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• W3198736895 abstract "•Carboxyl group as the primary active site for H2O2 electrosynthesis•Graphitic carbon edges as doping sites for the active functional groups•Record-high H2O2 electrosynthesis activity among the reported carbon catalysts•Excellent long-term stability over 168 h and near-unity H2O2 faradic efficiency Electrosynthesis has emerged as a promising alternative to the traditional chemical synthesis processes. The major benefit of the electrochemical process includes the use of ambient pressure, low-temperature operating conditions, and high product selectivity. Hydrogen peroxide electrosynthesis is particularly attractive because of the use of practically limitless and clean source of reagents—air and water. The efficiency of this technology critically relies on the active catalyst for the selective reduction of O2 to H2O2. The activity and selectivity of electrocatalysts are largely affected by the nature of the active sites and catalyst structures. In this work, the active oxygen functional groups in O-doped carbons are identified via systematic investigation using model catalysts and the insights into the key structural factor are provided. The best catalyst, optimized in this work, exhibits the record-high H2O2 electrosynthesis activity with near 100% of H2O2 faradic efficiency. The electrosynthesis of H2O2 via the 2e− oxygen reduction reaction (ORR) is an attractive method for the clean and continuous on-site production of H2O2, for which the development of active and selective electrocatalysts remains a significant challenge. Although carbon nanomaterials have demonstrated promising performance for H2O2 production, the lack of understanding of the active sites and key structural factors has impeded their development. In this work, we have prepared carbon-based model catalysts to investigate the active oxygen functional groups and structural factor. We have identified that the carboxyl group at the edge sites of graphitic carbons is the major active site for the 2e− ORR, and the carbonyl group is a secondary active site. The nanoporous carbon catalyst with abundant active edge sites and optimized structure exhibited the highest H2O2 electrosynthesis activity among the carbon-based catalysts reported to date and excellent long-term stability (168 h) with 99% H2O2 faradic efficiency. The electrosynthesis of H2O2 via the 2e− oxygen reduction reaction (ORR) is an attractive method for the clean and continuous on-site production of H2O2, for which the development of active and selective electrocatalysts remains a significant challenge. Although carbon nanomaterials have demonstrated promising performance for H2O2 production, the lack of understanding of the active sites and key structural factors has impeded their development. In this work, we have prepared carbon-based model catalysts to investigate the active oxygen functional groups and structural factor. We have identified that the carboxyl group at the edge sites of graphitic carbons is the major active site for the 2e− ORR, and the carbonyl group is a secondary active site. The nanoporous carbon catalyst with abundant active edge sites and optimized structure exhibited the highest H2O2 electrosynthesis activity among the carbon-based catalysts reported to date and excellent long-term stability (168 h) with 99% H2O2 faradic efficiency. IntroductionHydrogen peroxide (H2O2) is a key chemical that is widely used in areas such as pulp bleaching, food processing, and wastewater treatment. The global demand for H2O2 has gradually increased.1Imarc Market ResearchHydrogen peroxide market: global industry trends, share, size, growth, opportunity and forecast 2020–2025.2020https://www.imarcgroup.com/hydrogen-peroxide-technical-material-market-reportGoogle Scholar,2Reportlinker market research.Global hydrogen peroxide industry. Brooklyn, 2020https://www.reportlinker.com/p090603/World-Hydrogen-Peroxide-Market.htmlGoogle Scholar Most of this demand has been fulfilled using the anthraquinone process. However, this process requires pressurized H2 gas and Pd-based hydrogenation catalysts and involves energy-intensive purification and distillation steps, which increase the production cost.3Campos-Martin J.M. Blanco-Brieva G. Fierro J.L. Hydrogen peroxide synthesis: an outlook beyond the anthraquinone process.Angew. Chem. Int. Ed. Engl. 2006; 45: 6962-6984Crossref PubMed Scopus (1477) Google Scholar,4Ciriminna R. Albanese L. Meneguzzo F. Pagliaro M. 