构筑共轭聚合物基S型异质结分子内和界面电场以实现高效光催化制氢

doi:10.1016/S1872-2067(23)64602-9

摘要/Abstract

摘要：

能源短缺与环境问题已成为阻碍社会经济发展的重要因素, 并对人类生活质量产生了深远影响, 成为重大的全球性挑战. 传统的一次能源, 如煤、石油和天然气, 正面临着日益严重的短缺问题, 同时, 水体污染日趋严重. 因此, 迫切需要寻找绿色、可持续的能源解决方案. 其中, 利用太阳能进行光解水制氢以及降解水中污染物, 被视为一种极具潜力和前景的能源利用方式. 然而, 目前的光催化剂普遍面临光生载流子容易复合、迁移速率缓慢等问题, 这些问题限制了光生电荷的寿命, 往往只有几十皮秒, 从而降低了其在氧化还原反应中的有效性和光催化效率. 因此, 开发高效、稳定的光催化剂成为了当前研究的热点和迫切需求.

本文报道了一种新型光催化剂的合成与应用. 首先, 将1,6-二溴芘分子作为富电子供体(D)引入到氮化碳(g-C₃N₄)中, 合成了以C‒N键连接的g-C₃N₄-1,6-二溴芘(CNPy)材料. 随后, 通过多种手段对样品进行了表征. X射线衍射图谱、傅里叶红外光谱和核磁共振图谱证明了1,6-二溴芘分子的成功引入. 氮气等温吸附脱附曲线结果表明, 与纯g-C₃N₄相比, 芘基的引入增加了g-C₃N₄的比表面积, 暴露出更多的活性位点. X射线光电子能谱和表面电荷密度测试结果证实了CNPy分子内电场的成功构建. 当以铂为助催化剂时, CNPy-0.2(包含200 mg CNPy)表现出较高的光催化产氢性能, 产率达到6.1mmol·g^-1·h^-1. 在此基础上, 为了进一步提升催化性能, 将CNPy与具有宽光谱响应范围和匹配能带结构的CdSe纳米颗粒进行复合, 构筑了具有双电场(分子内和界面电场)的CdSe/CNPy S型异质结光催化剂. X射线衍射图谱、扫描电子显微镜及透射电子显微镜测试结果证实了CdSe与1,6-二溴芘修饰的g-C₃N₄的成功复合, 且CdSe纳米颗粒(200 nm左右)均匀地分布在CNPy上. 此外, 通过原位X射线光电子能谱、电子顺磁共振波谱和开尔文探针力显微镜等表征手段证实了S型异质结的形成以及CdSe与CNPy之间存在内建电场. 光电化学表征进一步证实了CdSe/CNPy S型异质结具有高效的载流子分离效率. 能带结构分析结果表明, 该CdSe/CNPy S型异质结在光激发后保留了CNPy的较强氧化能力与CdSe的较强还原能力. 在无Pt作助催化剂的情况下, 测试了CdSe/CNPy S型异质结的析氢与降解性能. 结果显示, 优化后的复合材料100% CdSe/CNPy-0.2在光催化产H₂反应中, 产率高达1.16 mmol·g^-1·h^-1, 分别是纯CNPy-0.2, CdSe和100% CdSe/CN的58倍, 2.2倍和2.32倍. 此外, 该S型异质结材料表现出较好的光催化降解四环素性能, 在全光谱照射下, 降解效率高达97%. 多次循环数据显示, 该S型异质结材料表现出良好的稳定性.

综上所述, 本研究通过分子结构设计, 在共轭聚合物分子内引入内建电场, 并结合异质结界面工程策略, 构筑了具有双电场的S型异质结光催化材料. 该材料表现出高效的光催化析氢和污染物降解性能, 为提升共轭半导体基光催化材料的性能提供了新思路.

关键词: g-C₃N₄, 分子内电场, 界面电场, S型异质结构, 光催化剂

Abstract:

Engineering a robust built-in electric field (IEF) is favorable for boosting carrier separation and achieving high photocatalytic performance. Herein, we developed a donor-acceptor conjugated polymer-based S-scheme heterojunction, utilizing both intramolecular and interfacial IEF to enhance carrier separation and achieve superior photocatalytic performance. Specifically, the intramolecular IEF was established by introducing 1,6-dibromopyrene into carbon nitride (CN) to form 1,6-dibromopyrene grafted CN (CNPy). Concurrently, the S-scheme heterojunction was formed by coupling CNPy with CdSe nanoparticles to create an interfacial IEF. Experimental findings demonstrated that the combined effect of intramolecular and interfacial IEF within the CdSe/CNPy heterojunction significantly improved the carrier separation and retained strong redox capacity. Benefiting from these advantages, the optimized composite, 100%CdSe/CNPy-0.2, showed the highest H₂ generation rate of 1.16 mmol•g^-1•h^-1, surpassing those of pure CNPy-0.2, CdSe and 100%CdSe/CN by 58, 2.2 and 2.32 times, respectively. This study introduces an innovative design strategy for IEF-regulated conjugated polymer-based materials, paving the way for efficient solar-to-chemical energy conversion.

