Single Metal-Embedded Nitrogen Heterocycle Aromatic Catalysts for Efficient and Selective Two-Electron Water Electrolysis Toward Hydrogen Peroxide

Abstract

Hydrogen peroxide (H₂O₂) is an eco-friendly chemical with widespread industrial applications. However, the commercial anthraquinone process for H₂O₂ production is energy-intensive and environmentally harmful, highlighting the need for more sustainable alternatives. The electrochemical production of H₂O₂ via the two-electron water oxidation reaction (2e⁻ WOR) presents a promising route but is often hindered by low efficiency and selectivity, due to the competition with the oxygen evolution reaction. In this study, we employed high-throughput computational screening and microkinetic modeling to design a series of efficient 2e⁻ WOR electrocatalysts from a library of 240 single-metal-embedded nitrogen heterocycle aromatic molecules (M-NHAMs). These catalysts, primarily comprising post-transition metals, such as Cu, Ni, Zn, and Pd, exhibit high activity for H₂O₂ conversion with a limiting potential approaching the optimal value of 1.76 V. Additionally, they exhibit excellent selectivity, with Faradaic efficiencies exceeding 80% at overpotentials below 300 mV. Structure-performance analysis reveals that the d-band center and magnetic moment of the metal center correlated strongly with the oxygen adsorption free energy ((ΔG_O*), suggesting these parameters as key catalytic descriptors for efficient screening and performance optimization. This study contributes to the rational design of highly efficient and selective electrocatalysts for electrochemical production of H₂O₂, offering a sustainable solution for green energy and industrial applications.

Keywords

high-throughput computation / hydrogen peroxide / microkinetic modeling / single-atom catalyst / two-electron water oxidation

References

[1] R. J. Lewis, K. Ueura, X. Liu, et al., “Highly Efficient Catalytic Production of Oximes From Ketones Using In Situ-Generated H₂O₂,” Science 376, no. 6593 (2022): 615-620.

[2] M. Deng, D. Wang, and Y. Li, “General Design Concept of High-Performance Single-Atom-Site Catalysts for H₂O₂ Electrosynthesis,” Advanced Materials 36, no. 24 (2024): e14340.

[3] L. Li, Z. Hu, and J. C. Yu, “On-Demand Synthesis of H₂O₂ by Water Oxidation for Sustainable Resource Production and Organic Pollutant Degradation,” Angewandte Chemie 132, no. 46 (2020): 20719-20725.

[4] C. Wen, J. Zhang, Y. Feng, Y. Duan, H. Ma, and H. Zhang, “Purification and Identification of Novel Antioxidant Peptides From Watermelon Seed Protein Hydrolysates and Their Cytoprotective Effects on H₂O₂-Induced Oxidative Stress,” Food Chemistry 327, no. 15 (2020): 127059.

[5] C. J. McDonnell-Worth and D. R. MacFarlane, “Progress Towards Direct Hydrogen Peroxide Fuel Cells (DHPFCs) as an Energy Storage Concept,” Australian Journal of Chemistry 71, no. 10 (2018): 781-788.

[6] J. M. Campos-Martin, G. Blanco-Brieva, and J. L. G. Fierro, “Hydrogen Peroxide Synthesis: An Outlook Beyond the Anthraquinone Process,” Angewandte Chemie International Edition 45, no. 42 (2006): 6962-6984.

[7] A. Arshad, L. Ding, R. Akram, W. Zhu, L. Long, and K. Wang, “Construction of a Novel Au@Os Mediated TMB-H₂O₂ Platform With Dual-Signal Output for Rapid and Accurate Detection of Ziram in Food,” Food Chemistry 462 (2025): 140988.

[8] S. Wu, N. Duan, Y. Qiu, J. Li, and Z. Wang, “Colorimetric Aptasensor for the Detection of Salmonella Enterica Serovar Typhimurium Using ZnFe₂O₄-Reduced Graphene Oxide Nanostructures as an Effective Peroxidase Mimetics,” International Journal of Food Microbiology 261, no. 16 (2017): 42-48.

[9] X. Shi, S. Back, T. M. Gill, S. Siahrostami, and X. Zheng, “Electrochemical Synthesis of H₂O₂ by Two-Electron Water Oxidation Reaction,” Chemical Science 7, no. 1 (2021): 38-63.

