Methylene Blue Incorporated Donor-Acceptor g-C3N4 Nanosheet Photocatalyst for H2 Production

Citation: Fangxin Yin, Pinquan Qin, Jingsan Xu, Shaowen Cao. Methylene Blue Incorporated Donor-Acceptor g-C₃N₄ Nanosheet Photocatalyst for H₂ Production[J]. Acta Physico-Chimica Sinica, 2023, 39(11): 221206. doi: 10.3866/PKU.WHXB202212062 shu

亚甲基蓝嵌入的供体受体型g-C₃N₄纳米片光催化剂用于产H₂

殷方鑫 ^1, ,
秦品权 ^{2,
,} ,
许景三 ^3, ,
曹少文 ^{1,
,}

1.
武汉理工大学, 材料复合新技术国家重点实验室, 武汉 430070
2.
武汉理工大学, 理学院, 武汉 430070
3.
昆士兰科技大学, 化学和物理学院, 澳大利亚布里斯班 QLD 4000

通讯作者: 秦品权, qinpqcu@whut.edu.cn
曹少文, swcao@whut.edu.cn

基金项目:
国家重点研发计划 2022YFE0114800

国家自然科学基金 51922081

摘要: 石墨相氮化碳(g-C₃N₄)是一种优异的产H₂光催化剂，但是其存在载流子分离效率低、光吸收能力较差和比表面积小的问题。本研究通过对二氰二胺和亚甲基蓝(MB)进行热共聚合，结合后续热剥离策略，成功合成了一种新型分子内供体-受体(D-A)结构g-C₃N₄纳米片光催化剂。实验结果和密度泛函理论(DFT)计算表明，将亚甲基蓝掺入g-C₃N₄框架中扩大了光吸收范围，促进了载流子的分离。此外，热剥离增加了催化剂的比表面积且进一步促进了载流子的分离。因此，D-A结构g-C₃N₄纳米片显示出大幅提升的光催化产氢活性(2275.6 μmol·h⁻¹·g⁻¹)，分别是块状g-C₃N₄、D-A结构g-C₃N₄、g-C₃N₄纳米片的5.30，2.60和1.30倍。这项工作为设计用于太阳能转换的D-A改性光催化材料提供了一个有价值的思路。

关键词:

English

Methylene Blue Incorporated Donor-Acceptor g-C₃N₄ Nanosheet Photocatalyst for H₂ Production

Fangxin Yin ^1, ,
Pinquan Qin ^{2,
,} ,
Jingsan Xu ^3, ,
Shaowen Cao ^{1,
,}

1.
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
2.
School of Science, Wuhan University of Technology, Wuhan 430070, China
3.
School of Chemistry and Physics, Queensland University of Technology, Brisbane, QLD 4000, Australia

Corresponding author: Pinquan Qin, qinpqcu@whut.edu.cn Shaowen Cao, swcao@whut.edu.cn

Received Date: 31 December 2022
Accepted Date: 27 February 2023
Revised Date: 25 February 2023
Available Online: 15 November 2023
Fund Project:

Abstract: Photocatalytic hydrogen production is a promising strategy for utilizing inexhaustible solar energy as a source of clean energy. Graphitic carbon nitride (g-C₃N₄) is a widely used photocatalytic material in photocatalytic hydrogen production because of its simple preparation process, suitable band structure, and high stability. However, the low charge carrier separation efficiency and small specific surface area of pristine g-C₃N₄ restrict its photocatalytic activity. It has been demonstrated that the construction of intramolecular donor-acceptor (D-A) systems and ultra-thin nanosheet structures are effective strategies for enhancing the photocatalytic activity of g-C₃N₄. Herein, an intramolecular D-A structured g-C₃N₄ nanosheet photocatalyst is synthesized through the thermal copolymerization of dicyandiamide and methylene blue (MB), followed by thermal exfoliation. X-ray diffraction, Fourier transform infrared spectrometry, solid-state ¹³C nuclear magnetic resonance, and X-ray photoelectron spectroscopy analyses reveal that MB is successfully incorporated into the g-C₃N₄ framework and well retained after thermal exfoliation. The resulting D-A system induces intramolecular charge transfer from the donor units (MB segment) to the acceptor units (tri-s-triazine rings) and extends the absorption edge to approximately 500 nm. The ultra-thin nanosheet structure produced by thermal exfoliation shortens the charge transfer distance from the interior to the surface of g-C₃N₄ and reduces the charge transfer resistance, which increases the charge carrier separation efficiency. Furthermore, the introduction of MB generates a flaky structure during copolymerization, which promotes thermal exfoliation and results in a remarkably increased specific surface area. The transient photocurrent response, electrochemical impedance spectra, and time-resolved photoluminescence decay spectra reveal that the charge transfer and separation of g-C₃N₄ are further promoted by integrating the intramolecular D-A system and ultra-thin nanosheet structure. Density functional theory calculations further demonstrate that MB donates electrons to tri-s-triazine rings (electron acceptor). Moreover, the highest occupied molecular orbit of D-A structured g-C₃N₄ is mostly distributed around the MB segment, while the lowest unoccupied molecular orbit is distributed around tri-s-triazine rings, resulting in spatially separated photogenerated electron-hole pairs. Through integrating the intramolecular D-A system and ultra-thin nanosheet structure, the obtained photocatalyst exhibits enhanced charge carrier separation, an extended absorption edge, and enlarged specific surface area. As a consequence, the D-A structured g-C₃N₄ nanosheet shows a considerably improved photocatalytic hydrogen production activity (2275.6 μmol·h⁻¹·g⁻¹), which is 5.30, 2.60, and 1.30 times that of bulk g-C₃N₄, D-A structured bulk g-C₃N₄, and g-C₃N₄ nanosheet, respectively. This work offers a valuable strategy for developing D-A-modified photocatalytic materials for solar energy conversion.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

亚甲基蓝嵌入的供体受体型g-C₃N₄纳米片光催化剂用于产H₂

通讯作者: 秦品权, qinpqcu@whut.edu.cn
曹少文, swcao@whut.edu.cn

English

Methylene Blue Incorporated Donor-Acceptor g-C₃N₄ Nanosheet Photocatalyst for H₂ Production

Corresponding author: Pinquan Qin, qinpqcu@whut.edu.cn Shaowen Cao, swcao@whut.edu.cn

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亚甲基蓝嵌入的供体受体型g-C3N4纳米片光催化剂用于产H2

通讯作者: 秦品权, qinpqcu@whut.edu.cn 曹少文, swcao@whut.edu.cn

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