The alpha ( α )-hematite (Fe 2 O 3 ) as photoanode has been used for photoelectrochemical applications due to low bandgap, low cost, high chemical stability, nontoxicity, and abundance in nature. The doping with various transition metals, formation of nanostructured and nanocomposite of α -Fe 2 O 3 have been attempted to enrich the carrier mobility, surface kinetics and carrier diffusion properties. The manuscript is an attempt to improve the photoelectrochemical properties of α -Fe 2 O 3 by formation of nanocomposite with dichalcogenide (molybdenum disulfide (MoS 2 ) nanomaterials. The nanocomposite of MoS 2 - α -Fe 2 O 3 have been synthesized by varying the amount of MoS 2 in sol-gel synthesis process. The nanocomposite MoS 2 - α -Fe 2 O 3 materials were characterized using UV-visible, FTIR, SEM, X-ray diffraction, Raman and particle analyzer. The photoelectrochemical properties were investigated using cyclic voltammetry and chronoamperometry studies. The optical and structural properties of MoS 2 - α -Fe 2 O 3 nanocomposite have been found to be dependent on MoS 2 doping. The band gap has shifted whereas; the structure is more prominent as flower-like morphology, which is a result of doping of MoS 2 . The photocurrent is more pronounced with and without light exposition to MoS 2 - α -Fe 2 O 3 based electrode in photoelectrochemical cell. We have understood the photoelectrochemical water splitting using nanocomposite α -Fe 2 O 3 -MoS 2 through schematic representation based on experimental results. The enhanced photoelectrochemical properties of nanocomposite α -Fe 2 O 3 -MoS 2 films have been observed as compared to pristine α -Fe 2 O 3 and transition metal doped α -Fe 2 O 3 nanostructured films.
Wheeler, D.A., Wang, G., Ling, Y., Li, Y. and Zhang, J.Z. (2012) Nanostructured Hematite: Synthesis, Characterization, Charge Carrier Dynamics, and Photoelectrochemical Properties. Energy & Environmental Science, 5, 6682-6702. https://doi.org/10.1039/c2ee00001f
Li, Y., Wang, H., Xie, L., Liang, Y., Hong, G. and Dai, H. (2011) MoS2 Nanoparticles Grown on Graphene: An Advanced Catalyst for the Hydrogen Evolution Reaction. Journal of the American Chemical Society, 133, 7296-7299. https://doi.org/10.1021/ja201269b
Sivula, K., Le Formal, F. and Gratzel, M. (2011) Solar Water Splitting: Progress Using Hematite (α-Fe2O3) Photoelectrodes. ChemSusChem, 4, 432-449. https://doi.org/10.1002/cssc.201000416
Hiralal, P., Saremi-Yarahmadi, S., Bayer, B.C., Wang, H., Hofmann, S., Wijayantha, K.U. and Amaratunga, G.A. (2011) Nanostructured Hematite Photoelectrochemical Electrodes Prepared by the Low Temperature Thermal Oxidation of Iron. Solar Energy Materials and Solar Cells, 95, 1819-1825. https://doi.org/10.1016/j.solmat.2011.01.049
Ahn, H.-J., Yoon, K.-Y., Kwak, M.-J., Lee, J.-S., Thiyagarajan, P. and Jang, J.-H. (2015) MoSx Supported Hematite with Enhanced Photoelectrochemical Performance. Journal of Materials Chemistry A, 3, 21444-21450. https://doi.org/10.1039/C5TA06743J
Hisatomi, T., Kubota, J. and Domen, K. (2014) Recent Advances in Semiconductors for Photocatalytic and Photoelectrochemical Water Splitting. Chemical Society Reviews, 43, 7520-7535. https://doi.org/10.1039/C3CS60378D
Kim, J.Y., Magesh, G., Youn, D.H., Jang, J.-W., Kubota, J., Domen, K. and Lee, J.S. (2013) Single-Crystalline, Wormlike Hematite Photoanodes for Efficient Solar Water Splitting. Scientific reports, 3, 2681. https://doi.org/10.1038/srep02681
Kment, S., Hubicka, Z., Krysa, J., Sekora, D., Zlamal, M., Olejnicek, J., Cada, M., Ksirova, P., Remes, Z. and Schmuki, P. (2015) On the Improvement of PEC Activity of Hematite Thin Films Deposited by High-Power Pulsed Magnetron Sputtering Method. Applied Catalysis B: Environmental, 165, 344-350. https://doi.org/10.1016/j.apcatb.2014.10.015
