具有高度有序氧空位的α-Fe2O3纳米带的制备及光电催化水氧化性能研究

doi:10.15541/jim20210175

无机材料学报 ›› 2021, Vol. 36 ›› Issue (12): 1290-1296.DOI: 10.15541/jim20210175

所属专题：【虚拟专辑】氢能材料(2020~2021)

具有高度有序氧空位的α-Fe₂O₃纳米带的制备及光电催化水氧化性能研究

张文进¹^,²(), 申倩倩¹^,²(), 薛晋波¹^,², 李琦³, 刘旭光¹^,², 贾虎生¹^,²

1.太原理工大学新材料界面科学与工程教育部重点实验室, 太原 030024
2.太原理工大学材料科学与工程学院, 太原030024
3.西南交通大学材料科学与工程学院, 成都 610031

收稿日期:2021-03-18 修回日期:2021-04-24 出版日期:2021-12-20 网络出版日期:2021-05-25
通讯作者: 申倩倩, 讲师. E-mail: shenqianqian@tyut.edu.cn
作者简介:张文进(1996-), 男, 硕士研究生. E-mail: zhang_wenjin1@163.com
基金资助:
国家自然科学基金(62004137);国家自然科学基金(21878257);国家自然科学基金(21978196);山西省自然科学基金(201701D221083);山西省重点研发计划(201803D421079);山西省高等学校科技创新项目(2019L0156);山西省科技创新重点研究团队(201605D131045-10);山西省回国留学人员科研资助项目(2020-050)

Preparation and Photoelectrochemical Water Oxidation of Hematite Nanobelts Containing Highly Ordered Oxygen Vacancies

ZHANG Wenjin¹^,²(), SHEN Qianqian¹^,²(), XUE Jinbo¹^,², LI Qi³, LIU Xuguang¹^,², JIA Husheng¹^,²

1. Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024, China
2. College of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, China
3. School of Materials Science and Engineering, Southwest Jiaotong University, Chengdu 610031, China

Received:2021-03-18 Revised:2021-04-24 Published:2021-12-20 Online:2021-05-25
Contact: SHEN Qianqian, lecturer. E-mail: shenqianqian@tyut.edu.cn
About author:ZHANG Wenjin(1996-), male, Master candidate. E-mail: zhang_wenjin1@163.com
Supported by:
National Natural Science Foundation of China(62004137);National Natural Science Foundation of China(21878257);National Natural Science Foundation of China(21978196);Natural Science Foundation of Shanxi Province(201701D221083);Key Research and Development Program of Shanxi Province(201803D421079);Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(2019L0156);Shanxi Provincial Key Innovative Research Team in Science and Technology(201605D131045-10);Research Project Supported by Shanxi Scholarship Council of China(2020-050)

摘要/Abstract

摘要：

本研究针对α-Fe₂O₃中空穴迁移距离短(2~4 nm)和水氧化动力学缓慢的问题, 通过钯催化氧化法构筑了有序氧空位掺杂的一维α-Fe₂O₃纳米带(α-Fe₂O₃ NBs)阵列, 以提高光电催化分解水产氢性能。采用不同表征方法对光阳极进行形貌、结构分析。结果表明：一维α-Fe₂O₃NBs表面形成了有序氧空位, 周期为1.48 nm, 对应于10倍的(11¯2)晶面间距。光电化学及产氢性能表明：α-Fe₂O₃ NBs起始电位为0.587 V (vs. RHE), 在1.6 V (vs. RHE)时光电流密度为3.3 mA·cm^-2, 产氢速率达29.46 μmol·cm^-2·h^-1。这归因于引入有序氧空位提高了载流子密度, 促进了空穴的分离传输, 并作为表面活性位点, 促使表面水氧化反应加速进行。

关键词: α-Fe₂O₃, 有序氧空位, 光电催化, 水氧化

Abstract:

Aiming at the performance-limiting characteristics of short hole diffusion length (2-4 nm) and sluggish water oxidation kinetics in hematite (α-Fe₂O₃), we developed hematite nanobelts containing ordered oxygen vacancies by catalyzed oxidation of palladium nanocrystals for efficient photoelectrochemical (PEC) water splitting. Morphologies and structures of as-prepared films were characterized by different methods. Results show that ordered oxygen vacancies was observed in hematite nanobelts with a periodicity of 1.48 nm corresponding to ten times of (11¯2) interplanar spacing. The PEC performance of the hematite nanobelts exhibits stable photocurrent density of 3.3 mA·cm^-2, the corresponding hydrogen evolution rate of 29.46 μmol·cm^-2·h^-1, and an early onset potential of 0.587 V (vs. RHE) without additional oxygen evolution reaction cocatalysts. The enhanced performance can be attributed to the introduced ordered oxygen vacancies which can increase the carrier density, greatly accelerate the surface holes transfer, and act as surface active sites to significantly promote the surface water oxidation reaction.

