Abstract
A simple, cost-effective method of two-step anodization is used to prepare environmentally benign zinc-doped iron oxide nanostructures for photocatalytic and antimicrobial applications. The effect of zinc doping on the structure and morphology of iron oxide nanostructure is analysed with the help of X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and field emission scanning electron microscopy. A detailed analysis of the changes in the binding energy positions of Fe 2p, O 1s, Zn 2p and valence band maximum with variation in doping concentration is carried out with X-ray photoelectron spectroscopy. A combined analysis of valence band X-ray photoelectron spectra and optical reflectance spectra indicates a shift in Fermi level characteristic to a conversion from n-type in pure α-Fe2O3 to p-type in 5-s zinc-doped α-Fe2O3. The room-temperature electrical conductivity of the doped is improved by five orders compared to the undoped nanostructures. The zinc-doped iron oxide nanostructures with p-type conductivity are found to show high photocatalytic degradation efficiency for the organic dye methylene blue. Significant antimicrobial activity is observed with the nanostructures for the microbes Pseudomonas aeruginosa, Bacillus subtilis and E. coli.
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Jack RS, Ayoko GA, Adebajo MO, Frost RL (2015) A review of iron species for visible-light photocatalytic water purification. Environ Sci Pollut Res 22:7439–7449. https://doi.org/10.1007/s11356-015-4346-5
Xu P, Ming G, Lian D et al (2012) Science of the Total environment use of iron oxide nanomaterials in wastewater treatment : a review. Sci Total Environ 424:1–10. https://doi.org/10.1016/j.scitotenv.2012.02.023
Zhong LS, Hu JS, Liang HP et al (2006) Self-assembled 3D flowerlike iron oxide nanostructures and their application in water treatment. Adv Mater 18:2426–2431. https://doi.org/10.1002/adma.200600504
Ashraf S, Siddiqa A, Shahida S, Qaisar S (2019) Titanium-based nanocomposite materials for arsenic removal from water: a review. Heliyon 5:e01577. https://doi.org/10.1016/j.heliyon.2019.e01577
Chen S, Li Y, Cheng YF (2017) Nanopatterning of steel by one-step anodization for anti-adhesion of bacteria. Sci Rep 7:1–9. https://doi.org/10.1038/s41598-017-05626-0
Mallick P, Dash BN (2013) X-ray Diffraction and UV-visible characterizations of α-Fe2O3 nanoparticles annealed at different temperature. Nanosci Nanotechnol 3:130–134. https://doi.org/10.5923/j.nn.20130305.04
Li Y, Feng J, Li H et al (2016) Photoelectrochemical splitting of natural seawater with α-Fe2O3/WO3 nanorod arrays. Int J Hydrogen Energy 41:4096–4105. https://doi.org/10.1016/j.ijhydene.2016.01.027
Zhang GY, Feng Y, Xu YY et al (2012) Controlled synthesis of mesoporous α-Fe2O3 nanorods and visible light photocatalytic property. Mater Res Bull 47:625–630. https://doi.org/10.1016/j.materresbull.2011.12.032
Kumar M, Sharma A, Maurya IK et al (2019) Synthesis of ultra small iron oxide and doped iron oxide nanostructures and their antimicrobial activities. J Taibah Univ Sci 13:280–285. https://doi.org/10.1080/16583655.2019.1565437
Stephen Inbaraj B, Tsai TY, Chen BH (2012) Synthesis, characterization and antibacterial activity of superparamagnetic nanoparticles modified with glycol chitosan. Sci Technol Adv Mater. https://doi.org/10.1088/1468-6996/13/1/015002