[10] S. Siahrostami, “H₂O₂ Electrosynthesis and Emerging Applications, Challenges, and Opportunities: A Computational Perspective,” Chem Catalysis 3, no. 3 (2023): 100568.

[11] M.-D. Zhang, J.-R. Huang, C.-P. Liang, X.-M. Chen, and P.-Q. Liao, “Continuous Electrosynthesis of Pure H₂O₂ Solution With Medical-Grade Concentration by a Conductive Ni-Phthalocyanine-Based Covalent Organic Framework,” Journal of the American Chemical Society 146, no. 45 (2024): 31034-31041.

[12] S. Yang, A. Verdaguer-Casadevall, L. Arnarson, et al., “Toward the Decentralized Electrochemical Production of H₂O₂: A Focus on the Catalysis,” ACS Catalysis 8, no. 5 (2018): 4064-4081.

[13] Q. Zhang, M. Zhou, G. Ren, Y. Li, Y. Li, and X. Du, “Highly Efficient Electrosynthesis of Hydrogen Peroxide on a Superhydrophobic Three-Phase Interface by Natural Air Diffusion,” Nature Communications 11 (2020): 1731.

[14] L. Bai, X. Su, J. Feng, and S. Ma, “Preparation of Sugarcane Bagasse Biochar/Nano-Iron Oxide Composite and Mechanism of Its Cr (VI) Adsorption in Water,” Journal of Cleaner Production 320, no. 20 (2021): 128723.

[15] C. Kim, S. O. Park, S. K. Kwak, Z. Xia, G. Kim, and L. Dai, “Concurrent Oxygen Reduction and Water Oxidation at High Ionic Strength for Scalable Electrosynthesis of Hydrogen Peroxide,” Nature Communications 14 (2023): 5822.

[16] J. Lin, X. Wang, Z. Zhao, et al., “Design of pH-Universal Electrocatalysts for Hydrogen Evolution Reaction,” Carbon Energy 6, no. 11 (2024): e555.

[17] Y. Jiang, J. Yu, H. Song, et al., “Enhanced Water-Splitting Performance: Interface-Engineered Tri-Metal Phosphides With Carbon Dots Modification,” Carbon Energy 6, no. 10 (2024): e631.

[18] H. Cao, G. Chen, Y. Yan, and D. Wang, “Advances in Two-Electron Water Oxidation Reaction for Hydrogen Peroxide Production: Catalyst Design and Interface Engineering,” Chemsuschem 18, no. 2 (2024): e01100.

[19] P. Chaudhary, I. Evazzade, R. Belosludov, and V. Alexandrov, “Computational Discovery of Active and Selective Metal-Nitrogen-Graphene Catalysts for Electrooxidation of Water to H₂O₂,” ChemCatChem 15, no. 10 (2023): e00055.

[20] W. Guo, S. Wang, Y. Xie, et al., “Hydrogen Peroxide Synthesis via Electrocatalytic Water Oxidation on Sp³ and Sp² Carbon Materials Mediated by Carbonates and Bicarbonates,” ACS Sustainable Chemistry & Engineering 11, no. 32 (2023): 12114-12122.

[21] T. M. Gill, L. Vallez, and X. Zheng, “The Role of Bicarbonate-Based Electrolytes in H₂O₂ Production Through Two-Electron Water Oxidation,” ACS Energy Letters 6, no. 8 (2021): 2854-2862.

[22] X. Hu, Z. Sun, G. Mei, X. Zhao, B. Y. Xia, and B. You, “Engineering Nonprecious Metal Oxides Electrocatalysts for Two-Electron Water Oxidation to H₂O₂,” Advanced Energy Materials 12, no. 32 (2022): e01466.

[23] L. Li, R. P. Antony, C. S. Santos, N. Limani, S. Dieckhöfer, and W. Schuhmann, “Anodic H₂O₂ Generation in Carbonate-Based Electrolytes—Mechanistic Insight From Scanning Electrochemical Microscopy,” Angewandte Chemie International Edition 63, no. 38 (2024): e06543.

[24] S. Mavrikis, S. C. Perry, P. K. Leung, L. Wang, and C. Ponce, “Recent Advances in Electrochemical Water Oxidation to Produce Hydrogen Peroxide: A Mechanistic Perspective,” ACS Sustainable Chemistry & Engineering 9, no. 1 (2020): 76-91.

