Abstract
The electroreduction of nitrate to ammonia is particularly important in mitigating environmental pollution and obtaining value-added products. Although non-toxic and inexpensive iron-based materials are expected to be a promising catalyst for electrochemical nitrate reduction, ensuring their sustained high activity and inhibiting spontaneous corrosion requires the implementation of complex design. Here we report an economical self-corrosion approach that utilizes Ni2+ ions in wastewater to control the formation of NiFe layered double hydroxide active phase on iron surface, resulting in high nitrate conversion (97.2%) and ammonia selectivity (90.3%). Coupling nitrate reduction with acid absorption, the conversion from NO3− to (NH4)2SO4(s) for applications such as acting as fertilizer are achieved. This distinctive ‘waste-to-treasure’ perspective not only challenges the conventional belief that corrosion diminishes active phase but also notably improves catalytic efficiency while harnessing valuable resources from wastewater, offering a practical method for converting nitrate to useful ammonia products.
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.Data availability
The data supporting the findings in this study are available within the paper (and its Supplementary Information).
References
Chen, F. et al. Efficient conversion of low-concentration nitrate sources into ammonia on a Ru-dispersed Cu nanowire electrocatalyst. Nat. Nanotechnol. 17, 759–767 (2022).
Fan, K. et al. Active hydrogen boosts electrochemical nitrate reduction to ammonia. Nat. Commun. 13, 7958 (2022).
Han, S. et al. Ultralow overpotential nitrate reduction to ammonia via a three-step relay mechanism. Nat. Catal. 6, 402–414 (2023).
Xu, H. et al. Electrocatalytic reduction of nitrate-a step towards a sustainable nitrogen cycle. Chem. Soc. Rev. 51, 2710–2758 (2022).
Zhang, S. et al. Fe/Cu diatomic catalysts for electrochemical nitrate reduction to ammonia. Nat. Commun. 14, 3634 (2023).
Chen, G. et al. Electrochemical reduction of nitrate to ammonia via direct eight-electron transfer using a copper-molecular solid catalyst. Nat. Energy 5, 605–613 (2020).
Fang, J. et al. Ampere-level current density ammonia electrochemical synthesis using CuCo nanosheets simulating nitrite reductase bifunctional nature. Nat. Commun. 13, 7899 (2022).
Gao, J. et al. Electrochemically selective ammonia extraction from nitrate by coupling electron-and phase-transfer reactions at a three-phase interface. Environ. Sci. Technol. 55, 10684–10694 (2021).
Zheng, W. et al. Self-activated Ni cathode for electrocatalytic nitrate reduction to ammonia: from fundamentals to scale-up for treatment of industrial wastewater. Environ. Sci. Technol. 55, 13231–13243 (2021).
Chen, X. et al. Binderless and oxygen vacancies rich FeNi/graphitized mesoporous carbon/Ni foam for electrocatalytic reduction of nitrate. Environ. Sci. Technol. 54, 13344–13353 (2020).
Wang, K. et al. Sulfur-dopant-promoted electrocatalytic reduction of nitrate by a self-supported iron cathode: selectivity, stability, and underlying mechanism. Appl. Catal. B 319, 121862 (2022).
Wu, Z. et al. Electrochemical ammonia synthesis via nitrate reduction on Fe single atom catalyst. Nat. Commun. 12, 2870 (2021).
Zhang, G. et al. Tandem electrocatalytic nitrate reduction to ammonia on MBenes. Angew. Chem. Int. Ed. 62, e202300054 (2023).
Zhai, P. et al. Engineering single-atomic ruthenium catalytic sites on defective nickel-iron layered double hydroxide for overall water splitting. Nat. Commun. 12, 4587 (2021).
Wu, Z. et al. Corrosion engineering on iron foam toward efficiently electrocatalytic overall water splitting powered by sustainable energy. Adv. Funct. Mater. 31, 2010437 (2021).
Liu, Y. et al. Corrosion engineering towards efficient oxygen evolution electrodes with stable catalytic activity for over 6,000 hours. Nat. Commun. 9, 2609 (2018).
