多面体SrTiO3原位生长N缺陷PCN中的纳米叠层效应助力光催化完全分解水: 内建电场调控的协同机制

doi:10.1016/S1872-2067(23)64414-6

催化学报 ›› 2023, Vol. 48: 279-289.DOI: 10.1016/S1872-2067(23)64414-6

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多面体SrTiO₃原位生长N缺陷PCN中的纳米叠层效应助力光催化完全分解水: 内建电场调控的协同机制

韦之栋^a^,^b^,^c, 严嘉玮^b^,^c, 郭伟琦^b^,^c, 上官文峰^b^,^c^,^*()

^a上海交通大学智慧能源创新学院, 上海200030
^b上海交通大学燃烧与环境技术中心, 上海200030
^c上海交通大学氢科学中心, 上海200030

收稿日期:2023-02-01 接受日期:2023-02-06 出版日期:2023-05-18 发布日期:2023-03-15
通讯作者: * 电子信箱: shangguan@sjtu.edu.cn.
基金资助:
国家自然科学基金(22102095);上海交通大学“双一流”建设项目启动经费(WH220545009);国家重点基础研究发展计划(2018YFB1502001);中国博士后基金面上项目(2020M681297)

Nanoscale lamination effect by nitrogen-deficient polymeric carbon nitride growth on polyhedral SrTiO₃ for photocatalytic overall water splitting: Synergy mechanism of internal electrical field modulation

Zhidong Wei^a^,^b^,^c, Jiawei Yan^b^,^c, Weiqi Guo^b^,^c, Wenfeng Shangguan^b^,^c^,^*()

^aCollege of Smart Energy, Shanghai Jiao Tong University, Shanghai 200030, China
^bResearch Center for Combustion and Environment Technology, Shanghai Jiao Tong University, Shanghai 200030, China
^cCenter of Hydrogen Science, Shanghai Jiao Tong University, Shanghai 200030, China

Received:2023-02-01 Accepted:2023-02-06 Online:2023-05-18 Published:2023-03-15
Contact: * E-mail: shangguan@sjtu.edu.cn (W. Shangguan).
Supported by:
National Natural Science Foundation of China(22102095);Project of Shanghai Jiao Tong University “Double First-Class” Construction(WH220545009);National Key Basic Research and Development Program(2018YFB1502001);China Postdoctoral Science Foundation(2020M681297)

摘要/Abstract

摘要：

光的钻穿效应使得纳米级光催化剂(粒径200 nm以下催化剂和低维催化剂等)能带弯曲程度降低, 无法有效利用“向阳背阴”的Dember效应, 进而削弱光生载流子从体相到表面的驱动力, 不利于完全分解水的实现. 我们前期研究发现, 催化剂微结构的极化率影响其扭曲度, 进而可以实现对催化剂内建电场的调控, 促进纳米颗粒光催化完全分解水的过程. 基于此, 本文在粒径小于200 nm的多面体SrTiO₃催化剂表面原位生长聚合物的氮化碳(PCN), 形成了薄层PCN包覆的SrTiO₃纳米叠层催化剂, 实现了完全分解水过程. 并利用物相结构分析、形貌分析、表面分析、光谱分析、同步辐射分析和理论计算等方法深入解析了SrTiO₃-PCN复合催化剂的结构, 揭示了由纳米尺度的叠层效应引发的内建电场协同调控机制.
催化剂的物相结构分析结果表明, SrTiO₃和PCN是组成复合催化剂的主要单体, 并没有新的物质生成, 复合后各元素微结构极化率发生变化, 表现为拉曼光谱峰强度的变化. 片层状的PCN包覆在多面体SrTiO₃的表面, 形成了独特的复合催化剂叠层结构. N 1s与Sr 3d的X射线光电子能谱结果表明, SrTiO₃与PCN的结合围绕着Sr和N两种元素进行. 随着SrTiO₃含量的增加, -NH₂中的N与SrTiO₃中的元素结合, 促进了-N-H-基团的生成, 而-N-H-基团受到化学环境改变的影响, 倾向于向氰基转变, 进而形成缺陷. 利用同步辐射研究了Sr原子配位数的变化, 揭示了N-Sr键的形成源自于Sr-Ti键中的Sr与-NH₂中的N结合, 促进了N缺陷态的形成, 显著提升了光吸收性能. 催化剂热力学分析结果表明, 体相氮缺陷引起价带位置上移, 而表面氮缺陷对价带位置影响较小. 当SrTiO₃/PCN的比为1:2时, 复合催化剂可以实现完全分解水过程, 氢氧比接近2:1. 其原因在于SrTiO₃与PCN之间的费米能级不同, N-Sr键的形成增强了表面电势, 促进了二者复合后内建电场的重构. 随着SrTiO₃含量的增加, 体相缺陷浓度增加, 进而使得分解水性能显著降低. 研究表明, 由N-Sr形成使得催化剂在光吸收率、热力学性质及动力学性质的改变所引起的纳米尺度叠层效应, 是引发内建电场协同调控进而实现光催化完全分解水的重要因素. 综上, 本文结果可以对调控内建电场实现完全分解水方面研究提供一定借鉴.

