Skip to main content
SpringerLink
Log in

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

  • Research Article
  • Published:
Frontiers of Environmental Science & Engineering Aims and scope Submit manuscript

Abstract

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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  • Abascal E, Gómez-Coma L, Ortiz I, Ortiz A (2022). Global diagnosis of nitrate pollution in groundwater and review of removal technologies. Science of the Total Environment, 810: 152233

    Article  CAS  Google Scholar 

  • Chen C, Li K, Li C, Sun T, Jia J (2019). Combination of Pd-Cu catalysis and electrolytic H2 evolution for selective nitrate reduction using protonated polypyrrole as a cathode. Environmental Science & Technology, 53(23): 13868–13877

    Article  CAS  Google Scholar 

  • Chu X, Duan D, Shen G, Yu R (2007). Amperometric glucose biosensor based on electrodeposition of platinum nanoparticles onto covalently immobilized carbon nanotube electrode. Talanta, 71(5): 2040–2047

    Article  CAS  Google Scholar 

  • Duan W, Li G, Lei Z, Zhu T, Xue Y, Wei C, Feng C (2019). Highly active and durable carbon electrocatalyst for nitrate reduction reaction. Water Research, 161: 126–135

    Article  CAS  Google Scholar 

  • Fan Z, Zeng W, Liu H, Jia Y, Peng Y (2022). A novel partial denitrification, anammox-biological phosphorus removal, fermentation and partial nitrification (PDA-PFPN) process for real domestic wastewater and waste activated sludge treatment. Water Research, 217: 118376

    Article  CAS  Google Scholar 

  • Gao G, Vecitis C D (2012). Doped carbon nanotube networks for electrochemical filtration of aqueous phenol: electrolyte precipitation and phenol polymerization. ACS Applied Materials & Interfaces, 4(3): 1478–1489

    Article  CAS  Google Scholar 

  • Garcia-Segura S, Lanzarini-Lopes M, Hristovski K, Westerhoff P (2018). Electrocatalytic reduction of nitrate: Fundamentals to full-scale water treatment applications. Applied Catalysis B: Environmental, 236: 546–568

    Article  CAS  Google Scholar 

  • Gayen P, Spataro J, Avasarala S, Ali A M, Cerrato J M, Chaplin B P (2018). Electrocatalytic reduction of nitrate using Magnéli phase TiO2 reactive electrochemical membranes doped with Pd-based catalysts. Environmental Science & Technology, 52(16): 9370–9379

    Article  CAS  Google Scholar 

  • Huang J, Xie Q, Tan Y, Fu Y, Su Z, Huang Y, Yao S (2009). Preparation of Pt/multiwalled carbon nanotubes modified Au electrodes via Pt—Cu co-electrodeposition/Cu stripping protocol for high-performance electrocatalytic oxidation of methanol. Materials Chemistry and Physics, 118(2–3): 371–378

    Article  CAS  Google Scholar 

  • Jiang W L, Xia X, Han J L, Ding Y C, Haider M R, Wang A J (2018). Graphene modified electro-Fenton catalytic membrane for in situ degradation of antibiotic florfenicol. Environmental Science & Technology, 52(17): 9972–9982

    Article  CAS  Google Scholar 

  • Lan H, Liu X, Liu H, Liu R, Hu C, Qu J (2016). Efficient nitrate reduction in a fluidized electrochemical reactor promoted by Pd-Sn/AC particles. Catalysis Letters, 146(1): 91–99

    Article  CAS  Google Scholar 

  • Lejarazu-Larrañaga A, Ortiz J M, Molina S, Pawlowski S, Galinha C F, Otero V, García-Calvo E, Velizarov S, Crespo J G (2022). Nitrate removal by Donnan dialysis and anion-exchange membrane bioreactor using upcycled end-of-life reverse osmosis membranes. Membranes (Basel), 12(2): 101

