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Received December 19, 2025
Revised January 14, 2026
Accepted January 15, 2026
Available online January 27, 2026
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Direct Synthesis of Hydrogen Peroxide over Pd Catalysts Supported on Glucose-derived N-doped Carbons: Effect of Nitrogen Doping on Catalytic Activity
Kunsan National University
ohseungyeol@kunsan.ac.kr, ymchung@kunsan.ac.kr
Korean Chemical Engineering Research, February 2026, 64(1), 105152
https://doi.org/10.9713/kcer.2026.64.1.105152
https://doi.org/10.9713/kcer.2026.64.1.105152
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Abstract
Nitrogen-doped porous carbons (CNx) were
prepared from glucose-derived hydrochar via hydrothermal treatment followed by
chemical activation with melamine, and then used as supports for Pd catalysts
(Pd/CNx, where x denotes the N content in wt%) for the direct
synthesis of H2O2 from H2 and O2
(DSHP). Optimal N doping played an important role in increasing the surface
area and the density of pyridinic/pyrrolic sites in CNx, thereby
improving Pd dispersion and reducing the mean Pd nanoparticle size. Among the
Pd/CNx catalysts tested, Pd/CN0.8 exhibited the best
performance, achieving 91% H2O2 selectivity and a
productivity of 7056 mmol H2O2/g-Pd·h at 39% H2 conversion. In
contrast, Pd/CN1.4 and Pd/CN8.5 showed sharply decreased
H2O2 selectivity and productivity due to accelerated H2O2
hydrogenation and decomposition over these catalysts. These results clearly
demonstrate the importance of an optimal N-doping level for achieving high H2O2
selectivity and productivity in the DSHP reaction over Pd/CNx catalysts.
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31. Lee, H., Kim, S., Lee, D. W. and Lee, K. Y., “Direct synthesis of Hydrogen Peroxide from Hydrogen and Oxygen over a Pd Core– silica Shell Catalyst,” Catal. Commun., 12, 968-971(2011).
32. Vu, H. T. T., Vo, V. L. N. and Chung, Y. M., “Geometric, Electronic, and Synergistic Effect in the Sulfonated Carbon-supported Pd Catalysts for the Direct Synthesis of Hydrogen Peroxide,” Appl. Catal. A: Gen., 607, 117867(2020).
2. Yi, Y., Wang, L., Li, G. and Guo, H., “A Review on Research Prog- ress in the Direct Synthesis of Hydrogen Peroxide From Hydrogen and Oxygen: Noble-metal Catalytic Method, Fuel-cell Method and Plasma Method,” Catal. Sci. Technol., 6, 1593-1610(2016).
3. Samanta, C., “Direct Synthesis of Hydrogen Peroxide From Hydro- gen and Oxygen: An Overview of Recent Developments in the Process,” Appl. Catal. A: Gen., 350, 133-149(2008).
4. Dittmeyer, R., Grunwaldt, J. D. and Pashkova, A., “A Review of Catalyst Performance and Novel Reaction Engineering Concepts in Direct Synthesis of Hydrogen Peroxide,” Catal. Today, 248, 149- 159(2015).
5. Chen, L., Medlin, J. W. and Grönbeck, H., “On the Reaction Mechanism of Direct H2O2 Formation over Pd Catalysts,” ACS Catal., 11, 2735-2745(2021).
6. Lee, S., Jeong, H. and Chung, Y.-M., “Direct Synthesis of Hydro- gen Peroxide over Pd/C Catalyst Prepared by Selective Adsorp- tion Deposition Method,” J. Catal., 365, 125-137(2018).
7. Lunsford, J. H., “The Direct Formation of H2O2 from H2 and O2 over Palladium Catalysts,” J. Catal., 216, 455-460(2003).
8. Dissanayake, D. P. and Lunsford, J. H., “Evidence for the Role of Colloidal Palladium in the Catalytic Formation of H2O2 from H2 and O2,” J. Catal., 206, 173-176(2002).
9. Choudhary, V. R., Samanta, C. and Choudhary, T. V., “Direct Oxi- dation of H2 to H2O2 over Pd-based Catalysts: Influence of Oxi- dation State, Support and Metal Additives,” Appl. Catal. A: Gen., 308, 128-133(2006).
10. Choudhary, V. R., Samanta, C. and Choudhary, T. V., “Factors Influencing Decomposition of H2O2 over Supported Pd Catalyst in Aqueous Medium,” J. Mol. Catal. A: Chem., 260, 115-120(2006).
11. Choudhary, V. R., Samanta, C. and Jana, P., “Formation from Direct Oxidation of H2 and Destruction by Decomposition/hydrogenation of H2O2 over Pd/C Catalyst in Aqueous Medium Containing Differ- ent Acids and Halide Anions,” Appl. Catal. A: Gen., 317, 234- 243(2007).
12. Choudhary, V. R., Samanta, C. and Gaikwad, A. G., “Drastic Increase of Selectivity for H2O2 Formation in Direct Oxidation of H2 to H2O2 over Supported Pd Catalysts Due to Their Bromination,” Chem. Commun., 2054-2055(2004).
13. Lewis, R. J., Edwards, J. K., Freakley, S. J. and Hutchings, G. J., “Solid Acid Additives as Recoverable Promoters for the Direct Synthesis of Hydrogen Peroxide,” Ind. Eng. Chem. Res., 56, 13287- 13293(2017).
