Abstract
Because of the growing concerns about environmental issues, the search of proficient semiconductor catalysts for pollutants degradation from contaminated water is one of the interesting areas of research. Due to the larger surface area, hollow nanomaterials with hollow interior and outer thickness illustrate a class of significant nanostructured materials. The enhanced surface area provides remarkable applications of the hollow nanomaterials in catalysis. In Kirkendall effect, pores are formed owing to the diverse diffusion rates of two nanomaterials in a diffusion couple. Here, we have introduced the facile hydrothermal synthesis of hollow nanorods of ZnO/ZnS via Kirkendall effect using ZnO nanorods (NRs). The morphologies, optical properties, compositions, and crystal structures of the as synthesized materials are systematically studied using UV–vis, PXRD, FESEM, TEM, EDS, XPS, etc. The process of synthesis and growth mechanism of hollow NRs is suggested based on the Kirkendall effect. A hollow nanomaterial, envisaged being highly efficient for molecule adsorption on its surface, the as synthesized materials were used for the photocatalytic degradation of methylene blue (MB) dye. MB degradation efficiency of 96% within 60 min was performed over ZnO/ZnS hollow NRs, which was 2.6-fold greater than that of ZnO. The rate constant of ZnO/ZnS heterostructure was 0.045 min−1, which was 5.5 times larger than that of bare ZnO. We have concluded our work in the directions towards the synthesis of various semiconductor hollow nanostructures for the varied catalytic reactions.
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References
Baruah S, Dutta J (2009) Hydrothermal growth of ZnO nanostructures. Sci Technol Adv Mater 10:013001. https://doi.org/10.1088/1468-6996/10/1/013001
Basu M, Garg N, Ganguli AK (2014) A type-II semiconductor (ZnO/CuS heterostructure) for visible light photocatalysis. J Mater Chem A 2:7517–7525. https://doi.org/10.1039/C3TA15446G
Cabot A, Ibanez M, Guardia P, Alivisatos AP (2009) Reaction regimes on the synthesis of hollow particles by the Kirkendall effect. J Am Chem Soc 131:11326–11328. https://doi.org/10.1021/ja903751p
Çifçi DI (2016) Decolorization of methylene blue and methyl orange with Ag doped TiO2 under UV-A and UV-visible conditions: process optimizatıon by response surface method and toxicity evaluation. Global NEST J, 18, 371–380. https://doi.org/10.30955/gnj.001899
Çifçi DI, Meriç S (2015) Optimization of suspended photocatalytic treatment of two biologically treated textile effluents using TiO2 and ZnO catalysts. Global NEST J, 17, 653–663. https://doi.org/10.30955/gnj.001715
Fageria P, Gangopadhyay S, Pande S (2014) Synthesis of ZnO/Au and ZnO/Ag nanoparticles and their photocatalytic application using UV and visible light. RSC Adv 4:24962–24972. https://doi.org/10.1039/C4RA03158J
Fan HJ, Gcsele U, Zacharias M (2007) Formation of nanotubes and hollow nanoparticles based on Kirkendall and diffusion processes. Nano Micro Small 3:1660–1671. https://doi.org/10.1002/smll.200700382
Fenoll J, Ruiz E, Hellin P, Flores P, Navarro S (2011) Heterogeneous photocatalytic oxidation of cyprodinil and fludioxonil in leaching water under solar irradiation. Chemosphere 2011(85):1262–1268. https://doi.org/10.1016/j.chemosphere.07.022
Gao X, Wang J, Yu J, Xu H (2015) Novel ZnO-ZnS nanowire arrays with heterostructures and enhanced photocatalytic properties. Crystal Eng Commun J 17:6328–6337. https://doi.org/10.1039/C5CE01078K
Guo P, Jiang J, Shen S, Guo L (2013) ZnS/ZnO heterojunction as photoelectrode: type-II band alignment towards enhanced photoelectrochemical performance. Int J Hydrogen Energy 38:13097–13103. https://doi.org/10.1016/j.ijhydene.2013.01.184
Hassan MA, Waseem A, Johar MA, Bagal IV, Hab JH, Sang-Wan R (2020) Single-step fabrication of 3D hierarchical ZnO/ZnS heterojunction branched nanowires by MOCVD for enhanced photoelectrochemical water splitting. J Mater Chem A 8:8300–8312. https://doi.org/10.1039/C9TA13714A
Houas A, Lachheb H, Ksibi M, Elaloui EC, Guillard M (2001) Herrmann, Photocatalytic degradation pathway of methylene blue in water. Appl Catal B 31:145–157. https://doi.org/10.1016/S0926-3373(00)00276-9
