电荷迁移方向调控的BiVO4量子点/苝四羧酸Z型异质结与纳米金修饰在人工光合成H2O2中的协同作用

doi:10.1016/S1872-2067(24)60058-6

催化学报 ›› 2024, Vol. 62: 277-286.DOI: 10.1016/S1872-2067(24)60058-6

电荷迁移方向调控的BiVO₄量子点/苝四羧酸Z型异质结与纳米金修饰在人工光合成H₂O₂中的协同作用

梁腾, 李雨彤, 徐帅, 姚宇欣, 许荣萍, 边辑^*(), 张紫晴^*(), 井立强^*()

黑龙江大学化学化工与材料学院, 功能无机材料化学教育部重点实验室, 催化技术国际联合研究中心实验室, 黑龙江哈尔滨 150080

收稿日期:2024-04-10 接受日期:2024-05-22 出版日期:2024-07-18 发布日期:2024-07-10
通讯作者: *电子信箱: bianji@hlju.edu.cn (边辑), zhangzq@hlju.edu.cn (张紫晴), jinglq@hlju.edu.cn (井立强).
基金资助:
国家自然科学基金(U2102211);国家自然科学基金(22105066);国家自然科学基金(22202064);国家自然科学基金(U23A20576);黑龙江省自然科学优秀青年基金(YQ2022B009);黑龙江省自然科学优秀青年基金(YQ2023B008)

Synergy of charge migration direction-manipulated Z-scheme heterojunction of BiVO₄ quantum dots/perylenetetracarboxylic acid and nanosized Au modification for artificial H₂O₂ photosynthesis

Teng Liang, Yutong Li, Shuai Xu, Yuxin Yao, Rongping Xu, Ji Bian^*(), Ziqing Zhang^*(), Liqiang Jing^*()

Key Laboratory of Functional Inorganic Materials Chemistry (Ministry of Education), School of Chemistry and Materials Science, International Joint Research Center for Catalytic Technology, Heilongjiang University, Harbin 150080, Heilongjiang, China

Received:2024-04-10 Accepted:2024-05-22 Online:2024-07-18 Published:2024-07-10
Contact: *E-mail: bianji@hlju.edu.cn (J. Bian), zhangzq@hlju.edu.cn (Z. Zhang), jinglq@hlju.edu.cn (L. Jing).
Supported by:
National Natural Science Foundation of China(U2102211);National Natural Science Foundation of China(22105066);National Natural Science Foundation of China(22202064);National Natural Science Foundation of China(U23A20576);Outstanding Youth Science Foundation of Heilongjiang Province(YQ2022B009);Outstanding Youth Science Foundation of Heilongjiang Province(YQ2023B008)

摘要/Abstract

摘要：

利用太阳能驱动的半导体光催化技术将H₂O和O₂转化为H₂O₂, 是传统蒽醌工艺的可持续替代方案之一. 在光催化O₂还原生产H₂O₂的过程中, 主要涉及到O₂的还原和H₂O的氧化两个半反应. 然而, 单一的窄带隙半导体往往难以满足整体反应的热力学电位要求. 为了克服这一挑战, 研究人员借鉴自然光合作用的原理, 提出了构建Z型异质结体系的策略. 这种体系不仅能有效促进电荷的分离, 从而增强光催化效率, 而且能保留光生电荷较强的氧化还原能力, 这对于H₂O₂的光合成至关重要. 此外, O₂的活化对于H₂O₂光合成同样重要. 然而, 目前在构建Z型异质结时, 对于Z型异质结的两组分自身电荷传输方向的匹配性鲜有关注. 因此, 构建具有电荷定向传输的Z型异质结, 并精准负载O₂活化位点, 对于提高H₂O₂的光合成效率和稳定性具有重要意义.

本文以苝-3,4,9,10-四羧酸二酐(PTCDA)为前驱体, 在水解的过程中, 引入预制备的钒酸铋量子点(BQD), 原位构建BQD/PTA Z型异质结. 然后, 通过低温辅助光还原策略将纳米Au精确修饰在苝四甲酸(PTA)上, 制得具有定向电荷传输的BQD/PTA-Au Z型异质结. 形貌表征结果表明, PTA的形态为平均厚度为3.5 nm的不规则纳米片, 其表面均匀负载了直径约为7 nm的BQD纳米颗粒, 而超小的Au纳米粒子(直径约为5 nm)则负载在PTA纳米片的边缘. 优化后的BQD/PTA-Au异质结光催化H₂O₂产率为218.6 μmol g^‒1 h^‒1, 约为PTA纳米片的6.4倍; 此外, 在405 nm波长下, 该异质结的表观量子产率为PTA的4.8倍. 在模拟太阳光条件下, BQD/PTA-Au异质结的太阳能到化学能转换效率(SCC)为0.47%; 且在连续5次的循环实验中表现出良好的稳定性. 光物理和光化学测试结果表明, BQD/PTA Z型异质结的构建显著促进了PTA的电荷分离, Au修饰后复合体的电荷分离进一步增强. 扫描开尔文探针(SKP)测试结果表明, BQD和PTA的能带结构满足Z型电荷传输路径, 电子顺磁共振和原位X射线光电子能谱分析结果表明, 所构建的Z型异质结由于电荷传输方向匹配, 显著促进·O₂^‒自由基的形成; 而后续的Au修饰则能够定向接受来自PTA的光生电子. 旋转圆盘电极测试结果表明, BQD/PTA-Au的平均电子转移数最接近2, 说明其遵循两电子氧还原反应(ORR)路径. 结合物种捕获实验推测, ·O₂^‒自由基是BQD/PTA-Au异质结光合成H₂O₂的主要活性物种. 原位漫反射红外光谱测试证实, 纳米Au修饰可进一步提高O₂在催化剂表面吸附, 并加速两电子的O₂还原反应.

