journal article·2025-12Open access

Tailoring TiO2 nanotubes photoanodes with electrodeposited Co3O4 and CoOOH cocatalysts for enhanced electrocatalytic and photoelectrocatalytic oxygen evolution

Mariusz Wtulich, Anna Lisowska-Oleksiak

Abstract

In this work, titanium dioxide nanotubes (TiO 2 -NTs) were functionalised with cobalt-based cocatalysts — Co 3 O 4 and CoOOH — via controlled electrodeposition to improve their performance in electrocatalytic and photoelectrocatalytic oxygen evolution reaction (OER). TiO 2 -NTs, prepared by anodization and hydrothermal annealing, provided a stable and photoactive platform. Structural and chemical characterisation (SEM, EDX, XRD, ATR-FTIR, XPS) confirmed successful deposition of the cocatalyst layers. Electrochemical measurements revealed a markedly superior performance of CoOOH-modified electrodes, which exhibited a significantly reduced OER onset potential (0.80 V vs. Ag/AgCl) compared to pristine TiO 2 -NTs and TiO 2 -NTs/Co 3 O 4 . Under illumination, TiO 2 -NTs/CoOOH generated up to twice the photocurrent of their Co 3 O 4 -modified counterparts. Mechanistic analysis attributed this enhancement to the proton-coupled electron transfer capability of CoOOH. Additionally, photocatalytic degradation of methylene blue confirmed that the presence of CoOOH enhances the catalytic performance of TiO 2, indicating improved overall activity of the composite material. These findings highlight CoOOH as a more effective cocatalyst than Co 3 O 4 for enhancing TiO 2 -NTs based systems in solar-assisted water splitting and pollutant degradation applications.
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Research context

OpenAlex topics: Advanced Photocatalysis Techniques · Electrocatalysts for Energy Conversion · TiO2 Photocatalysis and Solar Cells

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (100+)

