赤铁矿光阳极界面钛原子在析氧反应多位点机制中的作用: 反应活性位点还是助催化位点?

doi:10.1016/S1872-2067(24)60093-8

催化学报 ›› 2024, Vol. 64: 77-86.DOI: 10.1016/S1872-2067(24)60093-8

赤铁矿光阳极界面钛原子在析氧反应多位点机制中的作用: 反应活性位点还是助催化位点?

谢旻斐^a^,¹, 姬星^b^,¹, 孟华颖^b^,¹, 姜南冰^b, 罗贞玉^b, 黄千千^a, 孙耿^b^,^*(), 张云怀^b^,^*(), 肖鹏^a^,^*()

^a重庆大学物理学院, 重庆市界面物理能量转化重点实验室, 重庆 401331
^b重庆大学化学化工学院, 重庆 401331

收稿日期:2024-03-23 接受日期:2024-07-08 出版日期:2024-09-18 发布日期:2024-09-19
通讯作者: * 电子邮箱: sungengemail@cqu.edu.cn (孙耿),zyh2031@cqu.edu.cn (张云怀),xiaopeng@cqu.edu.cn (肖鹏).
作者简介:¹共同第一作者.
基金资助:
中央高校基础研究基金(2022CDJQY-007);中央高校基础研究基金(2022CDJJCLK001);中央高校基础研究基金(2023CDJXY-046)

The role of titanium at the interface of hematite photoanode in multisite mechanism: Reactive site or cocatalyst site?

Minfei Xie^a^,¹, Xing Ji^b^,¹, Huaying Meng^b^,¹, Nanbing Jiang^b, Zhenyu Luo^b, Qianqian Huang^a, Geng Sun^b^,^*(), Yunhuai Zhang^b^,^*(), Peng Xiao^a^,^*()

^aChongqing Key Laboratory of Interface Physics in Energy Conversion, College of Physics, Chongqing University, Chongqing 401331, China
^bCollege of Chemistry and Chemical Engineering, Chongqing University, Chongqing 401331, China

Received:2024-03-23 Accepted:2024-07-08 Online:2024-09-18 Published:2024-09-19
Contact: * E-mail: sungengemail@cqu.edu.cn (G. Sun),zyh2031@cqu.edu.cn (Y. Zhang),xiaopeng@cqu.edu.cn (P. Xiao).
About author:¹Contributed equally to this work.
Supported by:
Fundamental Research Funds for the Central Universities(2022CDJQY-007);Fundamental Research Funds for the Central Universities(2022CDJJCLK001);Fundamental Research Funds for the Central Universities(2023CDJXY-046)

摘要/Abstract

摘要：

赤铁矿(Fe₂O₃)是光电催化析氧反应(OER)中极具潜力的半导体光阳极材料之一, 其性能的提升一直是研究热点. 近期研究表明, 在碱性环境中, Fe₂O₃光阳极的OER反应速率与其表面空穴密度之间存在幂律依赖性. 与单位点质子耦合电子转移(PCET)机制(*OH → *O → *OOH → O₂)不同, Fe₂O₃上的OER遵循多位点反应机制, 即表面羟基(*OH)通过空穴的氧化积累转化为氧基(*O), 随后在相邻活性位点间发生O-O耦合. 钛(Ti)掺杂是提升Fe₂O₃上OER性能的重要手段之一, 但Ti等异质原子在多位点反应机制中的具体作用(是活性位点还是助催化位点)尚不明晰.

为探明Ti等异质原子的具体作用, 本文利用电化学光-暗态扫描方法识别碱性环境中OER反应中间态, 并结合密度泛函理论(DFT)计算, 考察了异质Ti原子在赤铁矿OER多位点反应路径中的作用机制. 首先, 通过水热法将Fe₂O₃纳米棒分别生长在金属Ti基底及氟掺杂二氧化锡(FTO)导电基底上, 构建了Fe₂O₃/Ti和Fe₂O₃/FTO两种复合材料体系. 实验发现, Fe₂O₃/Ti体系的最佳退火温度为550 °C. 在此条件下, X射线衍射分析不仅展现了α-Fe₂O₃衍射峰, 还检测到了金红石TiO₂(110)晶面的衍射峰. 侧面高分辨球差电镜测试结果表明, Fe₂O₃/Ti表面覆盖有一层约120 nm厚的Fe₂O₃层; 而在Ti基底与Fe₂O₃之间, 则存在厚度约为100 nm的Ti氧化层. 值得注意的是, 尽管在Fe₂O₃体相内并未观察到明显的Ti原子掺杂现象, 但推测在高温退火条件下, 可能有少量Ti原子会扩散到Fe₂O₃界面. X射线光电子能谱测试表明, Fe₂O₃/Ti复合材料界面处Fe与Ti元素间存在显著的相互作用, 其中Fe位点作为电子给体, Ti位点则作为电子受体.

