p-n异质结BiVO4/g-C3N4光阳极的制备及其光电化学水解性能

doi:10.15541/jim20220439

无机材料学报 ›› 2023, Vol. 38 ›› Issue (1): 87-96.DOI: 10.15541/jim20220439 CSTR: 32189.14.10.15541/jim20220439

所属专题：【能源环境】氢能材料(202409)

p-n异质结BiVO₄/g-C₃N₄光阳极的制备及其光电化学水解性能

王如意¹^,²(), 徐国良¹^,²^,³, 杨蕾¹^,²(), 邓崇海¹^,², 储德林⁴, 张苗⁵, 孙兆奇⁵()

1.合肥学院能源材料与化工学院, 合肥 230601
2.合肥学院先进电池材料与技术重点实验室, 合肥 230601
3.长鑫存储技术有限公司, 合肥 230000
4.安徽大学物质科学与信息技术研究院, 合肥 230039
5.安徽大学材料科学与工程学院, 合肥 230039

收稿日期:2022-07-28 修回日期:2022-09-25 出版日期:2023-01-20 网络出版日期:2022-09-30
通讯作者: 杨蕾, 副教授. E-mail: ylei531@163.com;
孙兆奇, 教授. E-mail: szq@ahu.edu.cn
作者简介:王如意(1996-), 男, 硕士研究生. E-mail: 445113000@qq.com
基金资助:
国家自然科学基金(61804039);安徽省高校自然科学研究项目(KJ2021A1017);合肥学院人才科研项目(20RC35);安徽省高校协同创新项目(GXXT-2021-013);合肥学院研究生教育教学研究项目(2021Yjyxm01);安徽省高校学科(专业)拔尖人才学术资助项目(gxbjZD2021085);安徽省重点研究与开发计划(201904b11020040)

p-n Heterostructured BiVO₄/g-C₃N₄ Photoanode: Construction and Its Photoelectrochemical Water Splitting Performance

WANG Ruyi¹^,²(), XU Guoliang¹^,²^,³, YANG Lei¹^,²(), DENG Chonghai¹^,², CHU Delin⁴, ZHANG Miao⁵, SUN Zhaoqi⁵()

1. School of Energy Materials and Chemical Engineering, Hefei University, Hefei 230601, China
2. Key Laboratory of Materials and Technologies for Advanced Batteries, Hefei University, Hefei 230601, China
3. Changxin Memory Technologies, Inc., Hefei 230000, China
4. Institute of Physical Science and Information Technology, Anhui University, Hefei 230039, China
5. School of Materials Science and Engineering, Anhui University, Hefei 230039, China

Received:2022-07-28 Revised:2022-09-25 Published:2023-01-20 Online:2022-09-30
Contact: YANG Lei, associate professor. E-mail: ylei531@163.com;
SUN Zhaoqi, professor. E-mail: szq@ahu.edu.cn
About author:WANG Ruyi (1996-), male, Master candidate. E-mail: 445113000@qq.com
Supported by:
National Natural Science Foundation of China(61804039);Key Project of Natural Science Research of Universities in Anhui Province(KJ2021A1017);Talent Research Fund of Hefei University(20RC35);University Synergy Innovation Program of Anhui Province(GXXT-2021-013);Graduate Education and Teaching Research Project of Hefei University(2021Yjyxm01);Academic Support Project for Academic (Professional) Top Talents in Anhui Universities(gxbjZD2021085);Key Projects of Research and Development Program of Anhui Province(201904b11020040)

摘要/Abstract

摘要：

钒酸铋(BVO)可用于光电化学(PEC)水解产氢, 但受限于其缓慢的表面水氧化动力学, 在电极表面修饰单一的析氧助催化剂达不到理想的性能。本工作在BVO电极表面修饰FeNiO_x助催化剂可以显著降低起始电压, 增强光电化学性能。此外, 沉积g-C₃N₄后修饰FeNiO_x助催化剂得到的光电极具有更优异的性能。厚度适合的g-C₃N₄纳米片与BVO构成Ⅱ型p-n异质结, 有效抑制了光生电子空穴的复合, 促进了电极的电荷分离。电化学测试结果表明, 沉积了g-C₃N₄后, 电极的电荷分离效率达到88.2%, 比BVO/FeNiO_x (60.6%)提升了近1.5倍。经过g-C₃N₄和FeNiO_x协同修饰的BVO/g-C₃N₄/FeNiO_x电极, 表面电荷注入效率达到了90.2%, 同时, 在1.23 V (vs. RHE)条件下光电流密度达到4.63 mA∙cm^-2, 是纯BVO (1.86 mA∙cm^-2)的2.48倍。本工作为开发制备高性能光阳极提供了一种有效的策略。

关键词: g-C₃N₄纳米片, BiVO₄, 光电化学水解, FeNiO_x助催化剂, p-n异质结

Abstract:

Bismuth vanadate (BVO) can be used for photoelectrochemical (PEC) water splitting to hydrogen. However, suffering from its high charge-recombination and slow surface catalytic reaction, the PEC performance is far below the expectation, and the modification of the co-catalysts only on the electrode cannot overcome this disadvantage. Here, we report FeNiO_x cocatalyst decorated on the BVO photoanode, which can restrict the onset potential and improve the PEC performance. Moreover, a more effective dual modified-BVO photoanode is formed, with the loading of g-C₃N₄before decoration of FeNiO_x cocatalyst. The type-II p-n heterojunction composed by g-C₃N₄ nanosheets and BVO, can inhibit recombination of photogenerated charge, and promote the separation of charge effectively at the electrode. Results show that the charge separation efficiency of the electrode reaches 88.2% after the insertion of g-C₃N₄, which is nearly 1.5 times that of BVO/FeNiO_x (60.6%). Moreover, surface charge injection efficiency of the dual-modified BVO/g-C₃N₄/FeNiO_xelectrode reaches 90.2%, while the current density reaches 4.63 mA∙cm^-2 at 1.23 V (vs. RHE). This work provides a facile approach to develope high performance photoanodes for PEC water splitting.