Show source-provided references
1. Smooth anodic TiO2 nanotubes: annealing and structure
2. Introduction to anodization of metals, Nanostructured Anodic Met
3. Improvement of TiO2 nanotubes for photoelectrochemical water splitting: Review10.1016/j.ijhydene.2020.11.063 ↗
4. Y.H. Wang, Y.-M. Shen, C.-C. Chang, G.E. Orizu, P.E. Ugwuoke, P.U. Asogwa, S.U. Offiah, IOP Conference Series: Earth and Environmental Science A review on the inference of doping TiO2 with metals/non-metals to improve its photocatalytic activities Characterization of Sn@TiO2 Anode Material for Li-Ion Battery Application A review on the inference of doping TiO2 with metals/non-metals to improve its photocatalytic activities, (n.d.). Doi: 10.1088/1755-1315/1178/1/012008.10.1088/1755-1315/1178/1/012008 ↗
5. Visible-light photocatalysis in nitrogen-doped titanium oxides10.1126/science.1061051 ↗
6. Novel carbon-doped TiO2 nanotubes arrays with high aspect ratios for efficient solar water splitting10.1021/nl051807y ↗
7. Carbon-doped tio2 nanotubes array platform for visible photocatalysis10.1166/nnl.2013.1681 ↗
8. Directly anodized sulfur-doped TiO2 nanotubes as improved anodes for Li-ion batteries10.3390/batteries6040051 ↗
9. Fabrication of sulfur-doped TiO2 nanotubes array as a conductive interlayer of PbO2 anode for efficient electrochemical oxidation of organic pollutants10.1016/j.seppur.2020.118035 ↗
10. Ni-doped TiO2 nanotubes photoanode for enhanced photoelectrochemical water splitting10.1016/j.apsusc.2018.03.031 ↗
11. Photoresponse in the visible range from Cr doped TiO2 nanotubes10.1016/j.cplett.2006.11.065 ↗
12. M. Wtulich, M. Szkoda, G. Gajowiec, M. Gazda, K. Jurak, M. Sawczak, A. Lisowska-Oleksiak, Hydrothermal cobalt doping of titanium dioxide nanotubes towards photoanode activity enhancement, Mater. 2021, Vol. 14, Page 1507 14 (2021) 1507. Doi: 10.3390/MA14061507.10.3390/ma14061507 ↗
13. Cobalt-doped black TiO2 nanotubes array as a stable anode for oxygen evolution and electrochemical wastewater treatment10.1021/acscatal.7b04340 ↗
14. Photoelectrochemical properties of BODIPY-sensitized anodic TiO2 layers decorated with AuNPs for enhanced solar performance10.1021/acs.jpcc.3c00931 ↗
15. Effect of structure on the photocatalytic activity of Pt-doped TiO2 nanotubes10.1016/j.apsusc.2011.05.133 ↗
16. Trace amounts of palladium-doped hollow TiO2 nanosphere as highly efficient electrocatalyst for hydrogen evolution reaction10.1016/j.ijhydene.2020.10.034 ↗
17. Developments and perspectives of oxide-based catalysts for the oxygen evolution reaction, Catal
18. Co3O4-modified TiO2 nanotubesarrays via atomic layer deposition for improved visible-light photoelectrochemical performance10.1021/am506392y ↗
19. Photoelectrochemical water splitting at low applied potential using a NiOOH coated codoped (Sn, Zr) α-Fe2O3 photoanode10.1039/C4TA06915C ↗
20. Photodeposited FeOOH vs electrodeposited Co-Pi to enhance nanoporous BiVO4 for photoelectrochemical water splitting10.1088/1674-4926/38/5/053004 ↗
21. Ultrasmall CoO(OH)x nanoparticles as a highly efficient “true” cocatalyst in porous photoanodes for water splitting10.1021/acscatal.7b01466 ↗
22. In situ formation of an oxygen-evolving catalyst in neutral water containing phosphate and Co2+10.1126/science.1162018 ↗
23. Nanoporous anodic titanium dioxide layers as potential drug delivery systems: drug release kinetics and mechanism10.1016/j.colsurfb.2016.03.073 ↗
24. M.B. Hanif, M. Sihor, V. Liapun, H. Makarov, O. Monfort, M. Motola, Porous vs. Nanotubular Anodic TiO2: Does the Morphology Really Matters for the Photodegradation of Caffeine?, Coatings 2022, Vol. 12, Page 1002 12 (2022) 1002. Doi: 10.3390/COATINGS12071002.10.3390/coatings12071002 ↗
25. Aligned metal oxide nanotubes arrays: key-aspects of anodic TiO2 nanotubes formation and properties10.1039/C6NH00054A ↗
26. Ultralong, small-diameter TiO2 nanotubes achieved by an optimized two-step anodization for efficient dye-sensitized solar cells10.1021/am404966e ↗
27. Scalable route toward superior photoresponse of UV-laser-treated TiO2 nanotubes10.1021/acsami.9b19206 ↗
28. Hydrothermal modification of TiO2 nanotubes in water and alkali metal electrolytes (LiNO3, NaNO3, KNO3) – Direct evidence for photocatalytic activity enhancement10.1016/j.electacta.2022.140802 ↗
29. Facet effect of TiO2 nanostructures from TiOF2 and their photocatalytic activity10.1016/j.cej.2020.126493 ↗
30. TiO2-C nanocomposite synthesized via facile surfactant-assisted method as a part of less energy-consuming LED-based photocatalytic system for environmental applications10.1016/j.jphotochem.2022.114428 ↗
31. D. Roda, K. Trzciński, M. Łapiński, M. Gazda, M. Sawczak, A.P. Nowak, M. Szkoda, The new method of ZnIn2S4 synthesis on the titania nanotubes substrate with enhanced stability and photoelectrochemical performance, Sci. Rep. 13 (2023) 21263 | Doi: 10.1038/s41598-023-48309-9.10.1038/s41598-023-48309-9 ↗
