Recent advances in 2D structured materials with defect-exploiting design strategies for electrocatalysis of nitrate to ammonia

Abstract

Ammonia has been used in a wide variety of applications, and with the recent interest in hydrogen energy as a green energy source, it is emerging as a cost-effective, high-density hydrogen carrier due to its three hydrogen atoms. Currently, ammonia is produced by the Haber-Bosch method at high temperatures and pressure, which is energy-intensive and emits large amounts of carbon dioxide. As a viable alternative, the electrochemical conversion of nitrate to ammonia has emerged as an efficient and eco-friendly synthesis method. To encourage further exploration in this field, this review offers insights into utilizing two-dimensional materials as electrochemical catalysts, focusing on designs that exploit defects for nitrate reduction to ammonia.

Keywords

Nitrate reduction reaction / ammonia synthesis / 2D electrocatalyst / defect engineering

References

[1] Klerke A,Nørskov JK.Ammonia for hydrogen storage: challenges and opportunities.J Mater Chem2008;18:2304-10

[2] Wang Y,Liu L.Theoretical investigation of the combustion performance of ammonia/hydrogen mixtures on a marine diesel engine.Int J Hydrog Energy2021;46:14805-12

[3] Chehade G.Progress in green ammonia production as potential carbon-free fuel.Fuel2021;299:120845

[4] Guo Y,An L.Carbon-free sustainable energy technology: direct ammonia fuel cells.J Power Sources2020;476:228454

[5] Valera-Medina A,Owen-Jones M,Bowen P.Ammonia for power.Prog Energy Combust Sci2018;69:63-102

[6] Cheng S.Ammonia treatment of carbon cloth anodes to enhance power generation of microbial fuel cells.Electrochem Commun2007;9:492-6

[7] Giddey S,Munnings C.Ammonia as a renewable energy transportation media.ACS Sustain Chem Eng2017;5:10231-9

[8] Wang W,Tsolakis A.Ammonia as hydrogen carrier for transportation; investigation of the ammonia exhaust gas fuel reforming.Int J Hydrog Energy2013;38:9907-17

[9] Fu E,Wang S.Chemical looping technology in mild-condition ammonia production: a comprehensive review and analysis.Small2024;20:e2305095

[10] Erisman JW,Galloway J,Winiwarter W.How a century of ammonia synthesis changed the world.Nature Geosci2008;1:636-9

[11] Gao Y,Li Y.Regulating dynamic equilibrium of active hydrogen for super-efficient nitrate electroreduction to ammonia.Chem Eng J2023;474:145546

[12] Yang B,Zhang H.Recent progress in electrochemical synthesis of ammonia from nitrogen: strategies to improve the catalytic activity and selectivity.Energy Environ Sci2021;14:672-87

[13] Noh H,Seo Y.Environmental and energy efficiency assessments of offshore hydrogen supply chains utilizing compressed gaseous hydrogen, liquefied hydrogen, liquid organic hydrogen carriers and ammonia.Int J Hydrog Energy2023;48:7515-32

[14] Asif M,Ahmed S.Recent advances in green hydrogen production, storage and commercial-scale use via catalytic ammonia cracking.Chem Eng J2023;473:145381

[15] Soloveichik G.Electrochemical synthesis of ammonia as a potential alternative to the Haber-Bosch process.Nat Catal2019;2:377-80

[16] El-shafie M.Recent advances in ammonia synthesis technologies: toward future zero carbon emissions.Int J Hydrog Energy2023;48:11237-73

[17] Lazouski N,Williams K,Manthiram K.Non-aqueous gas diffusion electrodes for rapid ammonia synthesis from nitrogen and water-splitting-derived hydrogen.Nat Catal2020;3:463-9

[18] Verleysen K,Contino F.How sensitive is a dynamic ammonia synthesis process? Global sensitivity analysis of a dynamic Haber-Bosch process (for flexible seasonal energy storage).Energy2021;232:121016

