Ceria nanocube with reactive {100} exposure planes: Simple and controllable synthesis under moderate conditions

{100} planes of CeO₂ are unstable polar surfaces and important to enhance the oxygen storage capacity. However, a convenient method is still needed for the synthesis of ceria nanocubes which expose six {100} facets. Here, a new and facile synthesis strategy has been developed to synthesize single-crystalline nanocubes of CeO₂. According to transmission electron microscopy, these nanocubes are enclosed by six {100} facets. It is proved that in the synthesis process, the acetate radical ions would adsorb on the positive charged Ce(OH)₃ formed from the reaction of Ce³⁺ and ammonia, then partially inhibit the redox between Ce(OH)₃ and NO₃⁻ and protect the {100} facets during crystal growth. Meanwhile, the Ce⁴⁺ ions would act as crystal seeds to facilitate the formation of single crystals. Both of the addition of Ce⁴⁺ ions and CH₃COO⁻ ions are necessary for the synthesis of monocrystal ceria nanocubes. Throughout the synthesis process, it is moderate reaction conditions that the pressure is atmospheric pressure and temperature is no higher than 80 °C.     

Enhanced sintering resistance of Fe2O3/CeO2 oxygen carrier for chemical looping hydrogen generation using core-shell structure

CeO₂-supported Fe₂O₃ is a satisfactory oxygen carrier for chemical looping hydrogen generation (CLHG). However, the sintering problem restrains its further improvement on redox reactivity and stability. In the present work, a core-shell-structured Fe₂O₃/CeO₂ (labeled Fe₂O₃@CeO₂) oxygen carrier prepared by the sol-gel method was studied in a fixed bed. The effect of the core-shell structure on the sintering resistance and redox performance was investigated with a homogenous composite sample of Fe₂O₃/CeO₂ as a reference. The results showed that the Fe₂O₃@CeO₂ exhibited much higher redox reactivity and stability than the Fe₂O₃/CeO₂ with no CO or CO₂ observed in the generated hydrogen, while the hydrogen yield for Fe₂O₃/CeO₂ decreased with redox cycles due to serious sintering. The satisfactory performance of Fe₂O₃@CeO₂ can be ascribed to its high sintering resistance, since the core-shell structure suppressed the outward migration of Fe cations from the bulk to the surface of the particles. On the other hand, the migration of Fe cations and their subsequent enrichment on the particle surface led to the serious sintering of Fe₂O₃/CeO₂. The crystallite size evolution of Fe₂O₃ and CeO₂ in redox cycles further demonstrated the higher sintering resistance of Fe₂O₃@CeO₂. Further, the particle size distribution (PSD) results indicated the agglomeration of Fe₂O₃/CeO₂ after cycles. In addition, the CeO₂ shell could facilitate the transport of oxygen ions between the iron oxide nanoparticle core and the shell surface. Therefore, the coating of nanoscale Fe₂O₃ with a CeO₂ shell did not reduce the redox reactivity and stability of Fe₂O₃@CeO₂, but rather promoted it, though less oxygen-ionic-conductive CeFeO₃ was generated.     

Hydrogen production by steam reforming of ethanol over Co/CeO2 catalysts: Effect of cobalt content

The Co/CeO₂ catalysts obtained by co-precipitation method were used in the steam reforming of ethanol (SRE). The influence of cobalt active phase content (15–29 wt%), the reaction temperature (420–600 °C) and H₂O/EtOH molar ratio (12/1 and 6/1) were examined. The physicochemical characterization revealed that the cobalt content of the catalyst influences the metal-support interaction which results in catalyst performance in SRE process. The differences between catalytic properties of the Co/CeO₂ catalysts with different metal loading in SRE process decayed at 500 °C for H₂O/EtOH = 12/1. The best performance among the tested catalysts showed the 29Co/CeO₂ catalyst with the highest cobalt content, exhibiting the highest ethanol conversion, selectivity to two most desirable products and the lowest selectivity to by-products in comparison with catalysts containing smaller amount of metal. Its catalytic properties results probably from its unique physicochemical properties, i.e this catalyst contains large amount of cobalt but the metal crystallites are relatively small. Regardless cobalt content, an increase in the water-to-ethanol molar ratio in the feed increased the concentration of hydrogen an carbon dioxide and decreased formation of carbon monoxide, acetone, aldehyde and ethylene.     