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Mater. 2019; 31: 3967-3973Crossref Scopus (63) Google Scholar carbonyl/quinone (C=O),50Han G.F. Li F. Zou W. Karamad M. Jeon J.P. Kim S.W. et al.Building and identifying highly active oxygenated groups in carbon materials for oxygen reduction to H2O2.Nat. Commun. 2020; 11: 2209Crossref PubMed Scopus (126) Google Scholar,51Wu K.-H. Wang D. Lu X. Zhang X. Xie Z. Liu Y. Su B.-J. Chen J.-M. Su D.-S. Qi W. Guo S. Highly selective hydrogen peroxide electrosynthesis on carbon: in situ interface engineering with surfactants.Chem. 2020; 6: 1443-1458Abstract Full Text Full Text PDF Scopus (65) Google Scholar and carboxyl (O–C=O),42Lu Z. Chen G. Siahrostami S. Chen Z. Liu K. Xie J. Liao L. Wu T. Lin D. Liu Y. et al.High-efficiency oxygen reduction to hydrogen peroxide catalyzed by oxidized carbon materials.Nat. Catal. 2018; 1: 156-162Crossref Scopus (707) Google Scholar,51Wu K.-H. Wang D. Lu X. Zhang X. Xie Z. Liu Y. Su B.-J. Chen J.-M. Su D.-S. Qi W. Guo S. Highly selective hydrogen peroxide electrosynthesis on carbon: in situ interface engineering with surfactants.Chem. 2020; 6: 1443-1458Abstract Full Text Full Text PDF Scopus (65) Google Scholar have been proposed as the active sites in previous studies.In addition, the structural properties of carbon-based materials play a substantial role on nanostructured electrocatalysts. The structural properties, including pore structure35Fellinger T.P. Hasché F. Strasser P. Antonietti M. Mesoporous nitrogen-doped carbon for the electrocatalytic synthesis of hydrogen peroxide.J. Am. Chem. Soc. 2012; 134: 4072-4075Crossref PubMed Scopus (518) Google Scholar, 36Park J. Nabae Y. Hayakawa T. Kakimoto M. Highly selective two-electron oxygen reduction catalyzed by mesoporous nitrogen-doped carbon.ACS Catal. 2014; 4: 3749-3754Crossref Scopus (276) Google Scholar, 37Chen Z. Chen S. Siahrostami S. Chakthranont P. Hahn C. Nordlund D. et al.Development of a reactor with carbon catalysts for modular-scale, low-cost electrochemical generation of H2O2.React. Chem. Eng. 2017; 2: 239-245Crossref Google Scholar,43Zhao K. Su Y. Quan X. Liu Y. Chen S. Yu H. Enhanced H2O2 production by selective electrochemical reduction of O2 on fluorine-doped hierarchically porous carbon.J. Catal. 2018; 357: 118-126Crossref Scopus (161) Google Scholar,44Sun Y. Sinev I. Ju W. Bergmann A. Dresp S. Kühl S. Spöri C. Schmies H. Wang H. Bernsmeier D. et al.Efficient electrochemical hydrogen peroxide production from molecular oxygen on nitrogen-doped mesoporous carbon catalysts.ACS Catal. 2018; 8: 2844-2856Crossref Scopus (244) Google Scholar,53Pang Y. Wang K. Xie H. Sun Y. Titirici M.-M. Chai G.-L. Mesoporous carbon hollow spheres as efficient electrocatalysts for oxygen reduction to hydrogen peroxide in neutral electrolytes.ACS Catal. 2020; 10: 7434-7442Crossref Scopus (59) Google Scholar,55San Roman D.S. Krishnamurthy D. Garg R. Hafiz H. Lamparski M. Nuhfer N.T. Meunier V. Viswanathan V. Cohen-Karni T. Engineering three-dimensional (3D) out-of-plane graphene edge sites for highly selective two-electron oxygen reduction electrocatalysis.ACS Catal. 2020; 10: 1993-2008Crossref Scopus (57) Google Scholar and surface area,44Sun Y. Sinev I. Ju W. Bergmann A. Dresp S. Kühl S. Spöri C. Schmies H. Wang H. Bernsmeier D. et al.Efficient electrochemical hydrogen peroxide production from molecular oxygen on nitrogen-doped mesoporous carbon catalysts.ACS Catal. 2018; 8: 2844-2856Crossref Scopus (244) Google Scholar,53Pang Y. Wang K. Xie H. Sun Y. Titirici M.-M. Chai G.-L. Mesoporous carbon hollow spheres as efficient electrocatalysts for oxygen reduction to hydrogen peroxide in neutral electrolytes.ACS Catal. 