Síntese verde de nanopartículas de Pd suportadas em Fe3O4@ZnO para reações de oxidação e hidrogenação em sistemas líquidos
DOI:
https://doi.org/10.33448/rsd-v11i14.36004Palavras-chave:
Nanomateriais; Separação magnética; Biossíntese.Resumo
Neste trabalho, nanopartículas de Pd imobilizadas em um suporte sólido híbrido composto de Fe3O4 revestido por uma camada de ZnO foram sintetizadas por um método verde que utiliza água, um substrato biológico de uma planta local (Rhamnidium elaeocarpum) e sais metálicos de Fe3+ e Zn2+. 1H-NMR e 13C-NM revelaram o β-sitosterol como o principal componente do substrato biológico. O suporte catalítico contendo nanopartículas de Pd foi aplicado em três modelos de sistemas catalíticos sólido-líquido, a saber: oxidação de álcool, redução de nitrocompostos e hidrogenação de olefinas. Para a oxidação do álcool, o álcool benzílico foi usado como substrato em uma condição livre de solvente, com alta seletividade em relação ao benzaldeído, e uma única amostra do catalisador pôde ser reciclada até 11 vezes antes que qualquer perda de atividade pudesse ser detectada. TOF (frequência de rotatividade) de 13.686 h-1 para a oxidação do substrato foi alcançado com uma taxa média de rendimento de 45,4% para a formação de benzaldeído e 81,6% de conversão média do substrato após 6 ciclos catalíticos. Para os experimentos de hidrogenação usando ciclohexeno e 4-nitrofenol como substratos modelo, a conversão foi de 96% para 4-aminofenol e ciclohexano, respectivamente, após 30 minutos de reação. Além disso, uma única amostra do catalisador pôde ser reciclada por até 17 vezes para a redução do 4-nitrofenol, e 21 vezes na hidrogenação do ciclohexeno. A reciclagem catalítica para todas as reações estudadas foi realizada de forma simples devido à propriedade superparamagnética do material, e o isolamento do catalisador após cada lote pôde ser realizado rapidamente usando um ímã de Nd. Esses resultados sugerem que um sistema catalítico altamente ativo e estável baseado em nanopartículas de Pd suportadas em um sólido multifuncional pode ser fabricado usando biomassa verde e barata em condições de síntese operacionalmente simples.
Referências
Al-Nuairi, A. G., Mosa, K. A., Mohammad, M. G., El-Keblawy, A., Soliman, S., & Alawadhi, H. (2020). Biosynthesis, Characterization, and Evaluation of the Cytotoxic Effects of Biologically Synthesized Silver Nanoparticles from Cyperus conglomeratus Root Extracts on Breast Cancer Cell Line MCF-7. Biological Trace Element Research, 194(2), 560–569. https://doi.org/10.1007/s12011-019-01791-7
Ammar, S. H., Abdulnabi, W. A., & kader, H. D. A. (2020). Synthesis, characterization and environmental remediation applications of polyoxometalates-based magnetic zinc oxide nanocomposites (Fe3O4@ZnO/PMOs). Environmental Nanotechnology, Monitoring & Management, 13, 100289. https://doi.org/https://doi.org/10.1016/j.enmm.2020.100289
Ayaz Ahmed, K. B., Subramaniam, S., Veerappan, G., Hari, N., Sivasubramanian, A., & Veerappan, A. (2014). β-Sitosterol-d-glucopyranoside isolated from Desmostachya bipinnata mediates photoinduced rapid green synthesis of silver nanoparticles. RSC Advances, 4(103), 59130–59136. https://doi.org/10.1039/C4RA10626A