[25] M. Mazzucato, A. Facchin, M. Parnigotto, and C. Durante, “New and Revised Aspects of the Electrochemical Synthesis of Hydrogen Peroxide: From Model Electrocatalytic Systems to Scalable Materials,” ACS Catalysis 14, no. 9 (2024): 6369-6403.

[26] Y. Sun, X. Chen, S. Ning, et al., “Efficient Electrochemical Water Oxidation to Hydrogen Peroxide Over Intrinsic Carbon Defect-Rich Carbon Nanofibers,” Journal of Materials Chemistry A 9, no. 42 (2021): 23994-24001.

[27] R. Wang, H. Luo, M. Sun, et al., “Characterization and H₂O₂ Production Mechanisms Study on Self-Oxidized Graphite During the Two-Electron Water Oxidation Electrochemical Process,” Journal of Catalysis 434 (2024): 115521.

[28] J. Wang, D. Kim, J. H. Park, et al., “Prospects and Promises in Two-Electron Water Oxidation for Hydrogen Peroxide Generation,” Energy & Fuels 37, no. 23 (2023): 17629-17651.

[29] S. R. Kelly, X. Shi, S. Back, et al., “ZnO as an Active and Selective Catalyst for Electrochemical Water Oxidation to Hydrogen Peroxide,” ACS Catalysis 9, no. 5 (2019): 4593-4599.

[30] S. Y. Park, H. Abroshan, X. Shi, H. S. Jung, S. Siahrostami, and X. Zheng, “CaSnO₃: An Electrocatalyst for Two-Electron Water Oxidation Reaction to Form H₂O₂,” ACS Energy Letters 4, no. 1 (2018): 352-357.

[31] X. Shi, S. Siahrostami, G.-L. Li, et al., “Understanding Activity Trends in Electrochemical Water Oxidation to Form Hydrogen Peroxide,” Nature Communications 8 (2017): 701.

[32] J. Baek, Q. Jin, N. S. Johnson, et al., “Discovery of LaAlO₃ as an Efficient Catalyst for Two-Electron Water Electrolysis Towards Hydrogen Peroxide,” Nature Communications 13 (2022): 7256.

[33] S. Mavrikis, M. Göltz, S. Rosiwal, L. Wang, and C. Ponce de León, “Boron-Doped Diamond Electrocatalyst for Enhanced Anodic H₂O₂ Production,” ACS Applied Energy Materials 3, no. 4 (2020): 3169-3173.

[34] R. Khan, J. Chakraborty, K. Singh Rawat, et al., “Super-Oxidizing Covalent Triazine Framework Electrocatalyst for Two-Electron Water Oxidation to H₂O₂,” Angewandte Chemie International Edition 62, no. 47 (2023): e13836.

[35] X.-F. Yang, A. Wang, B. Qiao, J. Li, J. Liu, and T. Zhang, “Single-Atom Catalysts: A New Frontier in Heterogeneous Catalysis,” Accounts of Chemical Research 46, no. 8 (2013): 1740-1748.

[36] C. Jing, J. Ding, P. Jia, et al., “Revealing the Origin of Single-Atom W Activity in H₂O₂ Electrocatalytic Production: Charge Symmetry-Breaking,” Carbon Energy 6, no. 10 (2024): e581.

[37] Y. Wang, D. Wang, and Y. Li, “Atom-Level Interfacial Synergy of Single-Atom Site Catalysts for Electrocatalysis,” Journal of Energy Chemistry 65 (2022): 103-115.

[38] S. N. Remello, F. Kuttassery, S. Mathew, et al., “Two-Electron Oxidation of Water to Form Hydrogen Peroxide Catalysed by Silicon-Porphyrins,” Sustainable Energy & Fuels 2, no. 9 (2018): 1966-1973.

[39] Q. e Huang, J. Chen, P. Luan, C. Ding, and C. Li, “Understanding the Factors Governing the Water Oxidation Reaction Pathway of Mononuclear and Binuclear Cobalt Phthalocyanine Catalysts,” Chemical Science 13, no. 30 (2022): 8797-8803.

[40] Y. Wang, Z. Zhang, X. Zhang, et al., “Theory-Driven Design of Electrocatalysts for the Two-Electron Oxygen Reduction Reaction Based on Dispersed Metal Phthalocyanines,” CCS Chemistry 4, no. 1 (2022): 228-236.

