Synthesis of M (M=Co²⁺, Co²⁺/Ni²⁺)-doped FeS₂ Nanospheres with Enhanced Visible-light-induced Photocatalytic Activity

Abstract

Nano-spherical Co²⁺-doped FeS₂ was synthesized through a simple solvothermal method. The products were investigated using XRD, FE-SEM, BET, ICP, EDS, TEM, HRTEM, XPS, and UV-vis spectroscopy. The results indicated that Co²⁺ ion could change the particle nucleation process and inhibited the particle growth of FeS₂. In addition, when the content of doped Co²⁺ was 15%, the degradation efficiency of methylene blue (MB) achieved 60.72% after 210 min irradiation, which increased by 52.01% than that of the undoped FeS₂. Moreover, comparison experiments also demonstrated that the M (M=Co²⁺, Co²⁺/Ni²⁺)-doped FeS₂ photocatalytic activity efficiency sequence was Co²⁺ > Ni²⁺>Co²⁺/Ni²⁺. This is ascribed to the fact that the Co²⁺ doping could induce the absorption edge shifting into the visible-light region and increased the surface area of the samples. The effect mechanisms of M-doping on the band gap and the photocatalytic activity of FeS₂ were also discussed.

Keywords

FeS₂ / solvothermal method / doping / photocatalytic / methylene blue

References

[1] Ferrer IJ, Sanchez C. Photoelectrochemical Response and Optical-Absorption Of Pyrite (FeS₂) Natural Single-Crystals[J]. Solid State Commun., 1992, 81(5): 371-374.

[2] Faber MS, Park K, Caban-Acevedo M, et al. Earth-Abundant Cobalt Pyrite (CoS₂) Thin Film on Glass as a Robust, High-Performance Counter Electrode for Quantum Dot-Sensitized Solar Cells[J]. J. Phys. Chem. Lett., 2013, 4(11): 1843-1849.

[3] Schuster C, Gatti M, Rubio A. Electronic and Magnetic Properties of NiS₂, NiSSe and NiSe₂ by a Combination of Theoretical Methods[J]. Eur. Phys. J. B, 2012, 85(9): 30384-30387.

[4] Jia TK, Min ZY, Cao J L, et al. Hydrothermal Synthesis and Visible-light Photocatalytic Activities of SnS₂ Nanoflakes[J]. J. Wuhan Univ. Technol., 2015, 30(2): 276-281.

[5] Jia ZM, Chen W, Liu TY, et al. Biomolecule-assisted Solvothermal Synthesis and Enhanced Visible Light Photocatalytic Performance of Bi₂S₃/BiOCl Composites[J]. J. Wuhan Univ. Technol., 2016, 31(4): 765-772.

[6] Ferrer IJ, Nevskaia DM, Delasheras C, et al. About the Band-Gap Nature of FeS₂ as Determined from Optical and Photoelectrochemical Measurements[J]. Solid State Commun., 1990, 74(9): 913-916.

[7] Hopfner C, Ellmer K, Ennaoui A, et al. Stoichiometry, Phase And Orientation-Controlled Growth of Polycrystalline Pyrite (FeS₂) Thin-Films by Mocvd[J]. J. Cryst. Growth, 1995, 151(3-4): 325-334.

[8] Ennaoui A, Fiechter S, Pettenkofer C, et al. Iron Disulfide for Solar-Energy Conversion[J]. Sol. Energ. Mat. Sol. C, 1993, 29(4): 289-370.

[9] Puthussery J, Seefeld S, Berry N, et al. Colloidal Iron Pyrite (FeS₂) Nanocrystal Inks for Thin-Film Photovoltaics[J]. J. Am. Chem. Soc., 2011, 133(4): 716-719.

[10] Wei ZH, Qiu YC, Chen HN, et al. Magnetic-field-assisted Aerosol Pyrolysis Synthesis of Iron Pyrite Sponge-like Nanochain Networks as Cost-efficient Counter Electrodes in Dye-sensitized Solar Cells[J]. J. Mater. Chem. A, 2014, 2(15): 5508-5515.

[11] Xu X, Liu W, Kim Y, et al. Nanostructured Transition Metal Sulfides for Lithium Ion Batteries: Progress and Challenges[J]. Nano Today, 2014, 9(5): 604-630.

