A novel Fe-Pd bifunctional catalyst supported on mesh-type γ-Al2O3/Al was prepared and applied in the degradation of Rhodamine B (RhB). The monolithic mesh-type Fe-Pd/γ-Al2O3/Al bifunctional catalyst could be separated from the solution directly and could synthesize H2O2 in situ. The characterization results showed that Fe could improve the dispersion of Pd0, and the electronic interactions between Pd and Fe could increase the Pd0 contents on the catalyst, which increased the productivity of H2O2. Furthermore, DFT calculations proved that the addition of Fe could inhibit the dissociation of O2 and promote the nondissociative hydrogenation of O2 on the surface of Fe-Pd/γ-Al2O3/Al, which resulted in the increasement of H2O2 selectivity. Finally, the in-situ synthesized H2O2 by Pd was furtherly decomposed in situ by Fe to generateOH radicals to degrade organic pollutants. Therefore, Fe-Pd/ γ-Al2O3/Al catalysts exhibited excellent catalytic activity in the in-situ synthesis of H2O2 and the degradation of RhB due to the synergistic effects between Pd and Fe on the catalyst. It provided a new idea for the design of bifunctional electro-Fenton catalysts. Ten cycles of experiments showed that the catalytic activity of Fe-Pd/γ-Al2O3/Al catalyst could be maintained for a long time.
References
[1]
Fernández-castro, P., Vallejo, M., Fresnedo, M., Román, S. and Ortiz, I. (2015) Insight on the Fundamentals of Advanced Oxidation Processes. Role and Review of the Determination Methods of Reactive Oxygen Species. Journal of Chemical Technology and Biotechnology, 90, 796-820. https://doi.org/10.1002/jctb.4634
[2]
Brillas, E., Sirés, I. and Oturan, M.A. (2009) Electro-Fenton Process and Related Electrochemical Technologies Based on Fenton’s Reaction Chemistry. Chemical Reviews, 109, 6570-6631. https://doi.org/10.1021/cr900136g
[3]
Guo, P. and Jin, X. (2018) The Catalytic Effect of Nano-Fe3O4 on RhB Decolorization by CGDE Process. Catalysis Communications, 106, 101-105. https://doi.org/10.1016/j.catcom.2017.12.022
[4]
Zhang, B., Hou, Y., Yu, Z., Liu, Y., Huang, J., Qian, L. and Xiong, J. (2019) Three-Dimensional Electro-Fenton Degradation of Rhodamine B with Efficient Fe-Cu/kaolin Particle Electrodes: Electrodes Optimization, Kinetics, Influencing Factors and Mechanism. Separation and Purification Technology, 210, 60-68. https://doi.org/10.1016/j.seppur.2018.07.084
[5]
Marco, J.F. and Escalona, N. (2016) Preparation and Characterization of Bimetallic Fe-Cu Allophane Nanoclays and their Activity in the Phenol Oxidation by Heterogeneous Electro-Fenton Reaction. Microporous and Mesoporous Materials, 225, 303-311. https://doi.org/10.1016/j.micromeso.2016.01.013
[6]
Ren, W., Tang, D., Huang, M., Sun, J. and Lv, K. (2018) Remarkable Improved Electro-Fenton Efficiency by Electric-Field-Induced Catalysis of CeO2. Journal of Hazardous Materials, 350, 88-97. https://doi.org/10.1016/j.jhazmat.2018.02.018
[7]
Yuan, S., Fan, Y., Zhang, Y., Tong, M. and Liao, P. (2011) Pd-Catalytic In-Situ Generation of H2O2 from H2 and O2 Produced by Water Electrolysis for the Efficient Electro-Fenton Degradation of Rhodamine B. Environmental Science and Technology, 45, 8514-8520. https://doi.org/10.1021/es2022939
[8]
Pi, L., Cai, J., Xiong, L., Cui, J., Hua, H., Tang, D. and Mao, X. (2020) Generation of H2O2 by On-Site Activation of Molecular Dioxygen for Environmental Remediation Applications: A Review. Chemical Engineering Journal, 389, Article ID: 123420. https://doi.org/10.1016/j.cej.2019.123420
[9]