Preparation and characterization of vitrified CeO2 coated cBN composites

The performances of vitrified cBN composites are deeply affected by the wettability of vitrified bonds on cBN particles. CeO₂ coated cBN particles were successfully prepared for the further improvement of the covering and wetting of cBN by vitrified bonds. The microstructure and properties of vitrified cBN composites were characterized by scanning electron microscope (SEM), hot stage microscope (HSM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and flexural strength. Results showed that the prepared CeO₂ coating on the surface of cBN was uniform and dense. Besides, the improved wettability of vitrified bonds on CeO₂ coated cBN particles accompanied with the formation of Ce–O–Al and N–Si confirmed by XPS were supposed to conduce to enhancing the holding power of the vitrified bonds to cBN particles, which resulted in increasing the flexural strength of vitrified cBN composites by 9.16%. Thus, coating cBN with CeO₂ was a potential and effective method to obtain vitrified cBN composites with higher flexural strength.     

Cooperative role of cobalt and gallium under the ethanol steam reforming on Co/CeGaOx

The performance of gallium promoted cobalt-ceria catalysts for ethanol steam reforming (ESR) was studied using H₂O/C₂H₅OH = 6/1 mol/mol at 500 °C. The catalysts were synthetized via cerium-gallium co-precipitation and wetness impregnation of cobalt. A detailed characterization by N₂-physisorption, XRD, H₂-TPR and TEM allowed the normalization of contact time and rationalization of the role of each catalysts component for ESR. The gallium promoted catalyst, Co/Ce₉₀Ga₁₀O_x, was more efficient for the ethanol conversion to H₂ and CO₂, and the production of oxygenated by-products (such as, acetaldehyde and acetone) than Co/CeO₂. The catalytic performance is explained assuming that: (i) bare ceria is able to dehydrogenate ethanol to ethylene; (ii) Ce–O–Ga interface catalyzes ethanol reforming; (iii) both Ce–O–Co and Ce–O–Ga interfaces takes part in acetone production; and (iv) cobalt sites further allow C–C scission. It is suggested that a cooperative role between Co and Ce–O–Ga sites enhance the H₂ and CO₂ yields under ESR conditions.     

Novel porous perovskite composite CeO2@LaMnO3/3DOM SiO2 as an effective catalyst for activation of PMS toward oxidation of urotropine

Perovskites with stable crystal structure and excellent catalytic performance have attracted extensive attention in peroxomonosulfate (PMS) activation, however, severe agglomeration has always been the main obstacle limiting the catalytic activity of them, so novel perovskite catalysts are urgently needed. In this study, three-dimensional ordered macroporous silica (3DOM SiO₂) was prepared by colloidal crystal template method, then CeO₂@LaMnO₃/3DOM SiO₂ was prepared by sol-gel method combined with impregnation method and used to activate PMS for urotropine (URO) degradation. CeO₂@LaMnO₃/3DOM SiO₂ activated PMS system exhibited high URO removal efficiency and quick kinetic, as 99.98 % URO was degraded even within 30 min. The catalyst has a wide pH range and still has high catalytic activity in the presence of organic matter and inorganic ions. The three components in CeO₂@LaMnO₃/3DOM SiO₂ showed a synergetic effect. CeO₂ and LaMnO₃ were uniformly loaded on 3DOM SiO₂, which effectively avoided agglomeration. The specific surface area of CeO₂@LaMnO₃/3DOM SiO₂ was 11.88 times that of LaMnO₃ prepared by sol-gel method. There are two redox cycles of Ce³⁺/Ce⁴⁺ and Mn²⁺/Mn³⁺/Mn⁴⁺ in CeO₂ and LaMnO₃, respectively, which synergistically realize the activation of PMS. Both quenching experiments and electron paramagnetic resonance (EPR) analysis revealed that that SO₄^?, OH and ¹O₂ jointly achieved the degradation of URO. In summary, CeO₂@LaMnO₃/3DOM SiO₂ would be a promising candidate for practical wastewater treatment.     