综上, 本文围绕着具有各向异性电荷迁移的PTA, 设计构建了电荷定向迁移的Z型异质结体系, 实现了高效的H₂O₂光合成, 为高效Z型异质结体系设计构建提供了新思路.

关键词: Z型异质结, 苝四甲酸, BiVO₄量子点, H₂O₂光合成, 氧还原

Abstract:

Herein, perylenetetracarboxylic acid (PTA) nanosheets with anisotropic charge migration driven by the formed internal electric fields are synthesized through a facile hydrolysis-reassembly process. Strategically, a Z-scheme heterojunction with free-flowing interfacial charge transfer and spatially separated redox centers is constructed based on the distinct photogenerated electrons and holes accumulation regions of PTA nanosheets by in-situ introducing BiVO₄quantum dots (BQD) and nanosized Au. The optimized BQD/PTA-Au exhibits a ca. 6.4-fold and 4.8-fold enhancement in H₂O₂ production rate and apparent quantum yield at 405 nm compared with pristine PTA, respectively. The exceptional activities are attributed to the cascade Z-scheme charge transfer followed the matched charge migration orientation, as well as the Au active sites for accelerating 2e⁻ oxygen reduction pathway induced by superoxide radicals, as unraveled by electron paramagnetic resonance, in-situ irradiated X-ray photoelectron spectroscopy and in-situ diffuse reflectance infrared Fourier transformation spectroscopy. This work provides a strategy to design an efficient Z-scheme system towards solar-driven H₂O₂ production.

Key words: Z-scheme heterojunction, Perylenetetracarboxylic acid, BiVO₄quantum dots, H₂O₂ photosynthesis, Oxygen reduction<br

梁腾, 李雨彤, 徐帅, 姚宇欣, 许荣萍, 边辑, 张紫晴, 井立强. 电荷迁移方向调控的BiVO₄量子点/苝四羧酸Z型异质结与纳米金修饰在人工光合成H₂O₂中的协同作用[J]. 催化学报, 2024, 62: 277-286.

Teng Liang, Yutong Li, Shuai Xu, Yuxin Yao, Rongping Xu, Ji Bian, Ziqing Zhang, Liqiang Jing. Synergy of charge migration direction-manipulated Z-scheme heterojunction of BiVO₄ quantum dots/perylenetetracarboxylic acid and nanosized Au modification for artificial H₂O₂ photosynthesis[J]. Chinese Journal of Catalysis, 2024, 62: 277-286.

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图/表 5

Fig. 1. TEM image (a), AFM image (b) and the corresponding height profiles (c) of PTA. TEM images of BQD (d) and BQD/PTA-Au (e) with the HRTEM images. (f) High-angle annular dark-field scanning TEM image of BQD/PTA-Au and the corresponding EDX mapping images of elemental C, O, Bi, V and Au. (g) XRD patterns of PTA, BQD, 7.5BQD/PTA and 7.5BQD/PTA-1Au. XPS analyses of Bi 4f (h) and V 2p (i) of BQD, BQD/PTA and BQD/PTA-Au.

Fig. 2. (a) Photocatalytic performance toward H2O2 production (pure water under visible-light irradiation, pH = 7.0) and the corresponding SCC efficiency (AM 1.5G simulated sunlight irradiation, pH = 7.0) for PTA, BQD, PTA-Au, BQD/PTA and BQD/PTA-Au. (b) Five consecutive runs of H2O2 production by BQD/PTA-Au with pure water under visible-light irradiation. (c) The formation rate constant (Kf) and decomposition rate constant (Kd) of H2O2 for PTA, BQD, PTA-Au, BQD/PTA and BQD/PTA-Au. (d) Overlayer of AQY and UV-vis absorption spectra. (e) Fluorescence spectra related to the formed hydroxyl radicals of PTA, PTA-Au, BQD/PTA and BQD/PTA-Au. (f) Photoelectrochemical I-t curves of PTA, PTA-Au, BQD/PTA and BQD/PTA-Au.

Fig. 3. (a) SKP maps and the work function diagrams of PTA and BQD. (b) Schematic diagram of formation of BQD/PTA Z-scheme heterojunction and the internal electric field induced charge transfer and separation under light irradiation. (c) DMPO spin-trapping EPR spectra recorded for ·O2? under light irradiation for PTA, BQD, BQD/PTA, and BQD/PTA-Au. Detection conditions: the concentration of DMPO is 50 mmol L?1. ·O2? were determined in methanolic solution. (d,e) In-situ irradiated XPS analyses for Bi 4f and Au 4f of BQD/PTA-Au.

Fig. 4. (a) The Koutecky-Levich plots obtained by RDE measurements at ?0.6 V (vs RHE). (b) The photocatalytic H2O2 generation rates of various samples under different reaction gases or sacrificial agents. (c) Mass spectra of luminol before and after oxidation with hydrogen peroxide generated by photocatalytic H218O splitting. (d) In situ DRIFT spectra of CHFs recorded during photocatalytic H2O2 evolution. (e,f) The intensity of the peaks at 1154 and 2848 cm?1 vs. illumination time.

Fig. 5. Schematic illustration of BQD and Au loaded on PTA (left) and the charge transfer and the involved redox reactions on BQD/PTA-Au (right).

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电荷迁移方向调控的BiVO₄量子点/苝四羧酸Z型异质结与纳米金修饰在人工光合成H₂O₂中的协同作用

Synergy of charge migration direction-manipulated Z-scheme heterojunction of BiVO₄ quantum dots/perylenetetracarboxylic acid and nanosized Au modification for artificial H₂O₂ photosynthesis

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