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

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

Abstract

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

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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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60104-X

https://www.cjcatal.com/EN/Y2024/V64/I9/98

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

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