Production of NiMn2O4 hollow spheres and $CoFe_2O_4$bowl-like structures by using block copolymer stabilized polystyrene spheres as a hard template

Production of NiMn2O4 hollow spheres and $CoFe_2O_4$bowl-like structures by using block copolymer stabilized polystyrene spheres as a hard template

The aim of this study is to highlight the use of polystyrene (PS) latexes stabilized with block copolymers as a hard template in the production of metal oxide hollow spheres. PS latexes produced by dispersion polymerization by stabilizing with tertiary amine methacrylate-based diblock copolymer were used as a hard template in the preparation of nickel manganese oxide $(NiMn_2 O_4 )$ hollow spheres and cobalt iron oxide $(CoFe_2 O_4 )$ bowl-like structures. Thanks to the diblock copolymer stabilizer with tertiary amine functional groups on the PS surface, precursor salts of $CoFe_2 O_4 and NiMn_2 O_4$ were first homogeneously deposited on the surface of PS latexes with a controlled precipitation technique. Then, metal oxide hollow spheres and bowl-like structures were produced by calcination. XRD results showed that $CoFe_2 O_4 and NiMn_2 O_4$ structures were successfully obtained after calcination. The thermogravimetric analysis results showed that the $CoFe_2 O_4 and NiMn_2 O_4$ contents of the hybrid PS spheres were in the range of 26.0–28.6 wt%. SEM images showed that the inorganic-polymer spheres fused with each other after calcination to form larger magnetic $CoFe_2 O_4$ bowl-like structures. SEM images also indicated successful production of highly rough $NiMn_2 O_4$ hollow spheres with nanosheets on the surface.

