AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article

Electron engineering of nickel phosphide for Niδ+ in electrochemical nitrate reduction to ammonia

Jie Hu1, Hao Huang2( ), Miao Yu1, Shuang Wang1,3( ), Jinping Li3
College of Environmental Science and Engineering, Taiyuan University of Technology, Jinzhong 030600, China
School of Sustainable Energy Materials and Science, Jinhua Advanced Research Institute, Jinhua 321000, China
Shanxi Key Laboratory of Gas Energy Efficient and Clean Utilization, Taiyuan University of Technology, Taiyuan 030024, China
Show Author Information

Graphical Abstract

In this work, a series of carbon-coated nickel phosphide (NiPC) nanosheets electrocatalysts are successfully obtained via one-step phosphating of Ni-metal-organic frameworks (MOFs) for electrochemical reduction of nitrate to ammonia (ENRA). Through electron engineering, the electrochemical ENRA activity of the NiPC-1 with the optimum Niẟ+ content is significantly improved.

Abstract

The electrochemical reduction of nitrate to ammonia (ENRA) provides an efficient approach to remove nitrate pollution and achieve ammonia production simultaneously. Herein, inspired by bio-enzyme in denitrifying bacteria, a carbon-coated nickel phosphide (NiPC) nanosheet derived from metal-organic frameworks (MOFs) is proposed as an efficient catalyst for ENRA. Through electron engineering, controllable Niδ+ in nickel phosphide is achieved by regulating the degree of phosphating, which enhances its activity for the hydrogenation of nitrate. As the result, Niδ+ becomes one of dominating factors determining the efficiency of the ENRA reaction in nickel phosphide. The optimal NiPC catalyst exhibits impressive property toward ENRA: NH4+ Faraday efficiency of 96.68%, NH4+ selectivity of 99.04%, and nitrate conversion rate of 90.43% under low nitrate concentration (200 mg·L−1). This work opens a new avenue for the design of next-generation catalysts through electron engineering for ENRA.

Keywords

electron engineeringtransition metal phosphidenitrate reductionammonia productionmetal-organic frameworks

Electronic Supplementary Material

Download File(s)
12274_2024_6470_MOESM1_ESM.pdf (4 MB)

References

[1]

Picetti, R.; Deeney, M.; Pastorino, S.; Miller, M. R.; Shah, A.; Leon, D. A.; Dangour, A. D.; Green, R. Nitrate and nitrite contamination in drinking water and cancer risk: A systematic review with meta-analysis. Environ. Res. 2022, 210, 112988.
Crossref Google Scholar
[2]

Xiao, Y.; Hao, Q. C.; Zhang, Y. H.; Zhu, Y. C.; Yin, S. Y.; Qin, L. M.; Li, X. H. Investigating sources, driving forces and potential health risks of nitrate and fluoride in groundwater of a typical alluvial fan plain. Sci. Total Environ. 2022, 802, 149909.
Crossref Google Scholar
[3]

Zhang, X.; Zhang, Y.; Shi, P.; Bi, Z. L.; Shan, Z. X.; Ren, L. J. The deep challenge of nitrate pollution in river water of China. Sci. Total Environ. 2021, 770, 144674.
Crossref Google Scholar
[4]

Raza, S.; Zamanian, K.; Ullah, S.; Kuzyakov, Y.; Virto, I.; Zhou, J. B. Inorganic carbon losses by soil acidification jeopardize global efforts on carbon sequestration and climate change mitigation. J. Cleaner Prod. 2021, 315, 128036.
Crossref Google Scholar
[5]

Camargo, J. A.; Alonso, Á. Ecological and toxicological effects of inorganic nitrogen pollution in aquatic ecosystems: A global assessment. Environ. Int. 2006, 32, 831–849.
Crossref Google Scholar
[6]

Rezvani, F.; Sarrafzadeh, M. H.; Ebrahimi, S.; Oh, H. M. Nitrate removal from drinking water with a focus on biological methods: A review. Environ. Sci. Pollut. Res. 2019, 26, 1124–1141.
Crossref Google Scholar
[7]