Lang, Z. et al. A corrosion-reconstructed and stabilized economical Fe-based catalyst for oxygen evolution. Nano Res. 16, 2224–2229 (2023).
Liu, X. et al. Turning waste into treasure: regulating the oxygen corrosion on Fe foam for efficient electrocatalysis. Small 16, 2000663 (2020).
Deng, J. et al. Generation of atomic hydrogen by Ni-Fe hydroxides: mechanism and activity for hydrodechlorination of trichloroethylene. Water Res. 207, 117802 (2021).
Lv, X. et al. Defective layered double hydroxide nanosheet boosts electrocatalytic hydrodechlorination reaction on supported palladium nanoparticles. ACS ES&T Water 2, 1451–1460 (2022).
Wang, Y. et al. Unveiling the activity origin of a copper-based electrocatalyst for selective nitrate reduction to ammonia. Angew. Chem. Int. Ed. 59, 5350–5354 (2020).
Wang, Q. et al. Recent advances in the synthesis and application of layered double hydroxide (LDH) nanosheets. Chem. Rev. 112, 4124–4155 (2012).
Kim, K.-H. et al. Energy-efficient electrochemical ammonia production from dilute nitrate solution. Energy Environ. Sci. 16, 663–672 (2023).
Li, C. et al. Electrochemical removal of nitrate using a nanosheet structured Co3O4/Ti cathode: effects of temperature, current and pH adjusting. Sep. Purif. Technol. 237, 116485 (2020).
Su, L. et al. Electrochemical nitrate reduction by using a novel Co3O4/Ti cathode. Water Res. 120, 1–11 (2017).
Duan, W. et al. Highly active and durable carbon electrocatalyst for nitrate reduction reaction. Water Res. 161, 126–135 (2019).
Gao, J. et al. Non-precious Co3O4-TiO2/Ti cathode based electrocatalytic nitrate reduction: preparation, performance and mechanism. Appl. Catal. B. 254, 391–402 (2019).
Zhang, Y. et al. Electrochemical reduction of nitrate via Cu/Ni composite cathode paired with Ir-Ru/Ti anode: high efficiency and N2 selectivity. Electrochim. Acta 291, 151–160 (2018).
Li, M. et al. Efficient electrochemical reduction of nitrate to nitrogen using Ti/IrO2–Pt anode and different cathodes. Electrochim. Acta 54, 4600–4606 (2009).
Li, Y. et al. Development of a mechanically flexible 2D-MXene membrane cathode for selective electrochemical reduction of nitrate to N2: mechanisms and implications. Environ. Sci. Technol. 55, 10695–10703 (2021).
Ma, J. et al. Electrochemical reduction of nitrate in a catalytic carbon membrane nano-reactor. Water Res. 208, 117862 (2022).
Cerrón-Calle, G. A. et al. Highly reactive Cu-Pt bimetallic 3D-electrocatalyst for selective nitrate reduction to ammonia. Appl. Catal. B 302, 120844 (2022).
Zhang, Z. et al. Electrochemical-catalytic reduction of nitrate over Pd–Cu/γAl2O3 catalyst in cathode chamber: enhanced removal efficiency and N2 selectivity. Chem. Eng. J. 290, 201–208 (2016).
Kang, J. et al. Realizing two-electron transfer in Ni(OH)2 nanosheets for energy storage. J. Am. Chem. Soc. 144, 8969–8976 (2022).
Wu, Y. et al. Evolution of cationic vacancy defects: a motif for surface restructuration of OER precatalyst. Angew. Chem. Int. Ed. 60, 26829–26836 (2021).
Wang, Y. et al. Nitrate electroreduction: mechanism insight, in situ characterization, performance evaluation, and challenges. Chem. Soc. Rev. 50, 6720–6733 (2021).
He, W. et al. Splicing the active phases of copper/cobalt-based catalysts achieves high-rate tandem electroreduction of nitrate to ammonia. Nat. Commun. 13, 1129 (2022).
