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Item Solubility Limits of Ceria-Zirconia-Lanthana Solid-Solutions(Elsevier Ltd, 2017) Abbas, Z.; Surendran, M.; Anjana, P.A.; Jidev, P.K.; Harshini, H.; Sudhakar Naidu, N.; Anandhan, S.; Bhat, K.U.; Bhaskar Babu, G.U.; Prasad Dasari, H.P.We demonstrate, the solubility limits of Ceria-Zirconia-Lanthana (CZLa) solid-solutions with the increase in heat-treatment temperature from 600°C to 1300°C. CZLa nano-crystalline samples were successfully synthesized by EDTA-Citrate complex method and were characterized by Raman Spectroscopy (RS) and Transmission Electron Microscopy (TEM) analysis. With an increase in temperature, it is noticed that the solubility limit is decreased in CZLa system. At 600°C, a very good solubility is observed in CZLa system and is confirmed from RS analysis. At higher heat-treatment temperatures (1000 and 1300°C), with an increase in La content, Zr precipitated in the CZLa system and is confirmed from RS analysis. The reason for such kind of behavior in this CZLa system is clearly explained in this work. © 2017 Elsevier Ltd.Item 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.Item 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.Item Surface morphology and phase stability effect of Ceria-Hafnia (CHx) binary metal oxides on soot oxidation activity(Elsevier B.V., 2018) Anjana, A.P.; Prasad Dasari, H.P.; Harshini, H.; Babu, G.U.B.CeO2-HfO2 (CHx) binary metal oxides over whole composition range (0–100%) are synthesised using the EDTA-Citrate method and calcined at 600 °C/5 h. From XRD analysis, the sample series are classified as fluorite (F) phase for CH10-CH30, hybrid (F + M) phase for CH40-CH90 and monoclinic (M) phase for CH100 sample, respectively and the results were further confirmed using Raman spectroscopy. From SEM analysis, a clear surface morphology change is noticed for fluorite, hybrid and monoclinic phases of the CHx binary metal oxides. Further, Selected Area Electron Diffraction (SAED) analysis also confirmed the single and hybrid phases of CHx binary metal oxides. The soot oxidation for the CHx binary metal oxides displayed high catalytic activity for Fluorite phase (CH10 ? CH30) samples and a decrease in catalytic activity is noticed for the Hybrid phase (CH40 ? CH90) samples. The change in catalytic activity coincides with the change in the surface morphology and phase change for the CHx binary metal oxides. Among the Fluorite phase samples, CH10 sample displayed the highest catalytic activity (T50 = 430 °C) with higher surface area (29 m2/g), lower particle size (26 nm), lower degree of agglomeration (? = 2.8) higher surface oxygen concentration (44%). Isothermal-Time-on-stream (ITOS) analysis also showed that the CH10 sample can achieve T50 in a shorter time than compared to other CHx binary metal oxides. Surface morphology and phase stability can also play as key descriptors in screening CHx binary metal oxides for soot oxidation activity. © 2018 Elsevier B.V.Item Effect of synthesis method on structural properties and soot oxidation activity of gadolinium-doped ceria(Springer International Publishing kasia@cesj.com, 2018) Anjana, A.P.; Gadiyar, H.J.; Surendran, M.; Rao, A.S.; Prasad Dasari, H.P.; Harshini, H.; Babu, G.U.B.Abstract: EDTA–citrate complex and solvothermal methods were adopted for the synthesis of gadolinium-doped ceria (GDC) (Ce0.9Gd0.1O2) solid solution, and the obtained GDC sample is tested for soot oxidation activity. Based on XRD results, it was evident that the reactive facet planes of {100} and {110} were highly intense [intensity ratio (%) of (200)/(100) (34.2%) and (220)/(111) (51.2%)] for GDC prepared by the EDTA–citrate method in comparison with the solvothermal method, and this highly intense reactive facet plane correlates to the lower energy for oxygen vacancy formation. Apart from the smaller crystallite size (10 nm) the GDC sample prepared by the EDTA–citrate method displayed lower band gap energy (2.99 eV), higher ratio of reducibility (45.45%) and lower binding energy (528.8 eV) for surface-adsorbed oxygen. The GDC obtained by EDTA–citrate method displayed a better soot oxidation activity (T50 = 468 °C) than compared to the GDC obtained by solvothermal method (T50 = 500 °C). The obtained results significantly show that the synthesis method plays a crucial role in controlling the structural properties and in enhancing the soot oxidation activity. © 2018, Institute of Chemistry, Slovak Academy of Sciences.Item 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.Item Effect of Nd-doping on soot oxidation activity of Ceria-based nanoparticles synthesized by Glycine Nitrate Process(Elsevier B.V., 2019) Patil, S.S.; Prasad Dasari, H.P.; Harshini, H.Neodymium-doped Ceria (NDC, Nd = 0, 1, 3, 5, 10, 20 and 30 mol %) catalysts were successfully synthesized by Glycine-Nitrate-Process (GNP) and tested for soot oxidation activity. For all NDC catalysts, XRD and Raman spectroscopy analyses showed a fluorite structure of ceria having an F2gRaman active symmetric breathing mode (O-Ce-O). 