^{• •}} + H^{O_{_{S}}}$
$H (O) + O H^{-} (S D C) \overset{}{\to} H_{2} O (S D C) + e^{-}$	$H_{2} O^{V_{O}^{• •}} \overset{}{\to} H_{2} O (g) + V_{O}^{• •}$	$H_{2} O^{V_{O}^{• •}} \overset{}{\to} H_{2} O (g) + V_{O}^{• •}$	$H^{O} + H^{O_{S}} \overset{}{\to} H_{2} O^{V_{O}^{\cdot \cdot}} + *^{O_{S}}$
$H_{2} O (S D C) \overset{}{\to} (S D C) + H_{2} O (g)$			$H_{2} O^{V_{O}^{• •}} \overset{}{\to} H_{2} O (g) + V_{O}^{• •}$

LH反应机理	MvK反应机理	Au-CeO₂界面作为反应分子的结合位点
$C O (g) + (A u) \overset{}{\to} C O (A u)$	$C O (g) + (A u) \overset{}{\to} C O (A u)$	$O_{2} + (i n t e r) \overset{}{\to} O_{2} (i n t e r)$
$O_{2} (g) + (A u) \overset{}{\to} O_{2} (A u)$	$C O (A u) + O (i n t e r) \overset{}{\to} C O_{2} (i n t e r)$	$C O (g) + (A u) \overset{}{\to} C O (A u)$
$C O (A u) + O_{2} (A u) \overset{}{\to} C O_{2} (A u) + O (A u)$	$C O_{2} (i n t e r) \overset{}{\to} C O_{2} (g) + V_{O}^{• •}$	$C O (A u) + O_{2} (i n t e r) \overset{}{\to} C O_{2} (g) + O (A u)$
$C O_{2} (A u) \overset{}{\to} C O_{2} (g)$	$O_{2} (g) + (V_{O}^{• •}) \overset{}{\to} O_{2} (V_{O}^{• •})$
	$O_{2} + (V_{O}^{• •}) + C O (g) \overset{}{\to} O (i n t e r) + C O_{2} (i n t e r)$
	$C O_{2} (i n t e r) \overset{}{\to} C O_{2} (g)$

LH反应机理	MvK反应机理	Au-CeO₂界面作为反应分子的结合位点
$C O (g) + (A u) \overset{}{\to} C O (A u)$	$C O (g) + (A u) \overset{}{\to} C O (A u)$	$O_{2} + (i n t e r) \overset{}{\to} O_{2} (i n t e r)$
$O_{2} (g) + (A u) \overset{}{\to} O_{2} (A u)$	$C O (A u) + O (i n t e r) \overset{}{\to} C O_{2} (i n t e r)$	$C O (g) + (A u) \overset{}{\to} C O (A u)$
$C O (A u) + O_{2} (A u) \overset{}{\to} C O_{2} (A u) + O (A u)$	$C O_{2} (i n t e r) \overset{}{\to} C O_{2} (g) + V_{O}^{• •}$	$C O (A u) + O_{2} (i n t e r) \overset{}{\to} C O_{2} (g) + O (A u)$
$C O_{2} (A u) \overset{}{\to} C O_{2} (g)$	$O_{2} (g) + (V_{O}^{• •}) \overset{}{\to} O_{2} (V_{O}^{• •})$
	$O_{2} + (V_{O}^{• •}) + C O (g) \overset{}{\to} O (i n t e r) + C O_{2} (i n t e r)$
	$C O_{2} (i n t e r) \overset{}{\to} C O_{2} (g)$

