Abstract
Nitrate is a water-soluble toxic pollutant that needs to be excluded from the environment. For this purpose, several electrochemical studies have been conducted but most of them focused on the nitrate reduction reaction (NRR) in alkaline and acidic media while insignificant research is available in neutral media with Pt electrode. In this work, we explored the effect of three coinage metals (Cu, Ag, and Au) on Pt electrode for the electrochemical reduction of nitrate in neutral solution. Among the three electrodes, Pt-Cu exhibited the best catalytic activity toward NRR, whereas Pt-Au electrode did not show any reactivity. An activity order of Pt-Cu > Pt–Ag > Pt-Au was observed pertaining to NRR. The Pt–Ag electrode produces nitrite ions by reducing nitrate ions (\({NO}_{3}^{-}\to {NO}_{2}^{-})\). Meanwhile, at Pt-Cu electrode, nitrate reduction yields ammonia via both direct (\({NO}_{3}^{-}\to { NH}_{3})\) and indirect (\({NO}_{3}^{-}\to { NO}_{2}^{-}\to { NH}_{3})\) reaction pathways depending on the potential. The cathodic transfer coefficients were estimated to be ca. 0.40 and ca. 0.52, while the standard rate constants for nitrate reduction were calculated as ca. 2.544 × 10–2 cm.s−1 and ca. 1.453 × 10–2 cm.s−1 for Pt-Cu and Pt–Ag electrodes, respectively. Importantly, Pt-Cu and Pt–Ag electrodes execute NRR in the neutral medium between their respective Hydrogen-Evolution Reaction (HER) and Open-Circuit Potential (OCP), implying that on these electrodes, HER and NRR do not compete and the latter is a corrosion-free process.
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Data available on request from the corresponding author.
References
Badea GE (2009) Electrocatalytic reduction of nitrate on copper electrode in alkaline solution. Electrochim Acta 54:996–1001. https://doi.org/10.1016/j.electacta.2008.08.003
Banasiak LJ, Schäfer AI (2009) Removal of boron, fluoride, and nitrate by electrodialysis in the presence of organic matter. J Memb Sci 334:101–109. https://doi.org/10.1016/j.memsci.2009.02.020
Bard AJ, Faulkner LR (2002) Electrochemical methods: fundamentals and applications. New York: Wiley, 2001, 2nd ed. Russ J Electrochem 38:1364–1365. https://doi.org/10.1023/A:1021637209564
Bhatnagar A, Sillanpää M (2011) A review of emerging adsorbents for nitrate removal from water. Chem Eng J 168(2):493–504. https://doi.org/10.1016/j.cej.2011.01.103
Birdja YY, Yang J, Koper MTM (2014) Electrocatalytic reduction of nitrate on tin-modified palladium electrodes. Electrochim Acta 140:518–524. https://doi.org/10.1016/j.electacta.2014.06.011
Chen JG, Crooks RM, Seefeldt LC, et al (2018) Beyond fossil fuel–driven nitrogen transformations. Science (1979) 360: https://doi.org/10.1126/science.aar6611
Chen T, Li H, Ma H, Koper MTM (2015) Surface modification of Pt (100) for electrocatalytic nitrate reduction to dinitrogen in alkaline solution. Langmuir. https://doi.org/10.1021/acs.langmuir.5b00283
Chen Y, Peng C, Wang J et al (2011) Effect of nitrate recycling ratio on simultaneous biological nutrient removal in a novel anaerobic/anoxic/oxic (A2/O)-biological aerated filter (BAF) system. Bioresour Technol 102:5722–5727. https://doi.org/10.1016/j.biortech.2011.02.114
Christophe J, Tsakova V, Buess-Herman C (2007) Electroreduction of nitrate at copper electrodes and copper-PANI composite layers. Zeitschrift Fur Physikalische Chemie. https://doi.org/10.1524/zpch.2007.221.9-10.1123
