Preparation and Characterization of CuFe2O4/TiO2 Photocatalyst for the Conversion of CO2 into Methanol under Visible Light
A systematic study was conducted to explore the photocatalytic reduction of carbon dioxide (CO2) into methanol on TiO2 loaded copper ferrite (CuFe2O4) photocatalyst under visible light irradiation. The phases and crystallite size of the photocatalysts were characterized by X-ray diffraction (XRD) and it indicates CuFe2O4 as tetragonal phase incorporation with anatase TiO2 in CuFe2O4/TiO2 hetero-structure. The XRD results confirmed the formation of spinel type tetragonal CuFe2O4 phases along with predominantly anatase phase of TiO2 in the CuFe2O4/TiO2 hetero-structure. UV-Vis absorption spectrum suggested the formation of the hetero-junction with relatively lower band gap than that of TiO2. Photoluminescence (PL) technique was used to study the electron–hole (e−/h+) recombination process. PL spectra analysis confirmed the slow-down of the recombination of electron–hole (e−/h+) pairs in the CuFe2O4/TiO2 hetero-structure. The photocatalytic performance of CuFe2O4/TiO2 was evaluated based on the methanol yield with varying amount of TiO2 over CuFe2O4 (0.5:1, 1:1, and 2:1) and changing light intensity. The mechanism of the photocatalysis was proposed based on the fact that the predominant species of CO2 in aqueous phase were dissolved CO2 and HCO3- at pH ~5.9. It was evident that the CuFe2O4 could harvest the electrons under visible light irradiation, which could further be injected to the conduction band of TiO2 to increase the life time of the electron and facilitating the reactions of CO2 to methanol. The developed catalyst showed good recycle ability up to four cycles where the loss of activity was ~25%. Methanol was observed as the main product over CuFe2O4, but loading with TiO2 remarkably increased the methanol yield. Methanol yield over CuFe2O4/TiO2 was found to be about three times higher (651 μmol/gcat L) than that of CuFe2O4 photocatalyst. This occurs because the energy of the band excited electrons lies above the redox potentials of the reaction products CO2/CH3OH.
Digital Object Identifier (DOI): doi.org/10.5281/zenodo.1126852Procedia APA BibTeX Chicago EndNote Harvard JSON MLA RIS XML ISO 690 PDF Downloads 1488
 A. Kezzim, N. Nasrallah, A. Abdi, M. Trari, “Visible light induced hydrogen on the novel hetero-system CuFe2O4/TiO2,” Energy Conversion and Management, vol. 52, no. 8–9, 2011, pp. 2800-2806.
 Y. Izumi, “Recent advances in the photocatalytic conversion of carbon dioxide to fuels with water and/or hydrogen using solar energy and beyond,” Coordination Chemistry Reviews, vol. 257, no. 1, 2013, pp. 171-186.
 S. C. Roy, O. K. Varghese, M. Paulose, C. A. Grimes, “Toward solar fuels: photocatalytic conversion of carbon dioxide to hydrocarbons,” ACS Nano, vol. 4, no. 3, 2010, pp. 1259-1278.
 Q. Zhang, C. F. Lin, B. Y. Chen, T. Ouyang, C. T. Chang, “Deciphering Visible Light Photoreductive Conversion of CO2 to Formic Acid and Methanol Using Waste Prepared Material,” Environ Sci Technol, vol. 49, no. 4, 2015, pp. 2405-2417.
 J. Mao, T. Peng, X. Zhang, K. Li, L. Zan, “Selective methanol production from photocatalytic reduction of CO2 on BiVO4 under visible light irradiation,” Catalysis Communications, vol. 28, no. 2012, pp. 38-41.
 K. Kočí, K. Matějů, L. Obalová, S. Krejčíková, Z. Lacný, D. Plachá, L. Čapek, A. Hospodková, O. Šolcová, “Effect of silver doping on the TiO2 for photocatalytic reduction of CO2,” Applied Catalysis B: Environmental, vol. 96, no. 3-4, 2010, pp. 239-244.
 M. Tahir, N. S. Amin, “Advances in visible light responsive titanium oxide-based photocatalysts for CO2 conversion to hydrocarbon fuels,” Energy Conversion and Management, vol. 76, no. 2013, pp. 194-214.
 H. Yang, J. Yan, Z. Lu, X. Cheng, Y. Tang, “Photocatalytic activity evaluation of tetragonal CuFe2O4 nanoparticles for the H2 evolution under visible light irradiation,” Journal of Alloys and Compounds, vol. 476, no. 1-2, 2009, pp. 715-719.
 X. Li, J. Chen, H. Li, J. Li, Y. Xu, Y. Liu, J. Zhou, “Photoreduction of CO2 to methanol over Bi2S3/CdS photocatalyst under visible light irradiation,” Journal of Natural Gas Chemistry, vol. 20, no. 4, 2011, pp. 413-417.
 A. Di Paola, M. Bellardita, L. Palmisano, “Brookite, the Least Known TiO2 Photocatalyst,” Catalysts, vol. 3, no. 1, 2013, pp. 36-73.
 A. Di Paola, E. García-López, G. Marcì, L. Palmisano, “A survey of photocatalytic materials for environmental remediation,” J Hazard Mater, vol. 211, no. 2012, pp. 3-29.
 W. Hou, W. H. Hung, P. Pavaskar, A. Goeppert, M. Aykol, S. B. Cronin, “Photocatalytic Conversion of CO2 to Hydrocarbon Fuels via Plasmon-Enhanced Absorption and Metallic Interband Transitions,” ACS Catalysis, vol. 1, no. 8, 2011, pp. 929-936.