Manna PK, Nickel R, Wroczynskyj Y et al (2018) Simple, hackable, size-selective, amine-functionalized Fe-oxide nanoparticles for biomedical applications. Langmuir 34:2748–2757. https://doi.org/10.1021/acs.langmuir.7b02822
Cornell RM, Schwertmann U (2003) Introduction to the iron oxides. Wiley, New York
Long NV, Yang Y, Yuasa M et al (2014) Controlled synthesis and characterization of iron oxide nanostructures with potential applications for gas sensors and the environment. RSC Adv 4:6383–6390. https://doi.org/10.1039/c3ra45925j
Belle CJ, Bonamin A, Simon U et al (2011) Size dependent gas sensing properties of spinel iron oxide nanoparticles. Sens Actuators B 160:942–950. https://doi.org/10.1016/j.snb.2011.09.008
Wu W, Xiao X, Zhang S et al (2010) Large-scale and controlled synthesis of iron oxide magnetic short nanotubes: shape evolution, growth mechanism, and magnetic properties. J Phys Chem C 114:16092–16103. https://doi.org/10.1021/jp1010154
Shenoy MR, Ayyasamy S, Reddy MVRV et al (2019) Preparation and characterization of porous iron oxide dendrites for photocatalytic application. Solid State Sci 95:105939. https://doi.org/10.1016/j.solidstatesciences.2019.105939
Wheeler DA, Wang G, Ling Y et al (2012) Nanostructured hematite: synthesis, characterization, charge carrier dynamics, and photoelectrochemical properties. Energy Environ Sci 5:6682–6702. https://doi.org/10.1039/c2ee00001f
Tamirat AG, Rick J, Dubale AA et al (2016) Using hematite for photoelectrochemical water splitting: a review of current progress and challenges. Nanoscale Horizons 1:243–267. https://doi.org/10.1039/c5nh00098j
Nagaraj G, Irudayaraj A, Josephine RL (2019) Tuning the optical band gap of pure TiO2 via photon induced method. Optik 179:889–894. https://doi.org/10.1016/j.ijleo.2018.11.009
Kamarulzaman N, Kasim MF, Rusdi R (2015) Band gap narrowing and widening of ZnO nanostructures and doped materials. Nanoscale Res Lett. https://doi.org/10.1186/s11671-015-1034-9
Mushove T, Breault TM, Thompson LT (2015) Synthesis and characterization of hematite nanotube arrays for photocatalysis. Ind Eng Chem Res 54:4285–4292. https://doi.org/10.1021/ie504585q
Cha HG, Noh HS, Kang MJ, Kang YS (2013) Photocatalysis: progress using manganese-doped hematite nanocrystals. New J Chem 37:4004–4009. https://doi.org/10.1039/c3nj00478c
Bin ASA, Khan SB, Asiri AM (2014) Efficient solar photocatalyst based on cobalt oxide/iron oxide composite nanofibers for the detoxification of organic pollutants. Nanoscale Res Lett 9:1–9. https://doi.org/10.1186/1556-276X-9-510
Sundaramurthy J, Kumar PS, Kalaivani M et al (2012) Superior photocatalytic behaviour of novel 1D nanobraid and nanoporous α-Fe2O3 structures. RSC Adv 2:8201–8208. https://doi.org/10.1039/c2ra20608k
Zhang Z, Hossain MF, Takahashi T (2010) Fabrication of shape-controlled α-Fe2O3 nanostructures by sonoelectrochemical anodization for visible light photocatalytic application. Mater Lett 64:435–438. https://doi.org/10.1016/j.matlet.2009.10.071
Jung A, Jik Y (2011) “ Nanoantibiotics ” : a new paradigm for treating infectious diseases using nanomaterials in the antibiotics resistant era. J Control Release 156:128–145. https://doi.org/10.1016/j.jconrel.2011.07.002
Gurunathan S, Han JW, Kwon DN, Kim JH (2014) Enhanced antibacterial and anti-biofilm activities of silver nanoparticles against Gram-negative and Gram-positive bacteria. Nanoscale Res Lett 9:1–17. https://doi.org/10.1186/1556-276X-9-373
