Pt/SrTiO3光催化全分解水过程中水氧化活性位点的研究

doi:10.1016/S1872-2067(21)64048-2

催化学报 ›› 2022, Vol. 43 ›› Issue (8): 2223-2230.DOI: 10.1016/S1872-2067(21)64048-2

Pt/SrTiO₃光催化全分解水过程中水氧化活性位点的研究

张宪文^a^,^b, 李政^a, 刘太丰^c, 李名润^a, 曾超斌^d, 松本弘昭^d, 韩洪宪^a^,^*()

^a中国科学院大连化学物理研究所, 催化基础国家重点实验室, 洁净能源国家实验室(筹), 辽宁大连116023
^b中国科学院大学, 北京100049
^c河南大学纳米杂化材料应用技术国家地方联合工程研究中心, 河南开封475004
^d日立高新技术(上海)国际贸易有限公司, 上海201203

收稿日期:2022-01-04 接受日期:2022-03-07 出版日期:2022-08-18 发布日期:2022-06-20
通讯作者: 韩洪宪
基金资助:
国家重点研发计划(2017YFA0204800);国家自然科学基金(21761142018);国家自然科学基金(22088102)

Water oxidation sites located at the interface of Pt/SrTiO₃ for photocatalytic overall water splitting

Xianwen Zhang^a^,^b, Zheng Li^a, Taifeng Liu^c, Mingrun Li^a, Chaobin Zeng^d, Hiroaki Matsumoto^d, Hongxian Han^a^,^*()

^aState Key Laboratory of Catalysis and Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bUniversity of Chinese Academy of Sciences, Beijing 100049, China
^cNational & Local Joint Engineering Research Center for Applied Technology of Hybrid Nanomaterials, Henan University, Kaifeng 475004, Henan, China
^dHitachi High-Tech (Shanghai) Co., Ltd., Shanghai 201203, China

Received:2022-01-04 Accepted:2022-03-07 Online:2022-08-18 Published:2022-06-20
Contact: Hongxian Han
Supported by:
National Key R&D Program of China(2017YFA0204800);National Natural Science Foundation of China(21761142018);National Natural Science Foundation of China(22088102)

摘要/Abstract

摘要：

光催化全分解水制氢是转换太阳能的理想途径之一. 目前, 实现光催化全分解水的半导体光催化剂多为n型半导体, 并且需要担载助催化剂. 当n型半导体担载产氢助催化剂时, 由于能带弯曲, 空穴更容易迁移至半导体的表面. 因此, n型半导体的表面被认为是产氧活性位点. 光催化全分解水过程中, 水氧化半反应被认为是速率决定步骤, 因此, 深入认识水氧化活性位点意义重大. SrTiO₃是一种能够高效光催化全分解水的n型半导体光催化剂, Pt是一种常见的产氢助催化剂.

本文以Pt/SrTiO₃为模型体系, 对光催化全分解水过程中水氧化活性位点进行了研究. 研究表明, 光催化全分解水过程中水氧化活性位点主要位于Pt与SrTiO₃的界面处. 首先, 利用光氧化沉积实验研究了水氧化活性位点. 光生空穴可以将Pb²⁺氧化为PbO₂, 因此, 可以利用电镜观察PbO₂的沉积位置, 并推测出水氧化活性位点位置. 扫描透射电镜结果表明, 更多的PbO₂沉积在Pt与SrTiO₃的界面处. 电子顺磁共振、热分析以及扫描透射电镜等结果表明, 真空热处理Pt/SrTiO₃样品时, Pt与SrTiO₃界面处的氧原子更容易失去, 同时伴随着氧空位的生成. 该界面氧空位的生成, 与Pt/SrTiO₃在真空热处理前的光催化全分解水过程密切相关, 与助催化剂的担载方式无关. 只有先经历光催化全分解水反应的Pt/SrTiO₃, 才更易生成界面氧空位. 利用密度泛函理论对水氧化活性位点进行了理论计算研究, 结果发现, 当水氧化反应发生在SrTiO₃的表面时, 第一个质子移除步骤是速率决定步骤, 过电势为2.17 V; 当水氧化反应发生在Pt与SrTiO₃的界面时, 第三步是速率决定步骤, 过电势仅为0.62 V. Pt与SrTiO₃界面处发生水氧化反应的过电势, 远低于SrTiO₃表面发生水氧化反应的过电势. 这表明水氧化活性位点主要位于界面处, 理论计算结果也与实验结果一致.

本文揭示了当n型半导体SrTiO₃担载产氢助催化剂Pt时, 光催化全分解水过程中水氧化活性位点主要位于Pt与SrTiO₃的界面处. 该结果加深了人们对产氢助催化与半导体界面的认识. 界面不仅可以调控光生载流子的分离、迁移, 也可提供光催化水氧化的活性位点. 本文结果有助于设计和构建高效的全分解水光催化剂.