___

  • 1. Wang XJ, Feng J, Bai YC, Zhang Q, Yin YD. Synthesis, properties, and applications of hollow micro-/nanostructures. Chemical Reviews 2016; 116 (18): 10983-11060. doi: 10.1021/acs.chemrev.5b00731
  • 2. HuJ, Chen M, Fang XS, Wu LW. Fabrication and application of inorganic hollow spheres. Chemical Society Reviews 2011; 40 (11): 5472- 5491. doi: 10.1039/c1cs15103g
  • 3. Liang J, Kou HR, Ding SJ. Complex hollow bowl-like nanostructures: synthesis, application, and perspective. Advanced Functional Materials 2021; 31 (10). ARTN 2007801, doi: 10.1002/adfm.202007801
  • 4. Yang SK, Lei Y. Recent progress on surface pattern fabrications based on monolayer colloidal crystal templates and related applications. Nanoscale 2011; 3 (7): 2768-2782. doi: 10.1039/c1nr10296f
  • 5. Ai B, Mohwald H, Wang DY,Zhang G. Advanced colloidal lithography beyond surface patterning. Advanced Materials Interfaces 2017; 4 (1): ARTN 1600271doi: 10.1002/admi.201600271
  • 6. Boyjoo Y, Wang MW, Pareek VK, Liu J, Jaroniec M. Synthesis and applications of porous non-silica metal oxide submicrospheres. Chemical Society Reviews 2016; 45 (21): 6013-6047. doi: 10.1039/c6cs00060f
  • 7. Zhang YQ, Huang ZB, Tang FQ, Ren J. Ferrite hollow spheres with tunable magnetic properties. Thin Solid Films 2006; 515 (4): 2555-2561. doi: 10.1016/j.tsf.2006.04.049
  • 8. Zhang DF, Zhang GZ, Zhang L. Multi-shelled $FeCo_2O_4$ hollow porous microspheres/CCFs magnetic hybrid and its dual-functional catalytic performance. Chemical Engineering Journal 2017; 330: 792-803. doi: 10.1016/j.cej.2017.08.018
  • 9. Bhuyan B, Paul B, Paul A, Dhar SS. Paederia foetida Linn. promoted synthesis of CoFe2O4 and NiFe2O4 nanostructures and their photocatalytic efficiency. Iet Nanobiotechnology 2018; 12 (3): 235-240. doi: 10.1049/iet-nbt.2017.0131
  • 10. Elmaci G. Magnetic hollow biocomposites prepared from lycopodium clavatum pollens as efficient recyclable catalyst. Chemistryselect 2020; 5 (7): 2225-2231. doi: 10.1002/slct.201904152
  • 11. Syouflan A, Inoue Y, Yada M, Nakashima K. Preparation of submicrometer-sized titania hollow spheres by ternplating sulfonated polystyrene latex particles. Materials Letters 2007; 61 (7): 1572-1575. doi: 10.1016/j.matlet.2006.07.081
  • 12. Watanabe M, Aritomo H, Yamaguchi I, Shinagawa T, Tamai T et al. Selective preparation of zinc oxide nanostructures by electrodeposition on the templates of surface-functionalized polymer particles. Chemistry Letters 2007; 36 (5): 680-681. doi: 10.1246/cl.2007.680
  • 13. Amari H, Guerrouache M, Mahouche-Chergui S, Abderrahim R, Carbonnier B. 2-Aminothiazole-functionalized triazine-modified polystyrene decorated with gold nanoparticles as composite catalyst for the reduction of 4-nitrophenol. Reactive & Functional Polymers 2017; 121: 58-66. doi: 10.1016/j.reactfunctpolym.2017.10.018
  • 14. Zhu Y, Chen KM, Wang X, Guo XH. Spherical polyelectrolyte brushes as a nanoreactor for synthesis of ultrafine magnetic nanoparticles. Nanotechnology 2012; 23 (26): ARTN 265601. doi: 10.1088/0957-4484/23/26/265601
  • 15. Nie G, Li G, Wang L, Zhang X. Nanocomposites of polymer brush and inorganic nanoparticles: preparation, characterization and application. Polymer Chemistry 2016; 7 (4): 753-769. doi: 10.1039/C5PY01333J
  • 16. Lu Y, Hoffmann M, Yelamanchili RS, Terrenoire A, Schrinner M et al. Well-Defined crystalline TiO2 nanoparticles generated and immobilized on a colloidal nanoreactor. Macromolecular Chemistry and Physics 2009; 210 (5): 377-386. doi: 10.1002/macp.200800608
  • 17. Polzer F, Holub-Krappe E, Rossner H, Erko A, Kirmse H et al. Structural analysis of colloidal MnOx composites. Colloid and Polymer Science 2013; 291 (3): 469-481. doi: 10.1007/s00396-012-2725-8
  • 18. Kocak G. Use of block copolymer stabilized polystyrene microspheres as templates for preparation of hollow metal oxide spheres. Afyon Kocatepe University Journal of Science and Engineering 2020; 20 (3): 398-406. doi: 10.35414/akufemubid.680013
  • 19. Kocak G. The use of block copolymer stabilized polystyrene microspheres as a template in the preparation of hollow nickel oxide spheres, In: The 32nd National Chemistry Congress; Online, Turkey; 2020. pp. 51. (in Turkish).
  • 20. Kocak G. Use of block copolymer stabilized polystyrene microspheres as templates for preparation of magnetic hollow $NiFe_2O_4$spheres, In: 4th International Mardin Artuklu Scientific Researches Conference; Mardin, Turkey; 2020. pp. 165-166.(in Turkish with an abstract in English).
