Abstract
Core-shell-nanostructured hematite@graphite (α-Fe2O3@C) for photoelectrochemical (PEC) water splitting was innovatively prepared from graphite-encapsulated iron (Fe@C) nanoparticles by the arc-discharge method. The graphite was successfully controlled from dozens to few layers, and Fe was transformed into α-Fe2O3 with particle size of 20–30 nm during the thermal oxidation. α-Fe2O3@C was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Raman spectroscopy techniques. The photocurrent density of α-Fe2O3@C reached a maximum of 20 μA/cm2 at 1.23 VRHE when there were 2–3 layers of graphite and the film thickness was 200 nm. Herein, graphite was proven to play the key role in coupling between light blocking and enhanced photocarrier separation rather than changing the density of the oxygen vacancies. The addition of graphite layers enhanced the photocurrent density by 20 times compared with that of the bare α-Fe2O3 particle film derived from the hydrothermal method, which was further demonstrated by electrochemical impedance spectra (EIS).
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References
Annamalai A, Kannan AG, Lee SY, Kim DW, Choi SH, Jang JS (2015) Role of graphene oxide as a sacrificial interlayer for enhanced photoelectrochemical water oxidation of hematite nanorods. J Phys Chem C 119:19996–20002. https://doi.org/10.1021/acs.jpcc.5b06450
Borse PH, Jun H, Choi SH, Hong SJ, Lee JS (2008) Phase and photoelectrochemical behavior of solution-processed Fe2O3 nanocrystals for oxidation of water under solar light. Appl Phys Lett 93:17310301−17310303. https://doi.org/10.1063/1.3005557
Cai J, Li S, Li Z, Wang J, Ren Y, Qin G (2013) Electrodeposition of Sn-doped hollow α-Fe2O3 nanostructures for photoelectrochemical water splitting. J Alloy Compd 574:421–426. https://doi.org/10.1016/j.jallcom.2013.05.152
Cai J, Li S, Liu Y et al (2016a) Orientation modulated charge transport in hematite for photoelectrochemical water splitting. Funct Mater Lett 9:1650047. https://doi.org/10.1142/S1793604716500478
Cai J, Li S, Pan H, Liu Y, Qin G (2016b) c-In2O3/α-Fe2O3 heterojunction photoanodes for water oxidation. J Mater Sci 51:8148–8155. https://doi.org/10.1007/s10853-016-0085-3
Cai J, Li S, Qin G et al (2019) Interface engineering of Co3O4 loaded CaFe2O4/Fe2O3 heterojunction for photoelectrochemical water oxidation. Appl Surf Sci 466:92–98. https://doi.org/10.1016/j.apsusc.2018.10.022
Cao F, Wang Y, Wang J et al (2016) Oxygen vacancy induced superior visible-light-driven photodegradation pollutant performance in BiOCl microflowers. New J Chem 40:101–106. https://doi.org/10.1039/C5NJ01718A
Deng J, Lv X, Gao J, Pu A, Li M, Sun X, Zhong J (2013) Facile synthesis of carbon-coated hematite nanostructures for solar water splitting. Energy Environ Sci 6:1965–1970. https://doi.org/10.1039/c3ee00066d
Dhanalakshmi J, Iyyapushpam S, Nishanthi ST, Malligavathy M, Pathinettam Padiyan D (2017) Investigation of oxygen vacancies in Ce coupled TiO2 nanocomposites by Raman and PL spectra. Adv Nat Sci-Nanosci 8:015015. https://doi.org/10.1088/2043-6254/aa5984
Duret A, Gratzel M (2005) Visible light-induced water oxidation on mesoscopic α- Fe2O3 films made by ultrasonic spray pyrolysis. J Phys Chem B 109:17184–17191. https://doi.org/10.1021/jp044127c
Jia L, Bogdanoff P, Ramírez A, Bloeck U, Stellmach D, Fiechter S (2016) Fe2O3 porous film with single grain layer for photoelectrochemical water oxidation: reducing of grain boundary effect. Adv Mater Interfaces 3:1500434. https://doi.org/10.1002/admi.201500434
