Rational Design of Photoanodes in Portable Devices to Enhance H₂O₂ Production for Microenvironment Control

Abstract

Hydrogen peroxide (H₂O₂) is a versatile oxidant with significant applications, particularly in regulating the microenvironment for healthcare purposes. Herein, a rational design of the photoanode is implemented to enhance H₂O₂ production by oxidizing H₂O in a portable photoelectrocatalysis (PEC) device. The obtained solution from this system is demonstrated for effective bactericidal activity against Staphylococcus aureus and Escherichia coli, while maintaining low toxicity toward hippocampal neuronal cells. The photoanode is achieved by Mo-doped BiVO₄ films, which are subsequently loaded with cobalt-porphyrin (Co-py) molecules as a co-catalyst. As a result, the optimal performance for H₂O₂ production rate was achieved at 8.4 μmol h⁻¹ cm⁻², which is 1.8 times that of the pristine BiVO₄ photoanode. Density functional theory (DFT) simulations reveal that the improved performance results from a 1.1 eV reduction in the energy of the rate-determining step of •OH adsorption by the optimal photoanode. This study demonstrates a PEC approach for promoting H₂O₂ production by converting H₂O for antibacterial purposes, offering potential applications in conventionally controlling microenvironments for healthcare applications.

Keywords

antibacterial / BiVO₄ / co-catalysts / H₂O₂ production / microenvironment / photoelectrocatalysis

References

[1] Y. Y. Yu, W. Z. Quan, Y. Cao, et al., “Boosting the Singlet Oxygen Production From H₂O₂ Activation With Highly Dispersed Co–N-Graphene for Pollutant Removal,” RSC Advances 12, no. 12 (2022): 17864–17872.

[2] X. Wang, J. Jing, M. Zhou, and R. Dewil, “Recent Advances in H₂O₂-Based Advanced Oxidation Processes for Removal of Antibiotics From Wastewater,” Chinese Chemical Letters 34, no. 3 (2023): 107621.

[3] F. Nawaz, B. Khan, H. Ullah, et al., “Efficient Hydroxyl Radical Production With Sodium Salts of Surfactants Ozonation for Treatment of Organic Acid Pollutants in Wastewater,” Environmental Technology & Innovation 22, (2021): 101451.

[4] Y. Dong, X. Yang, Y. Hu, et al., “Self-Cycled Photo-Fenton-Like System Based on an Artificial Leaf With a Solar-to-H₂O₂ Conversion Efficiency of 1.46%,” Nature Communications 13, no. 1 (2022): 4982.

[5] J. Gao, H. Yang, X. Huang, et al., “Enabling Direct H₂O₂ Production in Acidic Media Through Rational Design of Transition Metal Single Atom Catalyst,” Chem 6, no. 3 (2020): 658–674.

[6] E. Zhang, Q. Zhu, J. Huang, J. Liu, G. Tan, and C. Sun, “Visually Resolving the Direct Z-Scheme Heterojunction in CdS@ZnIn₂S₄ Hollow Cubes for Photocatalytic Evolution of H₂ and H₂O₂ From Pure Water,” Applied Catalysis, B: Environmental 293, no. 15 (2021): 120213.

[7] Y. Wang, J. Zhang, et al., “Elucidating Oxygen Evolution and Reduction Mechanisms in Nitrogen-Doped Carbon-Based Photocatalysts,” Chinese Chemical Letters 36, no. 2 (2025): 110439.

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

[9] G. Gao, Y. Tian, and X. Gong, “Advances in the Production Technology of Hydrogen Peroxide,” Chinese Journal of Catalysis 41, no. 7 (2020): 1039–1047.

[10] M. Martínez and C. Barreiro, “Analysis and Validation of the Pho Regulon in the Tacrolimus-Producer Strain Streptomyces tsukubaensis: Differences With the Model Organism Streptomyces coelicolor,” Applied Microbiology and Biotechnology 102, no. 16 (2018): 7029–7045.

