Theoretical advances in understanding the active site microenvironment toward the electrocatalytic nitrogen reduction reaction in aqueous media
Source abstract
Abstract
The electrocatalytic nitrogen reduction reaction (eNRR) in aqueous media has received substantial attention because it enables the direct conversion of N2 to NH3 under benign conditions. There are, however, many factors limiting the overall eNRR efficiency, including the competing hydrogen evolution reaction (HER) and sluggish reaction kinetics due to a strong N≡N bond. These challenges call for more systematic theoretical insight into the eNRR reaction mechanism to guide the rational optimization of experimental designs. In this review, we present the latest computational advances in eNRR in an aqueous medium, including the key aspects of both catalyst design and proton accessibility. Specifically, we discuss the importance of constant potential and explicit solvent simulations, the role of the electrochemical interface, and the impact of the active center microenvironment on eNRR activity and selectivity. Finally, the current challenges and the future prospects for eNRR are addressed.
Source: openalex_inverted_index · Quality: baseline
Research context
OpenAlex topics: Ammonia Synthesis and Nitrogen Reduction · Electrocatalysts for Energy Conversion · Advanced Photocatalysis Techniques
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (73)
Show source-provided references
1. Detonator of the population explosion10.1038/22672 ↗
2. Catalytic synthesis of ammonia－A“Never-ending-story10.1002/anie.200301553 ↗
3. Recent advances and challenges of electrocatalytic N2 reduction to ammonia10.1021/acs.chemrev.9b00659 ↗
4. Hellman · 2013 · 459
5. Identifying the origin of Ti3+ activity toward enhanced electrocatalytic N2 reduction over TiO2 nanoparticles modulated by mixed-valent copper10.1002/adma.202000299 ↗
6. A review of electrocatalytic reduction of dinitrogen to ammonia under ambient conditions10.1002/aenm.201800369 ↗
7. Current and future role of haber-bosch ammonia in a carbon-free energy landscape10.1039/C9EE02873K ↗
8. Beyond fossil fuel-driven nitrogen transformations10.1126/science.aar6611 ↗
9. The journey toward low temperature, low pressure catalytic nitrogen fixation10.1002/aenm.202000659 ↗
10. Importance of the volcano slope to comprehend activity and selectivity trends in electrocatalysis
11. How to explore ambient electrocatalytic nitrogen reduction reliably and insightfully10.1039/C9CS00280D ↗
12. Strategies toward selective electrochemical ammonia synthesis10.1021/acscatal.9b02245 ↗
13. Aqueous electrocatalytic N2 reduction for ambient NH3 synthesis: recent advances in catalyst development and performance improvement10.1039/C9TA13044F ↗
14. Continuous-flow electrosynthesis of ammonia by nitrogen reduction and hydrogen oxidation10.1126/science.adf4403 ↗
15. Greatly improving electrochemical N2 reduction over TiO2 nanoparticles by iron doping10.1002/anie.201911153 ↗
16. Enhancement of lithium-mediated ammonia synthesis by addition of oxygen10.1126/science.abl4300 ↗
17. Lithium-mediated electrochemical nitrogen reduction: tracking electrode-electrolyte interfaces via time-resolved neutron reflectometry10.1021/acsenergylett.1c02833 ↗
18. Strategies to suppress hydrogen evolution for highly selective electrocatalytic nitrogen reduction: challenges and perspectives10.1039/D0EE03596C ↗
19. Near ambient N2 fixation on solid electrodes versus enzymes and homogeneous catalysts10.1038/s41570-023-00462-5 ↗
20. Lithium-mediated electrochemical dinitrogen reduction reaction
21. Challenges in reduction of dinitrogen by proton and electron transfer10.1039/C4CS00085D ↗
22. Structural evidence for a dynamic metallocofactor during N2 reduction by Mo-nitrogenase10.1126/science.aaz6748 ↗
23. Evidence of substrate binding and product release via belt-sulfur mobilization of the nitrogenase cofactor10.1038/s41929-022-00782-7 ↗
24. Identification and elimination of false positives in electrochemical nitrogen reduction studies10.1038/s41467-020-19130-z ↗
25. The runt of ammonia production by N2 reduction: electrocatalysis in aqueous media10.1016/j.coelec.2023.101301 ↗
26. Challenges and prospects in the catalysis of electroreduction of nitrogen to ammonia10.1038/s41929-019-0252-4 ↗
27. Combining theory and experiment in electrocatalysis: insights into materials design10.1126/science.aad4998 ↗
28. Understanding the electrocatalytic interface for ambient ammonia synthesis10.1021/acsenergylett.9b02679 ↗
29. Rational catalyst design for N2 reduction under ambient conditions: strategies toward enhanced conversion efficiency10.1021/acscatal.0c01081 ↗
30. 2D electrocatalysts for converting earth-abundant simple molecules into value-added commodity chemicals: recent progress and perspectives
31. Ammonia synthesis from first-principles calculations10.1126/science.1106435 ↗
32. Role of steps in N2 activation on Ru (0001)10.1103/PhysRevLett.83.1814 ↗
33. A theoretical evaluation of possible transition metal electrocatalysts for N2 reduction10.1039/C1CP22271F ↗
34. The challenge of electrochemical ammonia synthesis: a new perspective on the role of nitrogen scaling relations10.1002/cssc.201500322 ↗
35. Building up a picture of the electrocatalytic nitrogen reduction activity of transition metal single-atom catalysts10.1021/jacs.9b03811 ↗
