K原子掺杂高度面间结晶的g-C3N4光催化剂及其高效H2O2光合成

引用本文: 钟威, 郑丹, 欧远新, 孟爱云, 苏耀荣. K原子掺杂高度面间结晶的g-C₃N₄光催化剂及其高效H₂O₂光合成[J]. 物理化学学报, 2024, 40(11): 240600. doi: 10.3866/PKU.WHXB202406005 shu

Citation: Wei Zhong, Dan Zheng, Yuanxin Ou, Aiyun Meng, Yaorong Su. Simultaneously Improving Inter-Plane Crystallization and Incorporating K Atoms in g-C₃N₄ Photocatalyst for Highly-Efficient H₂O₂ Photosynthesis[J]. Acta Physico-Chimica Sinica, 2024, 40(11): 240600. doi: 10.3866/PKU.WHXB202406005 shu

K原子掺杂高度面间结晶的g-C₃N₄光催化剂及其高效H₂O₂光合成

深圳技术大学新材料与新能源学院, 广东深圳 518118

通讯作者: 孟爱云, mengaiyun@sztu.edu.cn; 苏耀荣, suyaorong@sztu.edu.cn

基金项目:
国家自然科学基金项目 22178224

国家自然科学基金项目 22272110

广东省基础与应用基础研究基金 2023A1515110535

广东省基础与应用基础研究基金 2020A1515110873

深圳市科技计划资助 RCBS20231211090522041

深圳技术大学基础科研业务费 20211063010047

深圳市超金刚石与功能晶体应用技术重点实验室 ZDSYS20230626091303007

深圳市高校稳定支持项目 20231127203830001
^†These authors contributed equally to this work.

摘要: 石墨相氮化碳(g-C₃N₄)在光催化制备过氧化氢(H₂O₂)领域有巨大潜力。然而，低的两电子氧还原活性严重限制了g-C₃N₄的光催化产H₂O₂效率。在这项研究中，我们通过两步煅烧法在KI晶体表面重新晶化传统g-C₃N₄材料，合成了钾掺杂的高晶化g-C₃N₄光催化剂(CN-K)。所制备的CN-K光催化材料具有更高的面间结晶度、更窄的禁带宽度和更小的颗粒尺寸(大约20到50纳米)。更重要的是，掺入的钾原子作为优异的催化位点可以增强O₂吸附和稳定*OOH中间体，从而提高钾掺杂高晶化g-C₃N₄光催化剂的两电子氧还原活性。其中CN-K(1:6)样品具有显著增强的光催化产H₂O₂速率(7.8 mmol·L^-1·h^-1)，且在420 nm下的表观量子效率为5.17%，光催化活性是传统块状g-C₃N₄样品的220倍。这项研究不仅揭示了杂原子提高g-C₃N₄光催化剂两电子氧还原活性的机理，而且为设计高效g-C₃N₄基光催化剂提供了新的见解。

关键词:

English

Simultaneously Improving Inter-Plane Crystallization and Incorporating K Atoms in g-C₃N₄ Photocatalyst for Highly-Efficient H₂O₂ Photosynthesis

College of New Materials and New Energies, Shenzhen Technology University, Shenzhen 518118, Guangdong Province, China

Corresponding author: Email: mengaiyun@sztu.edu.cn (A.M.); Email: suyaorong@sztu.edu.cn (Y.S.); Tel: +86-755-2325-6080

Received Date: 05 June 2024
Accepted Date: 17 July 2024
Revised Date: 16 July 2024
Available Online: 15 November 2024
Fund Project:
the National Natural Science Foundation of China

the National Natural Science Foundation of China

Guangdong Basic and Applied Basic Research Foundation

Guangdong Basic and Applied Basic Research Foundation

Shenzhen Science and Technology Program

the Fundamental Research Funds for Shenzhen Technology University

Shenzhen Key Laboratory of Applied Technologies of Super-Diamond and Functional Crystals

Shenzhen Science and Technology Program

Abstract: Graphitic carbon nitride (g-C₃N₄) has gained growing attention in hydrogen peroxide (H₂O₂) photosynthesis, but the low activity of two-electron oxygen reduction reaction (2e^--ORR) still restricts its photocatalytic H₂O₂-generation performance. Herein, traditional g-C₃N₄ photocatalysts are recrystallized on KI crystal surfaces by a secondary calcination route to synthesize K incorporated highly-crystalline g-C₃N₄ photocatalysts. The synthesized CN-K photocatalyst exhibits improved inter-plane crystallization, narrowed bandgap structure, and smaller particle size from 20 to 50 nm. Moreover, the incorporated K atoms, as excellent catalytic sites, can enhance O₂ adsorption and stabilize the *OOH intermediates, thus improving the 2e^--ORR activity of the K incorporated high-crystallization g-C₃N₄ photocatalysts. Consequently, the optimized CN-K(1:6) photocatalyst exhibits a remarkably improved H₂O₂-generation rate of 7.8 mmol·L^-1·h^-1 with an AQE value of 5.17% at 420 nm, outperforming the traditional g-C₃N₄ sample by a factor of 220. This work uncovers the roles of heteroatoms in promoting the 2e^--ORR selectivity of the g-C₃N₄ photocatalyst, and offers novel insights to construct highly-active g-C₃N₄-based materials for H₂O₂ photosynthesis.

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

K原子掺杂高度面间结晶的g-C₃N₄光催化剂及其高效H₂O₂光合成

通讯作者: 孟爱云, mengaiyun@sztu.edu.cn; 苏耀荣, suyaorong@sztu.edu.cn

English

Simultaneously Improving Inter-Plane Crystallization and Incorporating K Atoms in g-C₃N₄ Photocatalyst for Highly-Efficient H₂O₂ Photosynthesis

Corresponding author: Email: mengaiyun@sztu.edu.cn (A.M.); Email: suyaorong@sztu.edu.cn (Y.S.); Tel: +86-755-2325-6080

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