Wang, Y. et al. Structurally disordered RuO2 nanosheets with rich oxygen vacancies for enhanced nitrate electroreduction to ammonia. Angew. Chem. Int. Ed. 134, e202202604 (2022).
Shen, J. et al. Oxygen-vacancy-rich nickel hydroxide nanosheet: a multifunctional layer between Ir and Si toward enhanced solar hydrogen production in alkaline media. Energy Environ. Sci. 15, 3051–3061 (2022).
Duan, W. et al. In situ reconstruction of metal oxide cathodes for ammonium generation from high-strength nitrate wastewater: elucidating the role of the substrate in the performance of Co3O4-x. Environ. Sci. Technol. 57, 3893–3904 (2023).
Dionigi, F. et al. In-situ structure and catalytic mechanism of NiFe and CoFe layered double hydroxides during oxygen evolution. Nat. Commun. 11, 2522 (2020).
Zhu, T. et al. Single‐atom Cu catalysts for enhanced electrocatalytic nitrate reduction with significant alleviation of nitrite production. Small 16, 2004526 (2020).
Peng, L. et al. Atomic cation‐vacancy engineering of NiFe‐layered double hydroxides for improved activity and stability towards the oxygen evolution reaction. Angew. Chem. Int. Ed. 60, 24612–24619 (2021).
Bo, X. et al. Operando Raman spectroscopy reveals Cr-induced-phase reconstruction of NiFe and CoFe oxyhydroxides for enhanced electrocatalytic water oxidation. Chem. Mater. 32, 4303–4311 (2020).
Liu, C. et al. Specifically adsorbed ferrous ions modulate interfacial affinity for high-rate ammonia electrosynthesis from nitrate in neutral media. Proc. Natl Acad. Sci. USA 120, e2209979120 (2023).
Mao, R. et al. Selective conversion of nitrate to nitrogen gas by enhanced electrochemical process assisted by reductive Fe (II)-Fe (III) hydroxides at cathode surface. Appl. Catal. B 298, 120552 (2021).
Hall, D. S. et al. Applications of in situ Raman spectroscopy for identifying nickel hydroxide materials and surface layers during chemical aging. ACS Appl. Mater. Interfaces 6, 3141–3149 (2014).
Hammer, B., Hansen, L. B. & Nørskov, J. K. Improved adsorption energetics within density-functional theory using revised Perdew–Burke–Ernzerhof functionals. Phys. Rev. B 59, 7413 (1999).
Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169 (1996).
Grimme, S. Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J. Comput. Chem. 27, 1787–1799 (2006).
Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (grant numbers 52270082 (R.M.), 22276210 (X.Z.) and 22106173 (J.Z.)) and Tianjin Science and Technology Program (grant number 22YFYSHZ00270 (R.M.)).
Author information
Authors and Affiliations
Contributions
X.Z. conceived and designed this project and revised this original manuscript. K.W. performed experiments, electrode materials preparation, characterization, data analysis and prepared the manuscript. R.M. contributed to the materials characterizations and experimental data analysis and revised the manuscript. R.L. contributed to discussion and draft editing. J.Z., H.Z. and W.R. discussed the results.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing interests.
Peer review
Peer review information
Nature Water thanks Jianzhou Gui and Li-Zhi Huang for their contribution to the peer review of this work.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Supplementary Information
Supplementary Methods, Figs. 1–35, Tables 1–6 and Refs. 1–12.
Source data
Source Data Fig. 1
Statistical source data.
Source Data Fig. 2
Statistical source data.
Source Data Fig. 3
Statistical source data.
Source Data Fig. 4
Statistical source data.
Source Data Fig. 5
Statistical source data.
Source Data Fig. 6
Statistical source data.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Wang, K., Mao, R., Liu, R. et al. Intentional corrosion-induced reconstruction of defective NiFe layered double hydroxide boosts electrocatalytic nitrate reduction to ammonia. Nat Water 1, 1068–1078 (2023). https://doi.org/10.1038/s44221-023-00169-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s44221-023-00169-3
- Springer Nature Limited