Luo, M., Yuan, S., Tong, M., Liao, P., Xie, W. and Xu, X. (2014) An Integrated Catalyst of Pd Supported on Magnetic Fe3O4 Nanoparticles: Simultaneous Production of H2O2 and Fe2+ for Efficient Electro-Fenton Degradation of Organic Contaminants. Water Research, 48, 190-199. https://doi.org/10.1016/j.watres.2013.09.029
[10]
Thokchom, B., Qiu, P., Cui, M., Park, B., Pandit, A.B. and Khim, J. (2017) Magnetic Pd@Fe3O4 Composite Nanostructure as Recoverable Catalyst for Sonoelectrohybrid Degradation of Ibuprofen. Ultrasonics Sonochemistry, 34, 262-272. https://doi.org/10.1016/j.ultsonch.2016.05.030
[11]
Xu, X., Liao, P., Yuan, S., Tong, M., Luo, M. and Xie, W. (2013) Cu-Catalytic Generation of Reactive Oxidizing Species from H2 and O2 Produced by Water Electrolysis for Electro-Fenton Degradation of Organic Contaminants. Chemical Engineering Journal, 233, 117-123. https://doi.org/10.1016/j.cej.2013.08.046
[12]
Jinisha, R., Gandhimathi, R., Ramesh, S.T., Nidheesh, P.V. and Velmathi, S. (2018) Removal of Rhodamine B Dye from Aqueous Solution by Electro-Fenton Process Using Iron-Doped Mesoporous Silica as a Heterogeneous Catalyst. Chemosphere, 200, 446-454. https://doi.org/10.1016/j.chemosphere.2018.02.117
[13]
Setayesh, S.R., Nazari, P. and Maghbool, R. (2020) Engineered FeVO4/CeO2 Nanocomposite as a Two-Way Superior Electro-Fenton Catalyst for Model and Real Wastewater Treatment. Journal of Environmental Sciences, 97, 110-119. https://doi.org/10.1016/j.jes.2020.04.035
[14]
Tian, P., Xu, X., Ao, C., Ding, D., Li, W., Si, R. and Tu, W. (2017) Direct and Selective Synthesis of Hydrogen Peroxide over Palladium-Tellurium Catalysts at Ambient Pressure. ChemSusChem, 10, 3342-3346. https://doi.org/10.1002/cssc.201701238
[15]
Wang, S., Gao, K., Li, W. and Zhang, J. (2017) Effect of Zn Addition on the Direct Synthesis of Hydrogen Peroxide over Supported Palladium Catalysts. Applied Catalysis A: General, 531, 89-95. https://doi.org/10.1016/j.apcata.2016.10.023
[16]
Li, J., Ishihara, T. and Yoshizawa, K. (2011) Theoretical Revisit of the Direct Synthesis of H2O2 on Pd and Au @ Pd Surfaces: A Comprehensive Mechanistic Study. Journal of Physical Chemistry A, 115, 25359-25367. https://doi.org/10.1021/jp208118e
[17]
Ding, D., Xu, X., Tian, P., Liu, X., Xu, J. and Fan, Y. (2018) Promotional Effects of Sb on Pd-Based Catalysts for the Direct Synthesis of Hydrogen Peroxide at Ambient Pressure. Chinese Journal of Catalysis, 39, 673-681. https://doi.org/10.1016/S1872-2067(18)63031-1
[18]
Maity, S. and Eswaramoorthy, M. (2016) Ni-Pd Bimetallic Catalysts for the Direct Synthesis of H2O2-Unusual Enhancement of Pd Activity in the Presence of Ni. Journal of Materials Chemistry A, 5, 3233-3237. https://doi.org/10.1039/C6TA00486E
[19]
Freakley, S.J., He, Q., Harrhy, J.H., Lu, L., Crole, D.A., Morgan, D.J., Ntainjua, E.N., Edwards, J.K., Carley, A.F., Borisevich, A.Y., Kiely, C.J. and Hutchings, G.J. (2016) Palladium-Tin Catalysts for the Direct Synthesis of H2O2 with High Selectivity. Science, 351, 965-968. https://doi.org/10.1126/science.aad5705
[20]
Edwards, J.K., Freakley, S.J., Carley, A.F., Kiely, C.J. and Hutchings, G.J. (2014) Strategies for Designing Supported Gold à Palladium Bimetallic Catalysts for the Direct Synthesis of Hydrogen Peroxide. Accounts of Chemical Research, 47, 845-854. https://doi.org/10.1021/ar400177c
[21]
Kresse, G. and Furthmiiller, J. (1996) Efficiency of Ab-Initio Total Energy Calculations for Metals and Semiconductors Using a Plane-Wave Basis Set. Computational Materials Science, 6, 15-50. https://doi.org/10.1016/0927-0256(96)00008-0
[22]