Hu Y, Qian H, Liu Y, Du G, Zhang F, Wang L, Hu X (2011) A microwave-assisted rapid route to synthesize ZnO/ZnS core-shell nanostructures via controllable surface sulfidation of ZnO nanorods. Crystal Eng Commun J 13:3438–3443. https://doi.org/10.1039/C1CE05111C
Huang X, Wang M, Willinger MG, Shao L, Su DS, Meng XM (2012) Assembly of three-dimensional hetero-epitaxial ZnO/ZnS core/shell nanorod and single crystalline hollow ZnS nanotube arrays. ACS Nano 6:7333–7339. https://doi.org/10.1021/nn3024514
Li F, Jiang Y, Hu L, Liu L, Li Z, Huang X (2009) Structural and luminescent properties of ZnO nanorods and ZnO/ZnS nanocomposites. J Alloys Comp 474:531–535. https://doi.org/10.1016/j.jallcom.2008.06.149
Lonkar SP, Pillai VV, Alhassan SM (2018) Facile and scalable production of heterostructured ZnS-ZnO/Graphene nano-photocatalysts for environmental remediation. Sci Rep 8:13401. https://doi.org/10.1038/s41598-018-31539-7
Lu Q, Gao F (2016) Synthesis and property studies of hollow nanostructures. Crystal Eng Commun J 18:7399–7409. https://doi.org/10.1039/C6CE01036A
Mohammad SA, Mohammad M (2022) Enhanced photodegradation of organic contaminants using V-ZnSQDs@TiO2 photocatalyst in an aqueous medium. Photochem Photobiol Sci, Dec 10. https://doi.org/10.1007/s43630-022-00345-6 PMID: 36495409
Moraes NP, Marins LGP, Yamanaka MYM, Bacani R, Rocha RS, Rodrigues AL (2021) Efficient photodegradation of 4-chlorophenol under solar radiation using a new ZnO/ZnS/carbon xerogel composite as a photocatalyst. J Photochem Photobiol 418:113377. https://doi.org/10.1016/j.jphotochem.2021.113377
Pande S, Fageria P, Nazir R, Gangopadhyay S, Barshilia H (2015) Graphitic-carbon nitride support for the synthesis of shape-dependent ZnO and their application in visible light photocatalysts. RSC Adv 5:80397–80409. https://doi.org/10.1039/C5RA12463H
Park JY, Park SJ, Lee JH, Hwang CH, Hwang KJ, Jin S, Choi DY, Yoon SD, Lee IH (2014) Synthesis and characterization of cauliflower-like ZnS microspheres by simple self-assembly method. Mater Lett 121:97–100. https://doi.org/10.1016/j.matlet.2014.01.012
Puttaswamy M, Wang Y, Bananakere NC, Wang W, Wang J, Miao J, Shi R, Liang Y, Mi G, Cheng C (2019) Nature inspired ZnO/ZnS nanobranch-like composites, decorated with Cu(OH)2 clusters for enhanced visible-light photocatalytic hydrogen evolution. Appl Catal B 253:379–390. https://doi.org/10.1016/j.apcatb.2019.04.008
Raidongia K, Rao CNR (2008) Study of the transformations of elemental nanowires to nanotubes of metal oxides and chalcogenides through the Kirkendall effect. J Phys Chem C 112:13366–13371. https://doi.org/10.1021/jp8043658
Ranjith KS, Senthamizhan A, Balusamy B, Uyar T (2017) Nanograined surface shell wall controlled ZnO-ZnS core-shell nanofibers and their shell wall thickness dependent visible photocatalytic properties. Catal Sci Technol 7:1167–1180. https://doi.org/10.1039/C6CY02556K
Rauf MA, Meetani MA, Khaleel A, Ahmed A (2010) Photocatalytic degradation of methylene blue using a mixed catalyst and product analysis by LC/MS. Chem Eng J 157:373–378. https://doi.org/10.1016/j.cej.2009.11.017
Sadollahkhani A, Kazeminezhad I, Lu J, Nur O, Hultman L, Willander M (2014) Synthesis, structural characterization and photocatalytic application of ZnO@ZnS core-shell nanoparticles. RSC Adv 4:36940. https://doi.org/10.1039/C4RA05247A
Sanad MF, Shalan AE, Bazid SM, Abdelbasir SM (2018) Pollutant degradation of different organic dyes using the photocatalytic activity of ZnO@ZnS nanocomposite materials. J Environ Chem Eng 6:3981–3990. https://doi.org/10.1016/j.jece.2018.05.035
Sanchez-Tovar R, Fernandez-Domene RM, Montanes MT, Sanz-Marco A, Garcia-Anton J (2016) ZnO/ZnS heterostructures for hydrogen production by photoelectrochemical water splitting. RSC Adv 6:30425–30435. https://doi.org/10.1039/C6RA03501A
Schrier J, Demchenko DO, Wang LW, Alivisatos AP (2007) Optical properties of ZnO/ZnS and ZnO/ZnTe heterostructures for photovoltaic applications. Nano Lett 7:2377–2382. https://doi.org/10.1021/nl071027k
She YY, Juan YANG, Qiu KQ (2010) Synthesis of ZnS nanoparticles by solid-liquid chemical reaction with ZnO and Na2S under ultrasonic. Trans Nonferrous Metals Soc China 20:s211–s215. https://doi.org/10.1016/S1003-6326(10)60041-6
