Recent Advances in Electrochemical H2O2 Production Via Oxygen Reduction Reaction: Fundamentals and Catalyst Design
DOI:
https://doi.org/10.54097/ex006g06Keywords:
Electrocatalysis, oxygen reduction reaction (ORR), electron transfer, catalyst design, H2O2 production.Abstract
The electrochemical synthesis of hydrogen peroxide (H2O2) through the two-electron oxygen reduction reaction (2e− ORR) presents a promising alternative to the conventional anthraquinone oxidation method. The successful commercialization of electrochemical H2O2 production depends critically on the fabrication of efficient cathode catalysts that exhibit high catalytic activity, selectivity, and stability. However, achieving significant H2O2 yields with advanced electrocatalysts remains challenging. This paper presents a systematic review of the latest advancements in the design, synthesis, and application of electrocatalysts for H2O2 production, with a focus on noble metals, transition metals, and carbon-based catalytic systems. In addition, strategies for enhancing electrocatalytic activity and selectivity are also discussed, aiming at developing cost-effective, high-performance catalysts for the 2e− ORR. Finally, we summarize critical challenges in this field, providing a comprehensive reference to guide future research and development efforts in improving electrochemical H2O2 production technologies. By addressing these challenges and encouraging innovative approaches, the electrochemical production of H2O2 may advance toward more efficient and sustainable industrial applications.
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[1] Hage, R.; Lienke, A. Applications of Transition-Metal Catalysts to Textile and Wood-Pulp Bleaching. Angew. Chem. Int. Ed. 2006, 45: 206−222.
[2] Brillas, E.; Sirés, I.; Oturan, M. A. Electro-Fenton Process and Related Electrochemical Technologies Based on Fenton’s Reaction Chemistry. Chem. Rev. 2009, 109: 6570−6631.
[3] Myers, R. L. The 100 Most Important Chemical Compounds: A Reference Guide, 1st Ed.; Greenwood, 2000; p 352.
[4] Campos-Martin, J. M.; Blanco-Brieva, G.; Fierro, J. L. G. Hydrogen Peroxide Synthesis: An Outlook beyond the Anthraquinone Process. Angew. Chem. Int. Ed. 2006, 45: 6962−6984.
[5] Riedl, H.-J.; Pfleiderer, G. Production of hydrogen peroxide. US2, 1939.
[6] Yi, Y.; Wang, L.; Li, G.; Guo, H. A Review on Research Progress in the Direct Synthesis of Hydrogen Peroxide from Hydrogen and Oxygen: Noble-Metal Catalytic Method, Fuel-Cell Method and Plasma Method. Catal. Sci. Technol. 2016, 6: 1593−1610.
[7] Siahrostami, S.; Verdaguer-Casadevall, A.; Karamad, M.; Deiana, D.; Malacrida, P.; Wickman, B.; Escudero-Escribano, M.; Paoli, E. A.; Frydendal, R.; Hansen, T. W.; Chorkendorff, I.; Stephens, I. E. L.; Rossmeisl, J. Enabling Direct H2O2 Production through Rational Electrocatalyst Design. Nat. Mater. 2013, 12: 1137−1143.
[8] Jiang, K.; Zhao, J.; Wang, H. Catalyst Design for Electrochemical Oxygen Reduction toward Hydrogen Peroxide. Adv. Funct. Mater. 2020, 30: 2003321.
[9] Yang, X.; Zeng, Y.; Alnoush, W.; Hou, Y.; Higgins, D.; Wu, G. Tuning Two-Electron Oxygen-Reduction Pathways for H2O2 Electrosynthesis via Engineering Atomically Dispersed Single Metal Site Catalysts. Adv. Mater. 2022, 34: 2107954.
[10] Xia, C.; Back, S.; Ringe, S.; Jiang, K.; Chen, F.; Sun, X.; Siahrostami, S.; Chan, K.; Wang, H. Confined Local Oxygen Gas Promotes Electrochemical Water Oxidation to Hydrogen Peroxide. Nat. Catal. 2020, 3: 125−134.
[11] Tripković, V.; Skúlason, E.; Siahrostami, S.; Norskov, J. K.; Rossmeisl, J. The Oxygen Reduction Reaction Mechanism on Pt (111) from Density Functional Theory Calculations. Electrochim. Acta 2010, 55: 7975−7981.
