Cerium dioxide (CeO2, ceria) is becoming an ubiquitous constituent in catalytic systems for a variety of applications. 2016 sees the 40th anniversary since ceria was first employed by Ford Motor Company as an oxygen storage component in car converters, to become in the years since its inception an irreplaceable component in three-way catalysts (TWCs). Apart from this well-established use, ceria is looming as a catalyst component for a wide range of catalytic applications. For some of these, such as fuel cells, CeO2-based materials have almost reached the market stage, while for some other catalytic reactions, such as reforming processes, photocatalysis, water-gas shift reaction, thermochemical water splitting, and organic reactions, ceria is emerging as a unique material, holding great promise for future market breakthroughs. While much knowledge about the fundamental characteristics of CeO2-based materials has already been acquired, new characterization techniques and powerful theoretical methods are dee...

Fundamentals and Catalytic Applications of CeO2-Based Materials

There is increased recognition by the world’s scientific, industrial, and political communities that the concentrations of greenhouse gases in the earth’s
atmosphere, particularly CO_2, are increasing. For
example, recent studies of Antarctic ice cores to
depths of over 3600 m, spanning over 420 000 years,
indicate an 80 ppm increase in atmospheric CO_2 in
the past 200 years (with most of this increase
occurring in the past 50 years) compared to the
previous 80 ppm increase that required 10 000 years.2
The 160 nation Framework Convention for Climate
Change (FCCC) in Kyoto focused world attention on
possible links between CO2 and future climate change
and active discussion of these issues continues.3 In
the United States, the PCAST report4 “Federal
Energy Research and Development for the Challenges
of the Twenty First Century” focused attention
on the growing worldwide demand for energy and the
need to move away from current fossil fuel utilization.
According to the U.S. DOE Energy Information
Administration,5 carbon emission from the transportation
(air, ground, sea), industrial (heavy manufacturing,
agriculture, construction, mining, chemicals,
petroleum), buildings (internal heating, cooling, lighting),
and electrical (power generation) sectors of the
World economy amounted to ca. 1823 million metric
tons (MMT) in 1990, with an estimated increase to
2466 MMT in 2008-2012 (Table 1).

Catalysis Research of Relevance to Carbon Management: Progress, Challenges, and Opportunities

http://pubs.acs.org/doi/pdfplus/10.1021/cr500486u

Recent Developments in the Synthesis of Supported Catalysts

The E factor 25 years on: the rise of green chemistry and sustainability

Catalytic partial oxidation of methane has been reviewed with an emphasis on the reaction mechanisms over transition metal catalysts. The thermodynamics and aspects related to heat and mass transport is also evaluated, and an extensive table on research contributions to methane partial oxidation over transition metal catalysts in the literature is provided. Presented are both theoretical and experimental evidence pointing to inherent differences in the reaction mechanism over transition metals. These differences are related to methane dissociation, binding site preferences, the stability of OH surface species, surface residence times of active species and contributions from lattice oxygen atoms and support species. Methane dissociation requires a reduced metal surface, but at elevated temperatures oxides of active species may be reduced by direct interaction with methane or from the reaction with H, H2, C or CO. The comparison of elementary reaction steps on Pt and Rh illustrates that a key factor to produce hydrogen as a primary product is a high activation energy barrier to the formation of OH. Another essential property for the formation of H2 and CO as primary products is a low surface coverage of intermediates, such that the probability of O–H, OH–H and CO–O interactions are reduced. The local concentrations of reactants and products change rapidly through the catalyst bed. This influences the reaction mechanisms, but the product composition is typically close to equilibrated at the bed exit temperature.

A review of catalytic partial oxidation of methane to synthesis gas with emphasis on reaction mechanisms over transition metal catalysts

CeO2–Al2O3 mixed oxides with different CeO2 loading (in the range of 0.5–12 wt.%) were prepared by wetness impregnation of alumina with aqueous solution of di-ammonium hexanitrate cerate (NH4)2[Ce(NO3)6]. The samples after calcination at 773 and 1073 K were characterized by different techniques, using X-ray diffraction (XRD), UV–VIS diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (TPR). It is shown that different types of cerium oxide species are formed on the surface depending on the amount of CeO2 and temperature of calcination of the samples. XRD showed the formation of nanocrystallites of ceria on alumina surface when the amount of CeO2 is higher than 6 wt.%; at lower concentrations ceria was found to be amorphous. The ceria loading lower than 6 wt.% stabilizes the textural properties of alumina. At loading of 1 wt.% of CeO2 XPS spectra reveals the presence of a strong interaction between ceria and alumina leading to a formation of superficial CeAlO3-like phase. TPR results show that well dispersed CeO2 particles present on the surface of alumina form CeAlO3 at temperature of reduction in the range of 873–993 K, while for the reduction of CeO2 crystallites, a higher temperature of reduction of 1190 K is needed.

