COMPUTATIONAL AND WATER ELECTROLYSIS STUDY OF 5,10,15,20-TETRAKIS(3-HYDROXYPHENYL)-PORPHYRIN
DOI:
https://doi.org/10.24193/subbchem.2026.2.11Keywords:
quantum chemical calculations, electrocatalyst, aggregate, water-splitting, oxygen evolution reaction, correlation analysisAbstract
The free-base, symmetrically substituted 5,10,15,20-tetrakis(3-hydroxyphenyl)-porphyrin was the subject of a study combining computational and experimental analysis, with an emphasis on the molecule’s water-splitting electrocatalytic characteristics. Ab initio and DFT methods were used to investigate the porphyrin’s structural and electronic properties. The water-splitting experiments, performed in solutions with different pH values, were carried out with porphyrin-based electrodes that were modified using different strategies. The electrode manufactured by drop-casting a catalyst ink containing the porphyrin and carbon black on a graphite substrate displayed an overpotential value for the oxygen evolution reaction of 0.595 V vs. RHE and a Tafel slope of 0.337 V/dec in a neutral environment. Data acquired during the electrochemical experiments were used to perform statistical analysis. The correlation analysis indicated a significant association between pH and overpotential. The combined study improves the current scientific understanding of the porphyrin’s properties and shows the effect of the electrode modification strategies on its water-splitting electrocatalytic activity.
The Supplementary Material file can be downloaded at: https://doi.org/10.5281/zenodo.20571954
References
1. A. Dev; V. Kumar; A. S. L. V. Tummala; V. K. Verma; R. Gajjar; A. K. Chaudhary; G. Sarvaiya; B. Parmar; Discov. Appl. Sci., 2025, 7, 1336.
2. I. Ali; G. Imanova; O. M. L. Alharbi; A. M. Hameed; M. N. Siddiqui; J. Umm Al-Qura Univ. Appl. Sci., 2023, 10, 567-578.
3. H. A. Dhahri; M. Hussain; M. A. A. Ghani; A. Inayat; A. H. Al-Muhtaseb; L. Al-Haj; F. Jamil; Renew. Sust. Energ. Rev., 2026, 229, 116617.
4. K.-H. Lin; K.-H. Lee; A. Mukundan; R. Karmakar; E. Rahmawati; K. N. Abdullah; C.-C. Wang; H.-C. Wang; Energy Rep., 2025, 14, 5112-5127.
5. Y. Wu; P. Chen; Green Chem., 2026, 28, 3043-3072.
6. J. Guo; Y. Haghshenas; Y. Jiao; P. Kumar; B. I. Yakobson; A. Roy; Y. Jiao; K. Regenauer-Lieb; D. Nguyen; Z. Xia; Adv. Mater., 2024, 36, 2407102.
7. E. Fagadar-Cosma; D. Vlascici; G. Fagadar-Cosma; Porfirinele de la Sinteză la Aplicații; Eurostampa, Timisoara, Romania, 2008, pp. 10-94.
8. M. Birdeanu; E. Fagadar-Cosma; The self-assembly of porphyrin derivatives into 2D and 3D architectures, in Quantum nanosystems: Structure, properties and interactions, M.V. Putz, Ed.; Apple Academic Press, Toronto, Canada, 2014, Chapter 5, pp. 173-206.
9. N. Ocuane; Y. Ge; C. Sandocal-Pauker; D. Villagran; Dalton T., 2024, 53, 2306-2317.
10. I. A. Lane; R. Kumar; Inorg. Chim. Acta, 2025, 576, 122453.
11. N. Wang; Y. Wang; X. Liu; J. Liu; C. Guo; X. Deng; J. Liang; M. Cao; N. Wang; Int. J. Hydrogen Energ., 2025, 177, 151412.
12. E. Fagadar-Cosma; L. Cseh; V. Badea; G. Fagadar-Cosma; D. Vlascici; Comb. Chem. High T. Scr., 2007, 10, 466-472.
13. D. Vlascici; E. F. Cosma; E. M. Pica; V. Cosma; O. Bizerea; G. Mihailescu; L. Olenic; Sensors, 2008, 8, 4995-5004.
14. C. Cretu; C. Bucovicean; I. Armeanu; A. M. Lacrama; E. Fagadar-Cosma; Rev. Chim.-Bucharest, 2008, 59, 979-981.
15. E. Fagadar-Cosma; M. C. Mirica; I. Balcu; C. Bucovicean; C. Cretu; I. Armeanu; G. Fagadar-Cosma; Molecules, 2009, 14, 1370-1388.