  • 21. Dicker IB, Cohen GM, Farnham WB, Hertler WR, Laganis ED et al. Oxyanions catalyze group-transfer polymerization to give living polymers. Macromolecules 1990; 23 (18): 4034-4041. doi: 10.1021/ma00220a002
  • 22. Butun V, Armes SP, Billingham NC. Synthesis and aqueous solution properties of near-monodisperse tertiary amine methacrylate homopolymers and diblock copolymers. Polymer 2001; 42 (14): 5993-6008. doi: 10.1016/s0032-3861(01)00066-0.
  • 23. Bütün V, Kaynak B, Esenoğlu E, Gül G. Synthesis and selective quaternization of tertiary amine methacrylate-containing water-soluble copolymers and their use in latex synthesis as stabilizers, In: Polymer Processing and Recycling Symposium and Exhibition;Mersin, Turkey; 2004. pp. 1-12. (in Turkish).
  • 24. Suba V,Rathika G, Kumar ER, Saravanabhavan M. Influence of magnetic nanoparticles on surface changes in $CoFe_2O_4$ /nerium oleander leaf waste activated carbon nanocomposite for water treatment. Journal of Inorganic and Organometallic Polymers and Materials 2018; 28 (5): 1706-1717. doi: 10.1007/s10904-018-0831-x
  • 25. Narsimulu D, Padmaraj O, Srinadhu ES, Satyanarayana N. Synthesis, characterization and electrical properties of mesoporous nanocrystalline $CoFe_2 O_4$ as a negative electrode material for lithium battery applications. Journal of Materials Science-Materials in Electronics 2017; 28 (22): 17208-17214. doi: 10.1007/s10854-017-7650-7
  • 26. Li WC, Qiao XJ, Zheng QY, Zhang TL. One-step synthesis of $MFe_2 O_4$ (M = Fe, Co) hollow spheres by template-free solvothermal method. Journal of Alloys and Compounds 2011; 509 (21): 6206-6211. doi: 10.1016/j.jallcom.2011.02.157
  • 27. Yoon S. Facile microwave synthesis of $CoFe_2 O_4$ spheres and their application as an anode for lithium-ion batteries. Journal of Applied Electrochemistry 2014; 44 (9): 1069-1074. doi: 10.1007/s10800-014-0716-9
  • 28. Yan HL, Li T, Qiu KW, Lu Y, Cheng JB et al. Growth and electrochemical performance of porous $NiMn_2O_4$ nanosheets with high specific surface areas. Journal of Solid State Electrochemistry 2015; 19 (10): 3169-3175. doi: 10.1007/s10008-015-2946-0
  • 29. Wang XL, Zhang JQ, Yang SB, Yan HY, Hong XD et al. Interlayer space regulating of NiMn layered double hydroxides for supercapacitors by controlling hydrothermal reaction time. Electrochimica Acta 2019; 295: 1-6. doi: 10.1016/j.electacta.2018.10.021
  • 30. Bousquet A, Ibarboure E, Heroguez V, Papon E, Labrugere C et al. Single-step process to produce functionalized multiresponsive polymeric particles. Journal of Polymer Science Part A-Polymer Chemistry 2010; 48 (16): 3523-3533. doi: 10.1002/pola.24112
  • 31. Reis BM, Armes SP, Fujii S, Biggs S. Characterisation of the dispersion stability of a stimulus responsive core-shell colloidal latex. Colloids and Surfaces a-Physicochemical and Engineering Aspects 2010; 353 (2-3): 210-215. doi: 10.1016/j.colsurfa.2009.11.015
  • 32. Amalvy JI, Unali GF, Li Y, Granger-Bevan S, Armes SP et al. Synthesis of sterically stabilized polystyrene latex particles using cationic block copolymers and macromonomers and their application as stimulus-responsive particulate emulsifiers for oil-in-water emulsions. Langmuir 2004; 20 (11): 4345-4354. doi: 10.1021/la035921c
  • 33. Munoz-Bonilla A,Van Herk AM, Heuts JPA. Adding stimuli-responsive extensions to antifouling hairy particles. Polymer Chemistry 2010; 1 (5): 624-627. doi: 10.1039/c0py00054j
  • 34. Itoh T, Abe I, Tamamitsu T, Shimomoto H, Inoue K et al. Surface structure of stimuli-responsive polystyrene particles prepared by dispersion polymerization with a polystyrene/poly(L-lysine) block copolymer as a stabilizer. Polymer 2014; 55 (16): 3961-3969. doi: 10.1016/j.polymer.2014.06.069
  • 35. Baines FL, Dionisio S, Billingham NC, Armes, SP. Use of block copolymer stabilizers for the dispersion polymerization of styrene in alcoholic media. Macromolecules 1996; 29 (9): 3096-3102. doi: 10.1021/ma951767s
  • 36. Tuncel A, Kahraman R, Piskin E. Monosize polystyrene latices carrying functional-groups on their surfaces. Journal of Applied Polymer Science 1994; 51 (8): 1485-1498. doi: 10.1002/app.1994.070510816
  • 37. Wang Y, Angelatos AS, Caruso F. Template synthesis of nanostructured materials via layer-by-layer assembly. Chemistry of Materials 2008; 20 (3): 848-858. doi: 10.1021/cm7024813
  • 38. Rivas BL, Pereira ED, Moreno-Villoslada I. Water-soluble polymer-metal ion interactions. Progress in Polymer Science 2003; 28 (2): 173- 208. doi: 10.1016/s0079-6700(02)00028-x
