Markit, I. Nitric Acid-Chemical Economics Handbook (IHS Markit, 2015).
Chen, J. G. et al. Beyond fossil fuel–driven nitrogen transformations. Science 360, eaar6611 (2018).
Canfield, D. E., Glazer, A. N. & Falkowski, P. G. The evolution and future of Earth’s nitrogen cycle. Science 330, 192–196 (2010).
Galloway, J. N. et al. Transformation of the nitrogen cycle: recent trends, questions, and potential solutions. Science 320, 889–892 (2008).
Li, L. et al. Efficient nitrogen fixation to ammonia through integration of plasma oxidation with electrocatalytic reduction. Angew. Chem. Int. Ed. 60, 14131–14137 (2021).
Wang, Y., Li, T., Yu, Y. & Zhang, B. Electrochemical synthesis of nitric acid from nitrogen oxidation. Angew. Chem. Int. Ed. 61, e202115409 (2022).
Iriawan, H. et al. Methods for nitrogen activation by reduction and oxidation. Nat. Rev. Methods Primers 1, 56 (2021).
Nie, Z. et al. Catalytic kinetics regulation for enhanced electrochemical nitrogen oxidation by Ru-nanoclusters-coupled Mn3O4 catalysts decorated with atomically dispersed Ru atoms. Adv. Mater. 34, 2108180 (2022).
Kuang, M. et al. Efficient nitrate synthesis via ambient nitrogen oxidation with Ru-doped TiO2/RuO2 electrocatalysts. Adv. Mater. 32, 2002189 (2020).
Armstrong, D. A. et al. Standard electrode potentials involving radicals in aqueous solution: inorganic radicals (IUPAC Technical Report). Pure Appl. Chem. 87, 1139–1150 (2015).
Jin, H. et al. Dynamic rhenium dopant boosts ruthenium oxide for durable oxygen evolution. Nat. Commun. 14, 354 (2023).
Fei, H. et al. General synthesis and definitive structural identification of MN4C4 single-atom catalysts with tunable electrocatalytic activities. Nat. Catal. 1, 63–72 (2018).
Grdeń, M., Łukaszewski, M., Jerkiewicz, G. & Czerwiński, A. Electrochemical behaviour of palladium electrode: oxidation, electrodissolution and ionic adsorption. Electrochim. Acta 53, 7583–7598 (2008).
Plauck, A., Stangland, E. E., Dumesic, J. A. & Mavrikakis, M. Active sites and mechanisms for H2O2 decomposition over Pd catalysts. Proc. Natl Acad. Sci. USA 113, E1973–E1982 (2016).
Li, J., Staykov, A., Ishihara, T. & Yoshizawa, K. Theoretical study of the decomposition and hydrogenation of H2O2 on Pd and Au@Pd surfaces: understanding toward high selectivity of H2O2 synthesis. J. Phys. Chem. C 115, 7392–7398 (2011).
Nørskov, J. K. et al. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 108, 17886–17892 (2004).
Ignarro, L. J., f*ckuto, J. M., Griscavage, J. M., Rogers, N. E. & Byrns, R. E. Oxidation of nitric oxide in aqueous solution to nitrite but not nitrate: comparison with enzymatically formed nitric oxide from l-arginine. Proc. Natl Acad. Sci. USA 90, 8103–8107 (1993).
Anand, M., Abraham, C. S. & Nørskov, J. K. Electrochemical oxidation of molecular nitrogen to nitric acid-towards a molecular level understanding of the challenges. Chem. Sci. 12, 6442–6448 (2021).
Wan, H., Bagger, A. & Rossmeisl, J. Limitations of electrochemical nitrogen oxidation toward nitrate. J. Phys. Chem. Lett. 13, 8928–8934 (2022).
Guo, Y. et al. Electrochemical nitrate production via nitrogen oxidation with atomically dispersed Fe on N-doped carbon nanosheets. ACS Nano 16, 655–663 (2022).
A checklist for reproducibility in electrochemical nitrogen fixation. Nat. Commun. 13, 4642 (2022).
Choi, J. et al. Identification and elimination of false positives in electrochemical nitrogen reduction studies. Nat. Commun. 11, 5546 (2020).
