scholarly journals Hydrothermal Synthesis of ZnO–doped Ceria Nanorods: Effect of ZnO Content on the Redox Properties and the CO Oxidation Performance

2020 ◽  
Vol 10 (21) ◽  
pp. 7605
Author(s):  
Sofia Stefa ◽  
Maria Lykaki ◽  
Vasillios Binas ◽  
Pavlos K. Pandis ◽  
Vassilis N. Stathopoulos ◽  
...  

The rational design of highly efficient, noble metal-free metal oxides is one of the main research priorities in the area of catalysis. To this end, the fine tuning of ceria-based mixed oxides by means of aliovalent metal doping has currently received particular attention due to the peculiar metal-ceria synergistic interactions. Herein, we report on the synthesis, characterization and catalytic evaluation of ZnO–doped ceria nanorods (NR). In particular, a series of bare CeO2 and ZnO oxides along with CeO2/ZnO mixed oxides of different Zn/Ce atomic ratios (0.2, 0.4, 0.6) were prepared by the hydrothermal method. All prepared samples were characterized by X-ray diffraction (XRD), N2 physisorption, temperature-programmed reduction (TPR), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS) and transmission electron microscopy (TEM). The CO oxidation reaction was employed as a probe reaction to gain insight into structure-property relationships. The results clearly showed the superiority of mixed oxides as compared to bare ones, which could be ascribed to a synergistic ZnO–CeO2 interaction towards an improved reducibility and oxygen mobility. A close correlation between the catalytic activity and oxygen storage capacity (OSC) was disclosed. Comparison with relevant literature studies verifies the role of OSC as a key activity descriptor for reactions following a redox-type mechanism.

Processes ◽  
2020 ◽  
Vol 8 (7) ◽  
pp. 847 ◽  
Author(s):  
Sofia Stefa ◽  
Maria Lykaki ◽  
Dimitrios Fragkoulis ◽  
Vasileios Binas ◽  
Pavlos K. Pandis ◽  
...  

Ceria-based mixed oxides have been widely studied in catalysis due to their unique surface and redox properties, with implications in numerous energy- and environmental-related applications. In this regard, the rational design of ceria-based composites by means of advanced synthetic routes has gained particular attention. In the present work, ceria–titania composites were synthesized by four different methods (precipitation, hydrothermal in one and two steps, Stöber) and their effect on the physicochemical characteristics and the CO oxidation performance was investigated. A thorough characterization study, including N2 adsorption-desorption, X-ray diffraction (XRD), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDS), transmission electron microscopy (TEM) and H2 temperature-programmed reduction (H2-TPR) was performed. Ceria–titania samples prepared by the Stöber method, exhibited the optimum CO oxidation performance, followed by samples prepared by the hydrothermal method in one step, whereas the precipitation method led to almost inactive oxides. CeO2/TiO2 samples synthesized by the Stöber method display a rod-like morphology of ceria nanoparticles with a uniform distribution of TiO2, leading to enhanced reducibility and oxygen storage capacity (OSC). A linear relationship was disclosed among the catalytic performance of the samples prepared by different methods and the abundance of reducible oxygen species.


Catalysts ◽  
2019 ◽  
Vol 9 (4) ◽  
pp. 371 ◽  
Author(s):  
Maria Lykaki ◽  
Sofia Stefa ◽  
Sόnia Carabineiro ◽  
Pavlos Pandis ◽  
Vassilis Stathopoulos ◽  
...  

Ceria has been widely studied either as catalyst itself or support of various active phases in many catalytic reactions, due to its unique redox and surface properties in conjunction to its lower cost, compared to noble metal-based catalytic systems. The rational design of catalytic materials, through appropriate tailoring of the particles’ shape and size, in order to acquire highly efficient nanocatalysts, is of major significance. Iron is considered to be one of the cheapest transition metals while its interaction with ceria support and their shape-dependent catalytic activity has not been fully investigated. In this work, we report on ceria nanostructures morphological effects (cubes, polyhedra, rods) on the textural, structural, surface, redox properties and, consequently, on the CO oxidation performance of the iron-ceria mixed oxides (Fe2O3/CeO2). A full characterization study involving N2 adsorption at –196 °C, X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), temperature programmed reduction (TPR), and X-ray photoelectron spectroscopy (XPS) was performed. The results clearly revealed the key role of support morphology on the physicochemical properties and the catalytic behavior of the iron-ceria binary system, with the rod-shaped sample exhibiting the highest catalytic performance, both in terms of conversion and specific activity, due to its improved reducibility and oxygen mobility, along with its abundance in Fe2+ species.