[19] Guo J.Catalyst: NH₃ as an energy carrier.Chem2017;3:709-12

[20] Zhang L,Ren X.Electrochemical ammonia synthesis via nitrogen reduction reaction on a MoS₂ catalyst: theoretical and experimental studies.Adv Mater2018;30:e1800191

[21] Montoya JH,Vojvodic A.The challenge of electrochemical ammonia synthesis: a new perspective on the role of nitrogen scaling relations.ChemSusChem2015;8:2180-6

[22] Wu D,Li L.Commercial biogas plants: review on operational parameters and guide for performance optimization.Fuel2021;303:121282

[23] Giddey S,Kulkarni A.Review of electrochemical ammonia production technologies and materials.Int J Hydrog Energy2013;38:14576-94

[24] Shen H,Masa J.Electrochemical ammonia synthesis: mechanistic understanding and catalyst design.Chem2021;7:1708-54

[25] Long J,Zhang Y.Direct electrochemical ammonia synthesis from nitric oxide.Angew Chem Int Ed2020;59:9711-8

[26] Jiang H,Hai G.A nitrogen battery electrode involving eight-electron transfer per nitrogen for energy storage.Angew Chem Int Ed2023;62:e202305695

[27] Smith C,Torrente-murciano L.Current and future role of Haber-Bosch ammonia in a carbon-free energy landscape.Energy Environ Sci2020;13:331-44

[28] Thakur IS.Nitrification and denitrification processes for mitigation of nitrous oxide from waste water treatment plants for biovalorization: challenges and opportunities.Bioresour Technol2019;282:502-13

[29] Hon WM,Khoo HE.Nitric oxide in liver diseases: friend, foe, or just passerby?.Ann N Y Acad Sci2002;962:275-95

[30] Knobeloch L,Hogan A,Anderson H.Blue babies and nitrate-contaminated well water.Environ Health Perspect2000;108:675-8 PMCID:PMC1638204

[31] WHO. Nitrate and nitrite in drinking-water. 2016. Avaliable from: https://www.who.int/docs/default-source/wash-documents/wash-chemicals/nitrate-nitrite-background-document.pdf [Last accessed on 20 Feb 2024]

[32] Schoeman J.Nitrate removal with reverse osmosis in a rural area in South Africa.Desalination2003;155:15-26

[33] Cliford D.Ion exchange for nitrate removal.J Am Water Works Assoc1993;85:135-43

[34] Wei L,Rosales BA,Vela J.Mild and selective hydrogenation of nitrate to ammonia in the absence of noble metals.ACS Catal2020;10:3618-28

[35] Zhang X,Liu C,Lu S.Recent advances in non-noble metal electrocatalysts for nitrate reduction.Chem Eng J2021;403:126269

[36] Xu H,Chen J,Yang J.Electrocatalytic reduction of nitrate - a step towards a sustainable nitrogen cycle.Chem Soc Rev2022;51:2710-58

[37] Wang Y,Peng M.Dual-site electrocatalytic nitrate reduction to ammonia on oxygen vacancy-enriched and Pd-decorated MnO₂ nanosheets.Nanoscale2021;13:17504-11

[38] Cui Y,Dai C,Song C.Coupling of LaFeO₃ - plasma catalysis and Cu⁺/Cu⁰ electrocatalysis for direct ammonia synthesis from air.Ind Eng Chem Res2022;61:4816-23

[39] Deng X,Wang L,Luo JL.Metallic Co nanoarray catalyzes selective NH₃ production from electrochemical nitrate reduction at current densities exceeding 2 A cm^-2.Adv Sci2021;8:2004523 PMCID:PMC8025016

[40] Rosca V,de Groot MT.Nitrogen cycle electrocatalysis.Chem Rev2009;109:2209-44

[41] Jung W.Material strategies in the electrochemical nitrate reduction reaction to ammonia production.Mater Chem Front2021;5:6803-23

[42] Wang Q,Zhang J.Investigation of nitrate reduction on polycrystalline Pt nanoparticles with controlled crystal plane.J Electroanal Chem2015;755:210-4

[43] Lim J,Park J.Structure sensitivity of Pd facets for enhanced electrochemical nitrate reduction to ammonia.ACS Catal2021;11:7568-77