Bahruji, H., Bowker, M., Hutchings, G., Dimitratos, N., Wells, P., Gibson, E., Jones, W., Brookes, C., Morgan, D., & Lalev, G. (2016). Pd/ZnO catalysts for direct CO2 hydrogenation to methanol. Journal of Catalysis, 343, 133–146. https://doi.org/https://doi.org/10.1016/j.jcat.2016.03.017
Bahtiar, S., Taufiq, A., Utomo, J., Hidayat, N., & Sunaryono, S. (2019). Structural Characterizations of Magnetite/Zinc Oxide Nanocomposites Prepared by Co-precipitation Method. IOP Conference Series: Materials Science and Engineering, 515, 12076. https://doi.org/10.1088/1757-899X/515/1/012076
Bankar, D. B., Hawaldar, R. R., Arbuj, S. S., Shinde, S. T., Gadde, J. R., Rakshe, D. S., Amalnerkar, D. P., & Kanade, K. G. (2020). Palladium loaded on ZnO nanoparticles: Synthesis, characterization and application as heterogeneous catalyst for Suzuki–Miyaura cross-coupling reactions under ambient and ligand-free conditions. Materials Chemistry and Physics, 243, 122561. https://doi.org/https://doi.org/10.1016/j.matchemphys.2019.122561
Barrios, C. E., Bosco, M. V, Baltanás, M. A., & Bonivardi, A. L. (2015). Hydrogen production by methanol steam reforming: Catalytic performance of supported-Pd on zinc–cerium oxides’ nanocomposites. Applied Catalysis B: Environmental, 179, 262–275. https://doi.org/https://doi.org/10.1016/j.apcatb.2015.05.030
Batista, F. R. M., da S. Melo, I. E. M., dos Santos Pereira, L., Lima, A. A. G., Bashal, A. H., Costa, J. C. S., Magalhães, J. L., Lima, F. C. A., de Moura, C., Garcia, M. A. S., & de Moura, E. M. (2020). Screening of the Au:Pt Atomic Ratio Supported in SrCO3: Effects on the Performance of the Solvent-Free Oxidation of Benzyl Alcohol. Journal of the Brazilian Chemical Society, 31, 488. https://doi.org/https://doi.org/10.21577/0103-5053.20190207
Cable, R. E., & Schaak, R. E. (2007). Solution Synthesis of Nanocrystalline M−Zn (M = Pd, Au, Cu) Intermetallic Compounds via Chemical Conversion of Metal Nanoparticle Precursors. Chemistry of Materials, 19(16), 4098–4104. https://doi.org/10.1021/cm071214j
Camargo, P., Satyanarayana, K. G., & Wypych, F. (2009). Nanocomposites: Synthesis, Structure, Properties and New Application Opportunities. Materials Research-Ibero-American Journal of Materials - MATER RES-IBERO-AM J MATER, 12. https://doi.org/10.1590/S1516-14392009000100002
Cao, P., Yang, Z., Navale, S. T., Han, S., Liu, X., Liu, W., Lu, Y., Stadler, F. J., & Zhu, D. (2019). Ethanol sensing behavior of Pd-nanoparticles decorated ZnO-nanorod based chemiresistive gas sensors. Sensors and Actuators B: Chemical, 298, 126850. https://doi.org/https://doi.org/10.1016/j.snb.2019.126850
Chuc, L. T. N., Chen, C.-S., Lo, W.-S., Shen, P.-C., Hsuan, Y.-C., Tsai, H.-H. G., Shieh, F.-K., & Hou, D.-R. (2017). Long-Range Olefin Isomerization Catalyzed by Palladium(0) Nanoparticles. ACS Omega, 2(2), 698–711. https://doi.org/10.1021/acsomega.6b00509
Cristoforetti, G., Pitzalis, E., Spiniello, R., Ishak, R., & Muniz-Miranda, M. (2011). Production of Palladium Nanoparticles by Pulsed Laser Ablation in Water and Their Characterization. The Journal of Physical Chemistry C, 115(12), 5073–5083. https://doi.org/10.1021/jp109281q
da Silva, F. P., Fiorio, J. L., & Rossi, L. M. (2017). Tuning the Catalytic Activity and Selectivity of Pd Nanoparticles Using Ligand-Modified Supports and Surfaces. ACS Omega, 2(9), 6014–6022. https://doi.org/10.1021/acsomega.7b00836