  • 39. Rivas BL, Pereira E, Maureira A. Functional water-soluble polymers: polymer-metal ion removal and biocide properties. Polymer International 2009; 58 (10): 1093-1114. doi: 10.1002/pi.2632
  • 40. Jiang J, Yang YM, Li LC. Surfactant-assisted synthesis of nanostructured $NiFe_2O_4$ via a refluxing route. Materials Letters 2008; 62 (12-13): 1973-1975. doi: 10.1016/j.matlet.2007.10.063
  • 41. Periyasamy S, Subramanian P, Levi E, Aurbach D, Gedanken A et al. Exceptionally active and stable spinel nickel manganese oxide electrocatalysts for urea oxidation reaction. ACS Applied Materials & Interfaces 2016; 8 (19): 12176-12185. doi: 10.1021/acsami.6b02491
  • 42. Srivastava AK, Madhavi S, White TJ, Ramanujan RV. Cobalt-ferrite nanobowl arrays: Curved magnetic nanostructures. Journal of Materials Research 2007; 22 (5): 1250-1254. doi: 10.1557/JMR.2007.0149
  • 43. Li YY, Zhou F, Gao L, Duan GT. $Co_3 O_4$ nanosheet-built hollow spheres containing ultrafine neck-connected grains templated by PS@CoLDH and their ppb-level gas-sensing performance. Sensors and Actuators B-Chemical 2018; 261: 537-549. doi: 10.1016/j.snb.2018.01.162
  • 44. Chu SS, Li H, Wang YZ, Ma Q, Li H et al. Porous NiO/ZnO flower-like heterostructures consisting of interlaced nanosheet/particle framework for enhanced photodegradation of tetracycline. Materials Letters 2019; 252: 219-222. doi: 10.1016/j.matlet.2019.05.145
  • 45. Charan C, Shahi VK. Cobalt ferrite $(CoFe_2O_4)$ nanoparticles (size: similar to 10 nm) with high surface area for selective non-enzymatic detection of uric acid with excellent sensitivity and stability. Rsc Advances 2016; 6 (64): 59457-59467. doi: 10.1039/c6ra08746a
  • 46. Wang Y, Liu Q, Hu TJ, Zhang, LM, Deng YQ. Carbon supported $MnO_2-CoFe_2O_4$ with enhanced electrocatalytic activity for oxygen reduction and oxygen evolution. Applied Surface Science 2017; 403: 51-56. doi: 10.1016/j.apsusc.2017.01.127
  • 47. Kharat PB, Somvanshi SB, Khirade PP, Jadhav KM. Induction heating analysis of surface-functionalized nanoscale CoFe2O4 for magnetic fluid hyperthermia toward noninvasive cancer treatment. ACS Omega 2020; 5 (36): 23378-23384. doi: 10.1021/acsomega.0c03332
  • 48. Erdem D, Bingham NS, Heiligtag FJ, Pilet N, Warnicke P et al. CoFe2O4 and CoFe2O4-SiO2 nanoparticle thin films with perpendicular magnetic anisotropy for magnetic and magneto-optical applications. Advanced Functional Materials 2016; 26 (12): 1954-1963. doi: 10.1002/adfm.201504538
  • 49. Sapna, Budhiraja N, Kumar V, Singh SK. Synergistic effect in structural and supercapacitor performance of well dispersed $CoFe_2O_4/Co_3O4$ nano-hetrostructures. Ceramics International 2018; 44 (12): 13806-13814. doi: 10.1016/j.ceramint.2018.04.224 50. Casbeer E, Sharma VK, Li XZ. Synthesis and photocatalytic activity of ferrites under visible light: A review. Separation and Purification Technology 2012; 87: 1-14. doi: 10.1016/j.seppur.2011.11.034
  • 51. Umar A, Akhtar MS, Ameen S, Imran M, Kumar R et al. Colloidal synthesis of $NiMn_2O_4$ nanodisks decorated reduced graphene oxide for electrochemical applications. Microchemical Journal 2021; 160: ARTN 105630. doi: 10.1016/j.microc.2020.105630
  • 52. Schubert M, Munch C, Schuurman S, Poulain V, Kita J et al. Novel method for ntc thermistor production by aerosol co-deposition and combined sintering. Sensors 2019; 19 (7): ARTN 1632. doi: 10.3390/s19071632
  • 53. Abel MJ, Pramothkumar A, Archana V, Senthilkumar N, Jothivenkatachalam K et al. Facile synthesis of solar light active spinel nickel manganite $(NiMn_2O_4)$ by co-precipitation route for photocatalytic application. Research on Chemical Intermediates 2020; 46 (7): 3509- 3525. doi: 10.1007/s11164-020-04159-y
  • 54. Qin Q, Chen LL, Wei T, Wang YM, Liu XE. $Ni/NiM_2O_4$ (M = Mn or Fe) supported on N-doped carbon nanotubes as trifunctional electrocatalysts for ORR, OER and HER. Catalysis Science & Technology 2019; 9 (7): 1595-1601. doi:10.1039/c8cy02504e
  • 55. Li LJ, Yao Q, Liu JQ, Ye KB, Liu BY et al. Porous hollow superlattice $NiMn_2 O_4/NiCo_2O_4$ mesocrystals as a highly reversible anode material for lithium-ion batteries. Frontiers in Chemistry 2018; 6:ARTN 153. doi: 10.3389/fchem.2018.00153
  • 56. Wang ZB, Zhu ZH, Zhang CL, Xu CQ, Chen CN. Facile synthesis of reduced graphene oxide/$NiMn_2O_4$ nanorods hybrid materials for high-performance supercapacitors. Electrochimica Acta 2017; 230: 438-444. doi: 10.1016/j.electacta.2017.02.023
Turkish Journal of Chemistry-Cover
  • ISSN: 1300-0527
  • Yayın Aralığı: Yılda 6 Sayı
  • Yayıncı: TÜBİTAK
Sayıdaki Diğer Makaleler