Key words: α-Fe₂O₃, ordered oxygen vacancies, photoelectrochemical, water oxidation

中图分类号:

TQ174

张文进, 申倩倩, 薛晋波, 李琦, 刘旭光, 贾虎生. 具有高度有序氧空位的α-Fe₂O₃纳米带的制备及光电催化水氧化性能研究[J]. 无机材料学报, 2021, 36(12): 1290-1296.

ZHANG Wenjin, SHEN Qianqian, XUE Jinbo, LI Qi, LIU Xuguang, JIA Husheng. Preparation and Photoelectrochemical Water Oxidation of Hematite Nanobelts Containing Highly Ordered Oxygen Vacancies[J]. Journal of Inorganic Materials, 2021, 36(12): 1290-1296.

图/表 8

图1 Pd纳米颗粒的TEM照片(a)及粒径统计直方图(b)

Fig. 1 (a) TEM images and (b) corresponding histogram of particle size distribution of Pd nanocrystals

图2 (a)Fe3O4 NFs、(b)α-Fe2O3 NBs和(c)α-Fe2O3 NFs的表面SEM照片; (d, e)α-Fe2O3 NBs、(f, g)α-Fe2O3 NFs的(d, f)截面SEM照片和(e, g)EDS mapping图像; (h)三种光阳极样品的XRD图谱

Fig. 2 Surface SEM images of (a) Fe3O4 NFs, (b) α-Fe2O3 NBs and (c) α-Fe2O3 NFs, (d, f)cross-sectional SEM images and (e, g) EDS mapping images of (d, e) α-Fe2O3 NBs, (f, g) α-Fe2O3 NFs; (h) XRD patterns of 3 photoanodes

图3 (a)α-Fe2O3 NBs的明场TEM照片, (b)典型HRTEM照片((a)中方框区域)和(c)快速傅里叶变换(FFT)图, (d)放大的HRTEM照片, (e)晶面间距测量图

Fig. 3 (a) Bright field TEM image, (b) typical HRTEM image from rectangular region in (a) and (c) corresponding fast Fourier transform (FFT) pattern, (d) enlarged HRTEM image, (e) crystal plane spacing measurement of α-Fe2O3 NBs

图4 (a, b)Fe3O4 NFs和(c, d)α-Fe2O3 NFs的(a, c)TEM照片及(b, d)选区电子衍射图

Fig. 4 (a, c) TEM images and (b, d) corresponding SAED patterns of (a, b) Fe3O4 NFs and (c, d) α-Fe2O3 NFs

图5 Fe3O4 NFs、α-Fe2O3 NBs和α-Fe2O3 NFs的(a)XPS全谱图、(b)Fe2p、(c)O1s、(d)Pd3d的XPS高分辨谱图

Fig. 5 (a) XPS survey spectrum and high-resolution (b) Fe2p, (c) O1s, (d) Pd3d spectra of Fe3O4 NFs, α-Fe2O3 NBs and α-Fe2O3 NFs

图6 Fe3O4 NFs、α-Fe2O3 NBs和α-Fe2O3 NFs的(a)LSV曲线, (b)光电流密度对电位的一阶导数曲线, (c)1.23 V (vs. RHE)的I-t曲线, (d)1.6 V (vs. RHE)的稳定性测试, (e)光电催化产氢曲线和(f)光电催化产氢速率

Fig. 6 (a) LSV curves, (b) first-order derivatives of the photocurrent densities with respect to potential, (c) I-t curves at 1.23 V (vs. RHE), (d) stability test at 1.6 V (vs. RHE), (e) PEC hydrogen production diagram and (f) the hydrogen evolution rate diagram of Fe3O4 NFs, α-Fe2O3 NBs and α-Fe2O3 NFs The orange dashed line in (b) highlights the onset potential at a slope of 0.2 mA·cm-2·V-1

图7 Fe3O4 NFs、α-Fe2O3 NBs和α-Fe2O3 NFs的(a)表面光电压曲线, (b)电化学阻抗图谱, (c)Mott-Schottky曲线和(d)Tafel曲线

Fig. 7 (a) Surface photovoltage diagram, (b) electrochemical impedance spectra, (c) Mott-Schottky plots, and (d) Tafel plots of Fe3O4 NFs, α-Fe2O3 NBs and α-Fe2O3 NFs

图8 具有高度有序氧空位的α-Fe2O3 NBs的光电化学分解水制氢机理示意图

Fig. 8 Schematic of α-Fe2O3 NBs containing highly ordered oxygen vacancies for efficient photoelectronchemical water splitting

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具有高度有序氧空位的α-Fe₂O₃纳米带的制备及光电催化水氧化性能研究

Preparation and Photoelectrochemical Water Oxidation of Hematite Nanobelts Containing Highly Ordered Oxygen Vacancies

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