Lee, S. A., Lee, M. G. & Jang, H. W. Catalysts for electrochemical ammonia oxidation: trend, challenge, and promise. Sci. China Mater. 65, 3334–3352 (2022).
Liu, H. Y. et al. Electrochemical ammonia oxidation with molecular catalysts. ACS Catal. 13, 4675–4682 (2023).
Xia, Y. & Zweier, J. L. Direct measurement of nitric oxide generation from nitric oxide synthase. Proc. Natl Acad. Sci. USA 94, 12705–12710 (1997).
Bordignon, E. EPR spectroscopy of nitroxide spin probes. eMagRes 6, 235–254 (2017).
Li, Y. et al. Ternary PtIrNi catalysts for efficient electrochemical ammonia oxidation. ACS Catal. 10, 3945–3957 (2020).
Dong, K. et al. Plasma-induced defective TiO2-x with oxygen vacancies: a high-active and robust bifunctional catalyst toward H2O2 electrosynthesis. Chem Catal. 1, 1437–1448 (2021).
Zhang, X. et al. Photothermal-assisted photocatalytic nitrogen oxidation to nitric acid on palladium-decorated titanium oxide. Adv. Energy Mater. 12, 2103740 (2022).
Hu, X. et al. Simultaneous generation of H2O2 and formate by co-electrolysis of water and CO2 over bifunctional Zn/SnO2 nanodots. Angew. Chem. Int. Ed. 62, e202304050 (2023).
Yu, M. et al. Self-supported Mo-doped TiO2 electrode for ambient electrocatalytic nitrogen oxidation. Electrochim. Acta 435, 141333 (2022).
MacFarlane, D. R. et al. A roadmap to the ammonia economy. Joule 4, 1186–1205 (2020).
Lim, J., Fernández, C. A., Lee, S. W. & Hatzell, M. C. Ammonia and nitric acid demands for fertilizer use in 2050. ACS Energy Lett. 6, 3676–3685 (2021).
Dong, K. et al. Epoxidation of olefins enabled by an electro-organic system. Green Chem. 24, 8264–8269 (2022).
Dong, K. et al. Noble-metal-free electrocatalysts toward H2O2 production. J. Mater. Chem. A 8, 23123–23141 (2020).
Chen, W., He, F. & Chen, Y. X. in Encyclopedia of Solid–Liquid Interfaces, 497–513 (Elsevier, 2023).
Abdiaziz, K., Salvadori, E., Sokol, K. P., Reisner, E. & Roessler, M. M. Protein film electrochemical EPR spectroscopy as a technique to investigate redox reactions in biomolecules. Chem. Commun. 55, 8840–8843 (2019).
Chen, L. et al. Accurate identification of radicals by in-situ electron paramagnetic resonance in ultraviolet-based hom*ogenous advanced oxidation processes. Water Res. 221, 118747 (2022).
Dong, K. et al. Conductive two-dimensional magnesium metal–organic frameworks for high-efficiency O2 electroreduction to H2O2. ACS Catal. 12, 6092–6099 (2022).
Dong, K. et al. Honeycomb carbon nanofibers: a superhydrophilic O2-entrapping electrocatalyst enables ultrahigh mass activity for the two-electron oxygen reduction reaction. Angew. Chem. Int. Ed. 60, 10583–10587 (2021).
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, 7413–7421 (1999).
Kresse, G. & Furthmuller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).
Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).
Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H–Pu. J. Chem. Phys. 132, 154104 (2010).
Henkelman, G., Uberuaga, B. P. & Jónsson, H. Climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901–9904 (2000).
Monkhorst, H. J. & Pack, J. D. Special points for Brillonin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).
NIST Standard Reference Database Number 69. National Institute of Standards and Technology http://webbook.nist.gov/chemistry/ (2023).
Wang, V., Xu, N., Liu, J. C., Tang, G. & Geng, W. T. VASPKIT: a user-friendly interface facilitating high-throughput computing and analysis using VASP code. Comput. Phys. Commun. 267, 108033 (2021).
Mathew, K., Sundararaman, R., Letchworth-Weaver, K., Arias, T. A. & Hennig, R. G. Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways. J. Chem. Phys. 140, 084106 (2014).
Dong, K. H2O2-mediated electrosynthesis of nitrate from air. Mendeley Data https://doi.org/10.17632/kcwgbv68y6.1 (2024).
