单原子掺杂诱导电荷特异分布的Cu1-TiO2通过新机理催化苯胺选择性氧化

doi:10.1016/S1872-2067(24)60104-X

催化学报 ›› 2024, Vol. 64: 98-111.DOI: 10.1016/S1872-2067(24)60104-X

单原子掺杂诱导电荷特异分布的Cu₁-TiO₂通过新机理催化苯胺选择性氧化

秦嘉恒^a^,¹, 赵婉彤^b^,¹, 宋劼^a, 罗楠^a, 马正兰^a, 王宝俊^b, 马建泰^a, 章日光^b^,^*(), 龙雨^a^,^*()

^a兰州大学化学化工学院, 功能有机分子化学国家重点实验室, 甘肃省化工催化工程实验室, 甘肃兰州 730000
^b太原理工大学化学工程与技术学院, 煤炭清洁高效利用国家重点实验室, 山西太原 030024

收稿日期:2024-04-30 接受日期:2024-07-03 出版日期:2024-09-18 发布日期:2024-09-19
通讯作者: * 电子信箱: longyu@lzu.edu.cn (龙雨),zhangriguang@tyut.edu.cn (章日光).
作者简介:¹共同第一作者.
基金资助:
国家自然科学基金(22278199);国家自然科学基金(U21B2091);国家自然科学基金(22078221);国家自然科学基金(21776193);兰州市城关区科技计划(2023JSCX0049);国家资助博士后研究人员计划(GZC20231012);甘肃省科学技术协会创新驱动助力工程(GXH20230817-1);甘肃省科学技术协会创新驱动助力工程(GXH20230817-16);兰州大学中央高校基本科研业务费专项资金(lzujbky-2023-ct01)

Single atom doping induced charge-specific distribution of Cu₁-TiO₂ for selective aniline oxidation via a new mechanism

Jiaheng Qin^a^,¹, Wantong Zhao^b^,¹, Jie Song^a, Nan Luo^a, Zheng-Lan Ma^a, Baojun Wang^b, Jiantai Ma^a, Riguang Zhang^b^,^*(), Yu Long^a^,^*()

^aState Key Laboratory of Applied Organic Chemistry (SKLAOC), the Key Laboratory of Catalytic Engineering of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, Gansu, China
^bState Key Laboratory of Clean and Efficient Coal Utilization, College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China

Received:2024-04-30 Accepted:2024-07-03 Online:2024-09-18 Published:2024-09-19
Contact: * E-mail: longyu@lzu.edu.cn (Y. Long),zhangriguang@tyut.edu.cn (R. Zhang).
About author:¹Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22278199);National Natural Science Foundation of China(U21B2091);National Natural Science Foundation of China(22078221);National Natural Science Foundation of China(21776193);Science and Technology Planning Project of Chengguan District in Lanzhou(2023JSCX0049);Postdoctoral Fellowship Program of CPSF(GZC20231012);Innovation Driven Assistance Engineering Project(GXH20230817-1);Innovation Driven Assistance Engineering Project(GXH20230817-16);Fundamental Research Funds for the Central Universities(lzujbky-2023-ct01)

摘要/Abstract

摘要：

利用单原子掺杂金属氧化物来调控固有的活性位点, 实现复杂有机反应选择性的精准调控, 是一项极具吸引力但富有挑战性的工作. 苯胺选择性氧化可生成氧化偶氮苯、亚硝基苯等产物, 是一个重要的有机化学反应, 但苯胺氧化过程涉及多个竞争性氧化和缩合反应, 因此实现反应选择性精准调控的难度较高, 尤其是将反应控制在亚稳态的亚硝基苯产物. 目前仅有几个复杂的催化体系被报道, 但需使用昂贵的催化剂、配体、添加剂和有毒溶剂. 单原子掺杂金属氧化物是一类重要的单原子催化剂, 通过单原子掺杂可以改变金属氧化物的配位环境和电子性质, 从而显著影响其催化性能. 目前, 这类催化剂主要用于H₂O, CO₂, CO, CH₄等小分子的催化转化, 而对于复杂的催化反应, 特别是有机液相反应的选择性调控, 仍存在较大难度.