[12] Li LS, Caban-Acevedo M, Girard SN, et al. High-purity Iron Pyrite (FeS₂) Nanowires as High-capacity Nanostructured Cathodes for Lithium-ion Batteries[J]. Nanoscale, 2014, 6(4): 2112-2118.

[13] Lee G, Kang M. Physicochemical Properties of Core/shell Structured Pyrite FeS₂/Anatase TiO₂ Composites and Their Photocatalytic Hydrogen Production Performances[J]. Curr. Appl. Phys., 2013, 13(7): 1482-1489.

[14] Cho CL, Park SJ, Kim HS. Photocatalytic Hydrogen Evolution with Platinum Loaded Cadmium-iron-sulfide Mixed Crystal Powders in Aqueous Media[J]. B. Kor. Chem. Soc., 2000, 21(8): 805-808.

[15] Schwitzgebel J, Ekerdt J G, Gerischer H, et al. Role of the Oxygen Molecule and of the Photogenerated Electron in TiO₂-Photocatalyzed Air Oxidation Reactions[J]. J. Phys. Chem., 1995, 99(15): 5633-5638.

[16] Li JJ, Cai SC, Xu Z, et al. Solvothermal Syntheses of Si and Zn codoped TiO₂ with Enhanced Electron-hole Separation and Efficient Photodegradation of Gaseous Toluene Under Visible-light[J]. J. Hazard. Mater., 2017, 325: 261-270.

[17] Liu Y, Chen XD, Xu Y, et al. Highly Branched Sn-Doped ZnO Nanostructures for Sunlight Driven Photocatalytic Reactions[J]. J. Nanomater., 2014, 381819: 1-7.

[18] Zhou B, Zhao X, Liu HJ, et al. Visible-light Sensitive Cobalt-doped BiVO₄ (Co-BiVO₄) Photocatalytic Composites for the Degradation of Methylene Blue Dye in Dilute Aqueous Solutions[J]. Appl. Catal. B-Environ., 2010, 99(1-2): 214-221.

[19] Sun JH, Dong SY, Feng JL, et al. Enhanced Sunlight Photocatalytic Performance of Sn-doped ZnO for Methylene Blue Degradation[J]. J. Mol. Catal. A-Chem., 2011, 335(1-2): 145-150.

[20] Lv ML, Xie Y, Wang YW, et al. Bismuth and Chromium Co-doped Strontium Titanates and Their Photocatalytic Properties under Visible Light Irradiation[J]. Phys. Chem. Chem. Phys., 2015, 17(39): 26320-26329.

[21] Ouyang SX, Tong H, Umezawa N, et al. Surface-Alkalinization-Induced Enhancement of Photocatalytic H₂ Evolution over Sr-TiO₃-Based Photocatalysts[J]. J. Am. Chem. Soc., 2012, 134(4): 1974-1977.

[22] Xu XX, Lv ML, Sun XQ, et al. Role of Surface Composition upon the Photocatalytic Hydrogen Production of Cr-doped and La/Cr-codoped SrTiO3[J]. J. Mater. Sci., 2016, 51(13): 6464-6473.

[23] Lu LW, Lv ML, Wang D, et al. Efficient Photocatalytic Hydrogen Production over Solid Solutions Sr_1-xBi_xTi_1-xFe_xO₃ (0 <= x <= 0.5)[J]. Appl. Catal. B-Environ., 2017, 200: 412-419.

[24] Liu YB, Zhu GQ, Gao JZ, et al. Enhanced Photocatalytic Activity of Bi₄Ti₃O₁₂ Nanosheets by Fe³⁺-doping and the Addition of Au Nanoparticles: Photodegradation of Phenol and Bisphenol A[J]. Appl. Catal. B-Environ., 2017, 200: 72-82.

[25] Long F, He JY, Zhang MY, et al. Microwave-hydrothermal Synthesis of Co-doped FeS₂ as a Visible-light Photocatalyst[J]. J. Mater. Sci., 2015, 50(4): 1848-1854.

[26] Long F, Zhang J, Zhang M Y, et al. Ni-Doped FeS₂: Solvothermal Synthesis and the Visible-Light Photocatalytic Properties[J]. Chinese J. Inorg. Chem., 2015, 31(6): 1119-1124.

