Synthesis of Nitrogen-Doped TiO2 and Its Photocatalytic Performance in Tetracycline Degradation

doi:10.16552/j.cnki.issn1001-1625.2025.0798

Abstract

Abstract:

Photocatalysis is an effective method for degrading tetracycline （TC）， with photocatalytic materials serving as the core component of this process. Titanium dioxide （TiO₂） is a highly efficient and environmentally friendly photocatalytic material. However， it suffers from rapid recombination of photogenerated carriers and a narrow ultraviolet light response range. To address these limitations， this study employed a gradient nitrogen （N）-doping strategy to modify sea-urchin-like TiO₂. An in situ hydrothermal method was utilized to construct N-doped TiO₂ materials， systematically elucidating the regulatory effects of N-doping concentration on the structure and performance of photocatalyst. Experimental result indicate that when the nitrogen-to-titanium ratio （n_N∶n_Ti） is 5， the prepared photocatalyst （5N-TiO₂） exhibits the best photocatalytic performance， achieving a 64% degradation rate for TC under 120 min of visible light irradiation. This represents a 137% enhancement compared to undoped TiO₂. Characterization analysis reveals that 5N-TiO₂， rich in Ti³⁺ and oxygen vacancies， synergistically narrows the band gap of TiO₂ from 3.07 eV to 2.60 eV， and significantly improves the separation rate of photogenerated carriers. However， further increasing the N-doping concentration level shows that excessive N forms electron-hole recombination centers， thereby reducing carrier lifetime. Consequently， the photocatalytic performance of 10N-TiO₂ （n_N∶n_Ti=10） decrease to 41% of that of undoped TiO₂.

Key words: TiO₂, nitrogen doping, photocatalysis, tetracycline, electron-hole separation, band gap

CLC Number:

O644.1

YANG Shuai, LI Xia, YAO Mengqin, LIU Fei. Synthesis of Nitrogen-Doped TiO₂ and Its Photocatalytic Performance in Tetracycline Degradation[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(2): 684-694.

Figures/Tables 12

Fig.1 XRD patterns of different TiO2

Fig.2 SEM images of different TiO2

Fig.3 TEM， HRTEM and corresponding mapping images of different TiO2

Fig.4 N2 adsorption-desorption isotherms and pore size distribution curves of different TiO2

Table 1 Average pore diameter and SBET of different TiO2

Sample	Average pore diameter/nm	S_BET/（m²·g^-1）
TiO₂	5.80	45.50
0.4N-TiO₂	5.61	71.27
2N-TiO₂	4.85	75.61
5N-TiO₂	6.04	79.60
10N-TiO₂	10.12	66.75

Fig.5 XPS spectra of different TiO2

Table 2 Content of Ti3+ and peak area of OV in different TiO2

Sample	Ti³⁺/Ti⁴⁺ （atomic ratio）	O_V peak area
TiO₂	0.050	27 055.20
0.4N-TiO₂	0.074	29 363.40
2N-TiO₂	0.088	32 937.60
5N-TiO₂	0.094	37 759.30
10N-TiO₂	0.079	30 129.40

Fig 6 Optical property characterization of different TiO2

Table 3 Band gap energy of different TiO2

Sample	TiO₂	0.4N-TiO₂	2N-TiO₂	5N-TiO₂	10N-TiO₂
E_g/eV	3.07	2.89	2.81	2.60	2.71

Fig.7 Photoelectrochemical performance of different TiO2

Table 4 Time-resolved fluorescence decay parameter of different TiO2

Sample	τ₁/ns	A₁ （100%）	τ₂/ns	A₂ （100%）	τ_ave/ns
TiO₂	1.08	140.41	9.47	30.17	6.56
0.4N-TiO₂	0.91	179.62	11.35	17.86	6.69
2N-TiO₂	0.91	164.00	10.77	20.00	6.74
5N-TiO₂	0.92	141.04	11.01	34.35	8.43
10N-TiO₂	1.04	201.21	5.18	13.84	2.09

Fig.8 Photocatalytic degradation performance for TC of different TiO2

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Synthesis of Nitrogen-Doped TiO₂ and Its Photocatalytic Performance in Tetracycline Degradation

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