[12] Greeley, J.; Stephens, I. E. L.; Bondarenko, A. S.; Johansson, T. P.; Hansen, H. A.; Jaramillo, T. F.; Rossmeisl, J.; Chorkendorff, I.; Norskov, J. K. Alloys of Platinum and Early Transition Metals as Oxygen Reduction Electrocatalysts. Nat. Chem. 2009, 1: 552−556.
[13] Jirkovský, J. S.; Panas, I.; Ahlberg, E.; Halasa, M.; Romani, S.; Schiffrin, D. J. Single Atom Hot-spots at Au−Pd Nanoalloys for Electrocatalytic H2O2 Production. J. Am. Chem. Soc. 2011, 133: 19432−19441.
[14] Zhao, Q.; Wang, Y.; Lai, W. H.; Xiao, F.; Lyu, Y.; Liao, C.; Shao, M. Approaching a High-rate and Sustainable Production of Hydrogen Peroxide: Oxygen Reduction on Co−N−C Single-atom Electrocatalysts in Simulated Seawater. Energy Environ. Sci. 2021, 14: 5444−5456.
[15] Tang, C.; Chen, L.; Li, H.; Li, L.; Jiao, Y.; Zheng, Y.; Xu, H.; Davey, K.; Qiao, S. Z. Tailoring Acidic Oxygen Reduction Selectivity on Single-atom Catalysts via Modification of First and Second Coordination Spheres. J. Am. Chem. Soc. 2021, 143: 7819−7827
[16] Hu, C.; Dai, L. Carbon-based Metal-free Catalysts for Electrocatalysis beyond the ORR. Angew. Chem. Int. Ed. 2016, 55: 11736−11758.
[17] Wang, X.; Vasileff, A.; Jiao, Y.; Zheng, Y.; Qiao, S.-Z. Electronic and Structural Engineering of Carbon-based Metal-free Electrocatalysts for Water Splitting. Adv. Mater. 2019, 31: 1803625.
[18] Montemore, M. M.; Van Spronsen, M. A.; Madix, R. J.; Friend, C. M. O2 Activation by Metal Surfaces: Implications for Bonding and Reactivity on Heterogeneous Catalysts. Chem. Rev. 2018, 118: 2816−2862.
[19] Kulkarni, A.; Siahrostami, S.; Patel, A.; Norskov, J. K. Understanding Catalytic Activity Trends in the Oxygen Reduction Reaction. Chem. Rev. 2018, 118: 2302−2312.
[20] Calle-Vallejo, F.; Krabbe, A.; Garcia-Lastra, J. M. How Covalence Breaks Adsorption-Energy Scaling Relations and Solvation Restores Them. Chem. Sci. 2017, 8: 124−130.
[21] Sahoo, S. K.; Ye, Y.; Lee, S.; Park, J.; Lee, H.; Lee, J.; Han, J. W. Rational Design of TiC-Supported Single-Atom Electrocatalysts for Hydrogen Evolution and Selective Oxygen Reduction Reactions. ACS Energy Lett. 2019, 4: 126−132.
[22] Ding, S.; Xia, B.; Li, M.; Lou, F.; Cheng, C.; Gao, T.; Zhang, Y.; Yang, K.; Jiang, L.; Nie, Z.; Guan, H.; Duan, J.; Chen, S. An Abnormal Size Effect Enables Ampere-level O2 Electroreduction to Hydrogen Peroxide in Neutral Electrolytes. Energy Environ. Sci. 2023, 16: 3363.
[23] Yang, S.; Tak, Y. J.; Kim, J.; Soon, Al.; Lee, H. Support Effects in Single-Atom Platinum Catalysts for Electrochemical Oxygen Reduction. ACS Catal. 2017, 7: 1301−1307.
[24] Perry, S. C.; Pangotra, D.; Vieira, L.; Csepei, L. I.; Sieber, V.; Wang, L.; De León, C. P.; Walsh, F. C. Electrochemical Synthesis of Hydrogen Peroxide from Water and Oxygen. Nat. Rev. Chem. 2019, 3: 442−458.
[25] Li, H.-C.; Wan, Q.; Du, C.; Zhao, J.; Li, F.; Zhang, Y.; Zheng, Y.; Chen, M.; Zhang, K. H. L.; Huang, J.; Fu, G.; Lin, S.; Huang, X.; Xiong, H. Layered Pd Oxide on PdSn Nanowires for Boosting Direct H2O2 Synthesis. Nat. Commun. 2022, 13: 6072.