[41] Y.-L. Li, X.-L. Jiang, H. Cao, H. Y. Zhao, J. Li, and Y. G. Wang, “Potential Dependence and Substituent Effect in CO₂ Electroreduction on a Cobalt Phthalocyanine Catalyst,” ACS Catalysis 14, no. 12 (2024): 9575-9585.

[42] P. Hutchison, L. E. Smith, C. L. Rooney, H. Wang, and S. Hammes-Schiffer, “Proton-Coupled Electron Transfer Mechanisms for CO₂ Reduction to Methanol Catalyzed by Surface-Immobilized Cobalt Phthalocyanine,” Journal of the American Chemical Society 146, no. 29 (2024): 20230-20240.

[43] Q. Zhu, C. L. Rooney, H. Shema, et al., “The Solvation Environment of Molecularly Dispersed Cobalt Phthalocyanine Determines Methanol Selectivity During Electrocatalytic CO₂ Reduction,” Nature Catalysis 7, no. 9 (2024): 987-999.

[44] C. Liu, Z. Yu, F. She, et al., “Heterogeneous Molecular Co-N-C Catalysts for Efficient Electrochemical H₂O₂ Synthesis,” Energy & Environmental Science 16, no. 2 (2023): 446-459.

[45] C. Liu, H. Tong, P. Wang, et al., “Coordination Engineering Regulating Metal Single-Atom Anchored on N-Doped Carbon as a Bifunctional Catalyst for H₂O₂ Production via Dual Channels,” Chemical Engineering Journal 476 (2023): 146573.

[46] B. Mondal, S. Chattopadhyay, S. Dey, et al., “Elucidation of Factors That Govern the 2e^-/2H⁺ vs 4e^-/4H⁺ Selectivity of Water Oxidation by a Cobalt Corrole,” Journal of the American Chemical Society 142, no. 50 (2020): 21040-21049.

[47] W. Xu and N. Kumagai, “A Brief Introduction to Highly Symmetric N-Heteroarene-Based Macrocycles,” Tetrahedron 141 (2023): 133512.

[48] X. Guo, J. Gu, S. Lin, S. Zhang, Z. Chen, and S. Huang, “Tackling the Activity and Selectivity Challenges of Electrocatalysts Toward the Nitrogen Reduction Reaction via Atomically Dispersed Biatom Catalysts,” Journal of the American Chemical Society 142, no. 12 (2020): 5709-5721.

[49] J. Greeley and J. K. Nørskov, “Electrochemical Dissolution of Surface Alloys in Acids: Thermodynamic Trends from First-Principles Calculations,” Electrochimica Acta 52, no. 19 (2007): 5829-5836.

[50] A. S. Malik, T. Liu, M. Dupuis, R. Li, and C. Li, “Water Oxidation on TiO₂: A Comparative DFT Study of 1e^-, 2e^-, and 4e^- Processes on Rutile, Anatase, and Brookite,” Journal of Physical Chemistry C 124, no. 15 (2020): 8094-8100.

[51] S. Siahrostami, G.-L. Li, V. Viswanathan, and J. K. Nørskov, “One- or Two-Electron Water Oxidation, Hydroxyl Radical, or H₂O₂ Evolution,” Journal of Physical Chemistry Letters 8, no. 6 (2017): 1157-1160.

[52] S. Siahrostami, S. J. Villegas, A. H. Bagherzadeh Mostaghimi, et al., “A Review on Challenges and Successes in Atomic-Scale Design of Catalysts for Electrochemical Synthesis of Hydrogen Peroxide,” ACS Catalysis 10, no. 14 (2020): 7495-7511.

[53] R. H. Adnan and A. A. Jalil, “Gold Photocatalysis in Sustainable Hydrogen Peroxide Generation,” Materials Today Chemistry 27 (2023): 101322.

[54] D. W. Flaherty, “Direct Synthesis of H₂O₂ From H₂ and O₂ on Pd Catalysts: Current Understanding, Outstanding Questions, and Research Needs,” ACS Catalysis 8, no. 2 (2018): 1520-1527.

[55] Y. Chen, C. Zhen, Y. Chen, et al., “Oxygen Functional Groups Regulate Cobalt-Porphyrin Molecular Electrocatalyst for Acidic H₂O₂ Electrosynthesis at Industrial-Level Current,” Angewandte Chemie International Edition 63, no. 34 (2024): e07163.

