Combining molybdenum carbide with ceria overlayers to boost Mo/CeO2 catalyzed ammonia synthesis

The design of an efficient non-noble metal catalyst is of burgeoning interest for ammonia synthesis. Herein, we report a Mo₂C/CeO₂ catalyst that is superior in ammonia synthesis activity. In this catalyst, molybdenum carbide coexisted with the ceria overlayers which is from the ceria support as the strong metal–support interaction. There is a high proportion of low-valent Mo species, as well as high concentration of Ce³⁺ and surface oxygen species. The presence of Mo₂C and CeO₂ overlayers not only leads to enhancement of hydrogen and nitrogen adsorption, but also facilitates the desorption and exchange of adsorbed species with the gaseous reagents. Compared with the Mo/CeO₂ catalyst prepared without carbonization, the Mo₂C/CeO₂ catalyst is more than sevenfold higher in ammonia synthesis rate. This work not only presents an explicit example of designing Mo-based catalyst that is highly efficient for ammonia synthesis by tuning the adsorption and desorption properties of the reactant gases, but opens a perspective for other elements in ammonia synthesis.     

Unraveling the effect of alumina-supported Y- doped ceria composition and method of preparation on the WGS activity of gold catalysts

The demands for high-purity hydrogen required in fuel-cell applications impose new goals and challenges for design of well performing water-gas shift (WGS) catalysts. Gold-based catalysts have exhibited high activity in the WGS reaction at low temperature. Preparation of appropriate and economically viable supports with complex composition by various synthesis procedures is an attractive approach to WGS performance improvement. The effect of two different preparation methods (wet impregnation or mechanical mixing) and ceria content (10, 20 or 30 wt%) on textural, structural, surface and reductive properties and WGS activity of gold catalysts was studied. Additionally, the role of Y₂O₃ as a promoter of ceria was examined. Long-term stability test was carried out at 260 °C over the most active catalyst. The composition of the best performing sample (composed of about 70 wt% alumina), prepared by mechanical mixing, was considered promising in case of practical applications because of its cost efficiency. The combination of gold nanoparticles and alumina supported Y-doped ceria proved an advantageous approach for developing new catalytic formulations with high effectiveness in clean hydrogen production.     

Effects of strontium gallate additions on sintering behavior of gadolinia-doped ceria

The densification behavior and grain growth of Ce_0.8Gd_0.2O_1.9 ceramics were investigated with the strontium gallate concentration ranging from 0 to 5 mol%. Both the sintered density and grain size were found to increase rapidly up to 0.5 mol% Sr₂Ga₂O₅, and then to decrease with further addition. Dense Ce_0.8Gd_0.2O_1.9 ceramics with 97% of the theoretical density could be obtained for 0.5 mol% Sr₂Ga₂O₅-added specimen sintered at 1250^∘C for 5 h, whereas pure Ce_0.8Gd_0.2O_1.9 ceramics needed to be sintered at 1550^∘C in order to obtain an equivalent theoretical density. The addition of Sr₂Ga₂O₅ was found to promote the sintering properties of Gd₂O₃-doped CeO₂.     

Acid-Base Properties of Zirconium, Cerium and Lanthanum Oxides by Calorimetric and Catalytic Investigation

The combined use of calorimetric and catalytic methods for the investigation of the acid-base properties of oxide systems is discussed with reference to the authors' work on pure and doped zirconia samples, ceria-zirconia and ceria-lanthana solid solutions. Adsorption microcalorimetry of ammonia and carbon dioxide had been used to characterize the samples, whose chemical and thermal history was taken into account. The catalytic behavior of these samples in the conversion of 4-methylpentan-2-ol, route to 4-methylpent-1-ene (starting product for the manufacture of polymers of superior technological properties), had also been studied. On the basis of the calorimetric data, a rationale for interpreting the data for the transformation of 4-methylpentan-2-ol is formulated, which takes into account the role of the concentration and strength of the sites in governing the competition among the various mechanisms for dehydration and dehydrogenation.     