Kim JY, Magesh G, Youn DH, Jang JW, Kubota J, Domen K, Lee JS (2013) Single-crystalline, wormlike hematite photoanodes for efficient solar water splitting. Sci Rep 3:1–6. https://doi.org/10.1038/srep02681
Klahr B, Gimenez S, Fabregat SF et al (2012) Electrochemical and photoelectrochemical investigation of water oxidation with hematite electrodes. Energy Environ Sci 5:7626. https://doi.org/10.1039/c2ee21414h
Legodi MA (2008) Raman spectroscopy applied to iron oxide pigments from waste materials and earthenware archaeological objects. Diss. University of Pretoria
Li S, Cai J, Mei Y, Ren Y, Qin G (2014) Thermal oxidation preparation of doped hematite thin films for photoelectrochemical water splitting. Int J Photoenergy 2014:1–6. https://doi.org/10.1155/2014/794370
Li S, Cai J, Liu Y, Gao M, Cao F, Qin G (2017) Tuning orientation of doped hematite photoanodes for enhanced photoelectrochemical water oxidation. Sol Energy Mater Sol Cells 179:328–333. https://doi.org/10.1016/j.solmat.2017.12.028
Li Y, Wang J, Li S, Wu Y, Wang J, Cao F, Qin G (2018) Solar energy protects steels against corrosion: enhanced protection capability achieved by NiFeO decorated BiVO4 photoanode. Mater Res Bull 107:416–420. https://doi.org/10.1016/j.materresbull.2018.08.015
Lv X, Deng J, Wang J, Zhong J, Sun X (2015) Carbon-coated α-Fe2O3 nanostructures for efficient anode of Li-ion battery. J Mater Chem A 3:5183–5188. https://doi.org/10.1039/C4TA06415A
Magnan H, Stanescu D, Rioult M, Fonda E, Barbier A (2012) Enhanced photoanode properties of epitaxial Ti doped α-Fe2O3 (0001) thin films. Appl Phys Lett 101:133908. https://doi.org/10.1063/1.4755763
Murphy AB, Randeniya PRF, Plumb LC et al (2006) Efficiency of solar water splitting using semiconductor electrodes. Int J Hydrog Energy 31:1999–2017. https://doi.org/10.1016/j.ijhydene.2006.01.014
Park JH, Park OO, Kim S (2006) Photoelectrochemical water splitting at titanium dioxide nanotubes coated with tungsten trioxide. Appl Phys Lett 89:214–217. https://doi.org/10.1063/1.2357878
Sivula K, van de Krol R (2016) Semiconducting materials for photoelectrochemical energy conversion. Nat Rev Mater 1:15010. https://doi.org/10.1038/natrevmats.2015.10
Stiller M, Barzola-Quiquia J, Lorite I, Esquinazi P, Kirchgeorg R, Albu SP, Schmuki P (2013) Transport properties of single TiO2 nanotubes. Appl Phys Lett 103:173108. https://doi.org/10.1063/1.4826640
Sun S, Larry D (2008) Introduction to organic electronic and optoelectronic materials and devices, illustrated. Taylor & Francis
Tavakkoli M, Kallio T, Reynaud O, Nasibulin AG, Johans C, Sainio J, Jiang H, Kauppinen EI, Laasonen K (2015) Single-shell carbon-encapsulated iron nanoparticles: synthesis and high electrocatalytic activity for hydrogen evolution reaction. Angew Chem-Int Edit 54:4535–4538. https://doi.org/10.1002/anie.201411450
Theerthagiri J, Senthil RA, Priya A, Madhavan J, Michael RJV, Ashokkumar M (2014) Photocatalytic and photoelectrochemical studies of visible-light active α-Fe2O3–g-C3N4 nanocomposites. RSC Adv 4:38222. https://doi.org/10.1039/c4ra04266b
Tuinstra F, Koenig L (1970) Raman spectrum of graphite. J Chem Phys 53:1126–1130. https://doi.org/10.1063/1.1674108
Wang J, Wang Y, Liu Y, Lv X, Li S, Zhou J, Cao F, Qin G (2018) Facile fabrication of α-Fe2O3/Ag2S heterojunction with enhanced photoelectrochemical water splitting property. J Nanopart Res 20. https://doi.org/10.1007/s11051-018-4328-x