Nanomaterials ◽  
2019 ◽  
Vol 9 (8) ◽  
pp. 1118 ◽  
Author(s):  
Qiuwan Han ◽  
Dongyang Zhang ◽  
Jiuli Guo ◽  
Baolin Zhu ◽  
Weiping Huang ◽  
...  

The gold catalysts supported on various morphologies of α-Fe2O3 in carbon monoxide (CO) oxidation reaction have been studied for many researchers. However, how to improve the catalytic activity and thermal stability for CO oxidation is still important. In this work, an unusual morphology of α-Fe2O3 was prepared by hydrothermal method and gold nanoparticles were supported using a deposition-precipitation method. Au/α-Fe2O3 catalyst exhibited great activity for CO oxidation. The crystal structure and microstructure images of α-Fe2O3 were carried out by X-ray diffraction (XRD) and scanning electron microscopy (SEM) and the size of gold nanoparticles was determined by transmission electron microscopy (TEM). X-ray photoelectron spectra (XPS) and Fourier transform infrared spectra (FTIR) results confirmed that the state of gold was metallic. The 1.86% Au/α-Fe2O3 catalyst calcined at 300 °C had the best catalytic performance for CO oxidation reaction and the mechanism for CO oxidation reaction was also discussed. It is highly likely that the small size of gold nanoparticle, oxygen vacancies and active sites played the decisive roles in CO oxidation reaction.


Catalysts ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 452
Author(s):  
Michalis Konsolakis ◽  
Maria Lykaki

The rational design and fabrication of highly-active and cost-efficient catalytic materials constitutes the main research pillar in catalysis field. In this context, the fine-tuning of size and shape at the nanometer scale can exert an intense impact not only on the inherent reactivity of catalyst’s counterparts but also on their interfacial interactions; it can also opening up new horizons for the development of highly active and robust materials. The present critical review, focusing mainly on our recent advances on the topic, aims to highlight the pivotal role of shape engineering in catalysis, exemplified by noble metal-free, CeO2-based transition metal catalysts (TMs/CeO2). The underlying mechanism of facet-dependent reactivity is initially discussed. The main implications of ceria nanoparticles’ shape engineering (rods, cubes, and polyhedra) in catalysis are next discussed, on the ground of some of the most pertinent heterogeneous reactions, such as CO2 hydrogenation, CO oxidation, and N2O decomposition. It is clearly revealed that shape functionalization can remarkably affect the intrinsic features and in turn the reactivity of ceria nanoparticles. More importantly, by combining ceria nanoparticles (CeO2 NPs) of specific architecture with various transition metals (e.g., Cu, Fe, Co, and Ni) remarkably active multifunctional composites can be obtained due mainly to the synergistic metalceria interactions. From the practical point of view, novel catalyst formulations with similar or even superior reactivity to that of noble metals can be obtained by co-adjusting the shape and composition of mixed oxides, such as Cu/ceria nanorods for CO oxidation and Ni/ceria nanorods for CO2 hydrogenation. The conclusions derived could provide the design principles of earth-abundant metal oxide catalysts for various real-life environmental and energy applications.


2019 ◽  
Vol 25 (S2) ◽  
pp. 1448-1449 ◽  
Author(s):  
M. Plodinec ◽  
E. Stotz ◽  
L. Sandoval-Diaz ◽  
R. Schlögl ◽  
T. Lunkenbein

Catalysts ◽  
2020 ◽  
Vol 10 (6) ◽  
pp. 613
Author(s):  
Hussein Mahdi S. Al-Aani ◽  
Mihaela M. Trandafir ◽  
Ioana Fechete ◽  
Lucia N. Leonat ◽  
Mihaela Badea ◽  
...  

To improve the catalytic performance of an active layered double hydroxide (LDH)-derived CuCeMgAlO mixed oxide catalyst in the total oxidation of methane, it was promoted with different transition-metal cations. Thus, two series of multicationic mixed oxides were prepared by the thermal decomposition at 750 °C of their corresponding LDH precursors synthesized by coprecipitation at constant pH of 10 under ambient atmosphere. The first series of catalysts consisted of four M(3)CuCeMgAlO mixed oxides containing 3 at.% M (M = Mn, Fe, Co, Ni), 15 at.% Cu, 10 at.% Ce (at.% with respect to cations), and with Mg/Al atomic ratio fixed to 3. The second series consisted of four Co(x)CuCeMgAlO mixed oxides with x = 1, 3, 6, and 9 at.% Co, while keeping constant the Cu and Ce contents and the Mg/Al atomic ratio. All the mixed oxides were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) coupled with X-ray energy dispersion analysis (EDX), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption-desorption at −196 °C, temperature-programmed reduction under hydrogen (H2-TPR), and diffuse reflectance UV-VIS spectroscopy (DR UV-VIS), while thermogravimetric and differential thermal analyses (TG-DTG-DTA) together with XRD were used for the LDH precursors. The catalysts were evaluated in the total oxidation of methane, a test reaction for volatile organic compounds (VOC) abatement. Their catalytic performance was explained in correlation with their physicochemical properties and was compared with that of a reference Pd/Al2O3 catalyst. Among the mixed oxides studied, Co(3)CuCeMgAlO was found to be the most active catalyst, with a temperature corresponding to 50% methane conversion (T50) of 438 °C, which was only 19 °C higher than that of a reference Pd/Al2O3 catalyst. On the other hand, this T50 value was ca. 25 °C lower than that observed for the unpromoted CuCeMgAlO system, accounting for the improved performance of the Co-promoted catalyst, which also showed a good stability on stream.