[44] Liu H,Chen Y.Electrocatalytic nitrate reduction on oxide-derived silver with tunable selectivity to nitrite and ammonia.ACS Catal2021;11:8431-42

[45] Siriwatcharapiboon W,Yang J.Promotion effects of Sn on the electrocatalytic reduction of nitrate at Rh nanoparticles.ChemElectroChem2014;1:172-9

[46] Wang Y,Jia R,Zhang B.Unveiling the activity origin of a copper-based electrocatalyst for selective nitrate reduction to ammonia.Angew Chem Int Ed2020;59:5350-4

[47] He W,Dieckhöfer S.Splicing the active phases of copper/cobalt-based catalysts achieves high-rate tandem electroreduction of nitrate to ammonia.Nat Commun2022;13:1129 PMCID:PMC8891333

[48] Wang C,Shen J,Zhu Y.In situ loading of Cu₂O active sites on island-like copper for efficient electrochemical reduction of nitrate to ammonia.ACS Appl Mater Interfaces2022;14:6680-8

[49] Anastasiadou D,Hensen EJM.Ammonia electrocatalytic synthesis from nitrate.Electrochem Sci Adv2023;3:e2100220

[50] Chia X.Characteristics and performance of two-dimensional materials for electrocatalysis.Nat Catal2018;1:909-21

[51] Tao H,Ma T.Two-dimensional materials for energy conversion and storage.Prog Mater Sci2020;111:100637

[52] Du F,Wang C.Active sites-rich layered double hydroxide for nitrate-to-ammonia production with high selectivity and stability.Chem Eng J2022;434:134641

[53] Kim K,Huang X.Energy-efficient electrochemical ammonia production from dilute nitrate solution.Energy Environ Sci2023;16:663-72

[54] Li J,Liu C.3.4% Solar-to-ammonia efficiency from nitrate using Fe single atomic catalyst supported on MoS₂ nanosheets.Adv Funct Mater2022;32:2108316

[55] Li H,Lin X.Cooperative interaction between Cu and sulfur vacancies in SnS₂ nanoflowers for highly efficient nitrate electroreduction to ammonia.J Mater Chem A2023;11:2014-22

[56] Li Y,Waite TD,Wang Z.Development of a mechanically flexible 2D-MXene membrane cathode for selective electrochemical reduction of nitrate to N₂: mechanisms and implications.Environ Sci Technol2021;55:10695-703

[57] Karthikeyan P,Preethi J,Meenakshi S.Two-dimensional (2D) Ti₃C₂T_x MXene nanosheets with superior adsorption behavior for phosphate and nitrate ions from the aqueous environment.Ceram Int2021;47:732-9

[58] Pan F,Wang T.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 Sci2023;638:26-38

[59] Sivan SE,Han SJ.Facile MOF-derived one-pot synthetic approach toward Ru single atoms, nanoclusters, and nanoparticles dispersed on CeO₂ supports for enhanced ammonia synthesis.J Catal2022;408:316-28

[60] Wang H,Li C.Cu/CuO_x in-plane heterostructured nanosheet arrays with rich oxygen vacancies enhance nitrate electroreduction to ammonia.ACS Appl Mater Interfaces2022;14:34761-9

[61] Zhao F,Li X,Wang H.Enhanced electrocatalytic nitrate reduction to ammonia on cobalt oxide nanosheets via multiscale defect modulation.Chem Eng J2023;461:141960

[62] Wu ZY,Yong X.Electrochemical ammonia synthesis via nitrate reduction on Fe single atom catalyst.Nat Commun2021;12:2870 PMCID:PMC8128876

[63] Wang H,Niu P,Shi J.Porous Two-dimensional materials for photocatalytic and electrocatalytic applications.Matter2020;2:1377-413

[64] Jia R,Wang C,Yu Y.Boosting selective nitrate electroreduction to ammonium by constructing oxygen vacancies in TiO₂.ACS Catal2020;10:3533-40