关键词: 光催化全分解水, 活性位点, 氧空位, 界面, 助催化剂

Abstract:

When a proton reduction cocatalyst is loaded on an n-type semiconductor for photocatalytic overall water splitting (POWS), the location of water oxidation sites is generally considered at the surface of the semiconductor due to upward band-bending of n-type semiconductor which may ease the transfer of the photogenerated holes to the surface. However, this is not the case for Pt/SrTiO₃, a model semiconductor based photocatalyst for POWS. It was found that the photogenerated holes are more readily accumulated at the interface between Pt cocatalyst and SrTiO₃ photocatalyst as probed by photo-oxidative deposition of PbO₂, indicating that the water oxidation sites are located at the interface between Pt and SrTiO₃. Electron paramagnetic resonance and scanning transmission electron microscope studies suggest that the interfacial oxygen atoms between Pt and SrTiO₃ in Pt/SrTiO₃ after POWS are more readily lost to form oxygen vacancies upon vacuum heat treatment, regardless of Pt loading by photodeposition or impregnation methods, which may serve as additional support for the location of the active sites for water oxidation at the interface. Density functional theory calculations also suggest that the oxygen evolution reaction more readily occurs at the interfacial sites with the lowest overpotential. These experimental and theoretical studies reveal that the more active sites for water oxidation are located at the interface between Pt and SrTiO₃, rather than on the surface of SrTiO₃. Hence, the tailor design and control of the interfacial properties are extremely important for the achievement or improvement of the POWS on cocatalyst loaded semiconductor photocatalyst.

Key words: Photocatalytic overall water splitting, Active site, Oxygen vacancy, Interface, Cocatalyst

张宪文, 李政, 刘太丰, 李名润, 曾超斌, 松本弘昭, 韩洪宪. Pt/SrTiO₃光催化全分解水过程中水氧化活性位点的研究[J]. 催化学报, 2022, 43(8): 2223-2230.

Xianwen Zhang, Zheng Li, Taifeng Liu, Mingrun Li, Chaobin Zeng, Hiroaki Matsumoto, Hongxian Han. Water oxidation sites located at the interface of Pt/SrTiO₃ for photocatalytic overall water splitting[J]. Chinese Journal of Catalysis, 2022, 43(8): 2223-2230.

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图/表 7

Fig. 1. (a) HAADF-STEM and EDS mapping images of P-Pt/STO after photooxidation deposition of PbO2. (b) Diagram of PbO2 photooxidation deposition on the P-Pt/STO surface.

Fig. 2. (a,b) EPR spectra of P-Pt/STO and STO samples before and after vacuum heat treatment. (c) P-Pt/STO samples were further treated with oxygen heat treatment after vacuum heat treatment. Va: vacuum at room temperature for 1 h. Va-400: vacuum heat treatment at 400 °C for 1 h. Va-400-O2: further treated with oxygen heat treatment at 250 °C for 1 h after vacuum heat treatment. All EPR spectra were tested under vacuum at 295 K. (d) TGA curve of P-Pt/STO sample in argon containing 10% oxygen.

Fig. 3. (a) ABF-STEM image of the P-Pt/STO sample after vacuum heat treatment. The red doted circles indicate the oxygen vacancy. (b) The enlarged ABF-STEM image of the dotted line region in Fig. 3(a). The red circles, green circles and yellow circles represent oxygen, strontium and titanium atoms, respectively. (c) The line profiles along the [100] axis corresponding to the dotted line in Fig. 3(b).

Fig. 4. (a) POWS activities of I-Pt/STO. Reaction conditions: photocatalyst, 300 mg; de-ionized H2O, 150 mL; light source, Xenon lamp (300 W). (b) Before and after POWS, EPR spectra of I-Pt/STO samples which were treated with vacuum heat treatment before EPR test. All EPR spectra were tested under vacuum measured at 23 °C.

Fig. 5. In situ ABF images of I-Pt/STO samples after POWS test during vacuum heat treatment process.

Fig. 6. The structural model of the OER intermediates on (100) surfaces. (a) (100); (b) (100)-OH; (c) (100)-O; (d) (100)-OOH. The red, gray, green and white spheres represent for O, Ti, Sr and H atoms, respectively. (e) Free energy diagram of water oxidation on STO (100) surface.

Fig. 7. The structural model of the OER intermediates on (100)-Pt4 surfaces. (a) (100)-Pt4; (b) (100)-Pt4-OH; (c) (100)-Pt4-O; (d) (100)-Pt4-OOH. The red, gray, green, white and blue spheres represents for O, Ti, Sr, H and Pt atoms, respectively. (e) Free energy diagram for water oxidation at the interface between Pt4 and STO (100).

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Pt/SrTiO₃光催化全分解水过程中水氧化活性位点的研究

Water oxidation sites located at the interface of Pt/SrTiO₃ for photocatalytic overall water splitting

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