Catalysts ◽  
2019 ◽  
Vol 9 (3) ◽  
pp. 256 ◽  
Author(s):  
Feng Zhao ◽  
Shuangde Li ◽  
Xiaofeng Wu ◽  
Renliang Yue ◽  
Weiman Li ◽  
...  

CuO-CeO2 nanocatalysts with varying CuO contents (1, 5, 9, 14 and 17 wt %) were prepared by one-step flame spray pyrolysis (FSP) and applied to CO oxidation. The influences of CuO content on the as-prepared catalysts were systematically characterized by X-ray diffraction (XRD), N2 adsorption-desorption at −196 °C, field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and hydrogen-temperature programmed reduction (H2-TPR). A superior CO oxidation activity was observed for the 14 wt % CuO-CeO2 catalyst, with 90% CO conversion at 98 °C at space velocity (60,000 mL × g−1 × h−1), which was attributed to abundant surface defects (lattice distortion, Ce3+, and oxygen vacancies) and high reducibility supported by strong synergistic interaction. In addition, the catalyst also displayed excellent stability and resistance to water vapor. Significantly, in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS) showed that in the CO catalytic oxidation process, the strong synergistic interaction led readily to dehydroxylation and CO adsorption on Cu+ at low temperature. Furthermore, in the feed of water vapor, although there was an adverse effect on the access of CO adsorption, there was also a positive effect on the formation of fewer carbon intermediates. All these results showed the potential of highly active and water vapor-resistive CuO-CeO2 catalysts prepared by FSP.


2013 ◽  
Vol 313-314 ◽  
pp. 254-257
Author(s):  
Ling Fang Jin ◽  
Hong Zhuang

Nonepitaxially grown FePt (x)/FePt:C thin films were synthesized, where FePt (x) (x=2, 5, 8, 11, 14 nm) layers were served as underlayers and FePt:C layer was nanocomposite with thickness of 5 nm. The effect of FePt underlayer on the ordering, orientation and magnetic properties of FePt:C thin films has been investigated by adjusting FePt underlayer thicknesses from 2 nm to 14 nm. X-ray diffraction (XRD), together with transmission electron microscopy (TEM) confirmed that the desired L10 phase was formed and films were (001) textured with FePt underlayer thickness decreased less 5 nm. For 5 nm FePt:C nanocomposite thin film with 2 nm FePt underlayer, the coercivity was 8.2 KOe and the correlation length of FePt:C nanocomposite film was 67 nm. These results reveal that the better orientation and magnetic properties for FePt:C nanocomposite films can be tuned by decreasing FePt underlayer thickness.


2019 ◽  
Author(s):  
Corina E Ignat ◽  
Gabriela Carja ◽  
Laura E Romila ◽  
Doina Lutic

Nanoscaled self-assemblies with engineered architectonics are important for obtaining advanced materials with specific applications in nanotechnology. We investigated here the morphology features at the nanoscale of the assemblies of the mixed oxides obtained through the thermal transformation of Zn2+Me3+ (Me=Al/Ga) layered double hydroxides (LDHs), as their “as-synthesized” form or after they were reconstructed in the aqueous solution of Ga2(SO4)3. The characteristics of ZnMe LDHs and the derived assemblies of mixed oxides were assessed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM/EDX), N2 adsorption at −196°C and thermal analyses (TG/DTG/DSC). The results revealed the formation nanoscaled assemblies of ZnO/ZnAl2O4/ZnGa2O4 and ZnO/Ga2O3/ZnGa2O4 starting from ZnMe(Me=Al/Ga) as precursors. Results point out that both the composition of the LDHs and the calcination temperatures can be used as parameters for tuning the nanomorphology features of the studied mixed oxides.


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