酒石酸辅助溶液生长制备具有垂直晶粒的低缺陷Cu2O薄膜用于高效光电催化水分解

doi:10.1016/S1872-2067(26)65202-3

催化学报 ›› 2026, Vol. 90: 243-252.DOI: 10.1016/S1872-2067(26)65202-3

酒石酸辅助溶液生长制备具有垂直晶粒的低缺陷Cu₂O薄膜用于高效光电催化水分解

武琳晓^a^,¹, 韩雨萌^a^,¹, 程金水^a, 桑聿帅^b, 陈祥^c, 张亚卿^c, 付学文^c^,^e, 罗景山^a^,^d^,^e^,^*()

^a 南开大学光电子薄膜器件与技术研究所, 光伏材料与电池全国重点实验室, 天津市太阳能高效利用重点实验室, 教育部薄膜光电子技术工程研究中心, 天津 300350
^b 天津大学大型仪器平台, 电镜中心, 天津 300072
^c 南开大学物理科学学院, 弱光非线性光子学教育部重点实验室, 超快电子显微镜实验室, 天津 300071
^d 南开大学有机新物质创造前沿科学中心, 天津 300071
^e 南开大学前沿交叉学科研究院, 天津 300071

收稿日期:2026-02-06 接受日期:2026-03-19 出版日期:2026-11-18 发布日期:2026-09-09
通讯作者: *电子信箱: jingshan.luo@nankai.edu.cn (罗景山).
作者简介:¹共同第一作者.
基金资助:
国家重点研发计划(2019YFE0123400);国家自然科学基金(52072187);国家自然科学基金(22122903);天津市杰出青年科学基金(20JCJQJC00260)

Low-defect Cu₂O films with vertical grains via tartaric acid assisted solution growth for efficient photoelectrochemical water splitting

Linxiao Wu^a^,¹, Yumeng Han^a^,¹, Jinshui Cheng^a, Yushuai Sang^b, Xiang Chen^c, Yaqing Zhang^c, Xuewen Fu^c^,^e, Jingshan Luo^a^,^d^,^e^,^*()

^a Institute of Photoelectronic Thin Film Devices and Technology, State Key Laboratory of Photovoltaic Materials and Cells, Tianjin Key Laboratory of Efficient Utilization of Solar Energy, Ministry of Education Engineering Research Center of Thin Film Photoelectronic Technology, Nankai University, Tianjin 300350, China
^b Electron Microscope Center, Core Facility Platform, Tianjin University, Tianjin 300072, China
^c Ultrafast Electron Microscopy Laboratory MOE Key Laboratory of Weak-Light Nonlinear Photonics, School of Physics, Nankai University, Tianjin 300071, China
^d Frontiers Science Center for New Organic Matter, Nankai University, Tianjin 300071, China
^e Academy for Advanced Interdisciplinary Studies, Nankai University, Tianjin 300071, China

Received:2026-02-06 Accepted:2026-03-19 Online:2026-11-18 Published:2026-09-09
Contact: *E-mail:jingshan.luo@nankai.edu.cn(J. Luo).
About author:¹Contributed equally to this work.
Supported by:
National Key Research and Development Program of China(2019YFE0123400);National Natural Science Foundation of China(52072187);National Natural Science Foundation of China(22122903);Tianjin Distinguished Young Scholar Fund(20JCJQJC00260)

摘要/Abstract

摘要：

光电催化水分解技术是一种有前景、绿色且可持续的制氢方式. 金属氧化物光电极因其成本低, 元素含量丰富且无毒的特点受到广泛关注. 在金属氧化物半导体中, Cu₂O作为一种本征p型氧化物半导体, 因其2 eV的适宜带隙, 高达14.7 mA·cm^-2的理论光电流密度以及适合产氢的能带位置, 在光电催化水分解领域展现出巨大的应用潜力. 实现高效Cu₂O光阴极的策略包括晶面取向调控, 纳米线制备以及电荷传输层优化. 然而, 在接近室温下制备的Cu₂O薄膜仍存在薄膜质量差和电荷传输效率低的问题. 此外, 由于此类薄膜的最佳厚度薄于光学吸收深度, 导致Cu₂O吸收层内存在光学损耗. 因此, 制备微米级厚度、高质量的本征吸收层, 以同时增强光子利用率并促进电荷传输, 对于提升器件性能至关重要.