Comer BM, Fuentes P, Dimkpa CO, Liu YH, Fernandez CA, Arora P, Realff M, Singh U, Hatzell MC, Medford AJ (2019) Prospects and Challenges for Solar Fertilizers. Joule 3(7):1578–1605. https://doi.org/10.1016/j.joule.2019.05.001
Duca M, Koper MTM (2012) Powering denitrification: The perspectives of electrocatalytic nitrate reduction. Energy Environ Sci 5:9726–9742. https://doi.org/10.1039/C2EE23062C
Duca M, Sacré N, Wang A et al (2018) Enhanced electrocatalytic nitrate reduction by preferentially-oriented (100) PtRh and PtIr alloys: the hidden treasures of the ‘miscibility gap.’ Appl Catal B 221:86–96. https://doi.org/10.1016/j.apcatb.2017.08.081
Fan J, Qi K, Zhang L et al (2017) Engineering Pt/Pd interfacial electronic structures for highly efficient hydrogen evolution and alcohol oxidation. ACS Appl Mater Interfaces 9:18008–18014. https://doi.org/10.1021/acsami.7b05290
Fernández-Nava Y, Marañón E, Soons J, Castrillón L (2008) Denitrification of wastewater containing high nitrate and calcium concentrations. Bioresour Technol 99:7976–7981. https://doi.org/10.1016/j.biortech.2008.03.048
Helmke SM, Duncan MW (2007) Measurement of the NO metabolites, nitrite, and nitrate, in human biological fluids by GC-MS. J Chromatogr B Analyt Technol Biomed Life Sci 851:83–92. https://doi.org/10.1016/j.jchromb.2006.09.047
Karanasios KA, Vasiliadou IA, Pavlou S, Vayenas DV (2010) Hydrogenotrophic denitrification of potable water: a review. J Hazard Mater 180:20–37. https://doi.org/10.1016/j.jhazmat.2010.04.090
Karikalan N, Karthik R, Chen SM et al (2017) Sonochemical synthesis of sulfur doped reduced graphene oxide supported CuS nanoparticles for the non-enzymatic glucose sensor applications. Sci Rep 7:1–10. https://doi.org/10.1038/s41598-017-02479-5
Kato M, Okui M, Taguchi S, Yagi I (2017) Electrocatalytic nitrate reduction on well-defined surfaces of tin-modified platinum, palladium, and platinum-palladium single crystalline electrodes in acidic and neutral media. J Electroanal Chem 800:46–53. https://doi.org/10.1016/j.jelechem.2017.01.020
Kodamatani H, Yamazaki S, Saito K et al (2009) Selective determination method for measurement of nitrite and nitrate in water samples using high-performance liquid chromatography with post-column photochemical reaction and chemiluminescence detection. J Chromatogr A 1216:3163–3167. https://doi.org/10.1016/j.chroma.2009.01.096
Lei X, Liu F, Li M et al (2018) Fabrication and characterization of a Cu-Pd-TNPs polymetallic nanoelectrode for electrochemically removing nitrate from groundwater. Chemosphere 212:237–244. https://doi.org/10.1016/j.chemosphere.2018.08.082
Li H, Shin K, Henkelman G (2018) Effects of ensembles, ligand, and strain on adsorbate binding to alloy surfaces. Journal of Chemical Physics 149. https://doi.org/10.1063/1.5053894
Li H, Yan C, Guo H et al (2020a) Cu xIr1- xNanoalloy catalysts achieve near 100% selectivity for aqueous nitrite reduction to NH3. ACS Catal 10:7915–7921. https://doi.org/10.1021/acscatal.0c01604
Li J, Zhan G, Yang J et al (2020b) Efficient ammonia electrosynthesis from nitrate on strained ruthenium nanoclusters. J Am Chem Soc. https://doi.org/10.1021/jacs.0c00418