Ranghar S, Sirohi P, Verma P, Agarwal V (2014) Nanoparticle-based drug delivery systems: promising approaches against infections. Braz Arch Biol Technol 57:209–222
Rajakumar G, Rahuman AA, Roopan SM et al (2012) Fungus-mediated biosynthesis and characterization of TiO2 nanoparticles and their activity against pathogenic bacteria. Spectrochim Acta Part A 91:23–29. https://doi.org/10.1016/j.saa.2012.01.011
Ben-Sasson M, Zodrow KR, Genggeng Q et al (2014) Surface functionalization of thin-film composite membranes with copper nanoparticles for antimicrobial surface properties. Environ Sci Technol 48:384–393. https://doi.org/10.1021/es404232s
Lin QY, Lin Q, Zhang YQ et al (2017) Effect of modified iodine on defect structure and antibacterial properties of ZnO in visible light. Res Chem Intermed 43:5067–5081. https://doi.org/10.1007/s11164-017-3053-x
Gomathi M, Rajkumar PV, Prakasam A (2018) Study of dislocation density (defects such as Ag vacancies and interstitials) of silver nanoparticles, green-synthesized using Barleria cristata leaf extract and the impact of defects on the antibacterial activity. Results Phys 10:858–864. https://doi.org/10.1016/j.rinp.2018.08.011
Shebl RI, Farouk F, Azzazy HMES (2017) Effect of surface charge and hydrophobicity modulation on the antibacterial and antibiofilm potential of magnetic iron nanoparticles. J Nanomater. https://doi.org/10.1155/2017/3528295
Wang L, Hu C, Shao L (2017) The-antimicrobial-activity-of-nanoparticles–present-situati. Int J Nanomedicine 12:1227–1249. https://doi.org/10.2147/IJN.S121956
Rufus A, Sreeju N, Philip D (2016) Synthesis of biogenic hematite (α-Fe2O3) nanoparticles for antibacterial and nanofluid applications. RSC Adv 6:94206–94217. https://doi.org/10.1039/c6ra20240c
Saqib S, Munis MFH, Zaman W et al (2019) Synthesis, characterization and use of iron oxide nano particles for antibacterial activity. Microsc Res Tech 82:415–420. https://doi.org/10.1002/jemt.23182
Gordon T, Perlstein B, Houbara O et al (2011) Synthesis and characterization of zinc/iron oxide composite nanoparticles and their antibacterial properties. Colloids Surf A 374:1–8. https://doi.org/10.1016/j.colsurfa.2010.10.015
Joseph JA, Nair SB, John KA et al (2019) Aluminium doping in iron oxide nanoporous structures to tailor material properties for photocatalytic applications. J Appl Electrochem. https://doi.org/10.1007/s10800-019-01371-6
Albu SP, Ghicov A, Schmuki P (2009) High aspect ratio, self-ordered iron oxide nanopores formed by anodization of Fe in ethylene glycol/NH4F electrolytes. Phys Status Solidi Rapid Res Lett 3:64–66. https://doi.org/10.1002/pssr.200802285
Rozana M, Abdul Razak K, Yew CK et al (2016) Annealing temperature-dependent crystallinity and photocurrent response of anodic nanoporous iron oxide film. J Mater Res 31:1681–1690. https://doi.org/10.1557/jmr.2016.206
Sarma B, Jurovitzki AL, Smith YR et al (2014) Influence of annealing temperature on the morphology and the supercapacitance behavior of iron oxide nanotube (Fe-NT). J Power Sources 272:766–775. https://doi.org/10.1016/j.jpowsour.2014.07.022
Sarkar S, Das R (2018) Determination of structural elements of synthesized silver nano-hexagon from X-ray diffraction analysis. Indian J Pure Appl Phys 56:765–772
de Faria DLA, Silva SV, deOliveira MT (1997) Raman microspectroscopy of some iron oxides and oxyhydroxides. J Raman Spectrosc 28:873–878
Rahman G, Joo OS (2013) Facile preparation of nanostructured α-Fe2O3 thin films with enhanced photoelectrochemical water splitting activity. J Mater Chem A 1:5554–5561. https://doi.org/10.1039/c3ta10553a