32. Synthesis and application of N-doped TiO2/CdS/poly(1,8-diaminocarbazole) composite for photocatalytic degradation of 4-chlorophenol under visible light10.1016/j.electacta.2019.05.060 ↗
33. Speciation of oxygen functional groups on the carbon support controls the electrocatalytic activity of cobalt oxide nanoparticles in the oxygen evolution reaction10.1021/acsami.2c18403 ↗
34. Activation of peroxymonosulfate by oxygen vacancies-enriched cobalt-doped black TiO2 nanotubes for the removal of organic pollutants10.1021/acs.est.9b01449 ↗
35. Monitoring cobalt-oxide single particle electrochemistry with subdiffraction accuracy10.1021/acs.analchem.8b00649 ↗
36. Rational design and construction of cocatalysts for semiconductor-based photo-electrochemical oxygen evolution: a comprehensive review
37. Electrocrystallization of mercury, silver and palladium10.1039/tf9686400192 ↗
38. Coupling polyoxometalate with CoOOH on BiVO4 photoanodes towards efficient photoelectrochemical water oxidation10.1016/j.ijhydene.2024.03.010 ↗
39. Interfacial properties of gold and cobalt oxyhydroxide in plasmon-mediated oxygen evolution reaction
40. High-spin Co3+ in cobalt oxyhydroxide for efficient water oxidation
41. Superior inorganic ion cofactors of tetraborate species attaining highly efficient heterogeneous electrocatalysis for water oxidation on cobalt oxyhydroxide nanoparticles10.1021/acsami.7b13817 ↗
42. Concerted O atom-proton transfer in the O - O bond forming step in water oxidation10.1073/pnas.1001132107 ↗
43. X. Ren, Y. Ji, Y. Zhai, N. Yuan, J. Ding, Y. Li, J. Yan, S.F. Liu, Self-assembled CoOOH on TiO 2 for enhanced photoelectrochemical water oxidation, (2020). Doi: 10.1016/j.jechem.2020.11.038.10.1016/j.jechem.2020.11.038 ↗
44. Enhanced photoelectrochemical water splitting through synergistic carrier separation and transfer in TiO2-ferrihydrite-mxene nanowire arrays10.1021/acsaem.4c00308 ↗
45. X. ming song, Charge separation at BiVO4/Co3O4 and BiVO4/CoOOH interfaces: differences between dense and permeable cocatalysts10.1016/j.apsusc.2023.156965 ↗
46. Recent advances on water electrolysis based on nanoscale inorganic metal-oxides and metal-oxyhydroxides for hydrogen energy production10.1016/j.ijhydene.2024.11.348 ↗
47. Triggering lattice oxygen in in-situ evolved CoOOH for industrial-scale water oxidation10.1016/j.apcatb.2024.124838 ↗
48. Fityk: a general-purpose peak fitting program
49. Electrodeposition of cobalt from citrate containing baths10.1016/j.electacta.2014.03.130 ↗
50. Electroplating of cobalt from aqueous citrate baths10.1002/(SICI)1097-4660(199812)73:4<369::AID-JCTB971>3.0.CO;2-P ↗
51. Fleischmann · 1963 · 123
52. Electrochemical nucleation: Part I. General considerations10.1016/0022-0728(82)85080-8 ↗
53. The lithium/polymer electrolyte interface10.1016/0013-4686(95)00204-R ↗
54. Electrochemical nucleation and growth of nano- and microparticles: some theoretical and experimental aspects10.1016/S0013-4686(03)00355-4 ↗
55. Study of the electrochemical deposition and properties of cobalt oxide species in citrate alkaline solutions10.1016/S0022-0728(02)01100-2 ↗
56. Electrochemical reactivity of faceted β-Co(OH)2 single crystal platelet particles in alkaline electrolytes10.1021/acs.jpcc.9b03589 ↗
57. Roles of cocatalysts in photocatalysis and photoelectrocatalysis10.1021/ar300227e ↗
58. Gas sensing properties of p-Co3O4/n-TiO2 nanotubesheterostructures10.3390/s18040956 ↗
59. Electrochemically enhanced activation of Co3O4/TiO2 nanotubesarray anode for persulfate toward high catalytic activity, low energy consumption, and long lifespan performance10.1016/j.jcis.2023.11.045 ↗
60. Electrodeposited cobalt-based electrocatalysts for efficient oxygen evolution reaction and supercapacitors10.1016/j.rechem.2023.100879 ↗
61. Combined TPR, XRD, and FTIR studies on the reduction behavior of Co3O410.1016/j.matchemphys.2022.126367 ↗
62. Electrochemical Nucleation and growth, Encycl
63. Unveiling selective nitrate reduction to ammonia with Co 3 O4 nanosheets/TiO 2 nanobelt heterostructure catalyst10.1016/j.jcis.2022.10.050 ↗
64. Effect of mesoporous g-C 3 N 4 substrate on catalytic oxidation of CO over Co 3 O 410.1016/j.apsusc.2016.12.238 ↗
65. C. (United S.L.M.P. Lawrence Berkeley National Lab. (LBNL), Berkeley, Materials Data on Ti by Materials Project, (2020). Doi: 10.17188/1208281.
66. J. Zemann, Crystal structures, 2 nd edition. Vol. 1 by R. W. G. Wyckoff , Acta Crystallogr. 18 (1965) 139–139. Doi: 10.1107/s0365110x65000361.10.1107/S0365110X65000361 ↗
67. M. Szkoda, A. Lisowska-Oleksiak, K. Siuzdak, Optimization of boron-doping process of titania nanotubes via electrochemical method toward enhanced photoactivity, J. Solid State Electrochem. 20 (2016) 1765–1774. https:// DOI 10.1007/s10008-016-3185-8.10.1007/s10008-016-3185-8 ↗