本文通过“先凝胶-后酸处理”策略制备了单原子Cu掺杂的TiO₂催化剂(Cu₁-TiO₂). 利用球差电镜和同步辐射等表征手段, 证明了Cu成功地以单原子形式掺杂到TiO₂中. 在苯胺氧化反应中, 对制备的Cu₁-TiO₂催化剂进行了活性测试, 结果显示, 其能够选择性地氧化苯胺生成亚硝基苯, 且这一过程无需任何添加剂或改变溶剂条件, 这显著区别于未掺杂的TiO₂催化剂, 后者主要生成氧化偶氮苯. 进一步的研究揭示了这一选择性调控的机理. 中间体机理实验研究、原位红外实验和密度泛函理论计算结果表明, 在TiO₂催化体系中, 苯胺首先在Ti-O活性位点上被氧化为PhNOH中间体, 随后这些中间体进一步反应生成氧化偶氮苯. 然而, 在Cu₁-TiO₂催化体系中, 尽管苯胺的初始氧化步骤相似, 但Cu单原子与TiO₂之间的特殊电荷分布形成了独特的Cu₁-O-Ti杂化结构, 这一结构引入了九个催化活性位点. 其中, 八个活性位点能够促使PhNOH中间体发生自发解离生成亚硝基苯, 从而改变了反应选择性. 此外, Cu₁-TiO₂催化剂在循环性能测试、底物扩展实验和放大实验均具有良好的活性.

综上所述, 本文提出了一种基于新型PhNOH中间体的苯胺选择性氧化机理, 并且开发了一种构建单原子掺杂金属氧化物并探索其复杂活性位点的方法, 为设计能够精确调控有机反应选择性的多相催化剂提供了新思路.

关键词: 单原子掺杂金属氧化物, 苯胺氧化, 选择性, 新机理, 活性位点

Abstract:

Utilizing single atom sites doping into metal oxides to modulate their intrinsic active sites, achieving precise selectivity control in complex organic reactions, is a highly desirable yet challenging endeavor. Meanwhile, identifying the active site also represents a significant obstacle, primarily due to the intricate electronic environment of single atom site doped metal oxide. Herein, a single atom Cu doped TiO₂ catalyst (Cu₁-TiO₂) is prepared via a simple “colloid-acid treatment” strategy, which switches aniline oxidation selectivity of TiO₂ from azoxybenzene to nitrosobenzene, without using additives or changing solvent, while other metal or nonmetal doped TiO₂ did not possess. Comprehensive mechanistic investigations and DFT calculations unveil that Ti-O active site is responsible for triggering the aniline to form a new PhNOH intermediate, two PhNOH condense to azoxybenzene over TiO₂ catalyst. As for Cu₁-TiO₂, the charge-specific distribution between the isolated Cu and TiO₂ generates unique Cu₁-O-Ti hybridization structure with nine catalytic active sites, eight of them make PhNOH take place spontaneous dissociation to produce nitrosobenzene. This work not only unveils a new mechanistic pathway featuring the PhNOH intermediate in aniline oxidation for the first time but also presents a novel approach for constructing single-atom doped metal oxides and exploring their intricate active sites.

Key words: Single atom doped metal oxide, Aniline oxidation, Selectivity, New mechanism, Active site

秦嘉恒, 赵婉彤, 宋劼, 罗楠, 马正兰, 王宝俊, 马建泰, 章日光, 龙雨. 单原子掺杂诱导电荷特异分布的Cu₁-TiO₂通过新机理催化苯胺选择性氧化[J]. 催化学报, 2024, 64: 98-111.

Jiaheng Qin, Wantong Zhao, Jie Song, Nan Luo, Zheng-Lan Ma, Baojun Wang, Jiantai Ma, Riguang Zhang, Yu Long. Single atom doping induced charge-specific distribution of Cu₁-TiO₂ for selective aniline oxidation via a new mechanism[J]. Chinese Journal of Catalysis, 2024, 64: 98-111.

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图/表 11

Fig. 1. (a) Aniline oxidation over different catalysts. (b) Aniline oxidation over a series of Cu doped TiO2 based catalysts with different calcination temperature. (c) Optimization of the reaction temperature. (d) Optimization of the H2O2 amount.