Electrocatalysts based on low amounts of palladium combined with tin nanoparticles and cerium dioxide nanorods for application as ADEFC anodes

This study demonstrates the structural properties and evaluates the electrocatalytic activity of an ethanol oxidation reaction using ternary materials composed by Pd and Sn nanoparticles combined with CeO₂ nanorods (NR) anchored on Vulcan carbon black to be used as an anode in alkaline direct ethanol fuel cells (ADEFCs). The highest open circuit voltage (1010 mV), maximum power (30 mW cm⁻²) and current densities (113 mA cm⁻²) were achieved using (Pd₁Sn₃)₁₀(CeO₂ NR)₂₀(Vn)₇₀, while the commercial anode values were 968 mV, 23 mW cm⁻² and 123 mA cm⁻². Although similar performance for both anodes was observed, the ternary hybrid electrocatalyst contains an 8-fold lower Pd content than the commercial material. This outcome may be justified by the higher defect density presented by the carbon support observed by Raman spectroscopy and the metal oxidation state modifications detected by X-ray photoelectron spectroscopy, as well as the electrochemically active surface area presented by the ternary electrocatalyst. The combination of higher vacancies, defects and oxygenated species in the carbon support and the synergistic effect between the oxyphilic Sn and CeO₂ NR species and the Pd nanoparticles results in an electrochemical performance that makes these ternary electrocatalysts promising anode materials for ADEFC applications.     

Impact of Ce-Loading on Ni-catalyst supported over La2O3+ZrO2 in methane reforming with CO2

This paper investigated the effect of doping Ni supported catalysts with different ceria loading. The catalysts (5%Ni+x%Ce/La₂O₃+ZrO₂, where x = 0, 1, 2, 2.5, 3, 5) were synthesized via the wet impregnation technique and tested for methane reforming with carbon dioxide at atmospheric pressure, 700 °C and 42, 000 ml/g_cat.h gas hourly space velocity. The fresh catalysts were subjected to different characterization techniques such as X-ray diffraction, Surface area and pore analysis, H₂-temperature programmed reduction, CO₂-temperature programmed desorption and thermogravimetric analysis (TGA). A fine correlation between characterization results and catalytic activity is found. The results of the reactions indicated that 5%Ni/La₂O₃+ZrO₂ has the lowest conversion which increased with the percentage loading of CeO₂ up to 2.5 wt % and then began to decline. This suggests that 2.5 wt % loading is the optimum for CH₄ and CO₂ conversion. This particular catalyst composition has NiO species that could be reduced easily, as well as dense and wide distribution of all type of basic sites with respect to other catalyst system. The used catalysts were again subjected to TGA and RAMAN analysis where the least carbon deposition and the least deactivation factor was observed for 5%Ni+5%Ce/La₂O₃+ZrO₂ catalysts.     

Low temperature water gas shift: Type and loading of metal impacts forward decomposition of pseudo-stabilized formate over metal/ceria catalysts

A similar degree of surface shell reduction of ceria was obtained for a series of metal/ceria catalysts. Surface formate species were generated by reaction of CO with bridging OH groups associated with the Ce³⁺ defects. Forward decomposition of the pseudo-stable formates was followed in flowing H₂O, leading to the production of surface carbonate species. The forward formate decomposition rate was enhanced changing the promoter from Au to Pt, and by increasing the promoter loading (from 0.5 to 2.5%). Results suggest that formate CH bond breaking is not only facilitated by H₂O, but it is further enhanced by type and loading of metal promoter. From earlier kinetic isotope effect and isotopic tracer studies, the rate-limiting step of the forward formate decomposition (WGS reaction) was considered to be associated with CH bond rupture of the formate. The results can explain the promotion in the WGS rates observed for these samples by changing from Au to Pt and by increasing the promoter loading.     

Fuel-oxidizer ratio tuned luminescence properties of combustion synthesized Europium doped cerium oxide nanoparticles and its effect on antioxidant properties

Influential role of fuel to oxidizer ratio (F/O) as the controlling parameter in combustion synthesis of europium doped cerium oxide was studied in terms of defect chemistry, optical property and antioxidant capacity. Europium (5 mol%) doped cerium oxide nanoparticles synthesized by solution combustion in fuel deficient (F/O=0.6, 1.1) and stoichiometric (F/O=1.6) conditions resulted in size ranging from 6 to 25 nm while excess fuel (F/O=2.1) lead to the lower size of 17 nm. Raman spectroscopic analysis showed the formation of intrinsic and europium ion induced extrinsic oxygen vacancies and the defect concentration was found to be decreasing with F/O ratio. Photoluminescence emission was dominated by magnetic dipole transition in F/O=0.6, 1.1 and electrical dipole in F/O=1.6, 2.1 which resulted in a persistent luminescence. Fenton reaction generated hydroxyl radical scavenging activity was influenced by the surface oxygen vacancy concentration and crystallites size. In addition to size and defect, morphology of the nanoparticle plays a significant role in determining the antioxidant efficacy.