Faculty Publications

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    Soot Oxidation Activity of Redox and Non-Redox Metal Oxides Synthesised by EDTA–Citrate Method
    (Springer New York LLC barbara.b.bertram@gsk.com, 2017) Anjana, A.P.; Prasad Dasari, H.P.; Lee, J.-H.; Harshini, H.; Babu, G.U.B.
    Abstract: In the present study, redox (CeO2, SnO2, Pr6O11 and Mn3O4) and non-redox (Gd2O3, La2O3 ZrO2 and HfO2) metal oxides were successfully synthesised using the EDTA–citrate complexing method and tested for soot oxidation activity. The characterization of the metal oxides is carried out using FTIR, XRD, BET surface area, pore volume analyser, SEM and TEM. The redox nature and metal–oxygen bond information of the metal oxides are obtained from XPS analysis. In redox metal oxides, three critical parameters [lattice oxygen binding energy, reduction temperature and ?r (ionic size difference of the corresponding metal oxide oxidation states)] govern the soot oxidation activity. Among the redox metal oxide samples, Mn3O4 and Pr6O11 samples showed lower binding energy for oxygen (O?—529.4, 528.9 eV respectively), lower reduction temperature (T?—317 and 512 °C respectively) and have smaller ?r value (9 pm and 17 pm respectively). Thus, displayed a better soot oxidation activity (T50 = 484 and 482 °C respectively) than compared to other redox metal oxides. Among the non-redox metal oxides, HfO2 sample displayed higher BET surface area (21.06 m2/g), lattice strain (0.0157), smaller ionic radius (58.2 pm) and higher relative surface oxygen ratio (58%) and thus resulted in a significantly better soot oxidation activity (T50 = 483 °C) than compared to other non-redox metal oxides. Graphical Abstract: [Figure not available: see fulltext.]. © 2017, Springer Science+Business Media, LLC.
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    Ceria-samarium binary metal oxides: A comparative approach towards structural properties and soot oxidation activity
    (Elsevier B.V., 2018) Anjana, A.P.; Geethu, J.; P, M.R.; Prasad Dasari, H.P.; Lee, J.-H.; Harshini, H.; Bhaskar Babu, G.U.
    Binary metal oxides of CeO2-Sm2O3 (CSx, x varies from 10 to 90 mol%) along with pure CeO2 and Sm2O3 were synthesised successfully by the EDTA-Citrate method. From XRD, Raman spectroscopy and UV–vis DRS results, the whole composition of metal oxides exist in three phases: (fluorite phase (F) (CS10-CS30), bi-phase (fluorite (F) + cubic (C)) (CS30-CS90) and cubic phase (C) (Sm2O3)). For CSx samples, the calculated band gap energy values obtained from the UV–vis DRS results were in between 3.0–5.1 eV and fluorite phase samples (CS10–CS30) displayed lower band gap energy values (3.04–3.07 eV) than compared to the samples in other phases. Similarly, from XPS analysis, fluorite phase samples (CS10–CS30) showed higher surface oxygen vacancy concentration than compared to samples in other phases. Catalytic activity for soot oxidation is carried out on CSx samples, and the T50 temperature is in between 480–540 °C. Fluorite phase samples (CS10 CS30) showed higher surface area, lower degree of agglomeration, lower band gap energy, higher oxygen vacancy concentration and better catalytic activity for soot oxidation. Among all the CSx samples, CS10 sample displayed highest surface area (38 m2/g), lowest degree of agglomeration (0.36), lowest band gap energy (3.04 eV), highest oxygen vacancy concentration (64%) and highest soot oxidation activity (T50 = 480 °C). The order of the soot oxidation activity of CSx samples followed the same trend of band gap energy values. © 2018 Elsevier B.V.
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    Effect of ionic radius on soot oxidation activity for ceria-based binary metal oxides
    (John Wiley and Sons Ltd vgorayska@wiley.com Southern Gate Chichester, West Sussex PO19 8SQ, 2019) Anjana, A.P.; Prasad Dasari, H.P.; Harshini, H.; Babu, G.U.B.