Abascal, E.; Gómez-Coma, L.; Ortiz, I.; Ortiz, A. Global diagnosis of nitrate pollution in groundwater and review of removal technologies. Sci. Total Environ. 2022, 810, 152233.
Crossref Google Scholar
[8]

Hao, D.; Chen, Z. G.; Figiela, M.; Stepniak, I.; Wei, W.; Ni, B. J. Emerging alternative for artificial ammonia synthesis through catalytic nitrate reduction. J. Mater. Sci. Technol. 2021, 77, 163–168.
Crossref Google Scholar
[9]

Theerthagiri, J.; Park, J.; Das, H. T.; Rahamathulla, N.; Cardoso, E. S. F.; Murthy, A. P.; Maia, G.; Vo, D. N.; Choi, M. Y. Electrocatalytic conversion of nitrate waste into ammonia: A review. Environ. Chem. Lett. 2022, 20, 2929–2949.
Crossref Google Scholar
[10]

Gao, J. N.; Shi, N.; Guo, X. B.; Li, Y. F.; Bi, X. J.; Qi, Y. F.; Guan, J.; Jiang, B. Electrochemically selective ammonia extraction from nitrate by coupling electron- and phase-transfer reactions at a three-phase interface. Environ. Sci. Technol. 2021, 55, 10684–10694.
Crossref Google Scholar
[11]

Cesaro, Z.; Ives, M.; Nayak-Luke, R.; Mason, M.; Bañares-Alcántara, R. Ammonia to power: Forecasting the levelized cost of electricity from green ammonia in large-scale power plants. Appl. Energy 2021, 282, 116009.
Crossref Google Scholar
[12]

Liu, D.; Qiao, L. L.; Peng, S. Y.; Bai, H. Y.; Liu, C. F.; Ip, W. F.; Lo, K. H.; Liu, H. C.; Ng, K. W.; Wang, S. P. et al. Recent advances in electrocatalysts for efficient nitrate reduction to ammonia. Adv. Funct. Mater. 2023, 33, 2303480.
Crossref Google Scholar
[13]

Chen, W. D.; Yang, X. Y.; Chen, Z. D.; Ou, Z. J.; Hu, J. T.; Xu, Y.; Li, Y. L.; Ren, X. Z.; Ye, S. H.; Qiu, J. S. et al. Emerging applications, developments, prospects, and challenges of electrochemical nitrate-to-ammonia conversion. Adv. Funct. Mater. 2023, 33, 2300512.
Crossref Google Scholar
[14]

Zhou, J.; Wen, M.; Huang, R.; Wu, Q. S.; Luo, Y. X.; Tian, Y. K.; Wei, G. F.; Fu, Y. Q. Regulating active hydrogen adsorbed on grain boundary defects of nano-nickel for boosting ammonia electrosynthesis from nitrate. Energy Environ. Sci. 2023, 16, 2611–2620.
Crossref Google Scholar
[15]

Fan, K.; Xie, W. F.; Li, J. Z.; Sun, Y. N.; Xu, P. C.; Tang, Y.; Li, Z. H.; Shao, M. F. Active hydrogen boosts electrochemical nitrate reduction to ammonia. Nat. Commun. 2022, 13, 7958.
Crossref Google Scholar
[16]

Lubitz, W.; Ogata, H.; Rüdiger, O.; Reijerse, E. Hydrogenases. Chem. Rev. 2014, 114, 4081–4148.
Crossref Google Scholar
[17]

Duffner, C.; Kublik, S.; Fösel, B.; Frostegård, Å.; Schloter, M.; Bakken, L.; Schulz, S. Genotypic and phenotypic characterization of hydrogenotrophic denitrifiers. Environ. Microbiol. 2022, 24, 1887–1901.
Crossref Google Scholar
[18]

Kim, D. H.; Kim, M. S. Hydrogenases for biological hydrogen production. Bioresour. Technol. 2011, 102, 8423–8431.
Crossref Google Scholar
[19]