    Article  Google Scholar 

  • Li Q, Zhang Q, Ding L, Zhou D, Cui H, Wei Z, Zhai J (2013). Synthesis of silver/multi-walled carbon nanotubes composite and its application for electrocatalytic reduction of brómate. Chemical Engineering Journal, 217: 28–33

    Article  CAS  Google Scholar 

  • Li Y, Ma J, Waite T D, Hoffmann M R, Wang Z (2021). Development of a mechanically flexible 2D-MXene membrane cathode for selective electrochemical reduction of nitrate to N2: Mechanisms and implications. Environmental Science & Technology, 55(15): 10695–10703

    Article  CAS  Google Scholar 

  • Li Y, Zhang W, Dai Y, Su X, Xiao Y, Wu D, Sun F, Mei R, Chen J, Lin H (2022). Effective partial denitrification of biological effluent of landfill leachate for anammox process: start-up, influencing factors and stable operation. Science of the Total Environment, 807(Pt 3): 150975

    Article  CAS  Google Scholar 

  • Liu Y, Wang J (2019). Reduction of nitrate by zero valent iron (ZVI)-based materials: a review. Science of the Total Environment, 671: 388–403

    Article  CAS  Google Scholar 

  • Liu Y, Zhang X, Wang J (2022). A critical review of various adsorbents for selective removal of nitrate from water: structure, performance and mechanism. Chemosphere, 291(Pt 1): 132728

    Article  CAS  Google Scholar 

  • Luo S, Peng Y, Liu Y, Peng Y (2022). Research progress and prospects of complete ammonia oxidizing bacteria in wastewater treatment. Frontiers of Environmental Science & Engineering, 16(9): 123

    Article  CAS  Google Scholar 

  • Ma J, Wei W, Qin G, Xiao T, Tang W, Zhao S, Jiang L, Liu S (2022). Electrochemical reduction of nitrate in a catalytic carbon membrane nano-reactor. Water Research, 208: 117862

    Article  CAS  Google Scholar 

  • Martínez J, Ortiz A, Ortiz I (2017). State-of-the-art and perspectives of the catalytic and electrocatalytic reduction of aqueous nitrates. Applied Catalysis B: Environmental, 207: 42–59

    Article  Google Scholar 

  • Mattarozzi L, Cattarin S, Comisso N, Gerbasi R, Guerriero P, Musiani M, Verlato E (2017). Electrodeposition of compact and porous Cu-Pd alloy layers and their application to nitrate reduction in alkali. Electrochimica Acta, 230: 365–372

    Article  CAS  Google Scholar 

  • Rajic L, Fallahpour N, Nazari R, Alshawabkeh A N (2015). Influence of humic substances on electrochemical degradation of trichloroethylene in limestone aquifers. Electrochimica Acta, 181: 123–129

    Article  CAS  Google Scholar 

  • Safavi A, Maleki N, Tajabadi F, Farjami E (2007). High electrocatalytic effect of palladium nanoparticle arrays electrodeposited on carbon ionic liquid electrode. Electrochemistry Communications, 9(8): 1963–1968

    Article  CAS  Google Scholar 

  • Saha S, Gupta R, Sethi S, Biswas R (2022). Enhancing the efficiency of nitrogen removing bacterial population to a wide range of C:N ratio (1.5:1 to 14:1) for simultaneous C & N removal. Frontiers of Environmental Science & Engineering, 16(8): 101

    Article  CAS  Google Scholar 

  • Sanchis I, Diaz E, Pizarro A H, Rodriguez J J, Mohedano A F (2022). Nitrate reduction with bimetallic catalysts: a stability-addressed overview. Separation and Purification Technology, 290: 120750

    Article  CAS  Google Scholar 

  • Soares O S G P, Fan X, Órfão J J M, Lapkin A A, Pereira M F R (2012). Kinetic modeling of nitrate reduction catalyzed by Pd-Cu supported on carbon nanotubes. Industrial & Engineering Chemistry Research, 51(13): 4854–4860