Jubb AM, Allen HC (2010) Vibrational spectroscopic characterization of hematite, maghemite, and magnetite thin films produced by vapor deposition. ACS Appl Mater Interfaces 2:2804–2812. https://doi.org/10.1021/am1004943
Yang H, Mao X, Guo Y et al (2010) Porous α-Fe2O3 nanostructures with branched topology: growth, formation mechanism, and properties. CrystEngComm 12:1842–1849. https://doi.org/10.1039/b921618a
Yu J, Yu X (2008) Hydrothermal synthesis and photocatalytic activity of zinc oxide hollow spheres. Environ Sci Technol 42:4902–4907. https://doi.org/10.1021/es800036n
Chu D, Li K, Liu A et al (2018) Zn-doped hematite modified by graphene-like WS2: A p-type semiconductor hybrid photocathode for water splitting to produce hydrogen. Int J Hydrogen Energy 43:7307–7316. https://doi.org/10.1016/j.ijhydene.2018.02.152
PIPREK J (2003) Electron energy bands. In: Semiconductor optoelectronic devices-introduction to physics and simulation. Academic Press, pp 13–48
Gupta RP, Sen SK (1974) Calculation of multiplet structure of core p -vacancy levels. Phys Rev B 12:15–19. https://doi.org/10.1103/PhysRevB.12.15
Grosvenor AP, Kobe BA, Biesinger MC, McIntyre NS (2004) Investigation of multiplet splitting of Fe 2p XPS spectra and bonding in iron compounds. Surf Interface Anal 36:1564–1574. https://doi.org/10.1002/sia.1984
McIntyre NS, Zetaruk DG (1977) X-ray photoelectron spectroscopic studies of iron oxides. Anal Chem 49:1521–1529. https://doi.org/10.1021/ac50019a016
Hu X, Yu JC, Gong J et al (2007) α-Fe2O3 nanorings prepared by a microwave-assisted hydrothermal process and their sensing properties. Adv Mater 19:2324–2329. https://doi.org/10.1002/adma.200602176
Wang G, Ling Y, Wheeler DA et al (2011) Facile synthesis of highly photoactive α-Fe2O3-based films for water oxidation. Nano Lett 11:3503–3509. https://doi.org/10.1021/nl202316j
De Los Santos DM, Aguilar T, Sánchez-Coronilla A et al (2014) Electronic and structural properties of highly aluminum ion doped TiO 2 nanoparticles: a combined experimental and theoretical study. ChemPhysChem 15:2267–2280. https://doi.org/10.1002/cphc.201402071
Chen YC, Kuo CL, Hsu YK (2018) Facile preparation of Zn-doped hematite thin film as photocathode for solar hydrogen generation. J Alloys Compd 768:810–816. https://doi.org/10.1016/j.jallcom.2018.07.315
Fujii T, de Groot FMF, Sawatzky GA et al (1999) In situ xps analysis of various iron oxide films grown by (formula presented)-assisted molecular-beam epitaxy. Phys Rev B 59:3195–3202. https://doi.org/10.1103/PhysRevB.59.3195
Moulder JF, Stickle WF, Sobol PE, Bomben KD (1992) Handbook of photoelectron spectroscopy. Phys Electron . https://doi.org/10.1002/sia.740030412
Rahman H, Esthan C, Nair BG et al (2020) Band structure and diode characteristics of transparent pn-homojunction using delafossite CuInO2. J Phys . https://doi.org/10.1088/1361-6463/ab4757
Nair SB, John KA, Joseph JA et al (2020) Influence of p-n junction mechanism and alumina overlayer on the photocatalytic performance of TiO2 nanotubes. Nanotechnology. https://doi.org/10.1088/1361-6528/ab8043
Ingler WB, Baltrus JP, Khan SUM (2004) Photoresponse of p-type zinc-doped iron(III) oxide thin films. J Am Chem Soc 126:10238–10239. https://doi.org/10.1021/ja048461y
Kuo C-L, Hsu Y-K, Lin Y-G (2014) Facile synthesis of p -type Zn-doped α-Fe2O3 films for solar water splitting. Sol Hydrog Nanotechnol IX 9176:91760N. https://doi.org/10.1117/12.2060703