[11] S. Roy, R. Goel, S. Aggarwal, et al., “Proteome Analysis Revealed the Essential Functions of Protein Phosphatase PP2A in the Induction of Th9 Cells,” Scientific Reports 10, no. 1 (2020): 10992.

[12] Y. Xu, Y. Pan, Y. Wu, Y. Fang, et al., “Photoanodic H₂O₂ Synthesis and In-Situ Tetracycline Degradation Using Transition-Metal Phosphide Co-Catalysts,” Applied Catalysis, B: Environmental 331, (2023): 122701.

[13] Y. Wang, Y. Xu, X. Zhang, and R. Qian, “Integrating P-Doped Carbon Nitride Dots as Active Sites on P/Mo Co-Doped BiVO₄ Photoanodes Promotes H₂O₂ Production,” Small 21, no. 21 (2025): 2501656.

[14] K. Zhang, J. Liu, L. Wang, et al., “Near-Complete Suppression of Oxygen Evolution for Photoelectrochemical H₂O Oxidative H₂O₂ Synthesis,” Journal of the American Chemical Society 142, no. 19 (2020): 8641–8648.

[15] Y. Fang, Y. Xu, X. Li, Y. Ma, and X. Wang, “Coating Polymeric Carbon Nitride Photoanodes on Conductive Y: ZnO Nanorod Arrays for Overall Water Splitting,” Angewandte Chemie International Edition 57, no. 31 (2018): 9749–9753.

[16] M. A. Gaikwad, U. P. Suryawanshi, U. V. Ghorpade, J. S. Jang, M. P. Suryawanshi, and J. H. Kim, “Emerging Surface, Bulk, and Interface Engineering Strategies on BiVO₄ for Photoelectrochemical Water Splitting,” Small 18, no. 10 (2022): 2105084.

[17] J. Prakash, D. Nechiyil, K. Ali, et al., “Band Gap and Defect Engineering of Bismuth Vanadate Using La, Ce, Zr Dopants to Obtain a Photoelectrochemical System for Ultra-Sensitive Detection of Glucose in Blood Serum,” Dalton Transactions 52, no. 7 (2023): 1989–2001.

[18] A. Massaro, A. Pecoraro, et al., “Oxygen Evolution Reaction at the Mo/W-Doped Bismuth Vanadate Surface: Assessing the Dopant Role by DFT Calculations,” Molecular Catalysis 517, (2022): 112036.

[19] K. P. Parmar, H. J. Kang, A. Bist, P. Dua, J. S. Jang, and J. S. Lee, “Photocatalytic and Photoelectrochemical Water Oxidation Over Metal-Doped Monoclinic BiVO₄ Photoanodes,” Chemsuschem 5, no. 10 (2012): 1926–1934.

[20] T. W. Kim, K. S. Choi, et al., “Nanoporous BiVO₄ Photoanodes With Dual-Layer Oxygen Evolution Catalysts for Solar Water Splitting,” Science 343, no. 6174 (2014): 990–994.

[21] S. Wang, T. He, J. Yun, et al., “New Iron-Cobalt Oxide Catalysts Promoting BiVO₄ Films for Photoelectrochemical Water Splitting,” Advanced Functional Materials 28, no. 34 (2018): 1802685.

[22] J. A. Seabold, K. S. Choi, et al., “Efficient and Stable Photo-Oxidation of Water by a Bismuth Vanadate Photoanode Coupled With an Iron Oxyhydroxide Oxygen Evolution Catalyst,” Journal of the American Chemical Society 134, no. 4 (2012): 2186–2192.

[23] T. Vo, Y. Tai, C. Chiang, et al., “Novel Hierarchical Ferric Phosphate/Bismuth Vanadate Nanocactus for Highly Efficient and Stable Solar Water Splitting,” Applied Catalysis, B: Environmental 243 (2019): 657–666.

[24] M. Rohloff, B. Anke, S. Zhang, et al., “Mo-Doped BiVO₄ Thin Films—High Photoelectrochemical Water Splitting Performance Achieved by a Tailored Structure and Morphology,” Sustainable Energy & Fuels 1, no. 8 (2017): 1830–1846.