Warren SC, Voitchovsky K, Dotan H et al (2013) Identifying champion nanostructures for solar water splitting. Nat Mater 12:842–849. https://doi.org/10.1038/nmat368410.1038/NMAT3684
Xia Y, Yin L (2013) Core–shell structured α-Fe2O3@ TiO2 nanocomposites with improved photocatalytic activity in the visible light region. Phys Chem Chem Phys 15:18627–18634. https://doi.org/10.1039/c3cp53178c
Yan D, Liu J, Shang Z, Luo HA (2017) Ti-doped α-Fe2O3 nanorods with controllable morphology by carbon layer coating for enhanced photoelectrochemical water oxidation. Dalton Trans 46:10558–10563. https://doi.org/10.1039/C7DT00850C
Yang J, Zeng X, Chen L, Yuan W (2013) Photocatalytic water splitting to hydrogen production of reduced graphene oxide/SiC under visible light. Appl Phys Lett 102:083101. https://doi.org/10.1063/1.4792695
Ye Y, Zhang H, Chen Y, Deng P, Huang Z, Liu L, Qian Y, Li Y, Li Q (2015) Core–shell structure carbon coated ferric oxide (Fe2O3@C) nanoparticles for supercapacitors with superior electrochemical performance. J Alloy Compd 639:422–427. https://doi.org/10.1016/j.jallcom.2015.03.113
Yu XJ, Sun TY, Wan JF (2014) Preparation for Mn/Nanographite materials and study on electrochemical degradation of phenol by Mn/Nanographite cathodes. J Nanosci Nanotechnol 14:6835–6840. https://doi.org/10.1166/jnn.2014.8954
Zhang X, Guo J, Guan P, Liu C, Huang H, Xue F, Dong X, Pennycook SJ, Chisholm MF (2013a) Catalytically active single-atom niobium in graphitic layers. Nat Commun 4:1924. https://doi.org/10.1038/ncomms2929
Zhang K, Shi X, Kim JK, Lee JS, Park JH (2013b) Inverse opal structured α-Fe2O3 on graphene thin films: enhanced photo-assisted water splitting. Nanoscale 5:1939–1944. https://doi.org/10.1039/c2nr33036a
Zhu L, Bing N, Yang D et al (2011a) Synthesis and photocatalytic properties of core-shell structured α-Fe2O3@SnO2 shuttle-like nanocomposites. CrystEngComm 13:4486–4486. https://doi.org/10.1039/c1ce05238a
Zhu X, Zhu Y, Murali S, Stoller MD, Ruoff RS (2011b) Nanostructured reduced graphene oxide/Fe2O3 composite as a high-performance anode material for lithium ion batteries. ACS Nano 5:3333–3338. https://doi.org/10.1021/nn200493r
Zou Y, Kan J, Wang Y (2011) Fe2O3-graphene rice-on-sheet nanocomposite for high and fast lithium ion storage. J Phys Chem C 115:20747–20753. https://doi.org/10.1021/jp206876t
Funding
This work was supported by the Research Foundation of Young Teachers in Anhui University of Technology (QZ201720 and QZ201605), University Natural Science Research Project of Anhui Province (KJ2018A0055), and the Joint Funds of the National Natural Science Foundation of China (U1860201), Anhui Provincial Natural Science Foundation (1908085QE179, 1908085QE192).
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The supplementary information contains SEM, cross-section SEM, XPS, UV-Vis spectra, the space charge layer scheme of α-Fe2O3@C films, equivalent element values of the Nyquist plots and the J-V curve of the α-Fe2O3 film prepared with hydrothermal α-Fe2O3 particles.
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Cai, J., Chen, H., Ding, S. et al. Promoting photocarrier separation for photoelectrochemical water splitting in α-Fe2O3@C. J Nanopart Res 21, 153 (2019). https://doi.org/10.1007/s11051-019-4592-4
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DOI: https://doi.org/10.1007/s11051-019-4592-4