Chouki, T.; Machreki, M.; Rutkowska, I. A.; Rytelewska, B.; Kulesza, P. J.; Tyuliev, G.; Harb, M.; Azofra, L. M.; Emin, S. Highly active iron phosphide catalysts for selective electrochemical nitrate reduction to ammonia. J. Environ. Chem. Eng. 2023, 11, 109275.
Crossref Google Scholar
[20]

Gao, Y.; Wang, R.; Li, Y. D.; Han, E. S.; Song, M. S.; Yang, Z. Y.; Guo, F.; He, Y. Z.; Yang, X. H. Regulating dynamic equilibrium of active hydrogen for super-efficient nitrate electroreduction to ammonia. Chem. Eng. J. 2023, 474, 145546.
Crossref Google Scholar
[21]

Zhang, R.; Guo, Y.; Zhang, S. C.; Chen, D.; Zhao, Y. W.; Huang, Z. D.; Ma, L. T.; Li, P.; Yang, Q.; Liang, G. J. et al. Efficient ammonia electrosynthesis and energy conversion through a Zn-nitrate battery by iron doping engineered nickel phosphide catalyst. Adv. Energy Mater. 2022, 12, 2103872.
Crossref Google Scholar
[22]

Wei, L.; Liu, D. J.; Rosales, B. A.; Evans, J. W.; Vela, J. Mild and selective hydrogenation of nitrate to ammonia in the absence of noble metals. ACS Catal. 2020, 10, 3618–3628.
Crossref Google Scholar
[23]

Yao, Q. F.; Chen, J. B.; Xiao, S. Z.; Zhang, Y. L.; Zhou, X. F. Selective electrocatalytic reduction of nitrate to ammonia with nickel phosphide. ACS Appl. Mater. Interfaces 2021, 13, 30458–30467.
Crossref Google Scholar
[24]

Liu, P.; Rodriguez, J. A. Catalysts for hydrogen evolution from the [NiFe] hydrogenase to the Ni2P (001) surface: The importance of ensemble effect. J. Am. Chem. Soc. 2005, 127, 14871–14878.
Crossref Google Scholar
[25]

Jo, S.; Kang, B.; Oh, H.; Kwon, J.; Choi, P.; Cho, K. Y.; Lee, J. H.; Eom, K. Reconstruction of a surficial P-rich layer on Ni-P electrocatalysts for efficient hydrogen evolution applicable in acidic and alkaline media. Chem. Eng. J. 2023, 457, 141138.
Crossref Google Scholar
[26]

Shi, Y. M.; Li, M. Y.; Yu, Y. F.; Zhang, B. Recent advances in nanostructured transition metal phosphides: Synthesis and energy-related applications. Energy Environ. Sci. 2020, 13, 4564–4582.
Crossref Google Scholar
[27]

Lyu, C.; Cao, C. Y.; Cheng, J. R.; Yang, Y. Q.; Wu, K. L.; Wu, J. W.; Lau, W. M.; Qian, P.; Wang, N.; Zheng, J. L. Interfacial electronic structure modulation of Ni2P/Ni5P4 heterostructure nanosheets for enhanced pH-universal hydrogen evolution reaction performance. Chem. Eng. J. 2023, 464, 142538.
Crossref Google Scholar
[28]

Gong, Y. N.; Jiao, L.; Qian, Y. Y.; Pan, C. Y.; Zheng, L. R.; Cai, X. C.; Liu, B.; Yu, S. H.; Jiang, H. L. Regulating the coordination environment of MOF-templated single-atom nickel electrocatalysts for boosting CO2 reduction. Angew. Chem., Int. Ed. 2020, 59, 2705–2709.
Crossref Google Scholar
[29]

Han, B.; Ou, X. W.; Deng, Z. Q.; Song, Y.; Tian, C.; Deng, H.; Xu, Y. J.; Lin, Z. Nickel metal-organic framework monolayers for photoreduction of diluted CO2: Metal-node-dependent activity and selectivity. Angew. Chem., Int. Ed. 2018, 57, 16811–16815.
Crossref Google Scholar
[30]

