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

Today’s electric vehicles are almost exclusively powered by lithium-ion batteries, but there is a long way to go before electric vehicles become dominant in the global automotive market. In addition to policy support, widespread deployment of electric vehicles requires high-performance and low-cost energy storage technologies, including not only batteries but also alternative electrochemical devices. Here, we provide a comprehensive evaluation of various batteries and hydrogen fuel cells that have the greatest potential to succeed in commercial applications. Three sectors that are not well served by current lithium-ion-powered electric vehicles, namely the long-range, low-cost and high-utilization transportation markets, are discussed. The technological properties that must be improved to fully enable these electric vehicle markets include specific energy, cost, safety and power grid compatibility. Six energy storage and conversion technologies that possess varying combinations of these improved characteristics are compared and separately evaluated for each market. The remainder of the Review briefly discusses the technological status of these clean energy technologies, emphasizing barriers that must be overcome. Recent years have seen significant growth of electric vehicles and extensive development of energy storage technologies. This Review evaluates the potential of a series of promising batteries and hydrogen fuel cells in their deployment in automotive electrification.

Batteries and fuel cells for emerging electric vehicle markets

Fossil fuel consumption in transportation system and energy-intensive sectors as the principal pillar of civilization is associated with progressive release of greenhouse gases. Hydrogen as a promising energy carrier is a perfect candidate to supply the energy demand of the world and concomitantly reduce toxic emissions. This article gives an overview of the state-of-the-art hydrogen production technologies using renewable and sustainable energy resources. Hydrogen from supercritical water gasification (SCWG) of biomass is the most cost effective thermochemical process. Highly moisturized biomass is utilized directly in SCWG without any high cost drying process. In SCWG, hydrogen is produced at high pressure and small amount of energy is required to pressurize hydrogen in the storage tank. Tar and char formation decreases drastically in biomass SCWG. The low efficiency of solar to hydrogen system as well as expensive photovoltaic cell are the most important barriers for the widespread commercial development of solar-based hydrogen production. Since electricity costs play a crucial role on the final hydrogen price, to generate carbon free hydrogen from solar and wind energy at a competitive price with fossil fuels, the electrical energy cost should be four times less than commercial electricity prices.

Hydrogen production from renewable and sustainable energy resources: Promising green energy carrier for clean development

Developments in water gas shift (WGS) catalysis, especially during the last decade, are reviewed. Recent developments include the development of 1 chromium‐free catalysts that can operate at lower steam to gas ratios and 2 more active catalysts that can operate at gas hourly space velocities above 40,000 h−1. A current challenge is to develop catalysts for use in fuel cell applications. Precious metal catalysts supported on partially reducible oxide supports (Pt‐ceria, Pt‐titania, Au‐ceria, etc.) are the current front runners. A critical review of the mechanism of the WGS reaction is also presented.

Water Gas Shift Catalysis

The electronic properties of Pt nanoparticles deposited on CeO(2)(111) and CeO(x)/TiO(2)(110) model catalysts have been examined using valence photoemission experiments and density functional theory (DFT) calculations. The valence photoemission and DFT results point to a new type of "strong metal-support interaction" that produces large electronic perturbations for small Pt particles in contact with ceria and significantly enhances the ability of the admetal to dissociate the O-H bonds in water. When going from Pt(111) to Pt(8)/CeO(2)(111), the dissociation of water becomes a very exothermic process. The ceria-supported Pt(8) appears as a fluxional system that can change geometry and charge distribution to accommodate adsorbates better. In comparison with other water-gas shift (WGS) catalysts [Cu(111), Pt(111), Cu/CeO(2)(111), and Au/CeO(2)(111)], the Pt/CeO(2)(111) surface has the unique property that the admetal is able to dissociate water in an efficient way. Furthermore, for the codeposition of Pt and CeO(x) nanoparticles on TiO(2)(110), we have found a transfer of O from the ceria to Pt that opens new paths for the WGS process and makes the mixed-metal oxide an extremely active catalyst for the production of hydrogen.

A new type of strong metal-support interaction and the production of H2 through the transformation of water on Pt/CeO2(111) and Pt/CeO(x)/TiO2(110) catalysts.

Hydrogen (H2) is currently used mainly in the chemical industry for the production of ammonia and methanol. Nevertheless, in the near future, hydrogen is expected to become a significant fuel that will largely contribute to the quality of atmospheric air. Hydrogen as a chemical element (H) is the most widespread one on the earth and as molecular dihydrogen (H2) can be obtained from a number of sources both renewable and nonrenewable by various processes. Hydrogen global production has so far been dominated by fossil fuels, with the most significant contemporary technologies being the steam reforming of hydrocarbons (e.g., natural gas). Pure hydrogen is also produced by electrolysis of water, an energy demanding process. This work reviews the current technologies used for hydrogen (H2) production from both fossil and renewable biomass resources, including reforming (steam, partial oxidation, autothermal, plasma, and aqueous phase) and pyrolysis. In addition, other methods for generating hydrogen (e.g., electrolysis of water) and purification methods, such as desulfurization and water-gas shift reactions are discussed.

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Hydrogen Production Technologies: Current State and Future Developments

“Redox” vs “associative formate with –OH group regeneration” WGS reaction mechanism on Pt/CeO2: Effect of platinum particle size

Kinetic and mechanistic studies of the water-gas shift reaction on Pt/TiO2 catalyst

A series of y wt % Pt/CexZr1–xO2 catalysts (y = 0.1, 0.5, and 1.0; x = 0.3, 0.5, and 0.7) were synthesized and characterized to investigate the effect of CeO2 doping with Zr4+ and of Pt particle size (Pt/Ce0.5Zr0.5O2) on important mechanistic and kinetic aspects of the water–gas shift (WGS) reaction. These included the concentration (μmol·g–1 or θ (surface coverage based on Pts)) and chemical structure of active reaction intermediates present in the “carbon path” and “hydrogen path” of the WGS reaction in the 200–300 °C range and the prevailing mechanism among “redox” and “associative formate” largely considered in the literature. Toward this goal, steady-state isotopic transient kinetic analysis coupled with in situ DRIFTS and mass spectrometry experiments were performed for the first time using D2O and 13CO isotopic gases. A novel transient isotopic experiment allowed quantification of the initial transient rate of reaction of adsorbed formate (HCOO−) with water and that of adsorbed CO with water under ...

Christos M. Kalamaras

Papers

Hydrogen Production Technologies: Current State and Future Developments

“Redox” vs “associative formate with –OH group regeneration” WGS reaction mechanism on Pt/CeO2: Effect of platinum particle size

Kinetic and mechanistic studies of the water-gas shift reaction on Pt/TiO2 catalyst

Mechanistic Studies of the Water–Gas Shift Reaction over Pt/CexZr1–xO2 Catalysts: The Effect of Pt Particle Size and Zr Dopant

Mechanistic aspects of the water–gas shift reaction on alumina-supported noble metal catalysts: In situ DRIFTS and SSITKA-mass spectrometry studies