Perdew, J.P., Burke, K. and Ernzerhof, M. (1996) Generalized Gradient Approximation Made Simple. Physical Review Letters, 77, 3865-3868. https://doi.org/10.1103/PhysRevLett.77.3865
[23]
Hendrik, J. and James, D. (1977) Special Points for Brillouin-Zone Integrations. Physical Review B, 16, 1746-1747. https://doi.org/10.1103/PhysRevB.16.1746
[24]
Henkelman, G. and Jónsson, H. (2000) Improved Tangent Estimate in the Nudged Elastic Band Method for Finding Minimum Energy Paths and Saddle Points. The Journal of Chemical Physics, 113, 9978. https://doi.org/10.1063/1.1323224
[25]
Lari, G.M., Puértolas, B., Shahrokhi, M., López, N. and Pérez-Ramírez, J. (2017) Hybrid Palladium Nanoparticles for Direct Hydrogen Peroxide Synthesis: The Key Role of the Ligand. Angewandte Chemie, 129, 1801-1805. https://doi.org/10.1002/ange.201610552
[26]
Yalfani, M.S., Contreras, S., Medina, F. and Sueiras, J.E. (2011) Hydrogen Substitutes for the in Situ Generation of H2O2: An Application in the Fenton Reaction. Journal of Hazardous Materials, 192, 340-346. https://doi.org/10.1016/j.jhazmat.2011.05.029
[27]
Blanco-Brieva, G., De FrutosEscrig, M.P., Campos-Martin, J.M. and Fierro, J.L.G. (2010) Direct Synthesis of Hydrogen Peroxide on Palladium Catalyst Supported on Sulfonic Acid-Functionalized Silica. Green Chemistry, 12, 1163-1166. https://doi.org/10.1039/c003700a
[28]
Kim, J.K., Lee, J.K., Kang, K.H., Lee, J.W. and Song, I.K. (2015) Catalytic Decomposition of Phenethyl Phenyl Ether to Aromatics over Pd-Fe Bimetallic Catalysts Supported on Ordered Mesoporous Carbon. Journal of Molecular Catalysis A: Chemical, 410, 184-192. https://doi.org/10.1016/j.molcata.2015.09.023
[29]
Liao, M., Hu, Q., Zheng, J., Li, Y., Zhou, H., Zhong, C. and Chen, B.H. (2013) Pd Decorated Fe/C Nanocatalyst for Formic Acid Electrooxidation. Electrochimica Acta, 111, 504-509. https://doi.org/10.1016/j.electacta.2013.08.102
[30]
Sellers, R.M. (1990) Spectrophotometric Determination of Hydrogen Peroxide Using Potassium Titanium (IV) Oxalate. Analyst, 105, 950-954. https://doi.org/10.1039/an9800500950
[31]
Singla, R., Ashokkumar, M. and Grieser, F. (2004) The Mechanism of the Sonochemical Degradation of Benzoic Acid in Aqueous Solutions. Research on Chemical Intermediates, 30, 723-733. https://doi.org/10.1163/1568567041856963
[32]
Song, X., Sun, K., Hao, X., Su, H., Ma, X. and Xu, Y. (2019) Facet-Dependent of Catalytic Selectivity: The Case of H2O2 Direct Synthesis on Pd Surfaces. Journal of Physical Chemistry A, 123, 26324-26337. https://doi.org/10.1021/acs.jpcc.9b07097
[33]
Ouyang, L., Da, G., Tian, P., Chen, T., Liang, G., Xu, J. and Han, Y. (2014) Insight into Active Sites of Pd-Au/TiO2 Catalysts in Hydrogen Peroxide Synthesis Directly from H2 and O2. Journal of Catalysis, 311, 129-136. https://doi.org/10.1016/j.jcat.2013.11.008
[34]
Tian, P., Ding, D., Sun, Y., Xuan, F., Xu, X., Xu, J. and Han, Y. (2019) Theoretical Study of Size Effects on the Direct Synthesis of Hydrogen Peroxide over Palladium Catalysts. Journal of Catalysis, 369, 95-104. https://doi.org/10.1016/j.jcat.2018.10.029
[35]
Pengfei, T., Like, O., Xinchao, X.U., Jing, X.U. and Fan, H.A.N.Y. (2013) Density Functional Theory Study of Direct Synthesis of H2O2 from H2 and O2 on Pd(111), Pd(100), and Pd(110) Surfaces. ChineseJournal of Catalysis, 34, 1002-1012. https://doi.org/10.1016/S1872-2067(12)60537-3
[36]
Nidheesh, P. V., Gandhimathi, R., Velmathi, S. and Sanjini, N.S. (2014) Magnetite as a Heterogeneous Electro Fenton Catalyst for the Removal of Rhodamine B from Aqueous Solution. RSC Advances, 4, 5698-5708. https://doi.org/10.1039/c3ra46969g
![\"\"](\"Edit_e6a13073-7151-40b7-b2c3-a59a59d064fc.png\")
