Electrocatalytic reduction of nitrate using Pd-Cu modified carbon nanotube membranes

doi:10.1007/s11783-023-1640-1

Front. Environ. Sci. Eng.

2023, Vol. 17

Issue (4) : 40 https://doi.org/10.1007/s11783-023-1640-1

RESEARCH ARTICLE

Electrocatalytic reduction of nitrate using Pd-Cu modified carbon nanotube membranes

Zhijun Liu^1,², Xi Luo^1,³, Senlin Shao², Xue Xia¹(

)

¹. College of Life and Environmental Sciences, Minzu University of China, Beijing 100081, China
². School of Civil Engineering, Wuhan University, Wuhan 430072, China
³. Yangtze Ecology and Environment Co., Ltd., Wuhan 430062, China

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Abstract

● Pd-Cu modified CNT membranes were prepared successfully by electrodeposition method.

● The deposition voltage and deposition time were optimized for Pd-Cu co-deposition.

● NO₃⁻-N was removed efficiently from water by Pd-Cu modified CNT membranes.

● The presence of dissolved oxygen did not affect the nitrate reduction performance.

● Mass transfer rate was promoted significantly with the increase in membrane flux.

Excessive nitrate in water is harmful to the ecological environment and human health. Electrocatalytic reduction is a promising technology for nitrate removal. Herein, a Pd-Cu modified carbon nanotube membrane was fabricated with an electrodeposition method and used to reduce nitrate in a flow-through electrochemical reactor. The optimal potential and duration for codeposition of Pd and Cu were −0.7 V and 5 min, respectively, according to linear scan voltammetry results. The membrane obtained with a Pd:Cu ratio of 1:1 exhibited a relatively high nitrate removal efficiency and N₂ selectivity. Nitrate was almost completely reduced (~99 %) by the membrane at potentials lower than −1.2 V. However, −0.8 V was the optimal potential for nitrate reduction in terms of both nitrate removal efficiency and product selectivity. The nitrate removal efficiency was 56.2 %, and the N₂ selectivity was 23.8 % for the Pd:Cu=1:1 membrane operated at −0.8 V. Nitrate removal was enhanced under acidic conditions, while N₂ selectivity was decreased. The concentrations of Cl⁻ ions and dissolved oxygen showed little effect on nitrate reduction. The mass transfer rate constant was greatly improved by 6.6 times from 1.14 × 10⁻³ m/h at a membrane flux of 1 L/(m²·h) to 8.71 × 10⁻³ m/h at a membrane flux of 15 L/(m²·h), which resulted in a significant increase in the nitrate removal rate from 13.6 to 133.5 mg/(m²·h). These findings show that the Pd-Cu modified CNT membrane is an efficient material for nitrate reduction.

Keywords Pd-Cu modified CNT membrane Nitrate reduction Flow-through Electrodeposition Electrocatalytic reduction

Corresponding Author(s): Senlin Shao,Xue Xia

Just Accepted Date: 15 September 2022 Issue Date: 24 October 2022

Cite this article:

Zhijun Liu,Xi Luo,Senlin Shao, et al. Electrocatalytic reduction of nitrate using Pd-Cu modified carbon nanotube membranes[J]. Front. Environ. Sci. Eng., 2023, 17(4): 40.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-023-1640-1
https://academic.hep.com.cn/fese/EN/Y2023/V17/I4/40

Fig.1 LSV for (a) CNT membranes in 0.5 mol/L NaCl, 0.5 mol/L NaCl with 10 mmol/L PdCl₂, and 0.5 mol/L NaCl with 10 mmol/L Cu(NO₃)₂·3H₂O, (b) Pd-Cu modified CNT membranes (Pd:Cu = 1:1) obtained with different electrodeposition times (solution: 50 mmol/L Na₂SO₄ and 50 mg/L NO₃^?-N).

Fig.2 SEM images of (a) PVDF membrane, (b) PVDF supported CNT membrane, (c) Pd-Cu modified CNT membrane (Pd:Cu=1:1), and EDX elemental maps for (d) Pd, (e) Cu, and (f) full coverage of both Cu and Pd on the Pd-Cu modified CNT membrane (Pd:Cu=1:1).

Fig.3 LSV of Pd-Cu modified CNT membranes with different Pd:Cu ratios in a solution containing 50 mmol/L Na₂SO₄ and 50 mg/L NO₃^?-N.

Fig.4 (a) NO₃^?-N removal efficiency, (b) N₂ selectivity, (c) NO₂^?-N selectivity, and (d) NH₄⁺-N selectivity for Pd-Cu modified CNT membranes prepared with different Pd:Cu ratios (solution: 20 mg/L NO₃^?-N, 50 mmol/L Na₂SO₄ and 200 mg/L NaHCO₃, pH=8.0; membrane flux: 10 L/(m²·h)).

Fig.5 Nitrate removal efficiencies and product distributions at (a) different pH values, (b) different concentrations of Cl^?, and (c) different levels of DO. (Solution: 20 mg/L NO₃^?-N, 50 mmol/L Na₂SO₄ and 200 mg/L NaHCO₃; Potential: ?0.8 V; Pd:Cu=1:1; Membrane flux: 10 L/(m²·h))

Fig.6 (a) Nitrate removal efficiency and production distribution, (b) mass transfer rate constant and nitrate removal rate, and (c) electrical energy consumption per order nitrate reduction (E_EO) and current efficiency (CE) at different membrane fluxes (Solution: 20 mg/L NO₃^?-N, 50 mmol/L Na₂SO₄ and 200 mg/L NaHCO₃; Potential: ?0.8 V; Pd:Cu=1:1).

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