[56] C. F. Dickens, C. Kirk, and J. K. Nørskov, “Insights Into the Electrochemical Oxygen Evolution Reaction With Ab Initio Calculations and Microkinetic Modeling: Beyond the Limiting Potential Volcano,” Journal of Physical Chemistry C 123, no. 31 (2019): 18960-18977.

[57] G. Kresse and D. Joubert, “From Ultrasoft Pseudopotentials to the Projector Augmented-Wave Method,” Physical Review B 59, no. 3 (1999): 1758-1775.

[58] G. Kresse and J. Furthmüller, “Efficient Iterative Schemes for Ab Initio Total-Energy Calculations Using a Plane-Wave Basis Set,” Physical Review B 54, no. 16 (1996): 11169-11186.

[59] J. P. Perdew, K. Burke, and M. Ernzerhof, “Generalized Gradient Approximation Made Simple,” Physical Review Letters 78, no. 7 (1997): 1396.

[60] J. P. Perdew, K. Burke, and M. Ernzerhof, “Generalized Gradient Approximation Made Simple,” Physical Review Letters 77, no. 18 (1996): 3865-3868.

[61] S. Grimme, J. Antony, S. Ehrlich, and H. Krieg, “A Consistent and Accurate Ab Initio Parametrization of Density Functional Dispersion Correction (DFT-D) for the 94 Elements H-Pu,” Journal of Chemical Physics 132, no. 15 (2010): 154104.

[62] K. Mathew, R. Sundararaman, K. Letchworth-Weaver, T. A. Arias, and R. G. Hennig, “Implicit Solvation Model for Density-Functional Study of Nanocrystal Surfaces and Reaction Pathways,” Journal of Chemical Physics 140, no. 8 (2014): 084106.

[63] S. M. R. Islam, F. Khezeli, S. Ringe, and C. Plaisance, “An Implicit Electrolyte Model for Plane Wave Density Functional Theory Exhibiting Nonlinear Response and a Nonlocal Cavity Definition,” Journal of Chemical Physics 159, no. 23 (2023): e0176308.

[64] G. Henkelman, B. P. Uberuaga, and H. Jónsson, “A Climbing Image Nudged Elastic Band Method for Finding Saddle Points and Minimum Energy Paths,” Journal of Chemical Physics 113, no. 22 (2000): 9901-9904.

[65] J. Heyd, G. E. Scuseria, and M. Ernzerhof, “Hybrid Functionals Based on a Screened Coulomb Potential,” Journal of Chemical Physics 118, no. 18 (2003): 8207-8215.

[66] Z. Duan and G. Henkelman, “Theoretical Resolution of the Exceptional Oxygen Reduction Activity of Au(100) in Alkaline Media,” ACS Catalysis 9, no. 6 (2019): 5567-5573.

[67] V. Wang, N. Xu, J. C. Liu, G. Tang, and W. T. Geng, “VASPKIT: A User-Friendly Interface Facilitating High-Throughput Computing and Analysis Using VASP Code,” Computer Physics Communications 267 (2021): 108033.

[68] K. Momma and F. Izumi, “VESTA3 for Three-Dimensional Visualization of Crystal, Volumetric and Morphology Data,” Journal of Applied Crystallography 44, no. 6 (2011): 1272-1276.

[69] E. Skúlason, G. S. Karlberg, J. Rossmeisl, et al., “Density Functional Theory Calculations for the Hydrogen Evolution Reaction in an Electrochemical Double Layer on the Pt(111) Electrode,” Physical Chemistry Chemical Physics 9, no. 25 (2007): 3241-3250.

[70] J. K. Nørskov, T. Bligaard, A. Logadottir, et al., “Trends in the Exchange Current for Hydrogen Evolution,” Journal of the Electrochemical Society 152, no. 3 (2005): J23-J26.

[71] H. A. Hansen, V. Viswanathan, and J. K. Nørskov, “Unifying Kinetic and Thermodynamic Analysis of 2e^- and 4e^- Reduction of Oxygen on Metal Surfaces,” Journal of Physical Chemistry C 118, no. 13 (2014): 6706-6718.

[72] S. R. Kelly, C. Kirk, K. Chan, and J. K. Nørskov, “Electric Field Effects in Oxygen Reduction Kinetics: Rationalizing pH Dependence at the Pt (111), Au (111), and Au (100) Electrodes,” Journal of Physical Chemistry C 124, no. 27 (2020): 14581-14591.

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