da Silva, R. A., Jacinto, M. J., Silva, V. C., & Cabana, D. C. (2018). Urea-assisted fabrication of Fe3O4@ZnO@Au composites for the catalytic photodegradation of Rhodamine-B. Journal of Sol-Gel Science and Technology, 86(1), 94–103. https://doi.org/10.1007/s10971-018-4607-0
Gaikwad, D. S., Undale, K. A., Kalel, R. A., & Patil, D. B. (2019). Acacia concinna pods: a natural and new bioreductant for palladium nanoparticles and its application to Suzuki–Miyaura coupling. Journal of the Iranian Chemical Society, 16(10), 2135–2141. https://doi.org/10.1007/s13738-019-01682-7
Galvanin, F., Sankar, M., Cattaneo, S., Bethell, D., Dua, V., Hutchings, G. J., & Gavriilidis, A. (2018). On the development of kinetic models for solvent-free benzyl alcohol oxidation over a gold-palladium catalyst. Chemical Engineering Journal, 342, 196–210. https://doi.org/https://doi.org/10.1016/j.cej.2017.11.165
Guo, Y., Gao, Y., Li, X., Zhuang, G., Wang, K., Zheng, Y., Sun, D., Huang, J., & Li, Q. (2019). Catalytic benzene oxidation by biogenic Pd nanoparticles over 3D-ordered mesoporous CeO2. Chemical Engineering Journal, 362, 41–52. https://doi.org/https://doi.org/10.1016/j.cej.2019.01.012
Gupta, S. P., Pawbake, A. S., Sathe, B. R., Late, D. J., & Walke, P. S. (2019). Superior humidity sensor and photodetector of mesoporous ZnO nanosheets at room temperature. Sensors and Actuators B: Chemical, 293, 83–92. https://doi.org/https://doi.org/10.1016/j.snb.2019.04.086
Hu, Z., Zhou, G., Xu, L., Yang, J., Zhang, B., & Xiang, X. (2019). Preparation of ternary Pd/CeO2-nitrogen doped graphene composites as recyclable catalysts for solvent-free aerobic oxidation of benzyl alcohol. Applied Surface Science, 471, 852–861. https://doi.org/https://doi.org/10.1016/j.apsusc.2018.12.067
Ismaeel, S., Jaber, H., & Zayed, R. (2020). ISOLATION OF β-SITOSTEROL FROM TAMARIX APHYLLA OF IRAQ. Biochem. Cell. Arch. 20(2), 6497–6502. https://doi.org/https://connectjournals.com/03896.2020.20.6497
Jacinto, M. J., Souto, R. S., Silva, V. C. P., Prescilio, I. C., Kauffmann, A. C., Soares, M. A., de Souza, J. R., Bakuzis, A. F., & Fontana, L. C. (2021). Biosynthesis of Cube-Shaped Fe3O4 Nanoparticles for Removal of Dyes Using Fenton Process. Water, Air, & Soil Pollution, 232(7), 270. https://doi.org/10.1007/s11270-021-05233-w
Khataee, A. R., Karimi, A., Soltani, R. D. C., Safarpour, M., Hanifehpour, Y., & Joo, S. W. (2014). Europium-doped ZnO as a visible light responsive nanocatalyst: Sonochemical synthesis, characterization and response surface modeling of photocatalytic process. Applied Catalysis A: General, 488, 160–170. https://doi.org/https://doi.org/10.1016/j.apcata.2014.09.039
Kibis, L. S., Titkov, A. I., Stadnichenko, A. I., Koscheev, S. V, & Boronin, A. I. (2009). X-ray photoelectron spectroscopy study of Pd oxidation by RF discharge in oxygen. Applied Surface Science, 255(22), 9248–9254. https://doi.org/https://doi.org/10.1016/j.apsusc.2009.07.011
Kuai, L., Chen, Z., Liu, S., Kan, E., Yu, N., Ren, Y., Fang, C., Li, X., Li, Y., & Geng, B. (2020). Titania supported synergistic palladium single atoms and nanoparticles for room temperature ketone and aldehydes hydrogenation. Nature Communications, 11(1), 48. https://doi.org/10.1038/s41467-019-13941-5