Zheng, Y.; Zheng, S. S.; Xu, Y. X.; Xue, H. G.; Liu, C. S.; Pang, H. Ultrathin two-dimensional cobalt-organic frameworks nanosheets for electrochemical energy storage. Chem. Eng. J. 2019, 373, 1319–1328.
Crossref Google Scholar
[31]

Xu, H. K.; Wei, X. F.; Zeng, H.; Jiang, C. H.; Wang, Z. F.; Ouyang, Y. G.; Lu, C. Y.; Jing, Y.; Yao, S. W.; Dai, F. N. Recent progress of two-dimensional metal-organic-frameworks: From synthesis to electrocatalytic oxygen evolution. Nano Res. 2023, 16, 8614–8637.
Crossref Google Scholar
[32]

Liu, Y. Z.; Li, X. T.; Sun, Q. D.; Wang, Z. L.; Huang, W. H.; Guo, X. Y.; Fan, Z. X.; Ye, R. Q.; Zhu, Y.; Chueh, C. C. et al. Freestanding 2D NiFe metal-organic framework nanosheets: Facilitating proton transfer via organic ligands for efficient oxygen evolution reaction. Small 2022, 18, 2201076.
Crossref Google Scholar
[33]

Cao, L. M.; Zhang, J.; Ding, L. W.; Du, Z. Y.; He, C. T. Metal-organic frameworks derived transition metal phosphides for electrocatalytic water splitting. J. Energy Chem. 2022, 68, 494–520.
Crossref Google Scholar
[34]

Li, P.; Li, W. Q.; Huang, Y. Q.; Huang, Q. H.; Li, F. L.; Tian, S. H. Surface engineering over metal-organic framework nanoarray to realize boosted and sustained urea oxidation. Small 2023, 19, 2305585.
Crossref Google Scholar
[35]

Qu, H. Q.; Ma, Y. R.; Gou, Z. L.; Li, B.; Liu, Y. R.; Zhang, Z. X.; Wang, L. Ni2P/C nanosheets derived from oriented growth Ni-MOF on nickel foam for enhanced electrocatalytic hydrogen evolution. J. Colloid Interface Sci. 2020, 572, 83–90.
Crossref Google Scholar
[36]

Li, L. Y.; Jin, Y. H.; Zeng, C. T.; Ren, D. Y.; Zhou, K. L.; Zhang, Q. Q.; Liu, J. B.; Zhou, Q. Q.; Wang, H. Porous hierarchical Ni2P nanosheet arrays combined with Cu3P layers on copper foam as a binder-free battery-type cathode for high-energy-density asymmetrical all-solid-state electrochemical capacitors. J. Energy Storage 2022, 52, 104783.
Crossref Google Scholar
[37]

Qin, J. Z.; Wu, K.; Chen, L. Z.; Wang, X. T.; Zhao, Q. L.; Liu, B. J.; Ye, Z. F. Achieving high selectivity for nitrate electrochemical reduction to ammonia over MOF-supported Ru x O y clusters. J. Mater. Chem. A 2022, 10, 3963–3969.
Crossref Google Scholar
[38]

Ai, L. H.; Li, N.; Chen, M.; Jiang, H. L.; Jiang, J. Photothermally boosted water splitting electrocatalysis by broadband solar harvesting nickel phosphide within a quasi-MOF. J. Mater. Chem. A 2021, 9, 16479–16488.
Crossref Google Scholar
[39]

Pan, F.; Zhou, J. J.; Wang, T.; Zhu, Y. Q.; Ma, H. R.; Niu, J. F.; Wang, C. Y. Revealing the activity origin of ultrathin nickel metal-organic framework nanosheet catalysts for selective electrochemical nitrate reduction to ammonia: Experimental and density functional theory investigations. J. Colloid Interface Sci. 2023, 638, 26–38.
Crossref Google Scholar
[40]

Gong, S. H.; Xiao, X. X.; Wang, W. B.; Sam, D. K.; Lu, R. Q.; Xu, Y. G.; Liu, J.; Wu, C. D.; Lv, X. M. Silk fibroin-derived carbon aerogels embedded with copper nanoparticles for efficient electrocatalytic CO2-to-CO conversion. J. Colloid Interface Sci. 2021, 600, 412–420.
Crossref Google Scholar
[41]