14. Auer, E., Freund, A., Pietsch, J. and Tacke, T., “Carbons as Supports for Industrial Precious Metal Catalysts,” Appl. Catal. A: Gen., 173, 259-271(1998).
15. Edwards, J. K., Solsona, B., Carley, A. F., Herzing, A. A., Kiely, C. J. and Hutchings, G. J., “Switching off Hydrogen Peroxide Hydrogenation in the Direct Synthesis Process,” Science, 323, 1037-1041(2009).
16. Freakley, S. J., He, Q., Harrhy, J. H., Lu, L., Morgan, D. J. et al., “Palladium-tin Catalysts for the Direct Synthesis of H2O2 with High Selectivity,” Science, 351, 961-965(2016).
17. Tian, P., Xu, X., Ao, C., Ding, D., Li, W. et al., “Direct and Selective Synthesis of Hydrogen Peroxide over Palladium–tellurium Cata- lysts at Ambient Pressure,” ChemSusChem, 10, 3342-3346(2017).
18. Arrigo, R., Schuster, M. E., Abate, S., Giorgianni, G. et al., “Pd Supported on Carbon Nitride Boosts the Direct Hydrogen Per- oxide Synthesis,” ACS Catal., 6, 6959-6966(2016).
19. Arrigo, R., Schuster, M. E., Abate, S., Wrabetz, S. et al., “Dynam- ics of Palladium on Nanocarbon in the Direct Synthesis of H2O2,” ChemSusChem, 7, 179-194(2014).
20. Ye, Y., Chun, J., Park, S., Kim, T. J., Chung, Y. M., Oh, S. H., Song, I. K. and Lee, J., “A Study of the Palladium Size Effect on the Direct Synthesis of Hydrogen Peroxide from Hydrogen and Oxygen Using Highly Uniform Palladium Nanoparticles Supported on Carbon,” Korean J. Chem. Eng., 29, 1115-1118(2012).
21. Edwards, J. K., Freakley, S. J., Lewis, R. J., Pritchard, J. C. and Hutchings, G. J., “Advances in the Direct Synthesis of Hydrogen Peroxide from Hydrogen and Oxygen,” Catal. Today, 248, 3-9 (2015).
22. Sun, M., Zhang, J., Zhang, Q., Wang, Y. and Wan, H., “Polyox- ometalate-supported Pd Nanoparticles as Efficient Catalysts for the Direct Synthesis of Hydrogen Peroxide in the Absence of Acid or Halide Promoters,” Chem. Commun., 5174-5176(2009).
23. Jiang, D., Shi, Y., Zhou, L. and Ma, J., “Promotional Effect of Nitro- gen-doped and Pore Structure for the Direct Synthesis of Hydrogen Peroxide from Hydrogen and Oxygen by Pd/C Catalyst at Ambi- ent Pressure,” Arab. J. Chem., 16, 104452(2023).
24. Biasi, P., Sterchele, S., Bizzotto, F., Manzoli, M., Lindholm, S., Ek, P., Bobacka, J., Mikkola, J. P. and Salmi, T., “Application of the Catalyst Wet Pretreatment Method (CWPM) for Catalytic Direct Synthesis of H2O2,” Catal. Today, 246, 207-215(2015).
25. Zhang, Y., Pan, H., Murugananthan, M. and Sun, P., “Glucose and Melamine Derived Nitrogen-doped Carbonaceous Catalyst for Nonradical Peroxymonosulfate Activation,” Carbon, 156, 399- 409(2020).
26. Seredych, M., Biggs, M. J. and Bandosz, T. J., “Oxygen Reduc- tion on Chemically Heterogeneous Iron-containing Nanoporous Carbon: The Effects of Specific Surface Functionalities,” Micro- porous Mesoporous Mater., 221, 137-149(2015).
27. Zborowski, K. K. and Poater, J., “Pyrrole and Pyridine in the Water Environment: Effect of Discrete and Continuum Solvation Mod- els,” ACS Omega, 6, 24693-24699(2021).
28. Fuertes, A. B., Ferrero, G. A., Diez, N. and Sevilla, M., “A Green Route to High-surface-area Carbons by Chemical Activation of Biomass-based Products with Sodium Thiosulfate,” ACS Sustain. Chem. Eng., 6, 16323-16331(2018).
29. Sevilla, M., Díez, N. and Fuertes, A. B., “More Sustainable Chemical Activation Strategies for the Production of Porous Carbons,” ChemSusChem, 14, 94-117(2021).
30. Titirici, M. M. and Antonietti, M., “Chemistry and Materials Options of Sustainable Carbon Materials Made by Hydrothermal Car- bonization,” Chem. Soc. Rev., 39, 103-116(2010).
31. Lee, H., Kim, S., Lee, D. W. and Lee, K. Y., “Direct synthesis of Hydrogen Peroxide from Hydrogen and Oxygen over a Pd Core– silica Shell Catalyst,” Catal. Commun., 12, 968-971(2011).
32. Vu, H. T. T., Vo, V. L. N. and Chung, Y. M., “Geometric, Electronic, and Synergistic Effect in the Sulfonated Carbon-supported Pd Catalysts for the Direct Synthesis of Hydrogen Peroxide,” Appl. Catal. A: Gen., 607, 117867(2020).
