High Electron Affinity as a Determinant of Oxidizing Strength in Layered Birnessite
Keywords:
birnessite, electron affinity, oxidation rate, manganese oxide, surface change, environmental catalysis, density functional theoryAbstract
Birnessite, a layered manganese oxide, has strong oxidation ability, but the main factor that controls this activity is still unclear. In this study, twelve natural and synthetic birnessite samples with different interlayer cations and Mn (III)/Mn (IV) ratios were prepared to examine how electron affinity affects oxidation. The electron affinity measured by ultraviolet photoelectron spectroscopy ranged from 5.6 to 6.1 eV and changed with interlayer composition. Oxidation tests using Fe (II) and As (III) followed first-order kinetics, with rate constants between 0.013 and 0.072 min⁻¹ for Fe (II) and between 0.006 and 0.041 min⁻¹ for As (III). A clear linear relation (R² > 0.85) was found between electron affinity and oxidation rate, showing that higher electron affinity increases oxidation ability. X-ray photoelectron spectroscopy showed that part of Mn (IV) was reduced to Mn (II) and that surface hydroxyl groups increased after reaction, indicating surface changes that reduced activity over time. Density functional theory calculations supported these results by linking conduction-band position with electron affinity. The findings show that electron affinity is a useful parameter for predicting the oxidation behavior of birnessite and can help in developing manganese oxide catalysts for environmental oxidation and pollutant control.References
X. Sun, K. Meng, W. Wang, and Q. Wang, "Drone assisted freight transport in highway logistics coordinated scheduling and route planning," In 2025 4th International Symposium on Computer Applications and Information Technology (ISCAIT), March, 2025, pp. 1254-1257. doi: 10.1109/iscait64916.2025.11010302
K. Xu, Y. Lu, S. Hou, K. Liu, Y. Du, M. Huang, and X. Sun, "Detecting anomalous anatomic regions in spatial transcriptomics with STANDS," Nature Communications, vol. 15, no. 1, p. 8223, 2024. doi: 10.1038/s41467-024-52445-9
A. H. Abdelmohsen, S. A. El‐khodary, N. Ismail, Z. Song, and J. Lian, "Basics and advances of manganese‐based cathode materials for aqueous zinc‐ion batteries," Chemistry-A European Journal, vol. 31, no. 4, p. e202403425, 2025.
Q. Li, R. Pokharel, L. Zhou, M. Pasturel, and K. Hanna, "Coupled effects of Mn (II), pH and anionic ligands on the reactivity of nanostructured birnessite," Environmental Science: Nano, vol. 7, no. 12, pp. 4022-4031, 2020.
F. Chen, S. Li, H. Liang, P. Xu, and L. Yue, "Optimization study of thermal management of domestic SiC power semiconductor based on improved genetic algorithm," 2025. doi: 10.20944/preprints202505.2288.v1
M. M. Najafpour, G. Renger, M. Hołynska, A. N. Moghaddam, E. M. Aro, R. Carpentier, and S. I. Allakhverdiev, "Manganese compounds as water-oxidizing catalysts: From the natural water-oxidizing complex to nanosized manganese oxide structures," Chemical Reviews, vol. 116, no. 5, pp. 2886-2936, 2016.
H. Peng, N. Dong, Y. Liao, Y. Tang, and X. Hu, "Real-time turbidity monitoring using machine learning and environmental parameter integration for scalable water quality management," Journal of Theory and Practice in Engineering and Technology, vol. 1, no. 4, pp. 29-36, 2024. doi: 10.22541/essoar.175674608.88310773/v1
J. W. Ondersma, and T. W. Hamann, "Conduction band energy determination by variable temperature spectroelectrochemistry," Energy & Environmental Science, vol. 5, no. 11, pp. 9476-9480, 2012.
K. Xu, X. Xu, H. Wu, and R. Sun, "Venturi aeration systems design and performance evaluation in high density aquaculture," 2024. doi: 10.53469/wjimt.2024.07(06).16
M. F. Fink, M. Weiss, R. Marschall, and C. Roth, "Experimental correlation of Mn 3+ cation defects and electrocatalytic activity of α-MnO 2-an X-ray photoelectron spectroscopy study," Journal of Materials Chemistry A, vol. 10, no. 29, pp. 15811-15838, 2022.
C. Wang, N. Smieszek, and V. Chakrapani, "Unusually high electron affinity enables the high oxidizing power of layered birnessite," Chemistry of Materials, vol. 33, no. 19, pp. 7805-7817, 2021. doi: 10.1021/acs.chemmater.1c02234
S. Roy, and S. Roy, "Metal oxides for the oxygen evolution reaction: Tailoring electronic properties through structural modifications," Dalton Transactions, vol. 54, no. 34, pp. 12737-12748, 2025. doi: 10.1039/d5dt01174d
B. Wang, G. E. N. G. Linna, and V. W. Tam, "Effective carbon responsibility allocation in construction supply chain under the carbon trading policy," Energy, vol. 319, p. 135059, 2025.
M. Gómez, M. D. Murcia, E. Gómez, S. Ortega, A. Sánchez, O. Thaikovskaya, and N. Briantceva, "Modelling and experimental checking of the influence of substrate concentration on the first order kinetic constant in photo-processes," Journal of Environmental Management, vol. 183, pp. 818-825, 2016.
S. Sun, Y. Zhang, X. Shi, W. Sun, C. Felser, W. Li, and G. Li, "From charge to spin: An in‐depth exploration of electron transfer in energy electrocatalysis," Advanced Materials, vol. 36, no. 37, p. 2312524, 2024. doi: 10.1002/adma.202312524
J. Y. Park, L. R. Baker, and G. A. Somorjai, "Role of hot electrons and metal-oxide interfaces in surface chemistry and catalytic reactions," Chemical Reviews, vol. 115, no. 8, pp. 2781-2817, 2015. doi: 10.1021/cr400311p
W. Sun, “Integration of Market-Oriented Development Models and Marketing Strategies in Real Estate,” European Journal of Business, Economics & Management, vol. 1, no. 3, pp. 45–52, 2025
C. Spöri, J. T. H. Kwan, A. Bonakdarpour, D. P. Wilkinson, and P. Strasser, "The stability challenges of oxygen evolving catalysts: Towards a common fundamental understanding and mitigation of catalyst degradation," Angewandte Chemie International Edition, vol. 56, no. 22, pp. 5994-6021, 2017. doi: 10.1002/anie.201608601
S. Yuan, “Data Flow Mechanisms and Model Applications in Intelligent Business Operation Platforms”, Financial Economics Insights, vol. 2, no. 1, pp. 144–151, 2025, doi: 10.70088/m66tbm53.
K. Xu, X. Xu, H. Wu, R. Sun, and Y. Hong, "Ozonation and filtration system for sustainable treatment of aquaculture wastewater in Taizhou City," Innovations in Applied Engineering and Technology, pp. 1-7, 2023.
G. Wang, “Performance evaluation and optimization of photovoltaic systems in urban environments,” Int. J. New Dev. Eng. Soc., vol. 9, pp. 42–49, 2025, doi: 10.25236/IJNDES.2025.090106.
Y. He, S. Liu, C. Priest, Q. Shi, and G. Wu, "Atomically dispersed metal-nitrogen-carbon catalysts for fuel cells: Advances in catalyst design, electrode performance, and durability improvement," Chemical Society Reviews, vol. 49, no. 11, pp. 3484-3524, 2020. doi: 10.1039/c9cs00903e