[26] Markovic, N. M.; Ross, P. N. Surface Science Studies of Model Fuel Cell Electrocatalysts. Surf. Sci. Rep. 2002, 45: 117−229.
[27] Siahrostami, S.; Verdaguer-Casdevall, A.; Karamad, M.; Chorkendorff, I.; Stephens, I. E. L.; Rossmeisl, J. Activity and Selectivity for O2 Reduction to H2O2 on Transition Metal Surfaces. ECS Trans. 2013, 58: 53−62.
[28] Jirkovský, J. S.; Panas, I.; Ahlberg, E.; Halasa, M.; Romani, S.; Schiffrin, D. J. Single Atom Hot-Spots at Au-Pd Nanoalloys for Electrocatalytic H2O2 Production. J. Am. Chem. Soc. 2011, 133: 19432−19441.
[29] Zhao, X.; Yang, H.; Xu, J.; Cheng, T.; Li, Y. Bimetallic PdAu Nanoframes for Electrochemical H2O2 Production in Acids. ACS Mater. Lett. 2021, 3: 996−1002.
[30] Du, J.; Jiang, S.; Zhang, R.; Wang, P.; Ma, C.; Zhao, R.; Cui, C.; Zhang, Y.; Kang, Y. Generation of Pd−O for Promoting Electrochemical H2O2 Production. ACS Catal. 2023, 13: 6887−6892.
[31] Van Veen, J. A. R.; Van Baar, J. F.; Kroese, C. J.; Coolegem, J. G. F.; De Wit, N.; Colijn, H. A. Oxygen Reduction on Transition-Metal Porphyrins in Acid Electrolyte I. Activity. Ber. Bunsenges. Phys. Chem. 1981, 85: 693−700.
[32] Sun, Y.; Silvioli, L.; Sahraie, N. R.; Ju, W.; Li, J.; Zitolo, A.; Li, S.; Bagger, A.; Arnarson, L.; Wang, X.; Moeller, T.; Bernsmeier, D.; Rossmeisl, J.; Jaouen, F.; Strasser, P. Activity−Selectivity Trends in the Electrochemical Production of Hydrogen Peroxide over Single-Site Metal−Nitrogen−Carbon Catalysts. J. Am. Chem. Soc. 2019, 141: 12372−12381.
[33] Ye, C.; Zhang, L.; Shen, Y. Activity Origin and Catalytic Mechanism of the M−N−C Catalysts for the Oxygen Reduction Reaction. ACS Materials Lett. 2024, 6: 2858−2887.
[34] Gao, J.; Yang, H. B.; Huang, X.; Hung, S.-F.; Cai, W.; Jia, C.; Miao, S.; Chen, H. M.; Yang, X.; Huang, Y.; et al. Enabling Direct H2O2 Production in Acidic Media through Rational Design of Transition Metal Single Atom Catalyst. Chem. 2020, 6: 658.
[35] Jung, E.; Shin, H.; Lee, B.-H.; Efremov, V.; Lee, S.; Lee, H. S.; Kim, J.; Hooch Antink, W.; Park, S.; Lee, K.-S.; Cho, S.-P.; Yoo, J. S.; Sung, Y.-E.; Hyeon, T. Atomic-Level Tuning of Co−N−C Catalyst for High-Performance Electrochemical H2O2 Production. Nat. Mater. 2020, 19: 436−442.42-36
[36] Li, B. Q.; Zhao, C. X.; Liu, J. N.; Zhang, Q. Electrosynthesis of Hydrogen Peroxide Synergistically Catalyzed by Atomic Co−Nx−C Sites and Oxygen Functional Groups in Noble-Metal-Free Electrocatalysts. Adv. Mater. 2019, 31: 1808173.
[37] Jiang, K.; Back, S.; Akey, A. J.; Xia, C.; Hu, Y.; Liang, W.; Schaak, D.; Stavitski, E.; Norskov, J. K.; Siahrostami, S.; Wang, H. Highly Selective Oxygen Reduction to Hydrogen Peroxide on Transition Metal Single Atom Coordination. Nat. Commun., 2019, 10: 3997.
[38] Zhang, H.; Xu, H.; Yao, C.; Chen, S.; Li, F.; Zhao, D. Metal Atom–Support Interaction in Single Atom Catalysts toward Hydrogen Peroxide Electrosynthesis. ACS Nano 2024, 18: 21836−21854.
