International Journal of Nanoscience and Nanotechnology

International Journal of Nanoscience and Nanotechnology

Co-phthalocyanine/Graphene Quantum Dots/TiO2 as a New Hybrid for Photocatalytic Degradation of Formic Acid Toward Hydrogen Generation

Document Type : Research Paper

Authors
Sajjad Keshipour
Mina Hadidi
Mojtaba Abedi-Mehmandar
Department of Nanotechnology, Faculty of Science, Urmia University, Urmia, Iran
10.22034/ijnn.2024.548254.2162
Abstract
   Hydrogen has been considered as one of the worthy fuels for the high potential energy and nonpolluting combustion. With increasing the concerns about fossil fuels pollution for the environment, attempts have been concentrated on the improving of new green fuels such as hydrogen. Particularly, the safe and cost-effective production of hydrogen has been widely studied, in which the catalysts deserved remarkable progresses. Herein, photocatalytic activity of cobalt-phthalocyanine/graphene quantum dots/TiO2 was investigated in the formic acid degradation under visible irradiation toward hydrogen generation. TiO2 as a semiconductor trapped photons to generate electron/hole pairs and graphene quantum dots made delay in their recombination to provide long time for promoting the hydrogen and carbon dioxide evolution reactions by electrons/holes. Cobalt (II)-phthalocyanine as a catalyst utilized the electrons in the transformation of protons to H2, while in the positive region carbon dioxide was producing. The reaction was progressed efficiently affording H2 with the rate of 3.60 mmol.h-1 and activation energy was calculated to be 16 KJ.mol-1. This three-component catalyst showed satisfying stability to run the reaction for long time. Notable catalytic activity, and employing light power for the reaction done are two significant characteristics of this hybrid.
Keywords
Hydrogen generation
Photocatalysis
Green
Phthalocyanine
Graphene
Formic acid
Subjects
  1. Othman, M. F., Adam, A., Najafi, G., Mamat, R., "Green fuel as alternative fuel for diesel engine: A review", Sustain. Energy Rev., 80 (2017) 694-709.
  2. Acar, C., Dincer, I., "Review and evaluation of hydrogen production options for better environment", Clean. Prod., 218 (2019) 835-849.
  3. Eppinger, J. R., Huang, K.-W., "Formic acid as a hydrogen energy carrier", ACS Energy Lett., 2 (2017) 188-195.
  4. Bulushev, D. A., "Progress in catalytic hydrogen production from formic acid over supported metal complexes", Energies, 14 (2021) 1334.
  5. Kusuda, K., Ishihara, R., Yamaguchi, H., Izumi, I., "Electrochemical investigation of thin films of cobalt phthalocyanine and cobalt-4, 4′, 4 ″, 4′″-tetracarboxyphthalocyanine and the reduction of carbon monoxide, formic acid and formaldehyde mediated by the Co (I) complexes",Acta, 31 (1986) 657-663.
  6. Kudrik, E. V., Makarov, S. V., Ageeva, E. S., Derevenkov, I. A., "Cobalt Phthalocyanine–аn Effective Catalyst of Hydrogen Production from Formic Acid", Macroheterocyclic, 2 (2009) 69-70.
  7. Tanaka, S., Onishi, T., Tamaru, K., "Decomposition of Formic Acid over Metal Phthalocyanines", Chem. Soc. Jpn., 41 (1968) 2557-2562.
  8. Keshipour, S., Mohammad-Alizadeh, S., "Nickel phthalocyanine@ graphene oxide/TiO2 as an efficient degradation catalyst of formic acid toward hydrogen production", Sci. Rep., 11 (2021) 16148.
  9. Keshipour, S., Mohammad-Alizadeh, S., Razeghi, M. H., "Copper phthalocyanine@ graphene oxide as a cocatalyst of TiO2 in hydrogen generation", J. Phys. Chem. Solids., 161 (2022) 110434.
  10. Li, B., Wei, P., Frey, T., Pentzer, E., "Polymer composites with photo-responsive phthalocyanine for patterning in color and fluorescence", Eur. Polym. J., 89 (2017) 399-405.
  11. Bahluli, R., Keshipour, S., "Microcrystalline cellulose modified with Fe (II)–and Ni (II)–phthalocyanines: Syntheses, characterizations, and catalytic applications", Polyhedron, 169 (2019) 176-182.