Li S, Zhang H, Huang T et al (2020c) Aerobic denitrifying bacterial communities drive nitrate removal: performance, metabolic activity, dynamics and interactions of core species. Bioresour Technol 316:123922. https://doi.org/10.1016/j.biortech.2020.123922
Malko D, Kucernak A, Lopes T (2016) Performance of Fe-N/C oxygen reduction electrocatalysts toward NO2-, NO, and NH2OH electroreduction: from fundamental insights into the active center to a new method for environmental nitrite destruction. J Am Chem Soc. https://doi.org/10.1021/jacs.6b09622
Manea F, Remes A, Radovan C et al (2010) Simultaneous electrochemical determination of nitrate and nitrite in aqueous solution using Ag-doped zeolite-expanded graphite-epoxy electrode. Talanta 83:66–71. https://doi.org/10.1016/j.talanta.2010.08.042
Martínez J, Ortiz A, Ortiz I (2017) State-of-the-art and perspectives of the catalytic and electrocatalytic reduction of aqueous nitrates. Appl Catal B 207:42–59. https://doi.org/10.1016/j.apcatb.2017.02.016
Mumtarin Z, Rahman MM, Marwani HM, Hasnat MA (2020) Electro-kinetics of conversion of NO3− into NO2− and sensing of nitrate ions via reduction reactions at copper immobilized platinum surface in the neutral medium. Electrochim Acta 346. https://doi.org/10.1016/j.electacta.2020.135994
Pattrick RAD, Mosselmans JFW, Charnock JM et al (1997) The structure of amorphous copper sulfide precipitates: an X-ray absorption study. Geochim Cosmochim Acta 61:2023–2036. https://doi.org/10.1016/S0016-7037(97)00061-6
Reyter D, Bélanger D, Roué L (2008) Study of the electroreduction of nitrate on copper in alkaline solution. Electrochim Acta. https://doi.org/10.1016/j.electacta.2008.03.048
Rosca V, Duca M, DeGroot MT, Koper MTM (2009) Nitrogen cycle electrocatalysis. Chem Rev. https://doi.org/10.1021/cr8003696
Shen J, Birdja YY, Koper MTM (2015) Electrocatalytic nitrate reduction by a cobalt protoporphyrin immobilized on a pyrolytic graphite electrode. Langmuir. https://doi.org/10.1021/acs.langmuir.5b00977
Shi J, Long C, Li A (2016) Selective reduction of nitrate into nitrogen using Fe-Pd bimetallic nanoparticle supported on chelating resin at near-neutral pH. Chem Eng J 286:408–415. https://doi.org/10.1016/j.cej.2015.10.054
Shih YJ, Wu ZL, Lin CY et al (2020) Manipulating the crystalline morphology and facet orientation of copper and copper-palladium nanocatalysts supported on stainless steel mesh with the aid of cationic surfactant to improve the electrochemical reduction of nitrate and N2 selectivity. Appl Catal B. https://doi.org/10.1016/j.apcatb.2020.119053
Soto-Hernández J, Santiago-Ramirez CR, Ramirez-Meneses E et al (2019) Electrochemical reduction of NOx species at the interface of nanostructured Pd and PdCu catalysts in alkaline conditions. Appl Catal B. https://doi.org/10.1016/j.apcatb.2019.118048
Su JF, Ruzybayev I, Shah I, Huang CP (2016) The electrochemical reduction of nitrate over micro-architectured metal electrodes with stainless steel scaffold. Appl Catal B. https://doi.org/10.1016/j.apcatb.2015.06.028
Taguchi S, Feliu JM (2008) Kinetic study of nitrate reduction on Pt (1 1 0) electrode in perchloric acid solution. Electrochim Acta. https://doi.org/10.1016/j.electacta.2007.12.032
Tugaoen HON, Garcia-Segura S, Hristovski K, Westerhoff P (2017) Challenges in photocatalytic reduction of nitrate as a water treatment technology. Sci Total Environ 599–600:1524–1551. https://doi.org/10.1016/j.scitotenv.2017.04.238