Liu, X. B.; Li, W. X.; Zhao, X. D.; Liu, Y. C.; Nan, C. W.; Fan, L. Z. Two birds with one stone: Metal-organic framework derived micro-/nanostructured Ni2P/Ni hybrids embedded in porous carbon for electrocatalysis and energy storage. Adv. Funct. Mater. 2019, 29, 1901510.
Crossref Google Scholar
[42]

Ma, J. H.; Zhang, Y. T.; Wang, B. W.; Jiang, Z. X.; Zhang, Q. Y.; Zhuo, S. F. Interfacial engineering of bimetallic Ni/Co-MOFs with H-substituted graphdiyne for ammonia electrosynthesis from nitrate. ACS Nano 2023, 17, 6687–6697.
Crossref Google Scholar
[43]

Zhao, S. Y.; Zheng, Z. Q.; Qi, L.; Xue, Y. R.; Li, Y. L. Controlled growth of donor–bridge–acceptor interface for high-performance ammonia production. Small 2022, 18, 2107136.
Crossref Google Scholar
[44]

Ayiania, M.; Smith, M.; Hensley, A. J. R.; Scudiero, L.; McEwen, J. S.; Garcia-Perez, M. Deconvoluting the XPS spectra for nitrogen-doped chars: An analysis from first principles. Carbon 2020, 162, 528–544.
Crossref Google Scholar
[45]

Chen, G. F.; Yuan, Y. F.; Jiang, H. F.; Ren, S. Y.; Ding, L. X.; Ma, L.; Wu, T. P.; Lu, J.; Wang, H. H. Electrochemical reduction of nitrate to ammonia via direct eight-electron transfer using a copper-molecular solid catalyst. Nat. Energy 2020, 5, 605–613.
Crossref Google Scholar
[46]

Kim, K. H.; Lee, H.; Huang, X. P.; Choi, J. H.; Chen, C. P.; Kang, J. K.; O’Hare, D. Energy-efficient electrochemical ammonia production from dilute nitrate solution. Energy Environ. Sci. 2023, 16, 663–672.
Crossref Google Scholar
[47]

Song, Z. M.; Liu, Y.; Zhong, Y. Z.; Guo, Q.; Zeng, J.; Geng, Z. G. Efficient electroreduction of nitrate into ammonia at ultralow concentrations via an enrichment effect. Adv. Mater. 2022, 34, 2204306.
Crossref Google Scholar
[48]

Ge, Z. X.; Wang, T. J.; Ding, Y.; Yin, S. B.; Li, F. M.; Chen, P.; Chen, Y. Interfacial engineering enhances the electroactivity of frame-like concave RhCu bimetallic nanocubes for nitrate reduction. Adv. Energy Mater. 2022, 12, 2103916.
Crossref Google Scholar
[49]

Gao, Y. H.; Wang, K. P.; Xu, C.; Fang, H.; Yu, H. L.; Zhang, H.; Li, S. K.; Li, C. H.; Huang, F. Z. Enhanced electrocatalytic nitrate reduction through phosphorus-vacancy-mediated kinetics in heterogeneous bimetallic phosphide hollow nanotube array. Appl. Catal. B: Environ. 2023, 330, 122627.
Crossref Google Scholar
[50]

Wang, K. F.; Mao, R.; Liu, R.; Zhang, J. J.; Zhao, X. Sulfur-dopant-promoted electrocatalytic reduction of nitrate by a self-supported iron cathode: Selectivity, stability, and underlying mechanism. Appl. Catal. B: Environ. 2022, 319, 121862.
Crossref Google Scholar
[51]

Zhao, Y. L.; Liu, Y.; Zhang, Z. J.; Mo, Z. K.; Wang, C. Y.; Gao, S. Y. Flower-like open-structured polycrystalline copper with synergistic multi-crystal plane for efficient electrocatalytic reduction of nitrate to ammonia. Nano Energy 2022, 97, 107124.
Crossref Google Scholar
[52]

