双位点协同调控增强钙钛矿氧化物的水氧化活性

doi:10.16085/j.issn.1000-6613.2024-0808

摘要/Abstract

摘要：

钙钛矿氧化物是非常有潜力的析氧反应（OER）催化剂。然而，通过有效掺杂稳定钙钛矿氧化物中B位元素以实现高催化活性仍然是一大挑战。本文通过在A位引入缺陷，促进了电解液中Fe离子的强吸附，进而在施加电压下实现B位金属的高效掺杂及钙钛矿表面稳定结构的构筑。制备的La_1-_x Ni_1-_y Fe _y O_3‑_δ 具有粗糙纳米球形貌，这提供了更大的电化学活性表面积。外部Fe源（FeCl₃）具有较小离子半径，更容易实现高效掺杂和结构稳定。A位缺陷的引入和B位Fe掺杂增加了La_1-_x Ni_1-_y Fe _y O_3‑_δ 中的氧空位，有利于提升其析氧活性。在10mA/cm²的电流密度下，该催化剂仅需要345mV的过电位，就展示了超过68h的长期稳定性。这种通过A位缺陷工程与B位金属掺杂协同的调控策略，为设计高效碱性OER催化剂提供了新的方法。A位缺陷增强了关键氧中间体的吸附，B位Fe掺杂加强了Ni-O共价性。这种通过A位缺陷工程与B位金属掺杂协同的调控策略，为设计高效的碱性OER催化剂提供了新的方法。

关键词: 优化, 掺杂, 钙钛矿, 析氧反应, 电化学, 催化剂

Abstract:

Perovskite oxides represent promising catalysts for the oxygen evolution reaction (OER). However, achieving high catalytic activity through efficient doping of B-site elements within stable perovskite oxides remains a challenge. By introducing defects at the A-site, enhanced adsorption of Fe ions in the electrolyte was promoted, leading to efficient doping of the B-site metal and the construction of a stable structure on the perovskite surface under applied voltage. The synthesized La_1-_x Ni_1-_y Fe _y O_3‑_δ featured a rough nanospherical morphology, offering an increased electrochemically active surface area. The optimized incorporation of an external Fe source (FeCl₃) characterized by a smaller ionic radius facilitated more efficient doping and structural stability. The introduction of A-site defects and Fe doping led to an increase in oxygen vacancies at the B-site, which benefited the OER activity. At a current density of 10mA/cm², the material required only an overpotential of 345mV and demonstrated long-term durability over 68h. The A-site defect optimized adsorption of key oxygen intermediates and the B-site Fe doping modulates stronger Ni-O covalency. This strategy of synergistic regulation through A-site defect engineering and B-site metal doping offered a new approach to designing highly efficient alkaline OER catalysts.

Key words: optimization, doping, perovskite, oxygen evolution reaction, electrochemistry, catalyst

中图分类号:

TQ15

于宁, 王秋月, 王志才, 高子怡, 柴永明, 董斌. 双位点协同调控增强钙钛矿氧化物的水氧化活性[J]. 化工进展, 2025, 44(7): 3976-3984.

YU Ning, WANG Qiuyue, WANG Zhicai, GAO Ziyi, CHAI Yongming, DONG Bin. Double-sites synergistic regulation for boosting water oxidation of La_1-_x Ni_1-_y Fe _y O_3‑_δ[J]. Chemical Industry and Engineering Progress, 2025, 44(7): 3976-3984.

图/表 8

图1 La1-x Ni1-y Fe y O3-δ 的合成路线

图2 制备样品的XRD、SEM、TEM、HRTEM和元素分布图

图3 制备样品的XPS光谱和EPR谱图（1G=10-4T）

图4 La1-x NiO3-δ （x=1, 0.9, 0.8, 0.7, 0.6）及其外加Fe离子优化的极化曲线图

表1 本工作催化剂与相似类型催化剂性能对比分析

催化剂	过电位/mV	电解液	参考文献
La_0.8NiO_3-_δ +FeCl₃	345	1mol/L KOH	本工作
La₂NiMnO₆	370	1mol/L KOH	[27]
Sr_0.95Nb_0.1Co_0.9-_x Ni _x O_3-_δ	438	1mol/L KOH	[28]
LaCoO₃	470	1mol/L KOH	[29]
LaNiO₃/C	470	1mol/L KOH	[30]
Co₃O₄	420	1mol/L KOH	[31]
La_1-_x Sr _x CoO₃	495	1mol/L KOH	[32]
Ca₂FeCoO₅	390	1mol/L KOH	[33]
LaNi_0.8Fe_0.2O₃	510	1mol/L KOH	[34]
聚多巴胺/La₅Ni₃Co₂	360	1mol/L KOH	[35]

图5 制备催化剂的电化学性能

图6 各催化剂的EIS、OER活性比较和稳定性

图7 各催化的分波态密度及d带中心和p带中心位置变化的对比

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