Shenoy MR, Ayyasamy S, Venkateshreddy M et al (2019) Preparation and characterization of porous iron oxide dendrites for photocatalytic application. Solid State Sci 95:105939. https://doi.org/10.1016/j.solidstatesciences.2019.105939
Zulfiqar Ahmed MN, Chandrasekhar KB, Jahagirdar AA et al (2015) Photocatalytic activity of nanocrystalline ZnO, α-Fe2O3 and ZnFe2O4/ZnO. Appl Nanosci 5:961–968. https://doi.org/10.1007/s13204-014-0395-1
de Melo EJ, de Mesquita JP, Pereira MC et al (2017) Synthesis and characterization of αFe2−xMxO3 (M = Co, Ni, Cu or Zn) photocatalysts for the degradation of the indigo carmine dye in water. Hyperfine Interact. https://doi.org/10.1007/s10751-017-1429-3
Velev J, Bandyopadhyay A, Butler WH, Sarker S (2005) Electronic and magnetic structure of transition-metal-doped α -hematite. Phys Rev B 71:1–7. https://doi.org/10.1103/PhysRevB.71.205208
Anjana PM, Bindhu MR, Umadevi M, Rakhi RB (2018) Antimicrobial, electrochemical and photo catalytic activities of Zn doped Fe3O4 nanoparticles. J Mater Sci Mater Electron 29:6040–6050. https://doi.org/10.1007/s10854-018-8578-2
Behera SS, Patra JK, Pramanik K et al (2012) Characterization and evaluation of antibacterial activities of chemically synthesized iron oxide nanoparticles. World J Nano Sci Eng 02:196–200. https://doi.org/10.4236/wjnse.2012.24026
Veerapandian M, Yun K (2011) Functionalization of biomolecules on nanoparticles: specialized for antibacterial applications. Appl Microbiol Biotechnol 90:1655–1667. https://doi.org/10.1007/s00253-011-3291-6
Sies H (1997) Oxidative stress: oxidants and antioxidants. Exp Physiol 82:291–295. https://doi.org/10.1113/expphysiol.1997.sp004024
Yemmireddy VK, Hung YC (2017) Using photocatalyst metal oxides as antimicrobial surface coatings to ensure food safety—opportunities and challenges. Compr Rev Food Sci Food Saf 16:617–631. https://doi.org/10.1111/1541-4337.12267
Gold K, Slay B, Knackstedt M, Gaharwar AK (2018) Antimicrobial activity of metal and metal-oxide based nanoparticles. Adv Ther 1:1700033. https://doi.org/10.1002/adtp.201700033
Stankic S, Suman S, Haque F, Vidic J (2016) Pure and multi metal oxide nanoparticles: synthesis, antibacterial and cytotoxic properties. J Nanobiotechnology 14:1–20. https://doi.org/10.1186/s12951-016-0225-6
Zhang H, Chen G (2009) potent antibacterial activities of Ag/TiO2 nanocomposite powders synthesized by a one-pot sol-gel method. Environ Sci Technol 43:2905–2910. https://doi.org/10.1021/es803450f
Acknowledgements
The first author acknowledges Department of Science and Technology (DST) , Government of India for financial support vide reference number SR/WOS-A/ PM-7 /2017 under Woman Scientist Scheme (WOS-A) to carry out this work. Corresponding author acknowledges KSCSTE for funding through a major research project (Ref No: KSCSTE/5131/2017-SRSPS). The first author acknowledges Dr. Shinoj V.K, Department of Physics, Union Christian College, Aluva and DST –SERB (Ref No: ECR/ 2016/001708) for the optical analysis.
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Joseph, J.A., Nair, S.B., John, S.S. et al. Zinc-doped iron oxide nanostructures for enhanced photocatalytic and antimicrobial applications. J Appl Electrochem 51, 521–538 (2021). https://doi.org/10.1007/s10800-020-01512-2
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DOI: https://doi.org/10.1007/s10800-020-01512-2