36. Single-boron catalysts for nitrogen reduction reaction10.1021/jacs.8b13165 ↗
37. The rational design of single-atom catalysts for electrochemical ammonia synthesis via a descriptor-based approach10.1039/D0TA05943A ↗
38. Tackling the activity and selectivity challenges of electrocatalysts toward the nitrogen reduction reaction via atomically dispersed biatom catalysts10.1021/jacs.9b13349 ↗
39. Efficient modulation of the catalytic performance of electrocatalytic nitrogen reduction with transition metals anchored on N/O-codoped graphene by coordination engineering10.1039/D1TA08877G ↗
40. High-throughput screening of transition-metal-atom-embedded parallel tetracyanoethylene 2D networks as single-atom electrocatalysts for ammonia synthesis and its underlying microscopic mechanisms10.1021/acs.jpcc.2c05894 ↗
41. Electro-reduction of N2 on nanostructured materials and the design strategies of advanced catalysts based on descriptors10.1016/j.mtphys.2022.100609 ↗
42. Electrocatalytic mechanism of N2 reduction reaction by single-atom catalyst rectangular TM-TCNQ monolayers10.1021/acsami.1c06368 ↗
43. Dual transition metal atoms embedded in N-doped graphene for electrochemical nitrogen fixation under ambient conditions10.1039/D1TA11024A ↗
44. Using the N≡N dipole as a theoretical indicator for estimating the electrocatalytic performance of active sites in the nitrogen reduction reaction: single transition metal atoms embedded in two dimensional phthalocyanine10.1039/C9TA12345H ↗
45. Nitrogen fixation and reduction at boron10.1126/science.aaq1684 ↗
46. Prognostication of two-dimensional transition-metal atoms embedded rectangular tetrafluorotetracyanoquinodimethane single-atom catalysts for high-efficiency electrochemical nitrogen reduction10.1016/j.jcis.2022.04.005 ↗
47. Realizing a not-strong-not-weak polarization electric field in single-atom catalysts sandwiched by boron bitride and graphene sheets for efficient nitrogen fixation10.1021/jacs.0c09527 ↗
48. Activity origin and design principles for atomic vanadium anchoring on phosphorene monolayer for nitrogen reduction reaction10.1007/s12274-020-2949-8 ↗
49. Electrocatalytic rate constants from DFT simulations and theoretical models: learning from each other10.1016/j.coelec.2022.101110 ↗
50. Advances and challenges for experiment and theory for multi-electron multi-proton transfer at electrified solid-liquid interfaces10.1039/D0CP02741C ↗
51. Grand-canonical approach to density functional theory of electrocatalytic systems: thermodynamics of solid-liquid interfaces at constant ion and electrode potentials
52. Grand canonical ensemble approach to electrochemical thermodynamics, kinetics, and model Hamiltonians10.1016/j.coelec.2021.100749 ↗
53. Theoretical modeling of electrochemical proton-coupled electron transfer10.1021/acs.chemrev.1c00929 ↗
54. Approximating constant potential DFT with canonical DFT and electrostatic corrections
55. Nitrogen reduction reaction (NRR) modelling: a case that illustrates the challenges of DFT studies in electrocatalysis10.1016/j.coelec.2022.101073 ↗
56. Tezak
57. How the bioinspired Fe2Mo6S8 Chevrel breaks electrocatalytic nitrogen reduction scaling relations10.1021/jacs.2c03661 ↗
58. Synergistic multisites Fe2Mo6S8 electrocatalysts for ambient nitrogen conversion to ammonia10.1021/acsnano.1c07771 ↗
59. Critical role of explicit inclusion of solvent and electrode potential in the electrochemical description of nitrogen reduction10.1021/acscatal.2c03186 ↗
60. Coadsorption of N2RR and HER intermediates determines the performance of Ru-N4 toward electrocatalytic N2 reduction10.1021/acscatal.1c05820 ↗
61. Achieving a record-high yield rate of 120.9 for N2 electrochemical reduction over Ru single-atom catalysts
62. Understanding potential-dependent competition between electrocatalytic dinitrogen and proton reduction reactions10.1038/s41467-021-24539-1 ↗
63. Deciphering electrolyte selection for electrochemical reduction of carbon dioxide and nitrogen to high-value-added chemicals10.1002/adfm.202212483 ↗
64. Frozen or dynamic?—an atomistic simulation perspective on the timescales of electrochemical reactions10.1016/j.electacta.2023.142095 ↗
65. Competing effects of pH, cation identity, H2O saturation, and N2 concentration on the activity and selectivity of electrochemical reduction of N2 to NH3 on electrodeposited Cu at ambient conditions10.1021/acscatal.0c04864 ↗
66. Strategies in cell design and operation for the electrosynthesis of ammonia: status and prospects10.1039/D2EE00953F ↗
67. Rational electrode-electrolyte design for efficient ammonia electrosynthesis under ambient conditions10.1021/acsenergylett.8b00487 ↗
68. Enhancing electrocatalytic N2 reduction via tailoring the electric double layers10.1002/aic.17549 ↗
69. Proton-filtering covalent organic frameworks with superior nitrogen penetration flux promote ambient ammonia synthesis10.1038/s41929-021-00599-w ↗
70. Qin · 2022
71. Electrolyte effects on CO2 electrochemical reduction to CO10.1021/acs.accounts.2c00080 ↗
72. Enhancing oxygen reduction electrocatalysis by tuning interfacial hydrogen bonds10.1038/s41929-021-00668-0 ↗
73. Theories for electrolyte effects in CO2 electroreduction10.1021/acs.accounts.1c00679 ↗