    CeO2 (C) along with binary metal oxides of Ce0.9M0.1O2-? (M = Sn, Hf, Zr, Gd, Sm, and La; CT, CH, CZ CG, CS, and CL) are synthesized using the EDTA–citrate method. Samples having an ionic radius smaller (CT, CH, and CZ) and larger (CG, CS, and CL) than Ce4+ are classified separately, and their soot oxidation activity is analyzed. The incorporation of dopant is confirmed from lattice constant variation in X-ray diffraction result. The critical descriptors for the activity are dopant nature (ionic radius and oxidation-state), single-phase solid solution, lattice strain, reactive (200) and (220) planes, Raman intensity ration (Iov/IF2g), optical bandgap, reducibility ratio, and surface oxygen vacancy. Smaller ionic radius, isovalent dopants (CH and CZ) create a defect site by lowering the optical bandgap along with improved surface oxygen vacancy concentration and thus enhanced soot oxidation activity. Aliovalent dopant with larger ionic radius shows the involvement of lattice oxygen in oxidation reaction by charge compensation mechanism. CL showed the highest activity amongst larger ionic radius samples. © 2019 Curtin University and John Wiley & Sons, Ltd.
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    An investigation on copper-loaded ceria-praseodymium catalysts for soot oxidation activity and its kinetics
    (Springer Science and Business Media Deutschland GmbH, 2024) Patil, S.S.; Prasad Dasari, H.P.
    The Cu-loaded Ce-Pr catalyst series was successfully developed to study their performance on soot oxidation activity and its kinetic behavior. The doped samples showed a similar trend for cubic fluorite structure except for CuO, which possessed a monoclinic structure from the XRD analysis. Facet ratios [{100}/{111} and {110}/{111}] for the reactive planes were calculated from XRD spectra; the ratio was high for the 5 Cu-CP catalysts. The oxygen vacancy peaks were noticed from Raman spectra for the doped samples. 5 Cu-CP displayed the better catalytic activity of T50 = 402 °C, which may be attributed to high reactive planes and better reducibility. The addition of Cu showed a slight enhancement in catalytic activity compared to CP and pure Ce. The kinetic triplets were evaluated: the activation energy (Ea), pre-exponential factor (A), and the reaction model. Pure Ce displayed the lowest Ea and A values, whereas pure Cu showed high Ea and A values by all the methods. Graphical abstract: (Figure presented.) © The Author(s) under exclusive licence to Associação Brasileira de Engenharia Química 2023.
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    Soot oxidation activity and kinetics of Ce0.9M0.1O2-δ (M = Cs, Mg, Ca) catalysts: Impact of Cs doping in ceria and impact of nanorods on catalytic activity
    (Institution of Chemical Engineers, 2024) Nayak, A.S.; Patil, S.S.; Prasad Dasari, H.P.; Telaginatot, D.; Rynjah, M.; Cheruku, S.
    Solution combustion method is used to synthesize Ce0.9M0.1O2-δ (M = Cs, Mg, Ca) catalysts and calcined at 600 °C/5 h. XRD and Raman Spectroscopy Analyses the chemical structure, the phases observed, and the oxygen defects in the synthesized catalysts. A cubic fluorite structure of CeO2 has been noticed for all the catalysts from XRD and Raman Spectroscopy analyses. FE-SEM micrographs are used to analyze the morphology of the Ce0.9M0.1O2-δ (M = Cs, Mg, Ca) catalysts. Ce0.9Cs0.1O2-δ catalyst shows the presence of nanorods (diameter: 63 nm), which are not seen in the other catalysts. The redox and surface properties of the synthesized catalysts are tested by H2-Temperature Programmed Reduction (H2-TPR) and O2-Temperature Programmed Desorption (O2-TPD), respectively. The Ce0.9Cs0.1O2-δ catalyst shows the greatest degree of reducibility from TPR studies and for the Ce0.9Cs0.1O2-δ catalyst, the oxygen species evolved from the O2-TPD studies are also the highest. Thermogravimetric Analysis (TGA) has been used to carry the soot oxidation activity of the developed catalysts. Soot oxidation kinetic studies have been conducted at different heating rates (5, 10, and 15 °C/min) for the catalysts. The kinetic triplets for the developed catalysts have been obtained, and rate plots ([Formula presented] vs. temperature) and Arrhenius plots (ln(k) vs. [Formula presented]) have been developed for the catalysts. From the soot oxidation and kinetic studies for the developed catalysts, Ce0.9Cs0.1O2-δ shows better soot oxidation activity (T50 = 372 °C) than the other two catalysts, while Ce0.9Mg0.1O2-δ (T50 = 556 °C) shows the lowest soot oxidation activity. All the catalysts follow a non-integral exponential model for soot oxidation, and the Ce0.9Cs0.1O2-δ catalyst has the lowest activation energy. © 2024 Institution of Chemical Engineers