Ni/SDC体系CO₂电化学还原反应机理^[79]	对应电荷转移步骤的电化学表达式	推测CO电化学氧化反应机理
步骤1： $C O_{2} (g) + (N i) \overset{}{\to} C O_{2} (N i)$		$C O (g) \overset{}{\to} C O_{N i . a d s}$
步骤2： $C O_{2} (N i) + (N i) \overset{}{\to} C O (N i) + O (N i)$	$C O_{2} (N i) + (N i) + 2 e^{'} \overset{}{\to} C O (N i) + O^{″} (N i)$	$C O_{N i, a d s} + O_{N i, a d s} \overset{}{\to} C {O_{2}}_{N i, a d s}$
步骤3： $C O (N i) \overset{}{\to} C O (g) + (N i)$		$C {O_{2}}_{N i . a d s} \overset{}{\to} C O_{2} (g)$
$\begin{array}{l} 步骤 4 : O (N i) + V_{O}^{• •} (s u r f) \overset{}{\to} O (s u r f) + (N i) \\ O (N i) + V_{O}^{• •} (i n t e r) \overset{}{\to} O (i n t e r) + (N i) \end{array}$	$\begin{array}{l} O (N i) + V_{O}^{• •} (s u r f) + 2 e^{'} \overset{}{\to} O (s u r f) + (N i) \\ O (N i) + V_{O}^{• •} (i n t e r) + 2 e^{'} \overset{}{\to} O (i n t e r) + (N i) \end{array}$	$O_{O, i n t e r / s u r f}^{\times} \overset{}{\to} O_{N i, a d s} + V_{O}^{• •} + 2 e^{'}$
$\begin{array}{l} O (s u r f) + V_{O}^{• •} (b u l k) \overset{}{\to} O (b u l k) + V_{O}^{• •} (s u r f) \\ O (i n t e r) + V_{O}^{• •} (b u l k) \overset{}{\to} O (b u l k) + V_{O}^{• •} (i n t e r) \end{array}$		$\begin{array}{l} O_{O, i n t e r}^{\times} \overset{}{\to} O_{N i, a d s} + V_{O}^{•} + e^{'} \\ O_{O, s u r f}^{\times} \overset{}{\to} O_{N i, a d s} + V_{O}^{•} + e^{'} \end{array}$

Ni/SDC体系CO₂电化学还原反应机理^[79]	对应电荷转移步骤的电化学表达式	推测CO电化学氧化反应机理
步骤1： $C O_{2} (g) + (N i) \overset{}{\to} C O_{2} (N i)$		$C O (g) \overset{}{\to} C O_{N i . a d s}$
步骤2： $C O_{2} (N i) + (N i) \overset{}{\to} C O (N i) + O (N i)$	$C O_{2} (N i) + (N i) + 2 e^{'} \overset{}{\to} C O (N i) + O^{″} (N i)$	$C O_{N i, a d s} + O_{N i, a d s} \overset{}{\to} C {O_{2}}_{N i, a d s}$
步骤3： $C O (N i) \overset{}{\to} C O (g) + (N i)$		$C {O_{2}}_{N i . a d s} \overset{}{\to} C O_{2} (g)$
$\begin{array}{l} 步骤 4 : O (N i) + V_{O}^{• •} (s u r f) \overset{}{\to} O (s u r f) + (N i) \\ O (N i) + V_{O}^{• •} (i n t e r) \overset{}{\to} O (i n t e r) + (N i) \end{array}$	$\begin{array}{l} O (N i) + V_{O}^{• •} (s u r f) + 2 e^{'} \overset{}{\to} O (s u r f) + (N i) \\ O (N i) + V_{O}^{• •} (i n t e r) + 2 e^{'} \overset{}{\to} O (i n t e r) + (N i) \end{array}$	$O_{O, i n t e r / s u r f}^{\times} \overset{}{\to} O_{N i, a d s} + V_{O}^{• •} + 2 e^{'}$
$\begin{array}{l} O (s u r f) + V_{O}^{• •} (b u l k) \overset{}{\to} O (b u l k) + V_{O}^{• •} (s u r f) \\ O (i n t e r) + V_{O}^{• •} (b u l k) \overset{}{\to} O (b u l k) + V_{O}^{• •} (i n t e r) \end{array}$		$\begin{array}{l} O_{O, i n t e r}^{\times} \overset{}{\to} O_{N i, a d s} + V_{O}^{•} + e^{'} \\ O_{O, s u r f}^{\times} \overset{}{\to} O_{N i, a d s} + V_{O}^{•} + e^{'} \end{array}$