Li, X., Feng, J., Sun, J., Wang, Z., & Zhao, W. (2019). Solvent-Free Catalytic Oxidation of Benzyl Alcohol over Au-Pd Bimetal Deposited on TiO2: Comparison of Rutile, Brookite, and Anatase. Nanoscale Research Letters, 14(1), 394. https://doi.org/10.1186/s11671-019-3211-8
Li, X., Zeng, Z., Hu, B., Qian, L., & Hong, X. (2017). Surface-Atom Dependence of ZnO-Supported Ag@Pd Core@Shell Nanocatalysts in CO2 Hydrogenation to CH3OH. ChemCatChem, 9(6), 924–928. https://doi.org/https://doi.org/10.1002/cctc.201601119
Liqiang, J., Baiqi, W., Baifu, X., Shudan, L., Keying, S., Weimin, C., & Honggang, F. (2004). Investigations on the surface modification of ZnO nanoparticle photocatalyst by depositing Pd. Journal of Solid State Chemistry, 177(11), 4221–4227. https://doi.org/https://doi.org/10.1016/j.jssc.2004.08.016
López-Salazar, H., Camacho-Díaz, B. H., Ávila-Reyes, S. V, Pérez-García, M. D., González- Cortazar, M., Arenas Ocampo, M. L., & Jiménez-Aparicio, A. R. (2019). Identification and Quantification of β-Sitosterol β-d-Glucoside of an Ethanolic Extract Obtained by Microwave-Assisted Extraction from Agave angustifolia Haw. In Molecules (Vol. 24, Issue 21). https://doi.org/10.3390/molecules24213926
Ma, M., Yang, Y., Li, W., Feng, R., Li, Z., Lyu, P., & Ma, Y. (2019). Gold nanoparticles supported by amino groups on the surface of magnetite microspheres for the catalytic reduction of 4-nitrophenol. Journal of Materials Science, 54(1), 323–334. https://doi.org/10.1007/s10853-018-2868-1
Mallat, T., & Baiker, A. (2004). Oxidation of Alcohols with Molecular Oxygen on Solid Catalysts. Chemical Reviews, 104(6), 3037–3058. https://doi.org/10.1021/cr0200116
Miceli, M., Frontera, P., Macario, A., & Malara, A. (2021). Recovery/Reuse of Heterogeneous Supported Spent Catalysts. Catalysts, 11(5). https://doi.org/https://doi.org/10.3390/catal11050591
Miedziak, P. J., He, Q., Edwards, J. K., Taylor, S. H., Knight, D. W., Tarbit, B., Kiely, C. J., & Hutchings, G. J. (2011). Oxidation of benzyl alcohol using supported gold–palladium nanoparticles. Catalysis Today, 163(1), 47–54. https://doi.org/https://doi.org/10.1016/j.cattod.2010.02.051
Moon, J., Park, J.-A., Lee, S.-J., Zyung, T., & Kim, I.-D. (2010). Pd-doped TiO2 nanofiber networks for gas sensor applications. Sensors and Actuators B: Chemical, 149(1), 301–305. https://doi.org/https://doi.org/10.1016/j.snb.2010.06.033
Munvera, A., Nyemb, J. N., Alfred Ngenge, T., Mafo, M. A. F., Nuzhat, S., & Nkengfack, A. E. (2021). First report of isolation of antibacterial ceramides from the leaves of Euclinia longiflora Salisb. Natural Product Communications, 16(11), 1934578X211048628. https://doi.org/10.1177/1934578X211048628
Ododo, M. M., Choudhury, M. K., & Dekebo, A. H. (2016). Structure elucidation of β-sitosterol with antibacterial activity from the root bark of Malva parviflora. SpringerPlus, 5(1), 1210. https://doi.org/10.1186/s40064-016-2894-x
Odoom-Wubah, T., Li, Q., Wang, Q., Rukhsana Usha, M. Z., Huang, J., & Li, Q. (2019). Template-free synthesis of carbon self-doped ZnO superstructures as efficient support for ultra fine Pd nanoparticles and their catalytic activity towards benzene oxidation. Molecular Catalysis, 469, 118–130. https://doi.org/https://doi.org/10.1016/j.mcat.2019.03.013