Cheng, L.; Ma, T. H.; Zhang, B. H.; Huang, L. B.; Guo, W. H.; Hu, F. J.; Zhu, H.; Wang, Z. Y.; Zheng, T. T.; Yang, D. T. et al. Steering the topological defects in amorphous laser-induced graphene for direct nitrate-to-ammonia electroreduction. ACS Catal. 2022, 12, 11639–11650.
Crossref Google Scholar
[53]

Du, Z. Z.; Yang, K.; Du, H. F.; Li, B. X.; Wang, K.; He, S.; Wang, T. F.; Ai, W. Facile and scalable synthesis of self-supported Zn-doped CuO nanosheet arrays for efficient nitrate reduction to ammonium. ACS Appl. Mater. Interfaces 2023, 15, 5172–5179.
Crossref Google Scholar
[54]

Du, F.; Cui, G. H.; Yang, B. L.; Zhang, D. S.; Song, R. F.; Li, Z. X. Ingenious design of one mixed-valence dual-net copper metal-organic framework for deriving Cu2O/CuO heterojunction with highly electrocatalytic performances from NO3– to NH3. J. Power Sources 2022, 543, 231832.
Crossref Google Scholar
[55]

Tao, W. X.; Wang, P. F.; Hu, B.; Wang, X.; Zhou, G. Accelerating the reaction kinetics from nitrate to ammonia by anion substitution in NiCo-based catalysts. J. Environ. Chem. Eng. 2023, 11, 109117.
Crossref Google Scholar
[56]

Sun, W. J.; Li, L. X.; Zhang, H. Y.; He, J. H.; Lu, J. M. A bioinspired iron-centered electrocatalyst for selective catalytic reduction of nitrate to ammonia. ACS Sustainable Chem. Eng. 2022, 10, 5958–5965.
Crossref Google Scholar
[57]

Yin, Q.; Hu, S. H.; Liu, J. W.; Zhou, H. Electrochemical ammonia synthesis via nitrate reduction on perovskite La x FeO3− δ with enhanced efficiency by oxygen vacancy engineering. Sustain. Energy Fuels 2022, 6, 4716–4725.
Crossref Google Scholar
[58]

Yan, J. Y.; Liu, P.; Li, J. W.; Huang, H.; Song, W. B. Effect of valence state on electrochemical nitrate reduction to ammonia in molybdenum catalysts. Chem. Eng. J. 2023, 459, 141601.
Crossref Google Scholar
[59]

Zhao, J. X.; Ren, X.; Liu, X. J.; Kuang, X.; Wang, H.; Zhang, C. W.; Wei, Q.; Wu, D. Zn single atom on N-doped carbon: Highly active and selective catalyst for electrochemical reduction of nitrate to ammonia. Chem. Eng. J. 2023, 452, 139533.
Crossref Google Scholar
[60]

Li, P. P.; Jin, Z. Y.; Fang, Z. W.; Yu, G. H. A single-site iron catalyst with preoccupied active centers that achieves selective ammonia electrosynthesis from nitrate. Energy Environ. Sci. 2021, 14, 3522–3531.
Crossref Google Scholar
[61]

Liu, L. Y.; Xiao, T.; Fu, H. Y.; Chen, Z. J.; Qu, X. L.; Zheng, S. R. Construction and identification of highly active single-atom Fe1-NC catalytic site for electrocatalytic nitrate reduction. Appl. Catal. B: Environ. 2023, 323, 122181.
Crossref Google Scholar
Nano Research
Volume 17 Issue 6,
June 2024
Pages 4864-4871
DOI: 10.1007/s12274-024-6470-3
Cite this article:
Hu J, Huang H, Yu M, et al. Electron engineering of nickel phosphide for Niδ+ in electrochemical nitrate reduction to ammonia. Nano Research, 2024, 17(6): 4864-4871. https://doi.org/10.1007/s12274-024-6470-3
Topics:
Electrolytic reduction

816

Views

4

Crossref

3

Web of Science

4

Scopus

0

CSCD

Altmetrics
Received: 04 November 2023
Revised: 24 December 2023
Accepted: 03 January 2024
Published: 08 February 2024
© Tsinghua University Press 2024
Return