Selective adsorption of acidic gases from ternary mixture by acetate- and sulfonate-based ionic liquids at molecular level

Sadiye VELİOĞLU

DFT / TDDFT insights into excited state intra-molecular hydrogen atom transfer mechanism in Liqcoumarin: an EFP1 study

Kandigowda JAGADEESHA, Yelechakanahalli Lingaraju RAMU, Mariyappa RAMEGOWDA

Capillary zone electrophoresis as a quality assessment tool of paracetamol and phenylephrine hydrochloride in presence of paracetamol impurities

Joliana F. FARID, Nadia M. MOSTAFA, Yasmin M. FAYEZ, Hebatallah M. ESSAM

First determination of anticancer, cytotoxic, and in silico ADME evaluation of secondary metabolites of endemic Astragalus leucothrix Freyn & Bornm

Melda DÖLARSLAN, İbrahim DEMİRTAŞ, Duygu GÜNEŞ GÜRBÜZ, Ayşe ŞAHİN YAĞLIOĞLU

Preparation of surface plasmon resonance-based nanosensor for curcumin detection

Duygu ÇİMEN, Şebnem ÇIKRIK, Adil DENİZLİ, Nilay BERELİ

Investigation of antibacterial and photocatalytic efficiency of green ZnO nanoparticles that synthesized with Celosia Cristata flower extract

Özgür DUYGULU, Mahmure ÜSTÜN ÖZGÜR, Melda ALTIKATOĞLU YAPAÖZ

Solar light degradation of organic dye pollutants and preparation of bis(indolyl) methanes using core-shell $Fe_3 O_4 @SiO_2 @CuO$ nanocomposite

Mina MIRZAEI, Kaveh PARVANAK BOROUJENI, Zeinab TOHIDIYAN

Adsorption isotherms, kinetic and thermodynamic studies on cadmium and lead ions from water solutions using Amberlyst 15 resin

Adalet TUNÇELİ, Abdullah ULAŞ, Orhan ACAR, Ali Rehber TÜRKER

Synthesis of modified nanocomposite material and its use on removal of cesium from aqueous media

Bilal ÇETİN, Bektaş KARAKELLE, Mustafa ÖZCAN

The study of Fe3 O4 @SiO2 -NH2 nano-magnetic composite modified by glutaraldehyde to immobilized penicillin G acylase

Monier Alhadi Abdelrahman MOHAMMED, henbin CHEN, Ke LI, Boyuan ZHANG