[25] Y. Wang, Y. Fang, Y. Wang, et al., “Plasma-Enhanced Chemical-Vapor-Deposition Synthesis of Photoredox-Active Nitrogen-Doped Carbon From NH₃ and CH₄ Gases,” Angewandte Chemie International Edition 62, no. 33 (2023): e202307236.

[26] Y. Wang, H. Wang, et al., “Carbon- and Nitrogen-Based Complexes as Photocatalysts for Prebiotic and Oxygen Chemistry During Earth Evolution,” Angewandte Chemie International Edition 63, no. 51 (2024): e202413768.

[27] M. Yu, M. Tang, Y. Liao, et al., “Defect-Designed Mo-Doped BiVO₄ Photoanode for Efficient Photoelectrochemical Degradation of Phenol,” Journal of Materials Science & Technology 165 (2023): 225–234.

[28] L. Yang, H. Chen, Y. Xu, et al., “Synergetic Effects by Co²⁺ and PO₄^3- on Mo-Doped BiVO₄ for an Improved Photoanodic H₂O₂ Evolution,” Chemical Engineering Science 251 (2022): 117435.

[29] H. Wu, T. Miao, Q. Deng, et al., “Accelerating Nickel-Based Molecular Construction via DFT Guidance for Advanced Photocatalytic Hydrogen Production,” ACS Applied Materials & Interfaces 14, no. 15 (2022): 17486–17499.

[30] M. Sudi, L. Zhao, Q. Wang, et al., “Efficient Photoelectrochemical Water Splitting of Metal-Porphyrin Decorated on BiVO₄ Photoanode,” Applied Surface Science 606, (2022): 154753.

[31] X. Yin, W. Qiu, W. Li, et al., “High Porosity Mo Doped BiVO₄ Film by Vanadium Re-Substitution for Efficient Photoelectrochemical Water Splitting,” Chemical Engineering Journal 389, no. 1 (2020): 124365.

[32] H. Wu, Y. Wang, M. Huang, et al., “Alkene Epoxidation With Water by Confined Active Co Sites on BiVO₄ Photoanodes Under Visible Light,” Angewandte Chemie International Edition 64, no. 7 (2024): e202420188.

[33] Z. Yuan, B. Sun, Q. Hong, X. Ai, et al., “Rhodium Metallene With Wrinkle-Induced Lattice Strain for Acetonitrile Electroreduction Related Energy Conversion,” Carbon Energy 7, no. 6 (2025): e70020.

[34] Y. Wang, D. Chen, J. Zhang, et al., “Charge Relays via Dual Carbon-Actions on Nanostructured BiVO₄ for High Performance Photoelectrochemical Water Splitting,” Advanced Functional Materials 32, no. 13 (2022): 2112738.

[35] X. Li, X. Chen, Y. Fang, et al., “High-Performance Potassium Poly(Heptazine Imide) Films for Photoelectrochemical Water Splitting,” Chemical Science 13, no. 25 (2022): 7541–7551.

[36] Y. Fang, X. Li, X. Wang, et al., “Synthesis of Polymeric Carbon Nitride Films With Adhesive Interfaces for Solar Water Splitting Devices,” ACS Catalysis 8, no. 9 (2018): 8774–8780.

[37] H. Wu, T. Miao, Q. Deng, et al., “Unraveling Electron Structure and Reaction Mechanisms of Functionalized Nickel-Based Complexes for Efficient Hydrogen Evolution,” Journal of Physical Chemistry C 126, no. 4 (2022): 1857–1871.

[38] X. Xiao, H. Wang, X. Wang, et al., “Boosting Lignin-Based Photocatalyst With Photocorrosion Resistance for Efficient H₂O₂ Production via Hetero-Interfacial π-π Stacking Channels,” Carbon Energy 7, no. 4 (2025): e666.