[65] Liu Y,Wu R,Sun C.Oxygen vacancies for promoting the electrochemical nitrogen reduction reaction.J Mater Chem A2021;9:6694-709

[66] Wang C,Hu T.Metasequoia-like nanocrystal of iron-doped copper for efficient electrocatalytic nitrate reduction into ammonia in neutral media.ChemSusChem2021;14:1825-9

[67] Cui X,Zhang Q.A review of electrocatalytic reduction of dinitrogen to ammonia under ambient conditions.Adv Energy Mater2018;8:1800369

[68] Chen G,Zhang L.Advances in electrocatalytic N₂ reduction - strategies to tackle the selectivity challenge.Small Methods2019;3:1800337

[69] Wang Q.Recent advances in the synthesis and application of layered double hydroxide (LDH) nanosheets.Chem Rev2012;112:4124-55

[70] Yi H,Lai C.Recent advance of transition-metal-based layered double hydroxide nanosheets: synthesis, properties, modification, and electrocatalytic applications.Adv Energy Mater2021;11:2002863

[71] Zhang S,Shi R.Efficient photocatalytic nitrogen fixation over Cu^δ+ -modified defective ZnAl-layered double hydroxide nanosheets.Adv Energy Mater2020;10:1901973

[72] Li T,Luo H.Facile in situ growth of Ni/Co-LDH arrays by hypothermal chemical coprecipitation for all-solid-state asymmetric supercapacitors.J Mater Chem A2016;4:18922-30

[73] Xu J,Song J,Zhang L.Synthesis of hierarchical flower-like Mg₂Al-Cl layered double hydroxide in a surfactant-free reverse microemulsion.J Colloid Interface Sci2017;505:816-23

[74] Li J,Wang J,Jiang SP.Oxygen vacancy defects modulated electrocatalytic activity of iron-nickel layered double hydroxide on Ni foam as highly active electrodes for oxygen evolution reaction.Electrochim Acta2020;331:135395

[75] Li L,Yun Y,Huang Y.Characterization and electrochemical behaviour of nanoscale hydrotalcite-like compounds toward the reduction of nitrate.Nanomaterials2020;10:1926 PMCID:PMC7599484

[76] Yu MS,Surendran S,Sim U.Synergistic interaction of MoS₂ nanoflakes on La₂Zr₂O₇ nanofibers for improving photoelectrochemical nitrogen reduction.ACS Appl Mater Interfaces2022;14:31889-99

[77] Whittingham MS.Lithium batteries and cathode materials.Chem Rev2004;104:4271-301

[78] Choi W,Han GH,Akinwande D.Recent development of two-dimensional transition metal dichalcogenides and their applications.Mater Today2017;20:116-30

[79] Sukanya R,Breslin CB.Review - recent developments in the applications of 2D transition metal dichalcogenides as electrocatalysts in the generation of hydrogen for renewable energy conversion.J Electrochem Soc2022;169:064504

[80] Wang J,Li Y.Sulfur vacancy MoS₂ for electrocatalytic reduction of nitrate to ammonia with enhanced selectivity.J Alloys Compd2023;955:170199

[81] Mohanty B,Basu S.Single atom on the 2D matrix: an emerging electrocatalyst for energy applications.ACS Omega2020;5:1287-95 PMCID:PMC6990445

[82] Fan M,Wu J,Sun D.Improving the catalytic activity of carbon-supported single atom catalysts by polynary metal or heteroatom doping.Small2020;16:e1906782

[83] Ding J,Qiu Y.Iron-doping strategy promotes electroreduction of nitrate to ammonia on MoS₂ nanosheets.Inorg Chem Commun2023;151:110621

[84] Xu T,Li S.Recent advances in nonprecious metal oxide electrocatalysts and photocatalysts for N₂ reduction reaction under ambient condition.Small Sci2021;1:2000069

[85] Cui X,Liu XM,Ma W.Highly selective electrochemical reduction of dinitrogen to ammonia at ambient temperature and pressure over iron oxide catalysts.Chemistry2018;24:18494-501