Key words: g-C₃N₄nanosheets, BiVO₄, PEC water splitting, FeNiO_x co-catalyst, p-n heterojunction

中图分类号:

TQ174

王如意, 徐国良, 杨蕾, 邓崇海, 储德林, 张苗, 孙兆奇. p-n异质结BiVO₄/g-C₃N₄光阳极的制备及其光电化学水解性能[J]. 无机材料学报, 2023, 38(1): 87-96.

WANG Ruyi, XU Guoliang, YANG Lei, DENG Chonghai, CHU Delin, ZHANG Miao, SUN Zhaoqi. p-n Heterostructured BiVO₄/g-C₃N₄ Photoanode: Construction and Its Photoelectrochemical Water Splitting Performance[J]. Journal of Inorganic Materials, 2023, 38(1): 87-96.

图/表 17

图1 BVO及其复合电极的制备示意图

Fig. 1 Schematic diagram of the preparation for BVO and its composite electrode

图2 不同光阳极的(a) XRD谱图和(b) FT-IR谱图

Fig. 2 (a) X-ray diffraction (XRD) patterns and (b) Fourier transform infrared (FT-IR) spectra of different electrodes

图S1 g-C3N4纳米片的XRD图谱

Fig. S1 XRD pattern of g-C3N4 nanosheets

图S2 BVO/g-C3N4/FeNiOx光阳极的高倍率SEM照片

Fig. S2 High resolution SEM images of BVO/g-C3N4/FeNiOx

图3 (a) BVO, (b) BVO/g-C3N4, (c) BVO/g-C3N4/FeNiOx 的SEM照片及(d~j)BVO/g-C3N4/FeNiOx的EDS能谱

Fig. 3 Scanning electron microscope (SEM) images of (a) BVO, (b) BVO/g-C3N4, (c) BVO/g-C3N4/FeNiOx, and (d-j) energy dispersive spectrometer (EDS) mappings of BVO/g-C3N4/FeNiOx

图S3 纯g-C3N4纳米片的SEM照片

Fig. S3 SEM images of pure g-C3N4 nanosheets

图S4 BVO/g-C3N4/FeNiOx的截面SEM照片

Fig. S4 Cross-section SEM image of BVO/g-C3N4/FeNiOx

图4 BVO/g-C3N4/FeNiOx光阳极的XPS谱图

Fig. 4 X-ray photoelectron spectra (XPS) of BVO/g-C3N4/FeNiOx photoanode (a) Total survey and (b) Bi4f, (c) V2p, (d) O1s, (e) C1s, (f) N1s, (g) Ni2p, (h) Fe2p high resolution spectra

图5 (a) BVO和(b) g-C3N4电极的莫特-肖特基(M-S)曲线

Fig. 5 Mott-Schottky (M-S) curves of (a) BVO and (b) g-C3N4 electrodes

图S5 BVO/g-C3N4/FeNiOx在不同扫速的LSV曲线

Fig. S5 LSV curves of BVO/g-C3N4/FeNiOx at different scan rates

图6 不同光阳极的光电化学性能

Fig. 6 Photoelectrochemical performance of different photoanodes (a) Linear sweep voltammetry (LSV) curves under illumination and (b) corresponding Butler curves; (c) LSV curves in the dark; (d) Open circuit potential (OCP) curves; (e) I-t curves at 1.23 V (vs. RHE); (f) Transient decay time curves Colorful figures are available on website

图7 不同光阳极的(a) UV-Vis图谱, (b) Tauc曲线, (c)电解液含Na2SO3的LSV曲线, (d)ηsep, (e)ηinj和(f) PL光谱

Fig. 7 (a) Ultraviolet and visible (UV-Vis) spectra, (b) Tauc curves, (c) LSV curves with Na2SO3 in electrolyte, (d) bulk charge separation efficiency (ηsep), (e) surface charge injection efficiency (ηinj), and (f) photoluminescence (PL) spectra of different photoanodes Colorful figures are available on website

图S6 不同光阳极的光吸收效率

Fig. S6 Light harvesting efficiency (ηabs) curves of different photoanodes

图S7 太阳光谱积分得到各电极的理论光电流密度(Jabs)

Fig. S7 Theoretical photocurrent density (Jabs) obtained with integrated solar spectrum for each electrode

图8 不同光阳极的(a) ABPE和(b) EIS谱图

Fig. 8 (a) Application bias photon-to-current efficiency (ABPE) and (b) electrochemical impedance spectra (EIS) of photoanodes Colorful figures are available on website

图9 (a)气相色谱测试的BVO/g-C3N4/FeNiOx的析氢、析氧量及法拉第效率, (b) BVO/g-C3N4/FeNiOx的稳定性测试曲线

Fig. 9 (a)Gas evolutions detected by gas chromatography and Faradaic efficiency for BVO/g-C3N4/FeNiOx and (b) stability curve of BVO/g-C3N4/FeNiOx Colorful figures are available on website

图10 BVO/g-C3N4/FeNiOx光阳极的光生电荷转移机理示意图

Fig. 10 Schematic illustration of charge transfer for PEC water splitting

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p-n异质结BiVO₄/g-C₃N₄光阳极的制备及其光电化学水解性能

p-n Heterostructured BiVO₄/g-C₃N₄ Photoanode: Construction and Its Photoelectrochemical Water Splitting Performance

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