Hisatomi, T., Dotan, H., Stefik, M., Sivula, K., Rothschild, A., Gratzel, M. and Mathews, N. (2012) Enhancement in the Performance of Ultrathin Hematite Photoanode for Water Splitting by an Oxide Underlayer. Advanced Materials, 24, 2699-2702. https://doi.org/10.1002/adma.201104868
Ahn, H.-J., Kwak, M.-J., Lee, J.-S., Yoon, K.-Y. and Jang, J.-H. (2014) Nanoporous Hematite Structures to Overcome Short Diffusion Lengths in Water Splitting. Journal of Materials Chemistry A, 2, 19999-20003. https://doi.org/10.1039/C4TA04890C
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Satsangi, V.R., Kumari, S., Singh, A.P., Shrivastav, R. and Dass, S. (2008) Nanostructured Hematite for Photoelectrochemical Generation of Hydrogen. International Journal of Hydrogen Energy, 33, 312-318.
Du, C., Yang, X., Mayer, M.T., Hoyt, H., Xie, J., McMahon, G., Bischoping, G. and Wang, D. (2013) Hematite-Based Water Splitting with Low Turn-On Voltages. Angewandte Chemie International Edition, 52, 12692-12695. https://doi.org/10.1002/anie.201306263
Desai, J., Pathan, H., Min, S.-K., Jung, K.-D. and Joo, O.S. (2005) FT-IR, XPS and PEC Characterization of Spray Deposited Hematite Thin Films. Applied Surface Science, 252, 1870-1875.
Bassi, P.S., Wong, L.H. and Barber, J. (2014) Iron Based Photoanodes for Solar Fuel Production. Physical Chemistry Chemical Physics, 16, 11834-11842. https://doi.org/10.1039/c3cp55174a
Tamirat, A.G., Rick, J., Dubale, A.A., Su, W.-N. and Hwang, B.-J. (2016) Using Hematite for Photoelectrochemical Water Splitting: A Review of Current Progress and Challenges. Nanoscale Horizons, 1, 243-267.
Kumari, S., Tripathi, C., Singh, A.P., Chauhan, D., Shrivastav, R., Dass, S. and Satsangi, V.R. (2006) Characterization of Zn-Doped Hematite Thin Films for Photoelectrochemical Splitting of Water. Current Science, 91, 1062-1073.
Jorand Sartoretti, C., Alexander, B.D., Solarska, R., Rutkowska, I.A., Augustynski, J. and Cerny, R. (2005) Photoelectrochemical Oxidation of Water at Transparent Ferric Oxide Film Electrodes. The Journal of Physical Chemistry B, 109, 13685-13692. https://doi.org/10.1021/jp051546g
Kennedy, J.H. and Frese, K.W. (1978) Photooxidation of Water at α-Fe2O3 Electrodes. Journal of the Electrochemical Society, 125, 709-714. https://doi.org/10.1149/1.2131532
Kleiman-Shwarsctein, A., Hu, Y.-S., Forman, A.J., Stucky, G.D. and McFarland, E.W. (2008) Electrodeposition of α-Fe2O3 Doped with Mo or Cr as Photoanodes for Photocatalytic Water Splitting. The Journal of Physical Chemistry C, 112, 15900-15907. https://doi.org/10.1021/jp803775j
Kleiman-Shwarsctein, A., Huda, M.N., Walsh, A., Yan, Y., Stucky, G.D., Hu, Y.-S., Al-Jassim, M.M. and McFarland, E.W. (2009) Electrodeposited Aluminum-Doped α-Fe2O3 Photoelectrodes: Experiment and Theory. Chemistry of Materials, 22, 510-517. https://doi.org/10.1021/cm903135j
Hu, Y.-S., Kleiman-Shwarsctein, A., Forman, A.J., Hazen, D., Park, J.-N. and McFarland, E.W. (2008) Pt-Doped α-Fe2O3 Thin Films Active for Photoelectrochemical Water Splitting. Chemistry of Materials, 20, 3803-3805. https://doi.org/10.1021/cm800144q
Saremi-Yarahmadi, S., Wijayantha, K.U., Tahir, A.A. and Vaidhyanathan, B. (2009) Nanostructured α-Fe2O3 Electrodes for Solar Driven Water Splitting: Effect of Doping Agents on Preparation and Performance. The Journal of Physical Chemistry C, 113, 4768-4778. https://doi.org/10.1021/jp808453z
Kay, A., Cesar, I. and Gratzel, M. (2006) New Benchmark for Water Photooxidation by Nanostructured α-Fe2O3 Films. Journal of the American Chemical Society, 128, 15714-15721. https://doi.org/10.1021/ja064380l
Ding, Q., Meng, F., English, C.R., Caban-Acevedo, M., Shearer, M.J., Liang, D., Daniel, A.S., Hamers, R.J. and Jin, S. (2014) Efficient Photoelectrochemical Hydrogen Generation using Heterostructures of Si and Chemically Exfoliated Metallic MoS2. Journal of the American Chemical Society, 136, 8504-8507.
