Crystal facet engineering of electrocatalysts for nitrate reduction to ammonia: recent advances and future perspectives

Abstract

Ammonia (NH₃) is an important chemical feedstock and a clean energy carrier that has a pivotal impact on the sustainable energy circle. Its electrocatalytic production is evolving into a green alternative to the traditional Haber-Bosch process. A key strategy in enhancing the performance of this electrocatalytic ammonia synthesis is crystal facet engineering of electrocatalysts, which could significantly influence the reaction mechanism, kinetics, and thermodynamics. This review summarizes the recent advancements in crystal facet engineering for electrocatalytic nitrate reduction to ammonia. Through this review, we hope to shed light on the significant role of crystal facet engineering in advancing electrocatalytic ammonia production and provide useful guidance on the design of high-performance electrocatalysts.

Keywords

Nitrate reduction reaction / crystal facet engineering / electrocatalysts

References

[1] Foster SL,Duda RD.Catalysts for nitrogen reduction to ammonia.Nat Catal2018;1:490-500

[2] Kyriakou V,Vourros A,Stoukides M.An electrochemical Haber-Bosch process.Joule2020;4:142-58

[3] Chang F,Guo J.Emerging materials and methods toward ammonia-based energy storage and conversion.Adv Mater2021;33:e2005721

[4] Valera-Medina A,Owen-Jones M,Bowen P.Ammonia for power.Prog Energ Combust2018;69:63-102

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

[6] 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

[7] Zhu W,Wu Q.Weakened d–p orbital hybridization in in situ reconstructed Ru/β-Co(OH)₂ heterointerfaces for accelerated ammonia electrosynthesis from nitrates.Energy Environ Sci2023;16:2483-93

[8] Ren Y,Tan X.Strategies to activate inert nitrogen molecules for efficient ammonia electrosynthesis: current status, challenges, and perspectives.Energy Environ Sci2022;15:2776-805

[9] Macfarlane DR,Choi J.A roadmap to the ammonia economy.Joule2020;4:1186-205

[10] Zhang F,Chen J.Interfacial assembly of nanocrystals on nanofibers with strong interaction for electrocatalytic nitrate reduction.Angew Chem Int Ed Engl2023;62:e202310383

[11] Wang J,Chen J.Electrocatalytic nitrate/nitrite reduction to ammonia synthesis using metal nanocatalysts and bio-inspired metalloenzymes.Nano Energy2021;86:106088

[12] Wu Z,Liu Y,Li W.Electrocatalytic nitrate reduction: selectivity at the crossroads between ammonia and nitrogen.Chem Catal2023;3:100786

[13] Zhu W,Yao F.A hydrazine-nitrate flow battery catalyzed by a bimetallic RuCo precatalyst for wastewater purification along with simultaneous generation of ammonia and electricity.Angew Chem Int Ed Engl2023;62:e202300390

[14] Wang Z,Zhao X.Interfacial defect engineering triggered by single atom doping for highly efficient electrocatalytic nitrate reduction to ammonia.ACS Mater Lett2023;5:1018-26

[15] Sun N,Luo L,Shen S.Facile synthesis of CuCo-CoO composite electrocatalyst for nitrate reduction to ammonia with high activity, selectivity and stability.Appl Surf Sci2023;624:157118

[16] Bai Z,Ding L,Chang X.Artificial Cu-Ni catalyst towards highly efficient nitrate-to-ammonia conversion.Sci China Mater2023;66:2329-38

[17] Yin H,Bell S,Du A.Transition-metal-free, pure p-block alloy electrocatalysts for the highly efficient nitrate reduction to ammonia.Chem Mater2023;35:2884-91

[18] Zhang Z,Su X.Electro-triggered Joule heating method to synthesize single-phase CuNi nano-alloy catalyst for efficient electrocatalytic nitrate reduction toward ammonia.Nano Res2023;16:6632-41

[19] Xiao C,Xue P.High-index-facet- and high-surface-energy nanocrystals of metals and metal oxides as highly efficient catalysts.Joule2020;4:2562-98

[20] Li Y,Li S,Chen J.A review of energy and environment electrocatalysis based on high-index faceted nanocrystals.Rare Met2021;40:3406-41

[21] Feng S,Dong H.Tailoring the Mo-N/Mo-O configuration in MoO₂/Mo₂N heterostructure for ampere-level current density hydrogen production.Appl Catal B Environ2024;342:123451

[22] de Groot M, Koper M. The influence of nitrate concentration and acidity on the electrocatalytic reduction of nitrate on platinum.J Electroanal Chem2004;562:81-94

[23] Xu B,Zhao Q,Peng X.Electrochemical reduction of nitrate to ammonia using non-precious metal-based catalysts.Coord Chem Rev2024;502:215609

[24] Gao J,Ni C,Bi X.Enhanced reduction of nitrate by noble metal-free electrocatalysis on P doped three-dimensional Co₃O₄ cathode: mechanism exploration from both experimental and DFT studies.Chem Eng J2020;382:123034

[25] Tong W,Wang P,Huang X.Exposed facet-controlled N₂ electroreduction on distinct Pt₃Fe nanostructures of nanocubes, nanorods and nanowires.Natl Sci Rev2021;8:nwaa088 PMCID:PMC8288394