Key words: g-C₃N₄, Intramolecular built-in electric field, Interfacial built-in electric field, S-Scheme heterostructure, Photocatalyst

王乐乐, 程文瑶, 王嘉鑫, 杨娟, 刘芹芹. 构筑共轭聚合物基S型异质结分子内和界面电场以实现高效光催化制氢[J]. 催化学报, 2024, 58: 194-205.

Lele Wang, Wenyao Cheng, Jiaxin Wang, Juan Yang, Qinqin Liu. Construction of intramolecular and interfacial built-in electric field in a donor-acceptor conjugated polymers-based S-scheme heterojunction for high photocatalytic H₂ generation[J]. Chinese Journal of Catalysis, 2024, 58: 194-205.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64602-9

https://www.cjcatal.com/CN/Y2024/V58/I3/194

图/表 11

Scheme 1. Possible reaction pathway for the incorporation of 1,6-dibromopyrene into g-C3N4 networks, and the synthetic process of CdSe/CNPy composites.

Fig. 1. (a) XRD patterns of CN and CNPy samples. (b,c) FTIR spectra of CN and CNPy samples. (d) Molecular fragments of CNPy samples.

Fig. 2. (a) XPS survey spectra of CN and CNPy-0.2 sample. (b,c) The high-resolution C 1s and N 1s spectra for the CN and CNPy-0.2 sample. (d) Quantitative elemental analysis based on the XPS spectra of CN, CNPy-0.2 sample. (e) Schematic representation of D-A distribution in CNPy samples. The surface charge density (f), DRS spectra (g) and photocatalytic HER (h,i) of CN and CNPy samples.

Fig. 3. (a) XRD patterns of CdSe, CdSe/CN and CdSe/CNPy-0.2 samples. (b) XPS survey spectra of CdSe, 100%CdSe/CN and 100%CdSe/CNPy-0.2 samples. Quantitative elemental analysis from the XPS spectra of Cd 3d (c), Se 3d (d), C 1s (e) and N 1s (f).

Fig. 4. (a,c,e) SPV images (CPD = (Φs-Φp)/e). (b,d,f) Line profiles of the SPV difference.

Fig. 5. SEM and TEM images of CN (a,d), CNPy-0.2 (b,e), CdSe (c,f) and 100%CdSe/CNPy-0.2 (g,h) samples. (i-l) TEM element mapping images in 100%CdSe/CNPy-0.2 sample.

Fig. 6. (a,b) Photocatalytic hydrogen evolution and reaction rates of the CN, CNPy, CdSe, CdSe/CN and CdSe/CNPy samples. (c,d) Hydrogen evolution performance of different sacrificial agents or different lights. (e) The cycling photocatalytic hydrogen evolution of 100% CdSe/CNPy-0.2. (f) Degradation of tetracycline using different catalysts. (g) Degradation rate and (h) the cycling TC degradation of 100% CdSe/CNPy-0.2 sample. (i) XRD patterns of 100% CdSe/CNPy-0.2 sample before and after the reaction.

Fig. 7. Photocurrent response (a), Nyquist plots (b), steady state PL emission spectra (c) and surface photovoltage (d) of different samples including CN, CNPy-0.2, CdSe, 100% CdSe/CN and 100% CdSe/CNPy samples.

Fig. 8. (a) UV-vis diffuse reflectance spectra. Taus plots (b), Mott-Schottky plots (c), electronic bandgap structures (d) of CN, CNPy-0.2 and CdSe samples. EPR spectra of DMPO-·O2- (e) and DMPO-·OH (f) of CNPy-0.2, CdSe and 100%CdSe/CNPy-0.2 sample.

Fig. 9. The high-resolution analysis from the XPS spectra of C 1s (a), N 1s (b), Cd 3d (c) and Se 3d (d).

Fig. 10. The charge transfer mechanism of CdSe/CNPy composites before (a) and after (b) photoexcitation. (c) Photocatalytic HER mechanism of CdSe/CNPy composites under light excitation.

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