2020; 10: 7434-7442Crossref Scopus (59) Google Scholar,56Chen S. Chen Z. Siahrostami S. Kim T.R. Nordlund D. Sokaras D. Nowak S. To J.W.F. Higgins D. Sinclair R. et al.Defective carbon-based materials for the electrochemical synthesis of hydrogen peroxide.ACS Sustainable Chem. Eng. 2018; 6: 311-317Crossref Scopus (178) Google Scholar are closely linked to the mass transport and the utilization of the active sites on the catalyst surfaces. Moreover, nanostructuring itself contributes to the creation of high-curvature surfaces and vacancies that generally contain abundant defect sites, such as sp3 carbons, graphitic edges,45Sa Y.J. Kim J.H. Joo S.H. Active edge-site-rich carbon nanocatalysts with enhanced electron transfer for efficient electrochemical hydrogen peroxide production.Angew. Chem. Int. Ed. Engl. 2019; 58: 1100-1105Crossref PubMed Scopus (141) Google Scholar,55San Roman D.S. Krishnamurthy D. Garg R. Hafiz H. Lamparski M. Nuhfer N.T. Meunier V. Viswanathan V. Cohen-Karni T. Engineering three-dimensional (3D) out-of-plane graphene edge sites for highly selective two-electron oxygen reduction electrocatalysis.ACS Catal. 2020; 10: 1993-2008Crossref Scopus (57) Google Scholar and other defects,46Han L. Sun Y. Li S. Cheng C. Halbig C.E. Feicht P. Hübner J.L. Strasser P. Eigler S. In-plane carbon lattice-defect regulating electrochemical oxygen reduction to hydrogen peroxide production over nitrogen-doped graphene.ACS Catal. 2019; 9: 1283-1288Crossref Scopus (144) Google Scholar,47Kim H.W. Park H. Roh J.S. Shin J.E. Lee T.H. Zhang L. Cho Y.H. Yoon H.W. Bukas V.J. Guo J. et al.Carbon defect characterization of nitrogen-doped reduced graphene oxide electrocatalysts for the two-electron oxygen reduction reaction.Chem. Mater. 2019; 31: 3967-3973Crossref Scopus (63) Google Scholar,58Hasanzadeh A. Khataee A. Zarei M. Zhang Y. Two-electron oxygen reduction on fullerene C60-carbon nanotubes covalent hybrid as a metal-free electrocatalysts.Sci. Rep. 2019; 9: 13780Crossref PubMed Scopus (22) Google Scholar which have demonstrated high activity in the 2e− ORR. Both the nature and number of active species and the structural properties of the catalyst can simultaneously govern the electrocatalytic activity in a complex manner. Model catalysts that have controlled active sites with other structural features fixed (or vice versa) are important for revealing the key factors for activity. However, it is challenging to selectively modify either the active species or structural properties because they are strongly related to each other. For example, O-doping of carbon materials can generate pores and vacancies as well as oxygen functional groups.This paper describes a systematic study conducted to identify the catalytically active oxygen functional groups in O-doped carbon materials, understand the key structural factor, and optimize the structure to maximize the activity in H2O2 electrosynthesis. For this purpose, graphitic ordered mesoporous carbon (GOMC) model catalysts were prepared with controlled oxygen functionalities, while the other structural properties were fixed. The tuned surface oxygen functional groups were analyzed using X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared (FTIR) spectroscopy, near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, electrochemical pseudo-capacitive studies, and selective blocking of oxygen functional groups. The relationship between the surface functionality and 2e− ORR activity establishes that the carboxyl and carbonyl groups are the active sites with the carboxyl group exerting higher activity. We also identified the key structural factor using a second series of model catalysts containing a similar distribution of active species with tuned density of edge carbon sites. We observed a linear relationship between the edge carbon density and H2O2 electrosynthesis activity. Through active site identification and optimization of the catalyst structure, the optimum catalyst (O-GOMC-5.5) was obtained, which exhibited a high H2O2 faradic efficiency (FE) of 99% and" @default.
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• W3198736895 date "2021-11-01" @default.
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• W3198736895 title "Designing highly active nanoporous carbon H2O2 production electrocatalysts through active site identification" @default.
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