[39] L. Liu, M. Ruan, C. Wang, et al., “Optimization of the BiO₈ Polar Group of BiVO₄ by Cl⁻-Embedded Modification to Manipulate Bulk-Surface Carrier Separation for Achieving Efficient Piezo-PEC Water Oxidation,” Applied Catalysis, B: Environmental 354, no. 5 (2024): 124117.

[40] Y. Lu, Y. Yang, X. Fan, et al., “Boosting Charge Transport in BiVO₄ Photoanode for Solar Water Oxidation,” Advanced Materials 34, no. 8 (2022): 2108178.

[41] T. W. Kim, K. S. Choi, et al., “Nanoporous BiVO₄ Photoanodes With Dual-Layer Oxygen Evolution Catalysts for Solar Water Splitting,” Science 343, no. 6174 (2014): 990–994.

[42] J. Seabold, K. Zhu, N. Neale, et al., “Efficient Solar Photoelectrolysis by Nanoporous Mo:BiVO₄ Through Controlled Electron Transport,” Physical Chemistry Chemical Physics 16, no. 3 (2014): 1121–1131.

[43] Z. A. Lan, Y. Fang, Y. Zhang, and X. Wang, “Photocatalytic Oxygen Evolution From Functional Triazine-Based Polymers With Tunable Band Structures,” Angewandte Chemie International Edition 57, no. 2 (2018): 470–474.

[44] X. Li, Y. Wu, S. Zhang, et al., “CsPbX₃ Quantum Dots for Lighting and Displays: Room-Temperature Synthesis, Photoluminescence Superiorities, Underlying Origins and White Light-Emitting Diodes,” Advanced Function Materials 26, no. 15 (2016): 2435–2445.

[45] X. Gu, T. Chen, J. Lei, et al., “Self-Assembly Synthesis of S-Scheme G-C₃N₄/Bi₈(CrO₄)O₁₁ for Photocatalytic Degradation of Norfloxacin and Bisphenol A,” Chinese Journal of Catalysis 42, no. 10 (2022): 2569–2580.

[46] L. Xiao, C. Zhi, S. Xu, G. Liu, et al., “Bromide-Mediated Photoelectrochemical Epoxidation of Alkenes Using Water as an Oxygen Source With Conversion Efficiency and Selectivity up to 100%,” Journal of the American Chemical Society 144, no. 43 (2022): 19770–19777.

[47] W. Melitz, J. Shen, A. Kummel, S. Lee, et al., “Kelvin Probe Force Microscopy and Its Application,” Surface Science Reports 66, no. 1 (2011): 1–27.

[48] Q. Deng, Y. Yang, C. Mao, et al., “Electronic State Modulation and Reaction Pathway Regulation on Necklace-Like MnO_x-CeO₂@Polypyrrole Hierarchical Cathode for Advanced and Flexible Li–CO₂ Batteries,” Advanced Energy Materials 12, no. 14 (2022): 2103667.

[49] Y. Wang, C. Zhou, Z. Li, et al., “Injectable Immunoregulatory Hydrogels Sequentially Drive Phenotypic Polarization of Macrophages for Infected Wound Healing,” Bioactive Materials 41, no. 41 (2024): 193–206.

[50] S. Yan, Q. Ma, C. Wen, et al., “Enhanced Biological Behavior and Photothermal Antibacterial Performance of TiNbCT_x MXene Modified Mesoporous Bioactive Glass Nanocomposites,” Advanced Energy Materials 35, no. 24 (2025): 2419993.

[51] S. Xiong, X. Ding, L. Zhou, et al., “An Antibacterial and Antioxidant Rosmarinic Acid Hydrogel Normalizes Macrophage Polarization to Expedite Diabetic Wound Healing,” Journal of Colloid and Interface Science 683, no. 2 (2025): 357–371.

[52] Z. Hu, M. Li, Y. Pang, et al., “2D g-C₃N₄/Sodium Alginate-Chitosan Photocatalytic Hydrogel Coating With Electron-Rich Microenvironment Remarkably Enhances Synergistic Antibacterial and Anticorrosive Action,” Separation and Purification Technology 366 (2025): 132692.

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