Characterization of ceria-coated alumina carrier

Pt catalysts supported on mixed CeO2-Al2O3 carriers with different CeO2 loading (0.5–10.3 wt.%) were prepared by wetness impregnation method. The catalysts were characterized by SBET, X-ray diffraction (XRD), UV-Vis diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR) and thermogravimetric analysis (TG). It was shown that pretreatment temperature and the concentration of CeO2 in the support influences significantly on the morphology of Pt. XRD showed the formation of nanocrystallites of Pt on the surface of alumina and low-loaded CeO2 (≤6 wt.%) samples at higher temperature of calcination (1073 K). Amorphous Pt was observed in all reduced samples. XPS spectra showed the presence of interaction between Pt and Ce, which leads to easy surface reduction of both, ceria and platinum, as revealed by TPR patterns. The effect of CeO2 loading on the catalytic behavior of supported Pt catalysts in the reaction of CO2 reforming of CH4 was determined. Addition of cerium oxide results in improvement of catalytic performance for the reforming of methane with CO2. Pt catalyst with 1 wt.% of CeO2 exhibited the highest specific activity and stability, due to the increase in the metal–support interface area, caused by the higher Pt dispersion.

Effect of CeO2 loading on the surface and catalytic behaviors of CeO2-Al2O3-supported Pt catalysts

Effect of the ZrO2 phase on the structure and behavior of supported Cu catalysts for ethanol conversion

Steam reforming of ethanol (SRE) is a strategic reaction for H2 production. However, despite considerable work, several aspects of the mechanism and catalytic system for this reaction are not fully understood. There have been many efforts to improve the understanding of the catalysts’ behavior during SRE, using both theoretical studies and experimental investigations based on operando characterization techniques. Even though cobalt and nickel are considered the most promising catalytically active metals for industrial SRE, acquiring further knowledge on the reaction mechanism, metal–support interactions, and catalyst deactivation (due to carbon accumulation, sintering, or metal oxidation) will enable the successful design of new and stable catalysts. In this review, we analyze the reaction pathways for metal-catalyzed SRE and discuss the available experimental and theoretical data to suggest alternatives to address three major issues: (i) the impact of particle size and metal oxidation state in the SRE pe...

Toward Understanding Metal-Catalyzed Ethanol Reforming

The catalytic behavior of Ni/Al2O3 catalysts modified with La and Ag was investigated in the steam reforming of ethanol. The catalysts were characterized by SBET, X-ray diffraction (XRD), temperature-programmed reduction (TPR), and Fourier transform infrared spectroscopy (FTIR) of CO adsorption. The reaction rate for noncatalytic decomposition of ethanol in the homogeneous gas phase becomes significant only at high temperatures (T ≥ 890 K). FTIR results revealed that Ag strongly modifies the Ni surface, decreasing the intensity ratio of the bands for adsorbed CO in the bridging mode at low frequency (LF) and the linear mode at high frequency (HF). Similar but smaller effect was observed in the La-containing catalyst. The activity and stability against carbon depostion for steam reforming of ethanol of Ni/Al2O3 catalyst was only slightly sensitive to Ag but the activity was strongly dependent on the presence of La. The reaction data suggest that at temperatures lower than 650 K the Ni/Al2O3 catalyst was active for decomposition of ethanol via the acetaldehyde intermediate, showing high selectivity to methane and CO. The rate of steam reforming of ethanol became significant at temperature higher than 650 K. Comparing Ni/Al2O3 and Ni/La–Al2O3 catalysts the results pointed out that the Ni became more susceptible to modification by water in La-containing Ni catalyst. The Ni/La–Al2O3 catalysts become inactive at low temperatures, and the activity could be regenerated with reduction of NiO by ethanol on raising the reaction temperature. Differently from the steam reforming of methane, the coking cannot be suppressed by Ag promotion in the case of steam reforming of ethanol. Inversely, the La has a positive effect to decreasing coking on Ni catalysts. A scheme for ethanol reactions with H2O on Ni surfaces is proposed based on reaction tests.

José Maria C. Bueno

Papers

Characterization of ceria-coated alumina carrier

Effect of CeO2 loading on the surface and catalytic behaviors of CeO2-Al2O3-supported Pt catalysts

Effect of the ZrO2 phase on the structure and behavior of supported Cu catalysts for ethanol conversion

Toward Understanding Metal-Catalyzed Ethanol Reforming

Steam reforming of ethanol on supported nickel catalysts