Yoon, K.-Y., Lee, J.-S., Kim, K., Bak, C.H., Kim, S.-I., Kim, J.-B. and Jang, J.-H. (2014) Hematite-Based Photoelectrochemical Water Splitting Supported by Inverse Opal Structures of Graphene. ACS Applied Materials & Interfaces, 6, 22634-22639. https://doi.org/10.1021/am506721a
Meng, F., Li, J., Cushing, S.K., Bright, J., Zhi, M., Rowley, J.D., Hong, Z., Manivannan, A., Bristow, A.D. and Wu, N. (2013) Photocatalytic Water Oxidation by Hematite/Reduced Graphene Oxide Composites. ACS Catalysis, 3, 746-751. https://doi.org/10.1021/cs300740e
Liu, Y., Yu, Y.-X. and Zhang, W.-D. (2013) MoS2/CdS Heterojunction with High Photoelectrochemical Activity for H2 Evolution under Visible Light: The Role of MoS2. The Journal of Physical Chemistry C, 117, 12949-12957. https://doi.org/10.1021/jp4009652
Alrobei, H. (2017) A-Hematite-Molybdenum Disulfide and Polyhexylthiophene (RRPHTh)-Nanodiamond (ND) Electrodes for Photoelectrochemical Applications. 3rd International Conference on Smart Materials & Structures, Orlando.
Alrobei, H., Kumar, A. and Ram, M.K. (2015) Aluminum Doped α-Hematite for Photoelectrochemical Applications. Research Day 2015 at USF College of Engineering, Tampa.
Alrobei, H., Kumar, A. and Ram, M.K. (2017) Aluminum—A-Hematite Thin Films for Photoelectrochemical Applications. Surface Review and Letters (Communicated).
Chen, Z., Cummins, D., Reinecke, B.N., Clark, E., Sunkara, M.K. and Jaramillo, T.F. (2011) Core-Shell MoO3-MoS2 Nanowires for Hydrogen Evolution: A Functional Design for Electrocatalytic Materials. Nano Letters, 11, 4168-4175. https://doi.org/10.1021/nl2020476
Bonde, J., Moses, P.G., Jaramillo, T.F., Norskov, J.K. and Chorkendorff, I. (2009) Hydrogen Evolution on Nano-Particulate Transition Metal Sulfides. Faraday Discussions, 140, 219-231. https://doi.org/10.1039/B803857K
Kibsgaard, J., Chen, Z., Reinecke, B.N. and Jaramillo, T.F. (2012) Engineering the Surface Structure of MoS2 to Preferentially Expose Active Edge Sites for Electrocatalysis. Nature Materials, 11, 963-969. https://doi.org/10.1038/nmat3439
Thurston, T. and Wilcoxon, J. (1999) Photooxidation of Organic Chemicals Catalyzed by Nanoscale MoS2. The Journal of Physical Chemistry B, 103, 11-17. https://doi.org/10.1021/jp982337h
Han, S., Hu, L., Liang, Z., Wageh, S., Al-Ghamdi, A.A., Chen, Y. and Fang, X. (2014) One-Step Hydrothermal Synthesis of 2D Hexagonal Nanoplates of α-Fe2O3/Graphene Composites with Enhanced Photocatalytic Activity. Advanced Functional Materials, 24, 5719-5727. https://doi.org/10.1002/adfm.201401279
Alrobei, H., Kumar, A. and Ram, M.K. (2016) Doped A-Hematite with Molybdenum Sulfides MoS2 for Photoelectrochemical Applications. 9th Annual College of Engineering Research Day, Tam-pa.