1NDC catalyst displayed better T50 temperature (427?C) followed by 0NDC (435?C), and 30NDC showed the highest T50 temperature (460?C). From XPS analysis, 1NDC and 0NDC catalysts showed a high amount of Ce3+ concentration and the surface-active oxygen species than compared to other NDC catalysts and thus, resulted in better soot oxidation activity indicating that the surface Ce3+ concentration and surface-active oxygen species play a key descriptor role in tuning the soot oxidation activity of NDC catalysts. © 2019 Elsevier B.V.Item Studies on the Solid Oxide Cell Perovskite Electrode Materials for Soot Oxidation Activity(Springer, 2019) Shenoy, C.S.; Patil, S.S.; Govardhan, P.; Shourya, A.; Prasad Dasari, H.P.; Saidutta, M.B.; Harshini, H.Solid oxide cell (SOC) perovskite electrode materials (BSCF (Ba0.5Sr0.5Co0.8Fe0.2O3-?), LSCF (La0.6Sr0.4Co0.2Fe0.8O3-?) and LSCM (La0.75Sr0.25Cr0.5Mn0.5O3-?)) were synthesised using microwave-assisted reverse-strike co-precipitation method and tested for soot oxidation activity. The calcined perovskite materials were characterized using FT-IR, XRD, SEM and BSE, BET and BJH and XPS analysis. The mean activation energy for soot oxidation was calculated from Ozawa plots at various heating rates (5, 10, 15 and 20 K/min) at different levels of soot conversions (T10 to T90) for BSCF, LSCM and LSCF perovskite materials and was around 133 ± 11.5, 138 ± 9.9 and 152 ± 7.2 kJ/mol, respectively. Irrespective of the heating rates, BSCF material showed the lowest T50 temperature than compared to other samples, and it is correlated to the presence of Fe3O4 as a secondary phase. © 2019, Springer Nature Switzerland AG.Item Promotional effect of nickel addition on soot oxidation activity of Ce0.9Pr0.1O2 oxide catalysts(Springer, 2020) Rajvanshi, K.; Patil, S.S.; Lakhanlal, u.; Prasad Dasari, H.P.; Saidutta, M.B.; Harshini, H.The present study investigates the promotional effect of Ni addition on soot oxidation activity of Ce0.9Pr0.1O2 oxide catalysts. A series of xNi-PDC (x= 0, 3, 5, 7, 10, 15, and 20 mol%) catalysts were synthesized by solution combustion synthesis method and characterized by XRD, Raman spectroscopy and TEM analysis. XRD and SAED patterns of the catalysts show cubic fluorite structure of ceria with an average crystallite size of 6–8 nm, and only 20Ni-PDC display NiO as a secondary phase. Raman spectra of xNi-PDC catalysts display an increase in oxygen vacancies. With a minimum addition of 10 mol% Ni to PDC, i.e., the 10Ni-PDC catalyst showed optimum soot oxidation activity (T50 = 360 °C) than compared to PDC and other Ni-PDC catalysts. Lattice strain and oxygen vacancies played a key descriptor role in showing better soot oxidation activity of the 10Ni-PDC catalyst. From the soot oxidation kinetic studies, the activation energy obtained by Ozawa plots for the 10Ni-PDC catalyst is 137 kJ/mol. © 2020, Institute of Chemistry, Slovak Academy of Sciences.Item Dilatometer studies on LAMOX based electrolyte materials for solid oxide fuel cells(Elsevier Ltd, 2021) Das, A.; Lakhanlal, u.; Shajahan, I.; Prasad Dasari, H.P.; Saidutta, M.B.; Harshini, H.The present study deals with the citrate complexion synthesis of LAMOX-based Solid Oxide Fuel Cell (SOFC) electrolyte materials (La1.8Dy0.2Mo2-xWxO9 (x = 0, 0.1, 0.2, 0.5, and 1), La1.8Dy0.2Mo2-xGaxO9 (x = 0.1 and 0.2), and La1.8Dy0.2Mo2-xVxO9 (x = 0.025, 0.05, 0.1, and 0.2)) and their characterization to understand the sintering behaviour and phase stability. From the dilatometer studies, the linear shrinkage and shrinkage rate of the LDMW (x = 0, and 0.1) showed better shrinkage than LM and LDM. Gallium addition (LDMG) and Vanadium addition (LDMV) showed a negative impact on shrinkage behaviour. In the temperature range of 500–580 °C, the abrupt change in shrinkage rate showed the transition of phase from ? to ? for the LM. The modification of LM to LDM, LDMW, and LDMV suppressed the formation of the ? phase. During thermal expansion behaviour study in the temperature range of 100–500 °C and 550–800 °C, the LM sintered pellet showed the coefficient of thermal expansion (CTE) values of 13.3 ? 10?6/°C and 21.6 ? 10?6/°C respectively. The LDM and LDMW sintered pellets showed the CTE values in the range of 14–15 ? 10?6/°C and 16–19 ? 10?6/°C, respectively. The relative density of the sintered pellets (1100 °C/5 h in air) (LM, LDM, LDMW, and LDMG (x = 0.1)) is found to be >90%. It provides the suitability of these materials for further investigation as electrolytes of SOFCs/SOECs. © 2020 Elsevier B.V.