[27] Feng X, He XM, Pu WH, et al. FeS₂ Cathode Materials for Lithium Batteries[J]. Prog. Chem., 2008, 20(2-3): 396-404.

[28] Lowson RT. Aqueous Oxidation of Pyrite by Molecular Oxygen[J]. Chem. Rev., 1982, 82(5): 481-494.

[29] Verma KC, Kotnala RK. Understanding Lattice Defects to Influence Ferromagnetic Order of ZnO Nanoparticles by Ni, Cu, Ce ions[J]. J Solid State Chem., 2017, 246: 150-159.

[30] Zak AK, Majid WHA, Abrishami ME, et al. X-ray Analysis of ZnO Nanoparticles by Williamson-Hall and Size-strain Plot Methods[J]. Solid State Sci., 2011, 13(1): 251-6.

[31] Zhao WH, Wei ZQ, Zhang L, et al. Optical and Magnetic Properties of Co and Ni co-doped ZnS Nanorods Prepared by Hydrothermal Method[J]. J. Alloy Compd., 2017 698754-698760.

[32] Chao HE, Yun YU, Xingfang HU, et al. Effect of Silver Doping on the Phase Transformation and Grain Growth of Sol-gel Titania Powder[J]. J. Eur. Ceram. Soc., 2003, 23(9): 1457-1464.

[33] Chen PL, Chen I W. Grain growth in CeO₂: Dopant effects, Defect Mechanism, and Solute Drag[J]. J. Am. Ceram. Soc., 1996, 79(7): 1793-1800.

[34] Kirchheim R. Grain Coarsening Inhibited by Solute Segregation[J]. Acta Mater., 2002, 50(2): 413-419.

[35] Bai YX, Yeom J, Yang M, et al. Universal Synthesis of Single-Phase Pyrite FeS₂ Nanoparticles, Nanowires, and Nanosheets[J]. J. Phys. Chem. C, 2013, 117(6): 2567-2573.

[36] Zhao X, Fu Y, Wang J, et al. Ni-doped CoFe₂O₄ Hollow Nanospheres as Efficient Bi-functional Catalysts[J]. Electrochim. Acta, 2016, 201: 172-178.

[37] Yin WZ, Wang WZ, Zhou L, et al. CTAB-assisted Synthesis of Monoclinic BiVO4 Photocatalyst and Its Highly Efficient Degradation of Organic Dye under Visible-light Irradiation[J]. J. Hazard. Mater., 2010, 173(1-3): 194-199.

[38] Zhao W, Chen CC, Li XZ, et al. Photodegradation of Sulforhodamine-B Dye in Platinized Titania Dispersions under Visible Light Irradiation: Influence of Platinum as a Functional Co-catalyst[J]. J. Phys. Chem. B, 2002, 106(19): 5022-5028.

[39] Trandafilovic LV, Jovanovic DJ, Zhang X, et al. Enhanced Photocatalytic Degradation of Methylene Blue and Methyl Orange by ZnO:EuNanoparticles[J]. Appl. Catal. B-Environ., 2017, 203: 740-752.

[40] Fathinia S, Fathinia M, Rahmani AA, et al. Preparation of Natural Pyrite Nanoparticles by High Energy Planetary Ball Milling as a Nanocatalyst for Heterogeneous Fenton Process[J]. Appl. Surf. Sci., 2015, 327: 190-200.

[41] Zhao C, Shu X, Zhu DC, et al. High Visible Light Photocatalytic Property of CO₂+-doped TiO₂ Nanoparticles with Mixed Phases[J]. Superlattice Microst., 2015, 88: 32-42.

[42] James EH. Inorganic Chemisty[M]. 2008 New York: Academic Press. 182

[43] Choi WY, Termin A, Hoffmann M R. The Role of Metal-Ion Dopants in Quantum-Sized TiO₂ Correlation between Photoreactivity and Charge-Carrier Recombination Dynamics[J]. J. Phys. Chem., 1994, 98(51): 13669-13679.

[44] Giuseppe G, Giuseppe PP. Solid State Physics[M]. 2000 New York: Academic Press. 182-186.