为了深入理解这一相互作用对OER的影响, 进行了不同pH环境下的电化学光-暗态扫描研究. 结果发现, 在pH 7‒10的范围内, Fe₂O₃/Ti和Fe₂O₃/FTO两种光阳极都展现出了Fe=O中间态, 这表明在此条件下的OER遵循单位点PCET机制, 且Fe=O向Fe-OOH的转化是反应决速步骤. 然而, 当pH≥11时, Fe₂O₃/FTO的Fe=O中间态消失, Fe-OH中间态出现, 说明在碱性环境下OER反应机制转变为多位点主导, 其中*OH到*O的转化是新的反应决速步. 值得注意的是, 同样是在pH≥11条件下, Fe₂O₃/Ti体系则表现出不同的中间态特征, 仅检测到Ti-OH中间态而未观察到Fe-OH中间态. 根据这一现象推断, Ti-OH中的H可能来源于两个方面: 一是与溶液中的OH⁻离子及光生空穴反应生成; 二是从可能存在的Fe-OH结构上迁移而来. 为了进一步验证这一推断并深入理解反应机制, 结合DFT计算, 对多位点反应路径下的两种可能机制进行了自由能分析. 结果表明, 相较于Ti=O与Fe=O耦合生成O₂的路径, Fe=O之间直接耦合生成O₂的路径具有更低的反应能垒. 在此机制中, Ti位点作为助催化中心, 通过两个非电化学反应从Fe-OH上夺取质子, 从而促进了Fe=O之间的耦合. 值得注意的是, Ti-OH + Fe-OH → Ti-OH₂ + Fe=O这一非电化学反应过程需要吸热, 因此相对较难进行. 这也解释了为何在Fe₂O₃/Ti复合材料中, 能够在碱性环境下检测到Ti-OH中间态的存在.

综上所述, 本文通过电化学光-暗态扫描与DFT计算相结合的方法, 深入探讨了异质原子在Fe₂O₃光阳极多位点OER反应机制中的助催化作用. 研究发现, Ti位点作为助催化中心, 通过非电化学反应从Fe-OH上夺取质子, 促进了相邻Fe=O耦合生成O₂, 从而提升了反应动力. 这一发现不仅揭示了异质原子在光电催化OER中的作用机制, 也为开发更高效的光阳极材料提供了新的思路和理论依据.

关键词: 赤铁矿, 析氧反应, 多位点机制, 中间态, 质子捕获

Abstract:

Hematite (α-Fe₂O₃) constitutes one of the most promising photoanode materials for oxygen evolution reaction (OER). Recent research on Fe₂O₃ have found a fast OER rate dependence on surface hole density, suggesting a multisite reaction pathway. However, the effect of heteroatom in Fe₂O₃ on the multisite mechanism is still poorly understood. Herein we synthesized Fe₂O₃ on Ti substrates (Fe₂O₃/Ti) to study the oxygen intermediates of OER by light-dark electrochemical scans. We identified the Fe-OH species disappeared and Ti-OH intermediates appeared on Fe₂O₃/Ti when pH = 11‒14, which significantly improved the OER performance of Fe₂O₃/Ti. Combined with the density functional theory calculations, we propose that Ti atom acts as cocatalyst site and captures proton from neighboring Fe-OH species under highly alkaline condition, thereby promoting the coupling of Fe=O and reducing the energy barrier of the non-electrochemical step. Our work provides a new insight into the role of heteroatom in OER multisite mechanism based on clarifying the reaction intermediates.

Key words: Hematite, Oxygen evolution reaction, Multisite mechanism, Intermediate, Proton capture

谢旻斐, 姬星, 孟华颖, 姜南冰, 罗贞玉, 黄千千, 孙耿, 张云怀, 肖鹏. 赤铁矿光阳极界面钛原子在析氧反应多位点机制中的作用: 反应活性位点还是助催化位点?[J]. 催化学报, 2024, 64: 77-86.

Minfei Xie, Xing Ji, Huaying Meng, Nanbing Jiang, Zhenyu Luo, Qianqian Huang, Geng Sun, Yunhuai Zhang, Peng Xiao. The role of titanium at the interface of hematite photoanode in multisite mechanism: Reactive site or cocatalyst site?[J]. Chinese Journal of Catalysis, 2024, 64: 77-86.

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图/表 4

Fig. 1. XRD pattern (a) and SEM top view of Fe2O3/Ti (b) and Fe2O3/FTO (c). (d) Cross-sectional image of Fe2O3/FTO. (e) TEM cross-sectional image of Fe2O3/Ti. (f) HRTEM detail showing the blue squared interface area in (e). (g,h) Magnified HRTEM detail of the selected Fe2O3 and the Ti oxide layer, respectively. HAADF-STEM image of Fe2O3/Ti cross section (i) and the corresponding EDS elemental mapping images of Ti (j), Fe (k), and O (l), respectively.

Fig. 2. (a) Raman spectra. XPS spectra of Fe 2p (b), Ti 2p (c), and O 1s (d) obtained from the Fe2O3/Ti and Fe2O3/FTO.

Fig. 3. (a,b) Photocurrent curves of Fe2O3/FTO and Fe2O3/Ti at different pH. (c,d) Dark-state negative sweep curves. (e) The onset potential and photocurrent density at 1.23 VRHE plotted as a function of pH. (f) The reduction peak potential of S1 and S2 plotted as a function of pH.

Fig. 4. Two possible multisite reaction mechanisms. MSM1 (a) and MSM2 (b) of OER on Fe2O3/Ti photoanode under pH≥11 conditions, and the blue arrows correspond to the proton capture process. Free energy diagrams under a bias of 2.3 eV [55] and pH as 14 for mechanism MSM1 (c) and MSM2 (d) (). The marked number from 1 to 5 and 1 to 7 correspond to the reaction step number in mechanism (a) and (b) respectively.

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赤铁矿光阳极界面钛原子在析氧反应多位点机制中的作用: 反应活性位点还是助催化位点?

The role of titanium at the interface of hematite photoanode in multisite mechanism: Reactive site or cocatalyst site?

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