Preparation and Characterization of CuFe2O4/TiO2 Photocatalyst for the Conversion of CO2 into Methanol under Visible Light

Authors: Md. Maksudur Rahman Khan, M. Rahim Uddin, Hamidah Abdullah, Kaykobad Md. Rezaul Karim, Abu Yousuf, Chin Kui Cheng, Huei Ruey Ong

Abstract:

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/g_cat 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.

Keywords: Photocatalysis, CuFe2O4/TiO2, band-gap energy, methanol.

Digital Object Identifier (DOI): doi.org/10.5281/zenodo.1126852

References:

[1] 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.
[2] 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.
[3] 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.
[4] 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.
[5] 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.
[6] 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.
[7] 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.
[8] 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.
[9] 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.
[10] A. Di Paola, M. Bellardita, L. Palmisano, “Brookite, the Least Known TiO2 Photocatalyst,” Catalysts, vol. 3, no. 1, 2013, pp. 36-73.
[11] 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.
[12] 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.
[13] 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.
[14] 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.
[15] 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.
[16] 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.
[17] 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.
[18] 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.
[19] 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.
[20] 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.
[21] 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.
[22] 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.
[23] 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.
[24] 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.
[25] 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.
[26] 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.
[27] 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.
[28] 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.
[29] 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.
[30] 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.
[31] S. K. Lower, Carbonate equilibria in natural waters, in: Simon Fraser University, 1999.
[32] 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.