Ökte, A. N. (2014). Characterization and photocatalytic activity of Ln (La, Eu, Gd, Dy and Ho) loaded ZnO nanocatalysts. Applied Catalysis A: General, 475, 27–39. https://doi.org/https://doi.org/10.1016/j.apcata.2014.01.019
Parmanand, Kumari, S., Mittal, A., Kumar, A., Krishna, & Sharma, S. K. (2019). Palladium Nanoparticles Immobilized on Schiff Base-Functionalized Graphene-Oxide: Application in Carbon-Carbon Cross-Coupling Reactions. ChemistrySelect, 4(36), 10828–10837. https://doi.org/https://doi.org/10.1002/slct.201902242
Peng, S.-Y., Xu, Z.-N., Chen, Q.-S., Wang, Z.-Q., Lv, D.-M., Sun, J., Chen, Y., & Guo, G.-C. (2015). Enhanced Stability of Pd/ZnO Catalyst for CO Oxidative Coupling to Dimethyl Oxalate: Effect of Mg2+ Doping. ACS Catalysis, 5(7), 4410–4417. https://doi.org/10.1021/acscatal.5b00365
Raimundo e Silva, J. P., Policarpo, I. da S., Chaves, T. P., Coutinho, H. D. M., & Alves, H. da S. (2020). A glycosylated β-Sitosterol, isolated from Tacinga inamoena (Cactaceae), enhances the antibacterial activity of conventional antibiotics. South African Journal of Botany, 133, 193–200. https://doi.org/https://doi.org/10.1016/j.sajb.2020.07.017
Raj R, K., D, E., & S, R. (2020). β-Sitosterol-assisted silver nanoparticles activates Nrf2 and triggers mitochondrial apoptosis via oxidative stress in human hepatocellular cancer cell line. Journal of Biomedical Materials Research Part A, 108(9), 1899–1908. https://doi.org/https://doi.org/10.1002/jbm.a.36953
Rajeswari, R., & Gurumallesh Prabu, H. (2020). Palladium – Decorated reduced graphene oxide/zinc oxide nanocomposite for enhanced antimicrobial, antioxidant and cytotoxicity activities. Process Biochemistry, 93, 36–47. https://doi.org/https://doi.org/10.1016/j.procbio.2020.03.010
Rossi, L. M., Silva, F. P., Vono, L. L. R., Kiyohara, P. K., Duarte, E. L., Itri, R., Landers, R., & Machado, G. (2007). Superparamagnetic nanoparticle-supported palladium: a highly stable magnetically recoverable and reusable catalyst for hydrogenation reactions. Green Chemistry, 9(4), 379–385. https://doi.org/10.1039/B612980C
Shanmugam, P., Murthy, A. P., Theerthagiri, J., Wei, W., Madhavan, J., Kim, H.-S., Maiyalagan, T., & Xie, J. (2019). Robust bifunctional catalytic activities of N-doped carbon aerogel-nickel composites for electrocatalytic hydrogen evolution and hydrogenation of nitrocompounds. International Journal of Hydrogen Energy, 44(26), 13334–13344. https://doi.org/https://doi.org/10.1016/j.ijhydene.2019.03.225
Stadler, L., Homafar, M., Hartl, A., Najafishirtari, S., Colombo, M., Zboril, R., Martin, P., Gawande, M. B., Zhi, J., & Reiser, O. (2019). Recyclable Magnetic Microporous Organic Polymer (MOP) Encapsulated with Palladium Nanoparticles and Co/C Nanobeads for Hydrogenation Reactions. ACS Sustainable Chemistry & Engineering, 7(2), 2388–2399. https://doi.org/10.1021/acssuschemeng.8b05222
Vieira, Y., Silvestri, S., Leichtweis, J., Jahn, S. L., de Moraes Flores, É. M., Dotto, G. L., & Foletto, E. L. (2020). New insights into the mechanism of heterogeneous activation of nano–magnetite by microwave irradiation for use as Fenton catalyst. Journal of Environmental Chemical Engineering, 8(3), 103787. https://doi.org/https://doi.org/10.1016/j.jece.2020.103787
