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

To improve fuel efficiency, advanced combustion engines are being designed to minimize the amount of heat wasted in the exhaust. Hence, future generations of catalysts must perform at temperatures that are 100°C lower than current exhaust-treatment catalysts. Achieving low-temperature activity, while surviving the harsh conditions encountered at high engine loads, remains a formidable challenge. In this study, we demonstrate how atomically dispersed ionic platinum (Pt2+) on ceria (CeO2), which is already thermally stable, can be activated via steam treatment (at 750°C) to simultaneously achieve the goals of low-temperature carbon monoxide (CO) oxidation activity while providing outstanding hydrothermal stability. A new type of active site is created on CeO2 in the vicinity of Pt2+, which provides the improved reactivity. These active sites are stable up to 800°C in oxidizing environments.

http://science.sciencemag.org/content/sci/358/6369/1419.full.pdf

Activation of surface lattice oxygen in single-atom Pt/CeO2 for low-temperature CO oxidation

Acetoxylation of ethylene to vinyl acetate (VA) was used to investigate the mechanism of the promotional effect of gold (Au) in a palladium (Pd)-Au alloy catalyst. The enhanced rates of VA formation for low Pd coverages relative to high Pd coverages on Au single-crystal surfaces demonstrate that the critical reaction site for VA synthesis consists of two noncontiguous, suitably spaced, Pd monomers. The role of Au is to isolate single Pd sites that facilitate the coupling of critical surface species to product, while inhibiting the formation of undesirable reaction by-products.

https://science.sciencemag.org/content/sci/310/5746/291.full.pdf

The Promotional Effect of Gold in Catalysis by Palladium-Gold

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Chemicals from Alkynes with Palladium Catalysts

This critical review covers the recent development of the catalytic properties of gold in the selective oxidation of organic compounds, highlighting the exciting contribution to the art of catalysis. The unique, outstanding properties of nanometre-scale particles of gold, a biocompatible non-toxic metal, have allowed the development of a new generation of stable and selective catalysts for the conversion of many organic feedstocks to valuable chemicals. A critical discussion of the results of different research groups is presented along with attempts to correlate the catalytic properties with catalyst morphology in non-equivalent series of experiments. Particular emphasis has been given to the international efforts towards optimised synthesis of products of industrial appeal such as propylene oxide, vinyl acetate monomer, cyclohexanol/cyclohexanone, gluconic acid and glyceric acid (168 references).

Selective oxidation using gold

This study reports and compares the adsorption and dissociation of water on oxidized and reduced CeO2(100) and CeO2(111) thin films. Water adsorbs dissociatively on both surfaces. On fully oxidized...

Water Dissociation on CeO2(100) and CeO2(111) Thin Films

CeO2 cubes with {100} facets, octahedra with {111} facets, and wires with highly defective structures were utilized to probe the structure-dependent reactivity of acetaldehyde. Using temperature-programmed desorption (TPD), temperature-programmed surface reactions (TPSR), and in situ infrared spectroscopy, it was determined that acetaldehyde desorbs unreacted or undergoes reduction, coupling, or C–C bond scission reactions, depending on the surface structure of CeO2. Room-temperature FTIR indicates that acetaldehyde binds primarily as η1-acetaldehyde on the octahedra, in a variety of conformations on the cubes, including coupling products and acetate and enolate species, and primarily as coupling products on the wires. The percent consumption of acetaldehyde ranks in the following order: wires > cubes > octahedra. All the nanoshapes produce the coupling product crotonaldehyde; however, the selectivity to produce ethanol ranks in the following order: wires ≈ cubes ≫ octahedra. The selectivity and other dif...

Adsorption and Reaction of Acetaldehyde on Shape-Controlled CeO2 Nanocrystals: Elucidation of Structure–Function Relationships

The temperature-dependent adsorption and reaction of acetaldehyde (CH(3)CHO) on a fully oxidized and a highly reduced thin-film CeO(2)(111) surface have been investigated using a combination of reflection-absorption infrared spectroscopy (RAIRS) and periodic density functional theory (DFT+U) calculations. On the fully oxidized surface, acetaldehyde adsorbs weakly through its carbonyl O interacting with a lattice Ce(4+) cation in the η(1)-O configuration. This state desorbs at 210 K without reaction. On the highly reduced surface, new vibrational signatures appear below 220 K. They are identified by RAIRS and DFT as a dimer state formed from the coupling of the carbonyl O and the acyl C of two acetaldehyde molecules. This dimer state remains up to 400 K before decomposing to produce another distinct set of vibrational signatures, which are identified as the enolate form of acetaldehyde (CH(2)CHO¯). Furthermore, the calculated activation barriers for the coupling of acetaldehyde, the decomposition of the dimer state, and the recombinative desorption of enolate and H as acetaldehyde are in good agreement with previously reported TPD results for acetaldehyde adsorbed on reduced CeO(2)(111) [Chen et al. J. Phys. Chem. C 2011, 115, 3385]. The present findings demonstrate that surface oxygen vacancies alter the reactivity of the CeO(2)(111) surface and play a crucial role in stabilizing and activating acetaldehyde for coupling reactions.

Oxygen Vacancy-Assisted Coupling and Enolization of Acetaldehyde on CeO2(111)

http://surface.chem.uwm.edu/pubs/Tysoe191.pdf

Formation and characterization of Au/Pd surface alloys on Pd(1 1 1)

Cerium oxide is a principal component in many heterogeneous catalytic processes. One of its key characteristics is the ability to provide or remove oxygen in chemical reactions. The different crystallographic faces of ceria present significantly different surface structures and compositions that may alter the catalytic reactivity. The structure and composition determine the number of coordination vacancies surrounding surface atoms, the availability of adsorption sites, the spacing between adsorption sites and the ability to remove O from the surface. To investigate the role of surface orientation on reactivity, CeO2 films were grown with two different orientations. CeO2(100) films were grown ex situ by pulsed laser deposition on Nb-doped SrTiO3(100). CeO2(111) films were grown in situ by thermal deposition of Ce metal onto Ru(0001) in an oxygen atmosphere. The chemical reactivity was characterized by the adsorption and decomposition of various molecules such as alcohols, aldehydes and organic acids. In general the CeO2(100) surface was found to be more active, i.e. molecules adsorbed more readily and reacted to form new products, especially on a fully oxidized substrate. However the CeO2(100) surface was less selective with a greater propensity to produce CO, CO2 and water as products. The differences in chemical reactivity are discussed in light of possible structural terminations of the two surfaces. Recently nanocubes and nano-octahedra have been synthesized that display CeO2(100) and CeO2(111) faces, respectively. These nanoparticles enable us to correlate reactions on high surface area model catalysts at atmospheric pressure with model single crystal films in a UHV environment.

Florencia Calaza

Papers

Water Dissociation on CeO2(100) and CeO2(111) Thin Films

Adsorption and Reaction of Acetaldehyde on Shape-Controlled CeO2 Nanocrystals: Elucidation of Structure–Function Relationships

Oxygen Vacancy-Assisted Coupling and Enolization of Acetaldehyde on CeO2(111)

Formation and characterization of Au/Pd surface alloys on Pd(1 1 1)

Variations in Reactivity on Different Crystallographic Orientations of Cerium Oxide