利用N-羟基邻苯二甲酰亚胺研究可见光照射下Nb2O5中高度扭曲的NbO6单元作为电子转移位点

doi:10.1016/S1872-2067(21)64026-3

催化学报 ›› 2022, Vol. 43 ›› Issue (7): 1894-1905.DOI: 10.1016/S1872-2067(21)64026-3

利用N-羟基邻苯二甲酰亚胺研究可见光照射下Nb₂O₅中高度扭曲的NbO₆单元作为电子转移位点

苏凯艺^a^,^b, 张超锋^a^,^*(), 王业红^a, 张健^a, 郭强^a, 高著衍^a^,^b, 王峰^a^,^#()

^a中国科学院大连化学物理研究所, 催化基础国家重点实验室, 洁净能源国家实验室(筹), 辽宁大连116023
^b中国科学院大学, 北京100049

收稿日期:2021-12-30 接受日期:2022-01-17 出版日期:2022-05-20 发布日期:2022-05-20
通讯作者: 张超锋,王峰
基金资助:
国家自然科学基金(2025206);国家自然科学基金(21961130378);国家自然科学基金(21802137);大连市科技创新基金(2019J11CY009);辽宁省振兴英才计划(XLYC2002012);大连市高层次人才创新支撑计划(2020RT10);中国科学院青年创新促进会资助项目(2019185);牛顿高级合作伙伴(NAF\R1\191267)

Unveiling the highly disordered NbO₆ units as electron-transfer sites in Nb₂O₅ photocatalysis with N-hydroxyphthalimide under visible light irradiation

Kaiyi Su^a^,^b, Chaofeng Zhang^a^,^*(), Yehong Wang^a, Jian Zhang^a, Qiang Guo^a, Zhuyan Gao^a^,^b, Feng Wang^a^,^#()

^aState Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bUniversity of Chinese Academy of Sciences, Beijing 100049, China

Received:2021-12-30 Accepted:2022-01-17 Online:2022-05-20 Published:2022-05-20
Contact: Chaofeng Zhang, Feng Wang
Supported by:
National Natural Science Foundation of China(2025206);National Natural Science Foundation of China(21961130378);National Natural Science Foundation of China(21802137);Dalian Science and Technology Innovation Fund(2019J11CY009);Liaoning Revitalization Talents Program(XLYC2002012);Dalian Innovation Support Plan for High Level Talents(2020RT10);Youth Innovation Promotion Association (YIPA) of the Chinese Academy of Sciences(2019185);Newton Advanced Fellowships(NAF\R1\191267)

摘要/Abstract

摘要：

五氧化二铌(Nb₂O₅)具有独特酸碱性质和氧化能力, 在光催化尤其是光催化芳香化合物转化中引起了广泛的研究兴趣. 受限于自身的带隙宽度, 单纯Nb₂O₅只能吸收并利用太阳光中的紫外区能量. 近年来, 在Nb₂O₅上的可见光催化苄胺和苯甲醇选择氧化报道中, 底物活化和产物的高选择性归因于Nb₂O₅上Nb位点和底物的直接相互作用, 这系列工作为后续Nb₂O₅可见光催化过程提供研究基础, 被视为Nb₂O₅光催化作用研究中的里程碑工作. 此外, 研究发现Nb₂O₅的形貌改变会导致其活性有明显差异. 研究深入发现Nb₂O₅基催化剂中存在不同的NbO_x单元, 虽然在不同形貌的Nb₂O₅催化剂上也存在这一结构, 但它们与活性之间的相关性尚不清楚. 为了解决这些问题, 亟需开发时空分辨的表征手段或者探针分子辅助的研究手段. 结合以往的研究报道, 含羟基或胺基官能团的有机分子与Nb位点存在相互作用. 由此推测, 可通过监测特定多官能团探针分子化合物与Nb₂O₅间存在的强相互作用以及电荷传递过程, 研究表面NbO_x结构在光催化过程中的作用.

本文利用N-羟基邻苯二甲酰亚胺(NHPI)为探针分子, 区分不同NbO_x结构单元在可见光照射下对C-H键的催化活化作用. 利用水热法及焙烧处理, 制备了含不同扭曲程度NbO₆结构的Nb₂O₅催化剂, 结合紫外可见漫反射光谱、光电子能谱和电子顺磁共振波谱, 发现在可见光照下NHPI的电子明显转移到含高度扭曲NbO₆结构的Nb₂O₅催化剂上. 在可见光(455 nm)照射下评价NHPI和不同Nb₂O₅催化剂在乙苯氧化反应中的性能, 发现含高度扭曲NbO₆结构的催化剂上苯乙酮的生成速率明显高于含低度扭曲NbO₆结构的催化剂(419‒495 vs. 82 μmol·g^-1·h^-1). 结合EPR为电子顺磁共振谱和捕获剂对比试验结果, 表明苯乙酮生成速率差异归因于NHPI失去电子后生成氮氧自由基物种有利于乙苯的C-H键活化, 从而提高乙苯的转化率及产物苯乙酮生产速率. 本文关联高度扭曲NbO₆结构和光催化中电荷传递过程, 为研究光催化中NbO_x的作用提供参考. 为开发其他探针分子, 实现Nb₂O₅上C-H键的高效活化, 以及用于开发有机物-Nb₂O₅的光催化体系提供借鉴.