本文开发了一种基于酒石酸辅助溶液生长的新型电沉积方法, 成功制备了高质量的微米级厚度的Cu₂O薄膜(T-Cu₂O). 莫特肖特基测试显示, T-Cu₂O薄膜的载流子浓度低于传统乳酸辅助法制备的Cu₂O薄膜(L-Cu₂O). 光致发光和时间分辨光致发光光谱分析结果表明, 与L-Cu₂O相比, T-Cu₂O薄膜的缺陷密度降低, 载流子寿命明显延长. 截面电子背散射衍射测试揭示了T-Cu₂O薄膜具有更多垂直生长的柱状晶粒, 从而有效促进了载流子沿垂直于基底方向的传输. 随后, 利用原子层沉积技术依次沉积Ga₂O₃和ZnGeO_x缓冲层以及TiO₂保护层, 并通过光电化学沉积法负载RuO_x助催化剂, 构筑了完整的光阴极(Cu₂O/Ga₂O₃/ZnGeO_x/TiO₂/RuO_x). 在AM 1.5G模拟太阳光照射下, 优化后的T-Cu₂O光阴极取得优异的光电催化制氢性能, 起始电位为1 V, 在0 V(相对于RHE)的电流密度达到-8 mA·cm^-2, 比L-Cu₂O光阴极提高了23%. 此外, T-Cu₂O光阴极在0.5 V的光电流密度也能达到-6.5 mA·cm^-2, 是目前室温法制备的最先进的Cu₂O光阴极之一. 本文还系统地探究了薄膜厚度和电沉积的电流密度对Cu₂O光阴极光电催化性能的影响. 得益于更低的缺陷密度和更多的垂直柱状晶粒所带来的增强电荷传输能力, 性能最佳的T-Cu₂O光阴极的厚度大于L-Cu₂O的厚度. 微米级厚度的T-Cu₂O光阴极在光吸收最大化的同时保持高效的载流子提取效率, 最终实现光电催化水分解性能的提高. 最后, 表面光电压显微镜技术和光电化学阻抗谱的分析进一步证实, T-Cu₂O光阴极的电荷分离和传输效率较L-Cu₂O光阴极有大幅提高.

综上, 本工作开发了一种基于酒石酸辅助的新型电沉积方法, 实现了高质量Cu₂O薄膜的可控制备. 该策略有效降低了薄膜的缺陷密度, 并促进了柱状晶粒的垂直生长, 大幅提升了其光电催化制氢性能. 为设计高效Cu₂O光阴极以及推进光电催化水分解制氢的发展提供了具有前景的制备方法.

关键词: 光电催化水分解, 光电极, 氧化亚铜, 电沉积, 酒石酸

Abstract:

Cu₂O is among the most promising metal oxide semiconductors for solar water splitting, yet its performance is often limited by structural defects and poor charge transport. Here, we report a tartaric acid-assisted solution growth strategy to fabricate high-quality Cu₂O films (T-Cu₂O) with reduced defect density, prolonged carrier lifetimes, and enhanced electrical conductivity. Microstructural analysis reveals that T-Cu₂O films consist of vertically aligned columnar grains exceeding 1 μm in length, spanning the entire film thickness. This contrasts with the disordered grains formed in conventional lactic acid-assisted films (L-Cu₂O), which impede charge transport. Upon integration with overlayers and RuO_x cocatalysts, the T-Cu₂O photocathode delivers a photocurrent density of 8.0 mA cm^-2 at 0 V vs. RHE—23% higher than its L-Cu₂O counterpart. Surface photovoltage measurements further confirm significantly improved charge separation in T-Cu₂O. This work establishes a facile solution-based strategy for producing high-quality Cu₂O photoelectrodes with enhanced efficiency for photoelectrochemical water splitting.

Key words: Photoelectrochemical water splitting, Photoelectrode, Cu₂O, Electrodeposition, Tartaric acid

武琳晓, 韩雨萌, 程金水, 桑聿帅, 陈祥, 张亚卿, 付学文, 罗景山. 酒石酸辅助溶液生长制备具有垂直晶粒的低缺陷Cu₂O薄膜用于高效光电催化水分解[J]. 催化学报, 2026, 90: 243-252.