[86] Xiong W,Wu T.Challenges and opportunities of transition metal oxides as electrocatalysts.Chemistry2023;29:e202202872

[87] Sun Z,Dou Y.Generalized self-assembly of scalable two-dimensional transition metal oxide nanosheets.Nat Commun2014;5:3813

[88] Sun Y,Gao S.Pits confined in ultrathin cerium(IV) oxide for studying catalytic centers in carbon monoxide oxidation.Nat Commun2013;4:2899

[89] Huang Z,Wu J.Bottom-up preparation of ultrathin 2D aluminum oxide nanosheets by duplicating graphene oxide.Adv Mater2016;28:1703-8

[90] Li C,Kang J.Pristine MOF and COF materials for advanced batteries.Energy Stor Mater2020;31:115-34

[91] Sheberla D,Elias JS,Shao-Horn Y.Conductive MOF electrodes for stable supercapacitors with high areal capacitance.Nat Mater2017;16:220-4

[92] Wang Q.State of the art and prospects in metal-organic framework (MOF)-based and MOF-derived nanocatalysis.Chem Rev2020;120:1438-511

[93] Wu T,Liu Y.Application of QD-MOF composites for photocatalysis: energy production and environmental remediation.Coord Chem Rev2020;403:213097

[94] Ma T,Ma JG.Application of MOF-based materials in electrochemical sensing.Dalton Trans2020;49:17121-9

[95] Chae HK,Kim J.A route to high surface area, porosity and inclusion of large molecules in crystals.Nature2004;427:523-7

[96] Freund R,Arnauts G.The current status of MOF and COF applications.Angew Chem Int Ed2021;60:23975-4001

[97] Wang J,Xu Y.Two-dimensional MOF and COF nanosheets: synthesis and applications in electrochemistry.Chemistry2020;26:6402-22

[98] Lv Y,Gu Y.Atomically precise integration of multiple functional motifs in catalytic metal-organic frameworks for highly efficient nitrate electroreduction.JACS Au2022;2:2765-77

[99] Liu P,Huang H.Cu/Co bimetallic conductive MOFs: electronic modulation for enhanced nitrate reduction to ammonia.Chem Eng J2023;466:143134

[100] Fang Z,Tang S,Wu P.Porous two-dimensional iron-cyano nanosheets for high-rate electrochemical nitrate reduction.ACS Nano2022;16:1072-81

[101] Zhang T,Tang H.Synthesis of two-dimensional Ti₃C₂T_x MXene using HCl+LiF etchant: enhanced exfoliation and delamination.J Alloys Compd2017;695:818-26

[102] Ihsanullah I.MXenes (two-dimensional metal carbides) as emerging nanomaterials for water purification: progress, challenges and prospects.Chem Eng J2020;388:124340

[103] Wyatt BC,Anasori B.2D MXenes: tunable mechanical and tribological properties.Adv Mater2021;33:e2007973

[104] Qian A,Shi H,Chung CH.Surface functional groups and electrochemical behavior in dimethyl sulfoxide-delaminated Ti₃C₂T_x MXene.ChemSusChem2018;11:3719-23

[105] Tsounis C,Masood H.Advancing MXene electrocatalysts for energy conversion reactions: surface, stoichiometry, and stability.Angew Chem Int Ed2023;62:e202210828 PMCID:PMC10099934

[106] Yorulmaz U,Perkgöz NK,Sevik C.Vibrational and mechanical properties of single layer MXene structures: a first-principles investigation.Nanotechnology2016;27:335702

[107] Wu Y,Wu L,Zhang X.2D MXene/SnS₂ composites as high-performance anodes for sodium ion batteries.Chem Eng J2018;334:932-8

[108] Wu B,Shui L,Liu Z.Extraordinary electromechanical actuation of Ti₂C MXene.J Phys Chem C2021;125:1060-8

[109] Hu C,Wei Z,Shen G.Functionalized Ti₃C₂T_x MXene with layer-dependent band gap for flexible NIR photodetectors.Appl Phys Rev2023;10:021402