关键词: 光催化水分解, 纳米叠层效应, 内建电场, 氮缺陷的聚合物氮化碳, 纳米多面体钛酸锶

Abstract:

The light penetration effect will weaken the driving force of charge separation from phase to surface by the built-in electric field of nanoscale photocatalysts, like low-dimensional materials. Therefore, in this study, a novel nanoscale lamination catalyst design method was proposed using a polymeric carbon nitride (PCN)-nano polyhedral SrTiO₃ core-shell structure catalyst (PCN-SrTiO₃). The results showed that the nanoscale lamination effect could be generated by the formation of the N-Sr bond, which could regulate the built-in electric field of the PCN simultaneously. Moreover, detailed characterization indicated that the N-Sr bond, which facilitates the generation of N vacancies in PCN, could act as a novel channel for charge transfer. Both surface and interior core N-deficient PCN have been discovered, resulting in more positive and negative VB positions, respectively. Synchronously, the light absorption ability of the PCN-SrTiO₃ samples increased. Consequently, the enhanced photocatalytic overall water splitting could be ascribed to the synergism of the built-in electric field regulation caused by the N-Sr formation-induced nanoscale lamination effect, which was favorable for energy flow adaption on the spatiotemporal scale.

Key words: Photocatalytic overall water splitting, Nanoscale lamination effect, Built-in electric field, N-deficient PCN, Nano polyhedral SrTiO₃

韦之栋, 严嘉玮, 郭伟琦, 上官文峰. 多面体SrTiO₃原位生长N缺陷PCN中的纳米叠层效应助力光催化完全分解水: 内建电场调控的协同机制[J]. 催化学报, 2023, 48: 279-289.

Zhidong Wei, Jiawei Yan, Weiqi Guo, Wenfeng Shangguan. Nanoscale lamination effect by nitrogen-deficient polymeric carbon nitride growth on polyhedral SrTiO₃ for photocatalytic overall water splitting: Synergy mechanism of internal electrical field modulation[J]. Chinese Journal of Catalysis, 2023, 48: 279-289.

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图/表 8

Fig. 1. XRD (a), data-processing Raman spectra (b), and TEM, HADDF as well as element mapping results (c) of the prepared samples.

Fig. 2. SEM images of nano polyhedron SrTiO3 (a,b) and 0.5g-SrTiO3-PCN (c,d) under a style of backscattering, and 3D-HRTEM images of 0.5g-SrTiO3-PCN at different angles (e).

Fig. 3. XPS results of the prepared samples. (a) N 1s; (b) FT-IR spectra; (c) EPR results; (d) Cross Polarization Solid-state 13C MAS NMR spectra of selected samples as well as a possible structural change in heptazine units before and after N-Sr bond formation.

Fig. 4. Normalized Sr K-edge XANES spectra (a), the Fourier transform (FT) of EXAFS k2χ(k) spectra and the magnitude R-space experimental data fitting (b-f), and wavelet transform (WT) of k3-weighted EXAFS signals of the selected samples (g-j).

Fig. 5. UV-vis spectra (a), the VB position variation (b) after being calculated based on XPS VB, Mott-Schottky results.

Fig. 6. Photocatalytic overall water splitting performance with PtOx and CoOx as co-catalysts. 0.25g-SrTiO3-PCN (a), 0.5g-SrTiO3-PCN (b), recycle activity of 0.5g-SrTiO3-PCN results (c), 1 g-SrTiO3-PCN (d), 2g-SrTiO3-PCN (e), as well as 3g-SrTiO3-PCN (f).

Fig. 7. (a) The model of PCN deposited on the facets of SrTiO3 and the isosurface map of charge density differences at different visual angles. The C, N, O, Ti, and Sr atoms are represented as brown, silver, light blue, red, and green, respectively. (b) The SPV results of PCN, STO, and 0.5g-SrTiO3-PCN. (c) Theory work function of SrTiO3. (d) AFM results of SrTiO3 (SKPM pattern). (e) Mott-Schottky results of PCN; AFM results of PCN (SKPM pattern) (f) and the theoretical mechanisms (g) of the built-in electric field formation by PCN and SrTiO3.

Fig. 8. (a) AFM results of 0.5g-SrTiO3-PCN (SKPM pattern). The SPV intensity (b) and the zeta potential (c) of each sample.

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多面体SrTiO₃原位生长N缺陷PCN中的纳米叠层效应助力光催化完全分解水: 内建电场调控的协同机制

Nanoscale lamination effect by nitrogen-deficient polymeric carbon nitride growth on polyhedral SrTiO₃ for photocatalytic overall water splitting: Synergy mechanism of internal electrical field modulation

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