关键词: 光催化作用, Nb₂O₅, 高度扭曲NbO₆结构单元, 电荷传递过程, N-羟基邻苯二甲酰亚胺

Abstract:

Although different NbO_x units are present in Nb₂O₅-based catalysts, the correlations between these structures and activity remain unclear, which considerably hinders the further development of Nb₂O₅ photocatalysis. Herein, we utilized N-hydroxyphthalimide (NHPI) as the probe molecule to distinguish the role of different NbO_x units in the activation of C-H bond under visible light irradiation. With the addition of NHPI, Nb₂O₅ catalysts with highly disordered NbO₆ units exhibited higher activities than that with slightly disordered NbO₆ units (419‒495 vs. 82 μmol·g^-1·h^-1) in photocatalytic selective oxidation of ethylbenzene. Revealed by Raman spectra, electron paramagnetic resonance spectra, and transmission-electron-microscopy images, highly disordered NbO₆ units were confirmed to act as the active sites for the transfer of photogenerated electrons from NHPI, promoting the generation of phthalimide-N-oxyl (PINO) radicals for the enhanced conversion of ethylbenzene under visible light irradiation. This study provides guidance on the role of local NbO_x units in Nb₂O₅ photocatalysis.

Key words: Photocatalysis, Nb₂O₅, Highly disordered NbO₆ units, Charge-transfer process, N-hydroxyphthalimide

苏凯艺, 张超锋, 王业红, 张健, 郭强, 高著衍, 王峰. 利用N-羟基邻苯二甲酰亚胺研究可见光照射下Nb₂O₅中高度扭曲的NbO₆单元作为电子转移位点[J]. 催化学报, 2022, 43(7): 1894-1905.

Kaiyi Su, Chaofeng Zhang, Yehong Wang, Jian Zhang, Qiang Guo, Zhuyan Gao, Feng Wang. Unveiling the highly disordered NbO₆ units as electron-transfer sites in Nb₂O₅ photocatalysis with N-hydroxyphthalimide under visible light irradiation[J]. Chinese Journal of Catalysis, 2022, 43(7): 1894-1905.

图/表 11

Fig. 1. The plausible process for the electron transfer from NHPI molecules into Nb2O5 under visible light irradiation.

Fig. 2. XRD patterns (a), UV-Vis diffuse reflectance spectra (b), Tauc plots (c), and the electronic structures (d) of Nb2O5-450, Nb2O5-550, Nb2O5-650, and Nb2O5-850, respectively.

Fig. 3. The photoluminescence spectra (a) and Raman spectra (b) of as-synthesized Nb2O5-x catalysts.

Fig. 4. The HRTEM images and corresponding intensity plots of the lattice of Nb2O5-450 (a,e), Nb2O5-550 (b,f), Nb2O5-650 (c,g), and Nb2O5-850 (d,h). The scale bar is 10 nm.

Fig. 5. Comparison in the results of UV-Vis DRS for NHPI molecules, as-synthesized Nb2O5-x catalysts before and after the addition of NHPI molecules (NHPI + Nb2O5-x). (a) Nb2O5-450; (b) Nb2O5-550; (c) Nb2O5-650; (d) Nb2O5-850.

Fig. 6. The results of EPR for the mixture of different Nb2O5 catalysts and NHPI in CH3CN solution (designated as NHPI + Nb2O5-x) under dark and light irradiation (450 nm). (a,b) NHPI+Nb2O5-450; (c,d) NHPI+Nb2O5-550; (e,f) NHPI+Nb2O5-650; (g,h) NHPI+Nb2O5-850.

Fig. 7. XPS results of high resolution of Nb 3d spectra for different Nb2O5-x catalysts before and after the addition of NHPI. (a) Nb2O5-450; (b) Nb2O5-550; (c) Nb2O5-650; (d) Nb2O5-850.

Fig. 8. The photocatalytic performance of different Nb2O5 catalysts in the oxidation of ethylbenzene. Reaction conditions: as-synthesized Nb2O5-x (10 mg), CH3CN solution containing ethylbenzene (0.1mmol), O2 (0.1 Mpa), blue LEDs (455 nm), 20?30 °C, reaction time 12 h. a 3 mg NHPI without any Nb2O5 catalyst. b addition of 3 mg NHPI. The conversion is the average result.

Fig. 9. The influence of different scavengers in the conversion of ethylbenzene over the mixture of NHPI and different Nb2O5-x catalysts. (a) Nb2O5-450; (b) Nb2O5-550; and (c) Nb2O5-650. Reaction conditions: Nb2O5-x catalyst (10 mg), 3 mg NHPI and 0.1 mmol of ethylbenzene dissolved in CH3CN (1 mL), O2 (0.1 Mpa), blue LEDs (455 nm), ca. 20?30 °C, reaction time 12 h. The amounts of (NH4)2C2O4, AgNO3, BQ, t-BuOH, and BHT were 0.1 mmol, 0.1 mmol, 0.1 mmol, 0.2?0.3 mmol, 0.1 mmol, respectively.

Fig. 10. Proposed charge-transfer process and the activation of ethylbenzene to acetophenone over the mixture of NHPI and Nb2O5-x catalysts (Nb2O5-450, Nb2O5-550, and Nb2O5-650) under visible light irradiation.

Fig. 11. The plausible relationship between average lattice spacing and conversion of ethylbenzene over Nb2O5-x catalysts. Reaction conditions are the same as those shown in Fig. 8 with the addition of NHPI.

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利用N-羟基邻苯二甲酰亚胺研究可见光照射下Nb₂O₅中高度扭曲的NbO₆单元作为电子转移位点

Unveiling the highly disordered NbO₆ units as electron-transfer sites in Nb₂O₅ photocatalysis with N-hydroxyphthalimide under visible light irradiation

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