16. L. Salageanu; D. Muntean; M. Licker; A. Lascu; D. Anghel; E. Fagadar-Cosma; Farmacia, 2020, 68, 288-298.
17. J. Wang; J. Phys.: Conf. Ser., 2025, 3008, 012058.
18. T. T. Tran; M. R. Gan; Y. P. Tzeng; H. Shaw; T. K. Hoang; M. Y. Kuo; Y. O. Su; J. Electroanal. Chem., 2018, 815, 40-46.
19. M. Hasnain; S. Urrehman; A. Yousuf; M. A. Ali; T. Fatima; S. Bibi; F. Q. Bai; Chem. Pap., 2025, 79, 6809-6824.
20. C. B. Yildiz; Z. O. Sagir; T. Kilic; A. Azizoglu; Studia UBB Chemia, 2014, 59, 17-32.
21. S. Dhifaoui; A. Azaid; M. Bourass; L. Ben Haj Hassen; H. Nasri; M. Bouachrine; Phys. Chem. Res., 2021, 9, 701-713.
22. M. Karabacak; E. Yilan; Spectrochim. Acta A Mol. Biomol. Spectrosc., 2012, 87, 273-285.
23. M. T. M. Koper; Chem. Sci., 2013, 4, 2710–2723.
24. S. Liu; Z. Wang; S. Qiu; F. Deng; Carbon Lett., 2024, 34, 1269-1286.
25. B. O. Taranu; M. G. Ivanovici; P. Svera; P. Vlazan; P. Sfirloaga; M. Poienar; J. Alloy. Compd., 2020, 848, 156595.
26. M. Poienar; P. Svera; B.-O. Taranu; C. Ianasi; P. Sfirloaga; G. Buse; P. Veber; P. Vlazan; Crystals, 2022, 12, 1803.
27. P. W. Menezes; C. Panda; S. Loos; F. Bunschei-Bruns; C. Walter; M. Schwarze; X. Deng; H. Dau; M. Driess; Energy Environ. Sci., 2018, 11, 1287-1298.
28. B. O. Taranu; E. Fagadar-Cosma; Processes, 2022, 10, 611.
29. S. Seo; K. Lee; M. Min; Y. Cho; M. Kim; H. Lee; Nanoscale, 2017, 9, 3969-3979.
30. W. Zhang; W. Lai; R. Cao; Chem. Rev., 2017, 117, 3717-3797.
31. Z. Zhou; W. Q. Zaman; W. Sun; L. M. Cao; M. Tariq; J. Yang; Chem. Commun., 2018, 54, 4959-4962.
32. Y. Xu; C. Wang; Y. Huang; J. Fu; Nano Energ., 2021, 80, 105545.
33. G. Cai; L. Zeng; L. He; S. Sun; Y. Tong; J. Zhang; Chem-Asian J., 2020, 15, 1963-1969.
34. I. B. Alvarez; Y. Wu, J. Sanchez; Y. Ge; M. V. Ramos-Garces; T. Chu; T. F. Jaramillo; J. L. Colon; D. Villagran; Sustain. Energy Fuels, 2021, 5, 430-437.
35. H. Lei; Q. Zhang; Y. Wang; Y. Gao; Y. Wang; Z. Liang; W. Zhang; R. Cao; Dalton T., 2021, 50, 5120-5123.
36. H. Lv; H. Guo; K. Guo; H. Lei; W. Zhang; H. Zheng; Z. Liang; R. Cao; Chinese Chem. Lett., 2021, 32, 2841-2845.
37. A. Wang; L. Cheng; W. Zhao; X. Shen; W. Zhu; J. Colloid Interf. Sci., 2020, 579, 598-606.
38. D.-J. Li; Z.-G. Gu; W. Zhang; Y. Kang; J. Zhang; J. Mater. Chem. A, 2017, 5, 20126-20130.
39. S. Bhunia; K. Bhunia; B. C. Patra; S. K. Das; D. Pradhan; A. Bhaumik; A. Pradhan; S. Bhattacharya, ACS Appl. Mater. Inter., 2019, 11, 1520-1528.
40. J. Sun; H. Yin; P. Liu; Y. Wang; X. Yao; Z. Tang; H. Zhao; Chem. Sci., 2016, 7, 5640-5646.
41. H. Jia; Y. Yao; Y. Gao; D. Lu; P. Du; Chem. Commun., 2016, 52, 13483-13486.
42. H. Jia; Z. Sun; D. Jiang; P. Du; Chem. Mater., 2015, 27, 4586-4593.
43. B.-O. Taranu, E. Fagadar-Cosma, Nanomaterials, 2022, 12, 3788.
44. Y. Ge, Z. Lyu, M. Marcos-Hernandez, D. Villagran, Chem. Sci., 2022, 13 8597.
45. B.-O. Taranu, F. S. Rus, E. Fagadar-Cosma, Coatings, 2024, 14, 1048.
46. I. Fratilescu; A. Lascu; B. O. Taranu; C. Epuran; M. Birdeanu; A.-M. Macsim; E. Tanasa; E. Vasile; E. Fagadar-Cosma; Nanomaterials, 2022, 12, 1930.