[26] Tan L,Huang X.Synthesis of ammonia via electrochemical nitrogen reduction on high-index faceted Au nanoparticles with a high faradaic efficiency.Chem Commun2019;55:14482-5

[27] Bao D,Meng FL.Electrochemical reduction of N₂ under ambient conditions for artificial N₂ fixation and renewable energy storage using N₂/NH₃ cycle.Adv Mater2017;29:1604799

[28] Yu Y,Liu B.Synthesis of nanocrystals with variable high-index Pd facets through the controlled heteroepitaxial growth of trisoctahedral Au templates.J Am Chem Soc2010;132:18258-65

[29] Sun S,Cui J,Liang S.High-index faceted metal oxide micro-/nanostructures: a review on their characterization, synthesis and applications.Nanoscale2019;11:15739-62

[30] Rosen J,Lu Q.Mechanistic insights into the electrochemical reduction of CO₂ to CO on nanostructured Ag surfaces.ACS Catal2015;5:4293-9

[31] Dong JC,Briega-Martos V.Direct in situ raman spectroscopic evidence of oxygen reduction reaction intermediates at high-index Pt(hkl) surfaces.J Am Chem Soc2020;142:715-9

[32] Yin Y.Colloidal nanocrystal synthesis and the organic-inorganic interface.Nature2005;437:664-70

[33] Yang Y,Wei Y.Solvent-dependent evolution of cyclic penta-twinned rhodium icosahedral nanocrystals and their enhanced catalytic properties.Nano Res2018;11:656-64

[34] Liang H,Qi Z.Hematite concave nanocubes and their superior catalytic activity for low temperature CO oxidation.Nanoscale2014;6:7199-203

[35] Liang Y,Bian T.Shape-controlled synthesis of polyhedral 50-facet Cu₂O microcrystals with high-index facets.CrystEngComm2012;14:4431-6

[36] Hu S,Li M.Trapezohedral platinum nanocrystals with high-index facets for high-performance hydrazine electrooxidation.Chem Synth2023;3:4

[37] Huang L,Lin H.Shape regulation of high-index facet nanoparticles by dealloying.Science2019;365:1159-63

[38] Han Y,Cai W.Facet-controlled palladium nanocrystalline for enhanced nitrate reduction towards ammonia.J Colloid Interface Sci2021;600:620-8

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

[40] Guo Y,Shen S,Zhang J.Computational prediction and experimental evaluation of nitrate reduction to ammonia on rhodium.J Catal2021;402:1-9

[41] Liu H,Bai L.Low-coordination rhodium catalysts for an efficient electrochemical nitrate reduction to ammonia.ACS Catal2023;13:1513-21

[42] Katsounaros I,Chen X,Koper MT.Interconversions of nitrogen-containing species on Pt(100) and Pt(111) electrodes in acidic solutions containing nitrate.Electrochimica Acta2018;271:77-83

[43] Molodkina EB,Rudnev AV.Redox-transitions in NO/NH₃ adlayers on a Pt(111) electrode in an acidic solution.Electrochimica Acta2023;444:141997

[44] Hu T,Wang M,Guo C.Theoretical insights into superior nitrate reduction to ammonia performance of copper catalysts.ACS Catal2021;11:14417-27

[45] Fu Y,Wang Y.Enhancing electrochemical nitrate reduction to ammonia over Cu nanosheets via facet tandem catalysis.Angew Chem Int Ed Engl2023;62:e202303327

[46] Hu Q,Wang X.Reaction intermediate-mediated electrocatalyst synthesis favors specified facet and defect exposure for efficient nitrate–ammonia conversion.Energy Environ Sci2021;14:4989-97

[47] Zhong W,He Z.Modulating surface oxygen species via facet engineering for efficient conversion of nitrate to ammonia.J Energy Chem2023;78:211-21

[48] Yao Q,Xiao S,Zhou X.Selective electrocatalytic reduction of nitrate to ammonia with nickel phosphide.ACS Appl Mater Interfaces2021;13:30458-67

[49] Crawford J,Du A.Nitrate-to-ammonia conversion at an InSn-enriched liquid-metal electrode.Angew Chem Int Ed Engl2022;61:e202201604 PMCID:PMC9324788

[50] Zhang Y,Wang W,Crittenden JC.Electrocatalytic nitrate reduction to ammonia on defective Au₁Cu (111) single-atom alloys.Appl Catal B Environ2022;310:121346

[51] Yin H,Li J.Electrocatalytic reduction of nitrate to ammonia via a Au/Cu single atom alloy catalyst.Environ Sci Technol2023;57:3134-44

[52] Chen L,Lou Y,Zhou Z.Electrochemical synthesis of tetrahexahedral Cu nanocrystals with high-index facets for efficient nitrate electroreduction.J Electroanal Chem2022;907:116022

[53] Liu F,Jiang X.High-index surface structure engineering of Au–Pd concave triple-octahedrons for boosting electrocatalytic nitrate reduction to ammonia.ACS Sustain Chem Eng2023;11:1631-7

[54] Li S,Gao C.Reconstruction-induced NiCu-based catalysts towards paired electrochemical refining.Energy Environ Sci2022;15:3004-14