Electrocatalytic reduction of NO to NH<sub>3</sub> in ionic liquids by P-doped TiO<sub>2</sub> nanotubes

doi:10.1007/s11705-022-2274-8

Front. Chem. Sci. Eng.

2023, Vol. 17

Issue (6) : 726-734 https://doi.org/10.1007/s11705-022-2274-8

RESEARCH ARTICLE

Electrocatalytic reduction of NO to NH₃ in ionic liquids by P-doped TiO₂ nanotubes

Shangcong Zhang^1,², Qian Liu³, Xinyue Tang⁴, Zhiming Zhou⁴, Tieyan Fan⁴, Yingmin You^1,²(

), Qingcheng Zhang⁴(

), Shusheng Zhang⁵, Jun Luo⁶, Xijun Liu⁷(

)

¹. College of Electrical and Electronic Engineering, Wenzhou University, Wenzhou 325035, China
². Low Voltage Apparatus Technology Research Centre of Zhejiang, Wenzhou University, Wenzhou 325035, China
³. Institute for Advanced Study, Chengdu University, Chengdu 610106, China
⁴. College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, China
⁵. College of Chemistry, Zhengzhou University, Zhengzhou 450000, China
⁶. Tianjin Key Lab for Photoelectric Materials & Devices, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384, China
⁷. State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Compesite Structures, School of Resource, Environments and Materials, Guangxi University, Nanning 530004, China

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Abstract

Designing advanced and cost-effective electrocatalytic system for nitric oxide (NO) reduction reaction (NORR) is vital for sustainable NH₃ production and NO removal, yet it is a challenging task. Herein, it is shown that phosphorus (P)-doped titania (TiO₂) nanotubes can be adopted as highly efficient catalyst for NORR. The catalyst demonstrates impressive performance in ionic liquid (IL)-based electrolyte with a remarkable high Faradaic efficiency of 89% and NH₃ yield rate of 425 μg·h⁻¹·mg_cat.⁻¹, being close to the best-reported results. Noteworthy, the obtained performance metrics are significantly larger than those for N₂ reduction reaction. It also shows good durability with negligible activity decay even after 10 cycles. Theoretical simulations reveal that the introduction of P dopants tunes the electronic structure of Ti active sites, thereby enhancing the NO adsorption and facilitating the desorption of *NH₃. Moreover, the utilization of IL further suppresses the competitive hydrogen evolution reaction. This study highlights the advantage of the catalyst−electrolyte engineering strategy for producing NH₃ at a high efficiency and rate.

Keywords nitric oxide reduction reaction electrcatalysis ammonia production phosphorus-doped titania

Corresponding Author(s): Yingmin You,Qingcheng Zhang,Xijun Liu

Online First Date: 06 March 2023 Issue Date: 17 May 2023

Cite this article:

Shangcong Zhang,Qian Liu,Xinyue Tang, et al. Electrocatalytic reduction of NO to NH₃ in ionic liquids by P-doped TiO₂ nanotubes[J]. Front. Chem. Sci. Eng., 2023, 17(6): 726-734.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-022-2274-8
https://academic.hep.com.cn/fcse/EN/Y2023/V17/I6/726

Fig.1 Synthesis and structural characterizations for P-TNTs: (a) synthetic depiction illustrating preparation of P-TNTs sample, (b) typical SEM images, and (c) TEM images of P-TNTs, (d) high-resolution TEM (HRTEM) image of P-TNTs, and (e) high-angle annular dark-field scanning TEM (HAADF-STEM) image and elemental mapping of Ti, O, and P in P-TNTs.

Fig.2 Fine structure of P-TNTs: (a) XRD pattern of P-TNTs, (b) and (c) high-resolution XPS spectra for P 2p and Ti 2p, and (d) Raman spectrum.

Fig.3 NORR performance of P-TNTs in an IL-containing electrolyte: (a) Polarization curves of TNTs and P-TNTs in NO-saturated electrolyte, supported on carbon paper, (b, c)

F E N H 3

and yield rate at different applied potentials for TNTs and P-TNTs, respectively, (d)

F E N H 3

and yield rate of P-TNTs at ?0.8 V vs RHE detected by three independent quantification methods, (e)

F E N H 3

and yield rate of P-TNTs during 10 consecutive recycling electrolysis. Error bars depicted in (b–d) represent the standard deviation of three independent samples.

Fig.4 Experiments and theoretical simulations: (a) charging current density differences plotted against scan rates and (b) EIS spectra. The inset shows the equivalent circuit. (c) Calculated PDOS of P-TNTs and the adsorbed NO, corrected with Fermi level, and (d) calculated free energy diagrams of NORR.

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