Wang Y, Yu Y, Jia R et al (2019) Electrochemical synthesis of nitric acid from air and ammonia through waste utilization. Natl Sci Rev. https://doi.org/10.1093/nsr/nwz019
Wang Y, Zhou W, Jia R et al (2020) Unveiling the activity origin of a copper-based electrocatalyst for selective nitrate reduction to ammonia. Angewandte Chemie - Int Edition 59:5350–5354. https://doi.org/10.1002/anie.201915992
Wang Z, Zheng YR, Montoya J et al (2021) Origins of the instability of nonprecious hydrogen evolution reaction catalysts at open-circuit potential. ACS Energy Lett 6:2268–2274. https://doi.org/10.1021/acsenergylett.1c00876
Wu T, Kong X, Tong S et al (2019a) Self-supported Cu nanosheets derived from CuCl-CuO for highly efficient electrochemical degradation of NO3−. Appl Surf Sci. https://doi.org/10.1016/j.apsusc.2019.05.358
Wu Y, Lin Y, Xu J (2019b) Synthesis of Ag-Ho, Ag-Sm, Ag-Zn, Ag-Cu, Ag-Cs, Ag-Zr, Ag-Er, Ag-Y and Ag-Co metal organic nanoparticles for UV-Vis-NIR wide-range bio-tissue imaging. Photochem Photobiol Sci 18:1081–1091. https://doi.org/10.1039/c8pp00493e
Xie Y, Dimitrov N (2018) Highly active and durable Cu xAu(1–x) ultrathin-film catalysts for nitrate electroreduction synthesized by surface-limited redox replacement. ACS Omega. https://doi.org/10.1021/acsomega.8b02148
Yang J, Duca M, Schouten KJP, Koper MTM (2011) Formation of volatile products during nitrate reduction on a Sn-modified Pt electrode in acid solution. J Electroanal Chem. https://doi.org/10.1016/j.jelechem.2011.03.015
Yang J, Sebastian P, Duca M et al (2014) pH dependence of the electroreduction of nitrate on Rh and Pt polycrystalline electrodes. Chem Commun. https://doi.org/10.1039/c3cc49224a
Yoshioka T, Iwase K, Nakanishi S et al (2016) Electrocatalytic reduction of nitrate to nitrous oxide by a copper-modified covalent triazine framework. J Phys Chem C. https://doi.org/10.1021/acs.jpcc.5b10962
Yu J, Kolln AF, Jing D et al (2021) Precisely controlled synthesis of hybrid intermetallic–metal nanoparticles for nitrate electroreduction. ACS Appl Mater Interfaces. https://doi.org/10.1021/acsami.1c09301
Zhao D, Xie S, Wang Y, et al (2019) Synthesis of large-scale few-layer PtS 2 films by chemical vapor deposition. AIP Adv 9. https://doi.org/10.1063/1.5086447
Funding
This study is funded by the Shahjalal University of Science and Technology (Grant No. PS/2022/1/01) and the Ministry of Education (Grant No. PS 20201512).
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Humayra Begum: experimental and writing—original draft, Md. Nurnobi Islam: product analysis and corresponding experiment, Sami Ben Aoun: conceptualization and writing—review and editing, Jamil A. Safwan: experimental, Syed Shaheen Shah: surface analysis, Md. Abdul Aziz: surface analysis, Mohammad A. Hasnat: conceptualization, writing—review and editing, supervision, and funding acquisition.
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Begum, H., Islam, M.N., Ben Aoun, S. et al. Electrocatalytic reduction of nitrate ions in neutral medium at coinage metal-modified platinum electrodes. Environ Sci Pollut Res 30, 34904–34914 (2023). https://doi.org/10.1007/s11356-022-24372-z
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DOI: https://doi.org/10.1007/s11356-022-24372-z