47. C. Placke-Yan; G. Bendt; S. Salamon; J. Landers; H. Wende; U. Hagemann; S. Schulz; Mater. Adv., 2024, 5, 3482–3489.
48. R. Gao; Q. Dai; F. Du; D. Yan; L. Dai; J. Am. Chem. Soc., 2019, 141, 11658-11666.
49. A. Ghosh; M. Mondal; R. N. Manna; A. Bhaumik; J. Colloid Interface Sci., 2024, 658, 415-424.
50. Z. Liu; Z. Zhao; Y. Wang; S. Dou; D. Yan; D. Liu; Z. Xia; S. Wang; Adv. Mater., 2017, 29, 1606207.
51. Z. Gao; L. L. Gong; X. Q. He; X. M. Su; L. H. Xiao; F. Luo; Inorg. Chem., 2020, 59, 4995–5003.
52. Y. Zheng; H. Song; S. Chen; X. Yu; J. Zhu; J. Xu; K. A. I. Zhang; C. Zhang; T. Liu; Small, 2020, 16, 2004342.
53. J. Jiang; C. Zhang; L. Ai; Electrochim. Acta, 2016, 208, 17–24.
54. R. R. Katzbaer; F. M. S. Vieira; I. Dabo; Z. Mao; R. E. Schaak; J. Am. Chem. Soc., 2023, 145, 6753–6761.
55. A. Pineiro-Garcia; X. Wu; E. J. Canto-Aguilar; A. Kuzhikandathil; M. Rafei; E. Gracia-Espino; ACS Appl. Mater. Interfaces, 2024, 16, 70429–70441.
56. T. L. L. Doan; D. C. Nguyen; S. Prabhakaran; D. H. Kim; D. T. Tran; N. H. Kim; J. H. Lee; Adv. Funct. Mater., 2021, 31, 2100233.
57. I. K. Attatsi; W. Zhu; X. Liang; New J. Chem., 2020, 44, 4340-4345.
58. C. H. Chiang; Y. C. Yang; J. W. Lin; Y. C. Lin; P. T. Chen; C. L. Dong; H. M. Lin; K. M. Chan; Y. T. Kao; Suenaga, K.; P.-W. Chiu; C.-W. Chen; ACS Nano, 2022, 16, 18274–18283.
59. Y. Yang; H. Yao; Z. Yu; S.M. Islam; H. He; M. Yuan; Y. Yue; K. Xu; W. Hao; G. Sun; H. Li; S. Ma; P. Zapol; M. G. Kanatzidis; J. Am. Chem. Soc., 2019, 141, 10417–10430.
60. K. Li; J. Zhang; R. Wu; Y. Yu; B. Zhang; Adv. Sci., 2015, 3, 1500426.
61. M. J. Frisch; G. W. Trucks; H. B. Schlegel; G. E. Scuseria; M. A. Robb et al.; Gaussian 03, Revision C.02, 2004, Gaussian, Inc., Wallingford CT.
62. R. Dennington; T. A. Keith; J. M. Millam; GaussView, Version 6.1, 2016, Semichem Inc., Shawnee Mission, KS.
63. A. D. Becke; J. Chem. Phys., 1993, 98, 5648-5652.
64. C. Lee; W. Yang; R. G. Parr; Phys. Rev. B., 1988, 37, 785-789.
65. A. D. Becke; Phys. Rev. A., 1993, 48, 3098–3100.
66. J. P. Perdew; Y. Wang; Phys. Rev. B., 1992, 45, 13244–13249.
67. L. R. Snyder; J. J. Kirkland; J. L. Glajch; Practical HPLC Method Development; John Wiley & Sons, New Jersey, USA, 1997; pp. 721-728.
68. J. Chang; Q. Lv; G. Li; J. Ge; C. Liu; W. Xing; Appl. Catal. B-Environmental, 2017, 204, 486-496.
69. B. C. M. Martindale; E. Reisner; Adv. Energy Mater., 2016, 6, 1502095.
70. K. Zh. Bekmyrza; K. A. Kuterbekov; A. M. Kabyshev; M. M. Kubenova; A. A. Baratova; N. Aidarbekov; M. D. Chaka; N. E. Benti; Sci. Rep., 2025, 15, 28418.
71. Minitab, LLC, 2022. Minitab (Version 22.x). [Software]. State College, PA, USA: Minitab, LLC.
Downloads
Published
How to Cite
Issue
Section
License
Copyright (c) 2026 Studia Universitatis Babeș-Bolyai Chemia
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