Linxiao Wu, Yumeng Han, Jinshui Cheng, Yushuai Sang, Xiang Chen, Yaqing Zhang, Xuewen Fu, Jingshan Luo. Low-defect Cu₂O films with vertical grains via tartaric acid assisted solution growth for efficient photoelectrochemical water splitting[J]. Chinese Journal of Catalysis, 2026, 90: 243-252.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65202-3

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图/表 5

Fig. 1. (a) XRD patterns of T-Cu2O electrodeposited from a tartrate stabilized copper sulfate solution and L-Cu2O film from a lactate-stabilized copper sulfate solution. Indexes were taken from the following patterns: Au PDF#99-0056, Cu2O PDF#05-0667, FTO PDF#41-1445. XPS spectra Cu 2p (b) and XPS O 1s spectra (c) of T-Cu2O film and L-Cu2O film. Top-view SEM images of T-Cu2O films with electrodeposition time of 1 min (d), 5 min (e), and 50 min (f). Top-view SEM images of L-Cu2O films with electrodeposition time of 1 min (g), 5 min (h), and 100 min (i).

Fig. 2. Cross-sectional SEM image (a), EBSD pattern-quality map (b), and EBSD orientation-distribution map (c) perpendicular to substrate highlighted by false colors within the related inverse pole figure of T-Cu2O film (electrodeposition time for 50 min). Cross-sectional SEM image (d), EBSD pattern-quality map (e), and EBSD orientation-distribution maps (f) perpendicular to substrate of L-Cu2O film (electrodeposition time for 200 min). (g,h) Schematic diagram of charge transport in Cu2O films.

Fig. 3. Mott-Schottky plots (a) and PL spectra (b) of T-Cu2O and L-Cu2O films. Streak camera images of TRPL of T-Cu2O (c) and L-Cu2O (d) films. (e,f) Corresponding decay traces of the near band emission extracted from (c) and (d) fitted using a biexponential function. C-AFM current mapping images of T-Cu2O (g) and L-Cu2O (h) films. CPD of T-Cu2O (i) and L-Cu2O (j) films.

Fig. 4. (a) J-V curve of T-Cu2O and L-Cu2O photocathodes (Cu2O/Ga2O3/ZnGeOx/TiO2/RuOx) under continuous simulated one-sun AM 1.5 G (solid line) and dark condition (dashed line). (b) J-V curve of T-Cu2O and L-Cu2O photoelectrodes under chopped simulated AM 1.5G illumination. Statistical current density at 0 V vs. RHE (c) and onset potential (d) of Cu2O photoelectrodes under continuous simulated one-sun air mass 1.5 G condition. (e) IPCE spectra under monochromatic illumination of T-Cu2O and L-Cu2O photoelectrodes at 0 V vs. RHE. (f) Stability test of T-Cu2O photocathode at 0.5 V vs. RHE. All measurements were performed in a pH 5.0 electrolyte solution under constant stirring at 500 rpm.

Fig. 5. SPVM images of T-Cu2O (a) and L-Cu2O (b) photoelectrodes (Cu2O/Ga2O3/ZnGeOx/TiO2). SPVM images of T-Cu2O (d) and L-Cu2O (e) photoelectrodes with RuOx catalyst (Cu2O/Ga2O3/ZnGeOx/TiO2/RuOx). The vertical height gradient denotes film surface topography, and the color gradient represents CPD. SPV spectra for T-Cu2O and L-Cu2O photoelectrodes without (c) and with (f) catalyst. Charge transfer efficiency (ηtransfer) (g) and charge separation efficiency (ηsep) (h) of Cu2O photocathodes. (i) The open-circuit potential of Cu2O/Ga2O3/ZnGeOx/TiO2/RuOx photocathodes under chopped illumination condition in pH 5 electrolyte.

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酒石酸辅助溶液生长制备具有垂直晶粒的低缺陷Cu₂O薄膜用于高效光电催化水分解

Low-defect Cu₂O films with vertical grains via tartaric acid assisted solution growth for efficient photoelectrochemical water splitting

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