Microwave hydrothermal synthesis of lanthanum oxyfluoride nanorods for photocatalytic nitrogen fixation: Effect of Pr doping

doi:10.1007/s11706-020-0488-6

Front. Mater. Sci.

2020, Vol. 14

Issue (1) : 43-51 https://doi.org/10.1007/s11706-020-0488-6

RESEARCH ARTICLE

Microwave hydrothermal synthesis of lanthanum oxyfluoride nanorods for photocatalytic nitrogen fixation: Effect of Pr doping

Xiangyu YAN¹, Da DAI¹, Kun MA¹, Shixiang ZUO¹, Wenjie LIU¹, Xiazhang LI^1,²(

), Chao YAO¹(

)

¹. Advanced Catalysis and Green Manufacturing Collaborative Innovation Center, Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Changzhou University, Changzhou 213164, China
². Department of Materials Science and Engineering, University of Delaware, Newark, DE 19716, USA

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Abstract

Photocatalytic fixation of nitrogen has been recognized as a green and promising strategy for ammonia synthesis under ambient conditions. However, the efficient reduction of nitrogen remains a challenge due to high activation energy of nitrogen and low utilization of solar energy. Herein, lanthanum oxyfluoride with different doping content of Pr³⁺ (LaOF:xPr³⁺) upconversion nanorods were synthesized by microwave hydrothermal method. Results indicated that the doping of Pr³⁺ generated considerable defects on the surface of LaOF which acted as the adsorption and activation center for nitrogen. Meanwhile, the Pr³⁺ ion narrowed the band gap and broadened the light response range of LaOF because LaOF:Pr³⁺ can upconvert visible light into ultraviolet light, which excite LaOF nanorods and improve the utilization of solar light. The doping amount of Pr³⁺ had critical effect on the photocatalytic nitrogen fixation performance which reached as high as 180 μmol·L⁻¹·h⁻¹ when the molar ratio of Pr³⁺ to LaOF was optimized to be 2%.

Keywords LaOF defect upconversion photocatalysis nitrogen fixation

Corresponding Author(s): Xiazhang LI,Chao YAO

Online First Date: 25 December 2019 Issue Date: 05 March 2020

Cite this article:

Xiangyu YAN,Da DAI,Kun MA, et al. Microwave hydrothermal synthesis of lanthanum oxyfluoride nanorods for photocatalytic nitrogen fixation: Effect of Pr doping[J]. Front. Mater. Sci., 2020, 14(1): 43-51.

URL:

https://academic.hep.com.cn/foms/EN/10.1007/s11706-020-0488-6
https://academic.hep.com.cn/foms/EN/Y2020/V14/I1/43

Fig.1 (a) XRD patterns of LaOF:xPr³⁺ (x = 0%?4%). (b) Partial enlargement between 25° and 28°.

Fig.2 (a)(b) TEM images of LaOF:Pr³⁺ in water bath for 60 min (left) and 180 min (right). (c) HRTEM image, (d) SAED pattern and (e) EDS result of LaOF:Pr³⁺.

Fig.3 (a) Upconversion luminescence of of LaOF:xPr³⁺ (x = 0%?4%) under the excitation of 480 nm light. (b) PL spectra of of LaOF:xPr³⁺ (x = 0%?4%) under the excitation of 310 nm light.

Fig.4 XPS spectra of LaOF:Pr³⁺: (a) La 3d; (b) O 1s; (c) F 1s; (d) Pr 3d.

Fig.5 (a) Nyquist plots and (b) photocurrent?time curves of LaOF:xPr³⁺ (x = 0%?4%) under intermittent illumination.

Fig.6 (a) UV-vis spectra of LaOF:xPr³⁺ (x = 0%?4%) and (b) the band gap evaluation for linear dependence of (Ahv)² versus hv.

Fig.7 (a) Photocatalytic nitrogen fixation performance of LaOF:xPr³⁺ (x = 0%?4%) and (b) photocatalytic nitrogen fixation performance of LaOF:2% Pr³⁺ at different pH values (pH= 2, 4, 6, 8, 10).

Fig.8 The electronic energy-level diagram of LaOF and LaOF:2% Pr³⁺ (orange rectangle — LaOF; green rectangle — LaOF:2% Pr³⁺).

Fig.9 The photocatalytic nitrogen fixation mechanism of LaOF:Pr³⁺ (green cubes — LaOF, yellow spheres — Pr³⁺, white dots — defects).

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