  12. Lever, A., Pickens, S., Minor, P., Licoccia, S., Ramaswamy, B., Magnell, K., "Charge-transfer spectra of metallophthalocyanines: correlation with electrode potentials", Am. Chem. Soc., 103 (1981) 6800-6806.
  13. Facure, M. H., Schneider, R., Mercante, L. A., Correa, D. S., "A review on graphene quantum dots and their nanocomposites: from laboratory synthesis towards agricultural and environmental applications", Sci. Nano, 7 (2020) 3710-3734.
  14. Babazadeh, S., Moghaddam, P. A., Keshipour, S., Mollazade, K., "Colorimetric sensing of imidacloprid in cucumber fruits using a graphene quantum dot/Au (III) chemosensor", Rep., 10 (2020) 14327.
  15. Ahmadi, H., Keshipour, S., Ahour, F., "New water-soluble colorimetric pH and metal ione sensor based on graphene quantum dot modified with alizarine red S", Rep., 10 (2020) 14185.
  16. Keshipour, S., Al‐Azmi, A., "Synthesis and catalytic application of Pd/PdO/Fe3O4@ polymer‐like graphene quantum dots",Organomet. Chem., 34 (2020) e5311.
  17. Keshipour, S., Khezerloo, M., "Nanocomposite of hydrophobic cellulose aerogel/graphene quantum dot/Pd: Synthesis, characterization, and catalytic application", RSC Adv., 9 (2019) 17129-17136.
  18. Keshipour, S., Adak, K., "Pd (0) supported on N-doped graphene quantum dot modified cellulose as an efficient catalyst for the green reduction of nitroaromatics", RSC Adv., 6 (2016) 89407-89412.
  19. Bokare, A., Chinnusamy, S., Erogbogbo, F., "TiO2-graphene quantum dots nanocomposites for photocatalysis in energy and biomedical applications", , 11 (2021) 319.
  20. Yu, Y., Ren, J., Meng, M., "Photocatalytic hydrogen evolution on graphene quantum dots anchored TiO2 nanotubes-array", J. Hydr. Energy, 38 (2013) 12266-12272.
  21. Bayat, A., Saievar-Iranizad, E., "Graphene quantum dots decorated rutile TiO2 nanoflowers for water splitting application", Energy Chem., 27 (2018) 306-310.
  22. Samanta, S., Kumar, S., Battula, V., Jaryal, A., Sardana, N., Kailasam, K., "Quantum dot-sensitized O-linked heptazine polymer photocatalyst for the metal-free visible light hydrogen generation", RSC Adv., 10 (2020) 29633-29641.
  23. Al-Azmi, A., Keshipour, S., "Cross-linked chitosan aerogel modified with Pd (II)/phthalocyanine: Synthesis, characterization, and catalytic application", Rep., 9 (2019) 13849.
  24. Shaabani, A., Keshipour, S., Hamidzad, M., Shaabani, S., "Cobalt (II) phthalocyanine covalently anchored to cellulose as a recoverable and efficient catalyst for the aerobic oxidation of alkyl arenes and alcohols", Mol. Catal. A-Chem., 395 (2014) 494-499.
  25. Tayel, A., Ramadan, A. R., El Seoud, O. A., "Titanium dioxide/graphene and titanium dioxide/graphene oxide nanocomposites: Synthesis, characterization and photocatalytic applications for water decontamination", , 8 (2018) 491.
  26. Ertem, B., Yalazan, H., Güngör, Ö., Sarki, G., Durmuş, M., Saka, E. T., Kantekin, H., "Synthesis, structural characterization, and investigation on photophysical and photochemical features of new metallophthalocyanines", Lumin., 204 (2018) 464-471.
  27. Du, S., Zhang, C., Jiang, P., Leng, Y., "Palladium nanoparticles immobilized on nitride carbon-coated mesoporous tungsten oxide for formic acid dehydrogenation", ACS Appl. Nano Mater., 2 (2019) 7432-7440.
  28. Khorshidi, A. R., Shariati, Sh., "OSO3H Functionalized Mesoporous MCM-41 Coated on Fe3O4 Nanoparticles: an Efficient and Recyclable Nano-Catalyst for Preparation of 3,2′-Bisindoles", J. Nanosci. Nanotechnol., 12 (2016) 139-147.
  29. Shahbazi-Alavi, H., Safaei-Ghomi, J., "Ionic Liquid Attached to Colloidal Silica ‎Nanoparticles as Catalyst for the ‎Synthesis of Pyrimidines", J. Nanosci. Nanotechnol. 17 (2021) 133-140.
  30. Gharbani, P., Mehrizad, A., "The Effect of pH on Nanosized ZnO Catalyzed Degradation of 4-Chloro-2-Nitrophenol via Ozonation", Int. J. Nanosci. Nanotechnol., 8 (2012) 121-126.
International Journal of Nanoscience and Nanotechnology
Volume 20, Issue 1
2024
Pages 25-32