68. A novel fluorescent “turn-on” aptasensor based on nitrogen-doped graphene quantum dots and hexagonal cobalt oxyhydroxide nanoflakes to detect tetracycline10.1007/s00216-019-02361-5 ↗
69. Fabrication of dispersive α-Co(OH) 2 nanosheets on graphene nanoribbons for boosting their oxygen evolution performance10.1007/s10853-019-03421-y ↗
70. Time-resolved observations of water oxidation intermediates on a cobalt oxide nanoparticle catalyst10.1038/nchem.1874 ↗
71. Facile growth of mesoporous Co 3 O 4 nanowire arrays on Ni foam for high performance electrochemical capacitors10.1016/j.jpowsour.2011.12.001 ↗
72. Resonance Raman Studies of HOO-Co(III)Bleomycin and Co(III)Bleomycin: Identification of two Important Vibrational Modes, v(Co-OOH) and v(O-OH)10.1021/ja030622v ↗
73. Electrocatalysis for the oxygen evolution reaction: recent development and future perspectives10.1039/C6CS00328A ↗
74. Identification of cobalt oxides with raman scattering and fourier transform infrared spectroscopy10.1021/acs.jpcc.5b11185 ↗
75. XPS studies of solvated metal atom dispersed (SMAD) catalysts. evidence for layered cobalt-manganese particles on alumina and silica10.1021/ja00003a019 ↗
76. Raman spectrum of anatase, TiO210.1002/jrs.1250070606 ↗
77. The Raman spectra of Co3O410.1088/0022-3719/21/7/007 ↗
78. Optical and physical properties of cobalt oxide films electrogenerated in bicarbonate aqueous media10.1021/jp056689h ↗
79. Advances in oxygen evolution reaction electrocatalysts via direct oxygen–oxygen radical coupling pathway10.1002/adma.202416362 ↗
80. Identifying the geometric catalytic active sites of crystalline cobalt oxyhydroxides for oxygen evolution reaction
81. Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni10.1016/j.apsusc.2010.10.051 ↗
82. Active state of model cobalt foil catalyst studied by SEM, TPR/TPO, XPS and TG10.1016/S0920-5861(01)00399-6 ↗
83. Ambient-pressure X-ray photoelectron spectroscopy study of cobalt foil model catalyst under CO, H2, and their mixtures10.1021/acscatal.6b02835 ↗
84. A. Lemoine, R. Invernizzi, G. Salvato Vallverdu, L. Madec, J. Olchowka, L. Guerlou-Demourgues, I. Baraille, D. Flahaut, Surface Reactivity and Surface Characterization of the Layered β(III)-CoOOH Material: an Experimental and Computational Study, J. Phys. Chem. C 125 (2021) 8570–8581. Doi: 10.1021/acs.jpcc.1c00041.10.1021/acs.jpcc.1c00041 ↗
85. The cobalt oxide-based composite nanomaterial synthesis and its biomedical and engineering applications
86. Correlation between reactivity and oxidation state of cobalt oxide catalysts for CO preferential oxidation10.1021/acscatal.9b02582 ↗
87. Observing the electrochemical oxidation of Co metal at the solid/liquid interface using ambient pressure X-ray photoelectron spectroscopy10.1021/acs.jpcb.7b05982 ↗
88. Synthesis and characterization of Cobalt hydroxide, cobalt oxyhydroxide, and cobalt oxide nanodiscs10.1021/jp908548f ↗
89. Competing effect of Co3+reducibility and oxygen-deficient defects toward high oxygen evolution activity in Co3O4 systems in alkaline medium10.1021/acsaem.0c00297 ↗
90. Highly efficient photothermal catalysis of toluene over Co3O4/TiO2 p-n heterojunction: the crucial roles of interface defects and band structure10.1016/j.apcatb.2022.121550 ↗
91. Reducing the energy band gap of cobalt hydroxide nanosheets with silver atoms and enhancing their electrical conductivity with silver nanoparticles10.1021/acsomega.1c01908 ↗
92. How to correctly determine the band gap energy of modified semiconductor photocatalysts based on UV-Vis spectra10.1021/acs.jpclett.8b02892 ↗
93. Measurement method for carrier concentration in TiO2 via the Mott–Schottky approach10.1016/j.tsf.2010.10.071 ↗
94. Exploring the role of carbon nitrides (melem, melon, g-C3N4) in enhancing photoelectrocatalytic properties of TiO2 nanotubes for water electrooxidation10.1016/j.apsusc.2024.161994 ↗
95. Thermal selenization of electrochemically obtained cobalt thin-films and nanowire arrays10.1016/j.apsusc.2024.162070 ↗
96. Two-dimensional delafossite cobalt oxyhydroxide as a toxic gas sensor10.1016/j.apsusc.2019.01.057 ↗
97. iR Compensation for electrocatalysis studies: considerations and recommendations10.1021/acsenergylett.3c00366 ↗
98. (Photo)electrochemical methods for the determination of the band edge positions of TiO2-based nanomaterials10.1155/2011/786759 ↗
99. Y.Y. Gurevich, Y. V. Pleskov, Chapter 4 Photoelectrochemistry of Semiconductors, Semicond. Semimetals 19 (1983) 255–328. Doi: 10.1016/S0080-8784(08)60277-X.10.1016/S0080-8784(08)60277-X ↗
100. Enhanced photoelectrochemical performance of inorganic–organic hybrid consisting of BiVO4 and PEDOT:PSS10.1016/j.apsusc.2016.02.143 ↗