[39] Zhang, C.; Shen, W.; Guo, K.; Xiong, M.; Zhang, J.; Lu, X. A Pentagonal Defect-Rich Metal-Free Carbon Electrocatalyst for Boosting Acidic O2 Reduction to H2O2 Production. J. Am. Chem. Soc. 2023, 145: 11589−11598.
[40] Lee, K.; Lim, J.; Lee, M. J.; Ryu, K.; Lee, H.; Kim, J. Y.; Ju, H.; Cho, H.-S.; Kim, B.-H.; Hatzell, M. C.; Kang, J.; Lee, S. W. Structure-Controlled Graphene Electrocatalysts for High-Performance H2O2 Production. Energy Environ. Sci. 2022, 15: 2858−2866.
[41] Liu, J.; Li, C.; Zhang, Z.; Wang, J.; Yang, M. Green and Sustainable in situ Water Treatment: A Review of Noble-free Catalysts for Electrochemical Oxygen Reduction to Hydrogen Peroxide. Green Chem. 2024, 26: 8445−8460.
[42] Zhang, X.; Zhang, C.; Yu, C.; Liu, C. Metal−organic Frameworks for Electrocatalytic Hydrogen Peroxide Production. Mater. Chem. Front. 2024, 8: 1084−1100.
[43] Liu, Y.; Quan, X.; Fan, X.; Wang, H.; Chen, S. High-Yield Electrosynthesis of Hydrogen Peroxide from Oxygen Reduction by Hierarchically Porous Carbon. Angew. Chem. Int. Ed. 2015, 54: 6837−6841.
[44] Zhou, X.; Min, Y.; Zhao, C.; Chen, C.; Ke, M.-K.; Xu, S.-L.; Chen, J.-J.; Wu, Y.; Yu, H.-Q. Constructing Sulfur and Oxygen Super-coordinated Main-group Electrocatalysts for Selective and Cumulative H2O2 Production. Nat. Commun. 2024, 15: 193.
[45] Cao, P.; Quan, X.; Nie, X.; Zhao, K.; Liu, Y.; Chen, S.; Yu, H.; Chen, J. G. Metal Single-Site Catalyst Design for Electrocatalytic Production of Hydrogen Peroxide at Industrial-Relevant Currents. Nat. Commun. 2023, 14: 1−12.
[46] Kim, H. W.; Ross, M. B.; Kornienko, N.; Zhang, L.; Guo, J.; Yang, P.; Mccloskey, B. D. Efficient Hydrogen Peroxide Generation Using Reduced Graphene Oxide-based Oxygen Reduction Electrocatalysts. Nat. Catal. 2018, 1: 282−290.
[47] Tuci, G.; Zafferoni, C.; D’Ambrosio, P.; Caporali, S.; Ceppatelli, M.; Rossin, A.; Tsoufis, T.; Innocenti, M.; Giambastiani, G. Tailoring Carbon Nanotube N-Dopants while Designing Metal- Free Electrocatalysts for the Oxygen Reduction Reaction in Alkaline Medium. ACS Catal. 2013, 3: 2108−2111.
[48] Li, L.; Tang, C.; Zheng, Y.; Xia, B.; Zhou, X.; Xu, H.; Qiao, S.- Z. Tailoring Selectivity of Electrochemical Hydrogen Peroxide Generation by Tunable Pyrrolic-Nitrogen-Carbon. Adv. Energy Mater. 2020, 2000789
[49] He, C.; Xia, C.; Li, F.-M.; Zhang, J.; Guo, W.; Xia, B. Y. Rational Design of Oxygen Species Adsorption on Nonnoble Metal Catalysts for Two-Electron Oxygen Reduction. Adv. Energy Mater. 2024, 14: 2303233.
[50] Ghosh, M.; Ezhov, R.; Braley, S, E.; Losovyj, Y.; Bury, G.; Pushkar, Y. N; Smith, J. M. Metal-Dependent Electrocatalytic Oxygen Reduction in Surface-Conjugated Macrocyclic Electrodes. ACS Appl. Energy Mater. 2024, 7: 6717–6726.
[51] Jung, E.; Shin, H.; Hooch Antink, W.; Sung, Y. E.; Hyeon, T. Recent Advances in Electrochemical Oxygen Reduction to H2O2: Catalyst and Cell Design. ACS Energy Lett. 2020, 5: 1881–1892.
[52] Weekes, D. M.; Salvatore, D. A.; Reyes, A.; Huang, A.; Berlinguette, C. P. Electrolytic CO2 Reduction in a Flow Cell. Acc. Chem. Res. 2018, 51: 910−918.
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