 W.-N. Wang, J. Soulis, Y. J. Yang, P. Biswas, “Comparison of CO2 photoreduction systems: A review,” Aerosol and Air Quality Research, vol. 14, no. 2, 2014, pp. 533-549.
 M. L. P. Dalida, K. M. S. Amer, C.-C. Su, M.-C. Lu, “Photocatalytic degradation of acetaminophen in modified TiO2 under visible irradiation,” Environmental Science and Pollution Research, vol. 21, no. 2, 2014, pp. 1208-1216.
 H. Fan, H. Li, B. Liu, Y. Lu, T. Xie, D. Wang, “Photoinduced charge transfer properties and photocatalytic activity in Bi2O3/BaTiO3 composite photocatalyst,” ACS Appl Mater Interfaces, vol. 4, no. 9, 2012, pp. 4853-4857.
 D. Monllor-Satoca, R. Gomez, W. Choi, “Concentration-dependent photoredox conversion of As(III)/As(V) on illuminated titanium dioxide electrodes,” Environ Sci Technol, vol. 46, no. 10, 2012, pp. 5519-5527.
 P. Roy, A. P. Periasamy, C. T. Liang, H. T. Chang, “Synthesis of graphene-ZnO-Au nanocomposites for efficient photocatalytic reduction of nitrobenzene,” Environ Sci Technol, vol. 47, no. 12, 2013, pp. 6688-6695.
 M. R. Uddin, M. R. Khan, M. W. Rahman, A. Yousuf, C. K. Cheng, “Photocatalytic reduction of CO2 into methanol over CuFe2O4/TiO2 under visible light irradiation,” Reaction Kinetics, Mechanisms and Catalysis, vol. 116, no. 2, 2015, pp. 589-604.
 J. Yan, H. Yang, Y. Tang, Z. Lu, S. Zheng, M. Yao, Y. Han, “Synthesis and photocatalytic activity of CuYyFe2−yO4–CuCo2O4 nanocomposites for H2 evolution under visible light irradiation,” Renewable Energy, vol. 34, no. 11, 2009, pp. 2399-2403.
 O. Lemine, “Microstructural characterisation of nanoparticles using, XRD line profiles analysis, FE-SEM and FT-IR,” Superlattices and Microstructures, vol. 45, no. 6, 2009, pp. 576-582.
 L. Huang, F. Peng, H. Wang, H. Yu, Z. Li, “Preparation and characterization of Cu 2 O/TiO 2 nano–nano heterostructure photocatalysts,” Catalysis Communications, vol. 10, no. 14, 2009, pp. 1839-1843.
 X. Li, H. Liu, D. Luo, J. Li, Y. Huang, H. Li, Y. Fang, Y. Xu, L. Zhu, “Adsorption of CO2 on heterostructure CdS(Bi2S3)/TiO2 nanotube photocatalysts and their photocatalytic activities in the reduction of CO2 to methanol under visible light irradiation,” Chemical Engineering Journal, vol. 180, no. 2012, pp. 151-158.
 M. Hussain, N. Russo, G. Saracco, “Photocatalytic abatement of VOCs by novel optimized TiO2 nanoparticles,” Chemical Engineering Journal, vol. 166, no. 1, 2011, pp. 138-149.
 J. T. Carneiro, T. J. Savenije, J. A. Moulijn, G. Mul, “How phase composition influences optoelectronic and photocatalytic properties of TiO2,” The Journal of Physical Chemistry C, vol. 115, no. 5, 2011, pp. 2211-2217.
 M. Tahir, N. S. Amin, “Indium-doped TiO2 nanoparticles for photocatalytic CO2 reduction with H2O vapors to CH4,” Applied Catalysis B: Environmental, vol. 162, no. 2015, pp. 98-109.
 N. Ahmed, M. Morikawa, Y. Izumi, “Photocatalytic conversion of carbon dioxide into methanol using optimized layered double hydroxide catalysts,” Catalysis Today, vol. 185, no. 1, 2012, pp. 263-269.
 D.-H. Chen, X.-R. He, “Synthesis of nickel ferrite nanoparticles by sol-gel method,” Materials Research Bulletin, vol. 36, no. 7, 2001, pp. 1369-1377.
 C. G. Reddy, S. Manorama, V. Rao, “Preparation and characterization of ferrites as gas sensor materials,” Journal of materials science letters, vol. 19, no. 9, 2000, pp. 775-778.
 I. Sandu, L. Presmanes, P. Alphonse, P. Tailhades, “Nanostructured cobalt manganese ferrite thin films for gas sensor application,” Thin Solid Films, vol. 495, no. 1, 2006, pp. 130-133.
 L. L. Ma, H. Z. Sun, Y. G. Zhang, Y. L. Lin, J. L. Li, E. K. Wang, Y. Yu, M. Tan, J. B. Wang, “Preparation, characterization and photocatalytic properties of CdS nanoparticles dotted on the surface of carbon nanotubes,” Nanotechnology, vol. 19, no. 11, 2008, pp. 115709.
 S. K. Lower, Carbonate equilibria in natural waters, in: Simon Fraser University, 1999.
 L. Liu, “Understanding the Reaction Mechanism of Photocatalytic Reduction of CO2 with H2O on TiO2-Based Photocatalysts: A Review,” Aerosol and Air Quality Research, vol. no. 2014, pp.