Wang, J., Yang, J., Li, X., Wang, D., Wei, B., Song, H., Li, X., & Fu, S. (2016). Preparation and photocatalytic properties of magnetically reusable Fe3O4@ZnO core/shell nanoparticles. Physica E: Low-Dimensional Systems and Nanostructures, 75, 66–71. https://doi.org/https://doi.org/10.1016/j.physe.2015.08.040
Wu, W., Zhang, S., Xiao, X., Zhou, J., Ren, F., Sun, L., & Jiang, C. (2012). Controllable Synthesis, Magnetic Properties, and Enhanced Photocatalytic Activity of Spindlelike Mesoporous α-Fe2O3/ZnO Core–Shell Heterostructures. ACS Applied Materials & Interfaces, 4(7), 3602–3609. https://doi.org/10.1021/am300669a
Yadav, D., & Awasthi, S. K. (2020). A Pd confined hierarchically conjugated covalent organic polymer for hydrogenation of nitroaromatics: catalysis, kinetics, thermodynamics and mechanism. Green Chemistry, 22(13), 4295–4303. https://doi.org/10.1039/D0GC01469A
Yang, J., Zhu, Y., Fan, M., Sun, X., Wang, W. D., & Dong, Z. (2019). Ultrafine palladium nanoparticles confined in core–shell magnetic porous organic polymer nanospheres as highly efficient hydrogenation catalyst. Journal of Colloid and Interface Science, 554, 157–165. https://doi.org/https://doi.org/10.1016/j.jcis.2019.07.006
Yilmaz, F. (2018). Heterogen Catalysis in Sustainable Green Solvent: Alkenes Hydrogenation With New Silica Immobilized Palladium Complex Containing S,O-Chelating Ligand. Anadolu University Journal of Science and Technology-A Applied Sciences and Engineering, 1. https://doi.org/10.18038/aubtda.409518
Yu, T., Jiao, J., Song, P., Nie, W., Yi, C., Zhang, Q., & Li, P. (2020). Recent Progress in Continuous-Flow Hydrogenation. ChemSusChem, 13(11), 2876–2893. https://doi.org/https://doi.org/10.1002/cssc.202000778
Zhang, H., Guo, W., Lu, N., & Fan, B. (2020). Solvent-free selective oxidation of aromatic alcohol with O2 over MgAl-LDH supported Pd nanoparticles: Effects of preparation methods and solvents. Materials Chemistry and Physics, 252, 123193. https://doi.org/https://doi.org/10.1016/j.matchemphys.2020.123193
Downloads
Publicado
Como Citar
Edição
Seção
Licença
Copyright (c) 2022 Robson da Silva Souto; Samara da Silva Razini; Angélica Correa Kauffmann; Virgínia Claudia Paulino Silva; Paulo Teixeira de Sousa Jr; Andris Bakuzis; Luis Cesar Fontana; Marcos José Jacinto
Este trabalho está licenciado sob uma licença Creative Commons Attribution 4.0 International License.
Autores que publicam nesta revista concordam com os seguintes termos:
1) Autores mantém os direitos autorais e concedem à revista o direito de primeira publicação, com o trabalho simultaneamente licenciado sob a Licença Creative Commons Attribution que permite o compartilhamento do trabalho com reconhecimento da autoria e publicação inicial nesta revista.
2) Autores têm autorização para assumir contratos adicionais separadamente, para distribuição não-exclusiva da versão do trabalho publicada nesta revista (ex.: publicar em repositório institucional ou como capítulo de livro), com reconhecimento de autoria e publicação inicial nesta revista.
3) Autores têm permissão e são estimulados a publicar e distribuir seu trabalho online (ex.: em repositórios institucionais ou na sua página pessoal) a qualquer ponto antes ou durante o processo editorial, já que isso pode gerar alterações produtivas, bem como aumentar o impacto e a citação do trabalho publicado.