CO₂在Pt底部吸附	CO₂在Pt顶部吸附	推测CO电化学氧化反应机理
$C O_{2} (g) + e^{'} \overset{}{\to} C O_{2}^{'}$	$C O_{2} (g) + e^{'} \overset{}{\to} C O_{2}^{'}$	$C O (g) \overset{}{\to} C O_{m e t a l}$
$C O_{2}^{'} + V_{O}^{• •} + e^{'} \overset{}{\to} C O + O_{O}^{\times}$	$C O_{2}^{'} + e^{'} \overset{}{\to} C O + O_{i}^{″}$	$O_{O}^{\times} \overset{}{\to} O_{i}^{″} + V_{O}^{• •}$
$C O \overset{}{\to} C O (g)$	$O_{i}^{″} + V_{O}^{• •} \overset{}{\to} O_{O}^{\times}$	$C O + O_{i}^{″} \overset{}{\to} C O_{2}^{'} + e^{'}$
	$C O \overset{}{\to} C O (g)$	$C O_{2}^{'} \overset{}{\to} C O_{2} (g) + e^{'}$

CO₂在Pt底部吸附	CO₂在Pt顶部吸附	推测CO电化学氧化反应机理
$C O_{2} (g) + e^{'} \overset{}{\to} C O_{2}^{'}$	$C O_{2} (g) + e^{'} \overset{}{\to} C O_{2}^{'}$	$C O (g) \overset{}{\to} C O_{m e t a l}$
$C O_{2}^{'} + V_{O}^{• •} + e^{'} \overset{}{\to} C O + O_{O}^{\times}$	$C O_{2}^{'} + e^{'} \overset{}{\to} C O + O_{i}^{″}$	$O_{O}^{\times} \overset{}{\to} O_{i}^{″} + V_{O}^{• •}$
$C O \overset{}{\to} C O (g)$	$O_{i}^{″} + V_{O}^{• •} \overset{}{\to} O_{O}^{\times}$	$C O + O_{i}^{″} \overset{}{\to} C O_{2}^{'} + e^{'}$
	$C O \overset{}{\to} C O (g)$	$C O_{2}^{'} \overset{}{\to} C O_{2} (g) + e^{'}$

CO直接（电）氧化不形成碳酸盐结构		CO形成碳酸盐结构
氧化反应^[74]	电化学氧化^[52]	氧化反应^[74]	电化学氧化^[52]
$C O (g) + O (C e O_{2}) \overset{}{\to} C O_{2} (C e O_{2})$	$C O (g) \overset{}{\to} C O_{a d s}$	$C O (g) + 2 O (C e O_{2}) \overset{}{\to} C O_{3} (C e O_{2})$	$C O (g) + 2 O_{O}^{\times} \overset{}{\to} C O_{3, a d s}^{″}$
$C O_{2} (C e O_{2}) \overset{}{\to} C O_{2} (g) + (C e O_{2})$	$C O_{a d s} + O_{O}^{\times} \overset{}{\to} C O_{2, a d s} + 2 e^{'}$		$C O_{3 . a d s}^{″} \overset{}{\to} C O_{2} (g) + O_{O}^{\times} + 2 e^{'}$
	$C O_{2, a d s} \overset{}{\to} C O_{2} (g) + V_{i}$

CO直接（电）氧化不形成碳酸盐结构		CO形成碳酸盐结构
氧化反应^[74]	电化学氧化^[52]	氧化反应^[74]	电化学氧化^[52]
$C O (g) + O (C e O_{2}) \overset{}{\to} C O_{2} (C e O_{2})$	$C O (g) \overset{}{\to} C O_{a d s}$	$C O (g) + 2 O (C e O_{2}) \overset{}{\to} C O_{3} (C e O_{2})$	$C O (g) + 2 O_{O}^{\times} \overset{}{\to} C O_{3, a d s}^{″}$
$C O_{2} (C e O_{2}) \overset{}{\to} C O_{2} (g) + (C e O_{2})$	$C O_{a d s} + O_{O}^{\times} \overset{}{\to} C O_{2, a d s} + 2 e^{'}$		$C O_{3 . a d s}^{″} \overset{}{\to} C O_{2} (g) + O_{O}^{\times} + 2 e^{'}$
	$C O_{2, a d s} \overset{}{\to} C O_{2} (g) + V_{i}$

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Research progress of H₂ and CO electrochemical oxidation mechanisms in metal and doped ceria system

金属-掺杂氧化铈体系H₂/CO电化学反应机理研究进展

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