Fig. 2. Schematic illustration of the formation process of Cu1-TiO2 synthesis.

Fig. 3. (a) XRD patterns of the as-prepared catalysts. (b) Ti 2p XPS spectra of TiO2 and Cu1-TiO2. (c) Cu 2p XPS spectrum of Cu1-TiO2. (d) O 1s XPS spectrum of TiO2 and Cu1-TiO2. (e) AC-HAADF-STEM image of Cu1-TiO2 (left), the intensity profiles of the atoms on the lattice fringes marked (right).

Fig. 4. (a) Ti K-edge XANES spectra for the as-prepared catalysts. (b) Ti K-edge EXAFS spectra for the as-prepared catalysts. (c) Cu K-edge XANES spectra for the as-prepared catalysts. (d) Cu K-edge EXAFS spectra for the as-prepared catalysts.

Fig. 5. Electron density and Bader charge of surface atoms over TiO2 (a), Cu1-TiO2 (b) and CuO (c) catalysts. The black number represents the loss electron number of surface Cu or Ti atom; the white number represents the total gain electron number of O atom around Cu atoms, the orange, red and grey balls are Cu, O and Ti atom, respectively.

Table 1 Experiments on investigating the reaction mechanism over different catalysts.

Entry	Catalyst (mg)	Substrate (mmol)	PhNHOH Con. ^c (%)	BA Sel.^c (%)	AOB Sel. ^c (%)	NSB Sel. ^c (%)
1^a	—	PhNHOH (0.5)	16	12	85	3
2^a	TiO₂ (30)	PhNHOH (0.5)	100	—	96	4
3^a	CuO (30)	PhNHOH (0.5)	80	4	57	39
4^a	Cu₂O (30)	PhNHOH (0.5)	83	2	67	31
5^a	Cu₁-TiO₂ (30)	PhNHOH (0.5)	88	2	20	78
6^b	—	PhNHOH (0.5) + NSB (0.5)	28	—	100	—
7^b	TiO₂ (30)	PhNHOH (0.5) + NSB (0.5)	28	—	100	—
8^b	CuO (30)	PhNHOH (0.5) + NSB (0.5)	29	—	100	—
9^b	Cu₁-TiO₂ (30)	PhNHOH (0.5) + NSB (0.5)	28	—	100	—

Fig. 6. Time-resolved in situ DRIFT-IR spectra of oxidation of aniline (BA) on the TiO2 (a) and Cu1-TiO2 (b) after H2O2 dosing at different times.

Fig. 7. (a) Free energy profiles of AOB or NSB production from PhNHOH conversion over TiO2; Activation ways of PhNHOH and PhNOH at different adsorption sites and the barrier required for the corresponding process over (b) Cu1-TiO2 and (c) CuO catalysts, the balls in the dotted box are the possible adsorption sites. (d) Differential charge density of PhNOH adsorbed over TiO2, Cu1-TiO2 and CuO catalysts, the blue and yellow regions represent charge loss and gain, respectively.

Fig. 8. The d-band center of (a) Cu1-TiO2, (b) TiO2 and (c) CuO catalyst. (d) Liquid phase experimental of EPR spectra after the reaction of H2O2 with Cu1-TiO2 in presence of DMPO spin trap. (e) Traditional reaction mechanism for aniline oxidation reaction, (f) The possible reaction mechanism of aniline oxidation reaction in this work.

Fig. 9. Recycle tests of TiO2 and Cu1-TiO2 catalysts for aniline oxidation to form AOB (a) and NSB (b) under both low (pink and green) and high (purple and blue) conversion conditions. (c) 100 g scale up experiments for TiO2 and Cu1-TiO2 catalytic systems to produce AOB and NSB.

Table 2 Oxidative of substituted anilines to azoxybenzenes over TiO2 and to nitrosobenzenes over Cu1-TiO2 catalyst a.


86%	72%^b	88%	77%^b
81%	83%	87%	89%
90%	86%	82%	85%
83%	84%	84%	85%
86%		80%

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单原子掺杂诱导电荷特异分布的Cu₁-TiO₂通过新机理催化苯胺选择性氧化

Single atom doping induced charge-specific distribution of Cu₁-TiO₂ for selective aniline oxidation via a new mechanism

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