[110] Er D,Naguib M,Shenoy VB.Ti₃C₂ MXene as a high capacity electrode material for metal (Li, Na, K, Ca) ion batteries.ACS Appl Mater Interfaces2014;6:11173-9

[111] Yang Q,Li X.A wholly degradable, rechargeable Zn-Ti₃C₂ MXene capacitor with superior anti-self-discharge function.ACS Nano2019;13:8275-83

[112] Le TA,Hong Y,Lee H.Porosity-engineering of MXene as a support material for a highly efficient electrocatalyst toward overall water splitting.ChemSusChem2020;13:945-55

[113] Zhou Z,You Y,Zhang L.Tunable functional groups on MXene regulating the catalytic property of anchored cobalt phthalocyanine for electrochemical CO₂ reduction.Inorg Chem Front2023;10:5371-8

[114] Wang X,Han M.Surface redox pseudocapacitance of partially oxidized titanium carbide mxene in water-in-salt electrolyte.ACS Energy Lett2022;7:30-5

[115] Cai J,Cao A.Interfacial hydrogen bonding-involved electrocatalytic ammonia synthesis on OH-terminated MXene.Appl Catal B2023;328:122473

[116] Hu T,Guo C.Functionalized MXenes for efficient electrocatalytic nitrate reduction to ammonia.J Mater Chem A2022;10:8923-31

[117] Brownson DA,Banks CE.An overview of graphene in energy production and storage applications.J Power Sources2011;196:4873-85

[118] Zhuo HY,Liang JX,Xiao H.Theoretical understandings of graphene-based metal single-atom catalysts: stability and catalytic performance.Chem Rev2020;120:12315-41

[119] Cheng N,Doyle-davis K.Single-atom catalysts: from design to application.Electrochem Energ Rev2019;2:539-73

[120] Rehman F,Musgrave CB,Goddard WA.High-throughput screening to predict highly active dual-atom catalysts for electrocatalytic reduction of nitrate to ammonia.Nano Energy2022;103:107866

[121] Zhao T,Xu X.Homonuclear dual-atom catalysts embedded on N-doped graphene for highly efficient nitrate reduction to ammonia: from theoretical prediction to experimental validation.Appl Catal B2023;339:123156

[122] Huang L,Ma T.Direct synthesis of ammonia from nitrate on amorphous graphene with near 100% efficiency.Adv Mater2023;35:e2211856

[123] Luo Y,Shen P.B-doped MoS₂ for nitrate electroreduction to ammonia.J Colloid Interface Sci2023;629:950-7

[124] Li J,Du F.Microenvironmental corrosion and hydrolysis induced two-dimensional heterojunction of copper oxide@ferriferrous oxide for efficient electrochemical nitrate reduction to ammonia.Chem Eng J2023;471:144488

[125] Wang S,Cai Y.Interfacial polarization triggered by covalent-bonded MXene and black phosphorus for enhanced electrochemical nitrate to ammonia conversion.Adv Energy Mater2023;13:2301136

[126] Zhang H,Sun W,Xu Q.Highly dispersed in-situ grown Bi₂O₃ nanosheets on Ti₃C₂T_x MXene for selective electroreduction of nitrate to ammonia.ChemElectroChem2023;10:e202201001

[127] Wang Y,Sun WJ.Bimetallic Cu-Fe catalysts on MXene for synergistically electrocatalytic conversion of nitrate to ammonia.J Colloid Interface Sci2023;648:595-603

[128] Sun W,Zhang H,Lu J.A bioinspired iron-centered electrocatalyst for selective catalytic reduction of nitrate to ammonia.ACS Sustain Chem Eng2022;10:5958-65

[129] Sun WJ,Li LX.Built-in electric field triggered interfacial accumulation effect for efficient nitrate removal at ultra-low concentration and electroreduction to ammonia.Angew Chem Int Ed Engl2021;60:22933-9

[130] Zhu D,Yan X,Gao L.Electrochemical nitrate reduction to high-value ammonia on two-dimensional molybdenum carbide nanosheets for nitrate-containing wastewater upcycling.Sci Total Environ2023;878:163145