Gold nanoparticles on ceria: importance of O vacancies in the activation of gold

Synchrotron-based techniques (high-resolution photoemission, in-situ X-ray absorption spectroscopy, and time-resolved X-ray diffraction) have been used to study the destruction of SO₂ and the water-gas shift (WGS, CO + H₂O → H₂ + CO₂) reaction on a series of gold/ceria systems. The adsorption and chemistry of SO₂ was investigated on Au/CeO₂(111) and AuO _x /CeO₂ surfaces. The heat of adsorption of the molecule on Au nanoparticles supported on stoichiometric CeO₂(111) was 4–7 kcal/mol larger than on Au(111). However, there was negligible dissociation of SO₂ on the Au/CeO₂(111) surfaces. The full decomposition of SO₂ was observed only after introducing O vacancies in the ceria support. AuO _x /CeO₂ surfaces were found to be much less chemically active than Au/CeO₂(111) or Au/CeO_2−x (111) surfaces. In a separate set of experiments, in-situ time-resolved X-ray diffraction and X-ray absorption spectroscopy were used to monitor the behavior of nanostructured {Au + AuO _x }–CeO₂ catalysts under the WGS reaction. At temperatures above 250 °C, a complete AuO _x → Au transformation was observed with high catalytic activity. Photoemission results for the oxidation and reduction of Au nanoparticles supported on rough ceria films or a CeO₂(111) single crystal corroborate that cationic Au^δ+ species cannot be the key sites responsible for the WGS activity at high temperatures. The active sites in {Au + AuO _x }/ceria catalysts should involve pure gold nanoparticles in contact with O vacancies of the oxide.     

Redox properties of CeO2 and Pt-Rh/CeO2 studied by TAP method

Redox properties of CeO₂ and Pt-Rh/CeO₂ were studied by temporal analysis of products (TAP) method using alternative pulses of CO and O₂. A portion of pulsed CO was oxidized to CO₂ and a portion of CO was adsorbed on the surface. Pulsing ¹⁸O₂ onto the catalyst which has surface species derived from CO, evolved CO₂ contained no ¹⁸O suggesting that the surface species will be carbonate ions.     

Synergistic Catalysis of Carbon Dioxide Hydrogenation into Methanol by Yttria-Doped Ceria/γ-Alumina-Supported Copper Oxide Catalysts: Effect of Support and Dopant

Methanol synthesis from carbon dioxide hydrogenation was studied over ceria/-alumina- and yttria-doped ceria (YDC)/-alumina-supported copper oxide catalysts to seek insight into the catalysis at metal–support interfaces. It was found that, in comparison with Cu/-Al₂O₃, the Cu/CeO₂/-Al₂O₃ and Cu/YDC/-Al₂O₃ catalysts exhibited substantial enhancement in activity and selectivity toward methanol formation. The extent of enhancement was augmented by increased ceria loading on -alumina and with increased yttria doping into ceria. The enhancement is inferred to result from the synergistic effect between copper oxide and surface oxygen vacancies of ceria.     

Role and distribution of different Ba-containing phases in supported Pt–Ba NSR catalysts

Pt–Ba/MeO (where MeO = Al₂O₃, CeO₂, SiO₂ and ZrO₂) NO _x storage-reduction catalysts with Ba-loading varying from 0 wt.% to 28 wt.% were investigated concerning stability of Ba phases and NO _x storage-reduction efficiency. For Pt–Ba/Al₂O₃ three different Ba-containing phases with different thermal stability are distinguished based on their interaction with the support. The relative concentration of these phases varies with the Ba-loading and NO _x storage tests indicated that the BaCO₃ phase decomposing between 400 °C and 800 °C (LT-BaCO₃) is the most efficient Ba containing phase for NO _x storage. Similar investigations of Pt–Ba catalysts supported on CeO₂, SiO₂ and ZrO₂ showed that the relative amount of LT-BaCO₃ phase depends also on the support material. NO _x storage measurements confirmed a correlation between the concentration of LT-BaCO₃ and NO _x storage efficiency. Basicity and textural properties of the support are identified as crucial parameters for efficient NO _x storage catalysts.     

Atomic layer deposition of GDC cathodic functional thin films for oxide ion incorporation enhancement

In this paper, we report successful fabrication of a gadolinia-doped ceria (GDC) thin film using atomic layer deposition (ALD) for improving the performance of solid oxide fuel cells (SOFCs). By varying the deposition conditions and adjusting the configuration of the ALD supercycle, the doping ratio of ALD GDC was controlled. The morphology, crystallinity, and chemical composition of ALD GDC thin films were analyzed. ALD GDC showed different surface chemistry, including oxidation states, at different doping ratios. The application of ALD GDC in a SOFC led to an output power density enhancement greater than 2.5 times. With an anodic aluminum oxide (AAO) porous support structure, an ALD GDC thin film SOFC (TF-SOFC) showed a high power density of 288.24 mW/cm² at an operating temperature of 450°C.     

Sm2O3和Nd2O3共同掺杂CeO2基电解质材料的研究

采用柠檬酸-硝酸盐法合成出单一相、均匀的Ce0.8SmxNd0．2-xO19粉体，XRD结果表明该粉体为单相萤石结构，粒径约在11．7nm～20．1nm之间。将粉体干压成型，在1400℃下无压烧结5h可得到高致密度陶瓷。SEM照片显示陶瓷微观结构均匀，晶粒尺寸在2μm～4μm。经直流四端电极法测试得到该样品在500℃时电导率约在0．012 S／cm。该结果说明与单项掺杂相比，两相共掺杂会进一步提高材料的电导率。