Chemelewski, W.D., Mabayoje, O., Tang, D., Rettie, A.J. and Mullins, C.B. (2016) Bandgap Engineering of Fe2O3 with Cr-Application to Photoelectrochemical Oxidation. Physical Chemistry Chemical Physics, 18, 1644-1648. https://doi.org/10.1039/C5CP05154A
Sun, S., Sun, M., Kong, Y., Fang, Y. and Yao, Y. (2016) MoS2 and Graphene as Dual, Cocatalysts for Enhanced Visible Light Photocatalytic Activity of Fe2O3. Journal of Sol-Gel Science and Technology, 80, 719-727.
Srivastava, S. (2012) Synthesis and Characterization of Iron Oxide Nanoparticle from FeCl3 by Using Polyvinyl Alcohol. International Journal of Physical and Social Sciences, 2, 161-184.
Woo, K., Lee, H.J., Ahn, J.-P. and Park, Y.S. (2003) Sol-Gel Mediated Synthesis of Fe2O3 Nanorods. Advanced Materials, 15, 1761-1764. https://doi.org/10.1002/adma.200305561
Gao, D., Si, M., Li, J., Zhang, J., Zhang, Z., Yang, Z. and Xue, D. (2013) Ferromagnetism in Freestanding MoS2 Nanosheets. Nanoscale Research Letters, 8, 129. https://doi.org/10.1186/1556-276X-8-129
Zhang, Y., Chen, P., Wen, F., Meng, Y., Yuan, B. and Wang, H. (2016) Synthesis of S-Rich Flower-Like Fe2O3-MoS2 for Cr (VI) Removal. Separation Science and Technology, 51, 1779-1786.
Yang, X., Sun, H., Zhang, L., Zhao, L., Lian, J. and Jiang, Q. (2016) High Efficient Photo-Fenton Catalyst of α-Fe2O3/MoS2 Hierarchical Nanoheterostructures: Reutilization for Supercapacitors. Scientific Reports, 6, Article No. 31591. https://doi.org/10.1038/srep31591
Ye, L., Wang, D. and Chen, S. (2016) Fabrication and Enhanced Photoelectrochemical Performance of MoS2/S-Doped G-C3N4 Heterojunction Film. ACS Applied Materials & Interfaces, 8, 5280-5289. https://doi.org/10.1021/acsami.5b11326
Giambrone, N., McCrory, M., Kumar, A. and Ram, M.K. (2016) Comparative Photoelectrochemical Studies of Ragioregular Polyhexylthiophene with Microdiamond, Nanodiamond and Hexagonal Boron Nitride Hybrid Films. Thin Solid Films, 615, 226-232.
Basnayaka, P.A., Villalba, P., Ram, M.K., Stefanakos, L. and Kumar, A. (2013) Photovoltaic Properties of Multi Walled Carbon Nanotubes-Poly (3-Octathiophene) Conducting Polymer Blends Structures. In: MRS Proceedings, Cambridge University Press, Cambridge, 139-144.
Bard, A.J. and Faulkner, L.R. (1980) Electrochemical Methods. Wiley, New York.
Ram, M.K., Maccioni, E. and Nicolini, C. (1997) The Electrochromic Response of Polyaniline and Its Copolymeric Systems. Thin Solid Films, 303, 27-33.
Ram, M., Sundaresan, N. and Malhotra, B. (1994) Performance of Electrochromic Cells of Polyaniline in Polymeric Electrolytes. Journal of Materials Science Letters, 13, 1490-1493. https://doi.org/10.1007/BF00419144