Shuai XM, Shen WZ (2011) A Facile Chemical Conversion Synthesis of ZnO/ZnS core/shell nanorods and diverse metal sulfide nanotubes. J Phys Chem C 115:6415–6422. https://doi.org/10.1021/jp2005716
Sugunan A, Warad HC, Boman M, Dutta J (2006) Zinc oxide nanowires in chemical bath on seeded substrates: role of hexamine. J Sol-Gel Sci Technol 39:49–56. https://doi.org/10.1007/s10971-006-6969-y
Wang G, Li Z, Li M, Chen C, Lv S, Liao J (2016) Aqueous phase synthesis and enhanced field emission properties of ZnO-sulfide heterojunction nanowires. Scientific Report 6:29470. https://doi.org/10.1038/srep29470
Wang W, Dahl M, Yin Y (2013) Hollow nanocrystals through the nanoscale Kirkendall effect. Chem Mater 25:1179–1189. https://doi.org/10.1021/cm3030928
Wang Z, Li C, Domen K (2019) Recent developments in heterogeneous photocatalysts for solar-driven overall water splitting. Chem Soc Rev 48:2109–2125. https://doi.org/10.1039/C8CS00542G
Wei C, Hong R, Yin H, Danzhen Li, Zhixin C, Jiangjun Xi, Jing C, Xianzhi F, Shao Y, Zheng Y (2012) One-step preparation of hollow ZnO core/ZnS shell structures with enhanced photocatalytic properties. Crystal Eng Commun 14:6295–6305. https://doi.org/10.1039/C2CE25591J
Wen L, Tianpei H, Wang Y, Ning G, Zhenggang X, Xiao YC, Xin HJ, Yaohui W, Zhao Y (2020) Synergistic adsorption-photocatalytic degradation effect and norfloxacin mechanism of ZnO/ZnS@BC under UV-light irradiation. Scientific Report 10:11903. https://doi.org/10.1038/s41598-020-68517-x
Wu A, Jing L, Wang J, Qu Y, Xie Y, Jiang B, Tian C, Fu H (2015) ZnO-Dotted Porous ZnS cluster microspheres for high efficient Pt-free photocatalytic hydrogen evolution. Scientific Report 5:8858. https://doi.org/10.1038/srep08858
Yang L, Zhao Z, Wang H, Dong J, Wang L, Zhou Q, Wan X, Zhao R, Cai Z (2020) Synthesis of ZnO/ZnS core/shell microsphere and its photocatalytic activity for methylene blue and eosin dyes degradation. J Dispers Sci Technol 14:2152–2158. https://doi.org/10.1080/01932691.2019.1653768
Yang Z, Yang N, Pileni MP (2015) Nano Kirkendall effect related to nanocrystallinity of metal nanocrystals: influence of the outward and inward atomic diffusion on the final nanoparticle structure. J Phys Chem C 119:22249–22260. https://doi.org/10.1021/acs.jpcc.5b06000
Yu XL, Ji HM, Wang HL, Sun J, Wen DX (2010) Synthesis and sensing properties of ZnO/ZnS nanocages. Nanoscale Res Lett 5:644–648. https://doi.org/10.1007/s11671-010-9528-y
Zhang W, Wang S, Wang Y, Zhu Z, Gao X, Yang J, Zhang XH (2015) ZnO@ ZnS Core/shell microrods with enhanced gas sensing properties. RSC Adv 5:2620–2629. https://doi.org/10.1039/C4RA12803F
Zhou LC, Ma JJ, Zhang H, Shao YM, Li YF (2015) Fabrication of magnetic carbon composites from peanut shells and its application as a heterogeneous Fenton catalyst in removal of methylene blue. Appl Surf Sci 324:490–498. https://doi.org/10.1016/j.apsusc.2014.10.152
Acknowledgements
Ms. Poonam gratefully acknowledge the CSIR- New Delhi (File no. 09/149(0826)/2020-EMR-I) for funding. PF thanks University of Rajasthan, Jaipur, BITS, Pilani and Dr. Mrinmoyee Basu for the support. The instrumental support from MRC, MNIT Jaipur, and AIRF JNU, New Delhi, is highly acknowledged. We also thank to Dr. Riya Sailani and Asha Rulaniya for their help.
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All authors contributed to the study conception, design, and writing. Material preparation, characterization, data collection, analysis, interpretation, and the draft of manuscript were written by Poonam Kumari. Interpretation of data, validation, and supervision are conducted by Surojit Pande. Supervision, validation, and manuscript review are done by Pragati Fageria. All authors read and approved the final manuscript.
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Kumari, P., Pande, S. & Fageria, P. Facile synthesis of ZnO/ZnS hollow nanorods via Kirkendall effect with enhanced photocatalytic degradation of methylene blue. Environ Sci Pollut Res 30, 61927–61944 (2023). https://doi.org/10.1007/s11356-023-26192-1
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DOI: https://doi.org/10.1007/s11356-023-26192-1