Theoretical study of structure sensitivity on ceria-supported single platinum atoms and its influence on carbon monoxide adsorption.

Density functional theory (DFT) calculations explore the stability of a single platinum atom on various flat, stepped, and defective ceria surfaces, in the context of single-atom catalysts (SACs) for the water-gas shift (WGS) reaction. The adsorption properties and diffusion kinetics of the metal strongly depend on the support termination with large stability on metastable and stepped CeO2(100) and (210) surfaces where the diffusion of the platinum atom is hindered. At the opposite, the more stable CeO2(111) and (110) terminations weakly bind the platinum atom and can promote the growth of metallic clusters thanks to fast diffusion kinetics. The adsorption of carbon monoxide on the single platinum atom supported on the various ceria terminations is also sensitive to the surface structure. Carbon monoxide weakly binds to the single platinum atom supported on reduced CeO2(111) and (211) terminations. The desorption of the CO2 formed during the WGS reaction is thus facilitated on the latter terminations. A vibrational analysis underlines the significant changes in the calculated scaled anharmonic CO stretching frequency on these catalysts.

Identifying the Structure of Supported Metal Catalysts Using Vibrational Fingerprints from Ab Initio Nanoscale Models.

Identifying active sites of supported noble metal nanocatalysts remains challenging, since their size and shape undergo changes depending on the support, temperature, and gas mixture composition. Herein, the anharmonic infrared spectrum of adsorbed CO is simulated using density functional theory (DFT) to gain insight into the nature of Pd nanoparticles (NPs) supported on ceria. The authors systematically determine how the simulated infrared spectra are affected by CO coverage, NP size (0.5-1.5 nm), NP morphology (octahedral, icosahedral), and metal-support contact angle, by exploring a diversity of realistic models inspired by ab initio molecular dynamics. The simulated spectra are then used as a spectroscopic fingerprint to characterize nanoparticles in a real catalyst, by comparison with in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments. Truncated octahedral NPs with an acute Pd-ceria angle reproduce most of the measurements. In particular, the authors isolate features characteristic of CO adsorbed at the metal-support interface appearing at low frequencies, both seen in simulation and experiment. This work illustrates the strong need for realistic models to provide a robust description of the active sites, especially at the interface of supported metal nanocatalysts, which can be highly dynamic and evolve considerably during reaction.

Nature of the Active Sites on Ni/CeO2 Catalysts for Methane Conversions.

Effective catalysts for the direct conversion of methane to methanol and for methane's dry reforming to syngas are Holy Grails of catalysis research toward clean energy technologies. It has recently been discovered that Ni at low loadings on CeO2(111) is very active for both of these reactions. Revealing the nature of the active sites in such systems is paramount to a rational design of improved catalysts. Here, we correlate experimental measurements on the CeO2(111) surface to show that the most active sites are cationic Ni atoms in clusters at step edges, with a small size wherein they have the highest Ni chemical potential. We clarify the reasons for this observation using density functional theory calculations. Focusing on the activation barrier for C-H bond cleavage during the dissociative adsorption of CH4 as an example, we show that the size and morphology of the supported Ni nanoparticles together with strong Ni-support bonding and charge transfer at the step edge are key to the high catalytic activity. We anticipate that this knowledge will inspire the development of more efficient catalysts for these reactions.

Reaction Pathway for Coke-Free Methane Steam Reforming on a Ni/CeO2 Catalyst: Active Sites and the Role of Metal-Support Interactions.

Methane steam reforming (MSR) plays a key role in the production of syngas and hydrogen from natural gas. The increasing interest in the use of hydrogen for fuel cell applications demands development of catalysts with high activity at reduced operating temperatures. Ni-based catalysts are promising systems because of their high activity and low cost, but coke formation generally poses a severe problem. Studies of ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) indicate that CH4/H2O gas mixtures react with Ni/CeO2(111) surfaces to form OH, CH x , and CH x O at 300 K. All of these species are easy to form and desorb at temperatures below 700 K when the rate of the MSR process is accelerated. Density functional theory (DFT) modeling of the reaction over ceria-supported small Ni nanoparticles predicts relatively low activation barriers between 0.3 and 0.7 eV for complete dehydrogenation of methane to carbon and the barrierless activation of water at interfacial Ni sites. Hydroxyls resulting from water activation allow for CO formation via a COH intermediate with a barrier of about 0.9 eV, which is much lower than that through a pathway involving lattice oxygen from ceria. Neither methane nor water activation is a rate-determining step, and the OH-assisted CO formation through the COH intermediate constitutes a low-barrier pathway that prevents carbon accumulation. The interactions between Ni and the ceria support and the low metal loading are crucial for the reaction to proceed in a coke-free and efficient way. These results pave the way for further advances in the design of stable and highly active Ni-based catalysts for hydrogen production.

Ce=O Terminated CeO2.

Multiply bonded lanthanide oxo groups are rare in coordination compounds and have not previously been reported for a surface termination of a lanthanide oxide. Here we report the observation of a Ce=O terminated ceria surface in a CeO2 (111)-( 3 × 3 )R30° reconstruction of ≈3 nm thick ceria islands prepared on Pt(111). This is evidenced by scanning tunnelling microscopy (STM), low energy electron diffraction (LEED) and high-resolution electron energy loss spectroscopy (HREELS) measurements in conjunction with density functional theory (DFT) calculations. A Ce=O stretching frequency of 775 cm-1 is observed in HREELS, compared with 766 cm-1 calculated by DFT. The calculations also predict that the Ce=O bond is weak, with an oxygen vacancy formation energy of 0.85 eV. This could play an important role in the facile removal of lattice oxygen from CeO2 , accompanied by the reduction of CeIV to CeIII , which is a key attribute of ceria-based systems in connection with their unique catalytic properties.

DFT insights into structural effects of Ni-Cu/CeO2 catalysts for CO selective reaction towards water-gas shift.

The water-gas shift (WGS) reaction is a key step in hydrogen production, particularly to meet the high-purity H2 requirement of PEM fuel cells. The catalysts currently employed in large-scale WGS plants require a two-step process to overcome thermodynamic and kinetic limitations. Ni-Cu/CeO2 solids are promising catalysts for the one-step process required for small-scale applications, as the addition of Cu hinders undesired methanation reactions occurring on Ni/CeO2. In this work, we performed calculations on Ni4-xCux/CeO2(111) systems to evaluate the influence of cluster conformation on the selectivity towards water-gas shift. The structure and miscibility of CeO2-supported Ni4-xCux clusters were investigated and compared with those of gas-phase clusters to understand the effect of metal-support interactions. The adsorption of CO onto apical Ni and Cu atoms of Ni4-xCux/CeO2(111) systems was studied, and changes in the C-O bond strength were confirmed at the electronic level by investigating shifts in the 3σ and 1π orbitals. The selectivity towards WGS was evaluated using Brønsted-Evans-Polanyi relations for the C-O activation energy. Overall, a strengthening of the C-O bond and an increase in CO dissociation energy were verified on Cu-containing clusters, explaining the improvement in selectivity of Ni4-xCux/CeO2(111) systems.