    Article  CAS  Google Scholar 

  • Su J F, Kuan W F, Chen C L, Huang C P (2020). Enhancing electrochemical nitrate reduction toward dinitrogen selectivity on Sn-Pd bimetallic electrodes by surface structure design. Applied Catalysis A, General, 606: 117809

    Article  CAS  Google Scholar 

  • Tang Y, Ma Y W, Wan J Q, Wang Y, Ye G (2021). Two-stage denitrification process performance with solid slow-release carbon source. Environmental Science, 42(7): 3392–3399 (in Chinese)

    Google Scholar 

  • Trellu C, Chaplin B P, Coetsier C, Esmilaire R, Cerneaux S, Causserand C, Cretin M (2018). Electro-oxidation of organic pollutants by reactive electrochemical membranes. Chemosphere, 208: 159–175

    Article  CAS  Google Scholar 

  • Xu S, Wu X, Lu H (2021). Overlooked nitrogen-cycling microorganisms in biological wastewater treatment. Frontiers of Environmental Science & Engineering, 15(6): 133

    Article  CAS  Google Scholar 

  • Yang J, Wang J, Jia J (2009). Improvement of electrochemical wastewater treatment through mass transfer in a seepage carbon nanotube electrode reactor. Environmental Science & Technology, 43(10): 3796–3802

    Article  CAS  Google Scholar 

  • Zhang Q, Ding L, Cui H, Zhai J, Wei Z, Li Q (2014). Electrodeposition of Cu-Pd alloys onto electrophoretic deposited carbon nanotubes for nitrate electroreduction. Applied Surface Science, 308: 113–120

    Article  CAS  Google Scholar 

  • Zhou C, Bai J, Zhang Y, Li J, Li Z, Jiang P, Fang F, Zhou M, Mei X, Zhou B (2021). Novel 3D Pd-Cu(OH)2/CF cathode for rapid reduction of nitrate-N and simultaneous total nitrogen removal from wastewater. Journal of Hazardous Materials, 401: 123232

    Article  CAS  Google Scholar 

  • Zhou Q, Sun H, Jia L, Wu W, Wang J (2022). Simultaneous biological removal of nitrogen and phosphorus from secondary effluent of wastewater treatment plants by advanced treatment: a review. Chemosphere, 296: 134054

    Article  CAS  Google Scholar 

  • Zhu B Z, Zhao H T, Kalyanaraman B, Frei B (2002). Metal-independent production of hydroxyl radicals by halogenated quinones and hydrogen peroxide: an ESR spin trapping study. Free Radical Biology & Medicine, 32(5): 465–473

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by grants from the National Natural Science Foundation of China (Nos. 52070147 and 52270077), the Special Fund of the State Key Joint Laboratory of Environment Simulation and Pollution Control (No. 22K06ESPCT), and the Promotion Plan for Young Teachers’ Scientific Research Ability of Minzu University of China (Nos. 2021QNPY83 and 2022QNPY51).

Author information

Authors and Affiliations

  1. College of Life and Environmental Sciences, Minzu University of China, Beijing, 100081, China

    Zhijun Liu, Xi Luo & Xue Xia

  2. School of Civil Engineering, Wuhan University, Wuhan, 430072, China

    Zhijun Liu & Senlin Shao

  3. Yangtze Ecology and Environment Co., Ltd., Wuhan, 430062, China

    Xi Luo

Authors
  1. Zhijun Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xi Luo
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Senlin Shao
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Xue Xia
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Senlin Shao or Xue Xia.

Additional information

Highlights

• 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.

Supporting Information

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Liu, Z., Luo, X., Shao, S. et al. Electrocatalytic reduction of nitrate using Pd-Cu modified carbon nanotube membranes. Front. Environ. Sci. Eng. 17, 40 (2023). https://doi.org/10.1007/s11783-023-1640-1

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s11783-023-1640-1

Keywords

Search

Navigation