Lars C. Grabow

The critical role of water at the gold-titania interface in catalytic CO oxidation

Easier oxidation over gold with added water Gold adsorbed on metal oxides is an excellent catalyst for the room-temperature oxidation of CO to CO2. However, there has been continuing disagreement between different studies on the key aspects of this catalyst. Saveeda et al. now show through kinetics and infrared spectroscopy that the presence of water can lower the reaction activation barrier by enabling OOH groups to form from adsorbed oxygen (see the Perspective by Mullen and Mullins). The OOH then reacts readily with CO. It thus seems that the main role of oxide support and its interface with the metal is in activating water, but that the steps of the reaction that involve CO occur on gold. Science, this issue p. 1599; see also p. 1564 Adsorbed water enables proton-transfer steps that lower the activation barrier for carbon monoxide oxidation. [Also see Perspective by Mullen and Mullins] We provide direct evidence of a water-mediated reaction mechanism for room-temperature CO oxidation over Au/TiO2 catalysts. A hydrogen/deuterium kinetic isotope effect of nearly 2 implicates O-H(D) bond breaking in the rate-determining step. Kinetics and in situ infrared spectroscopy experiments showed that the coverage of weakly adsorbed water on TiO2 largely determines catalyst activity by changing the number of active sites. Density functional theory calculations indicated that proton transfer at the metal-support interface facilitates O2 binding and activation; the resulting Au-OOH species readily reacts with adsorbed Au-CO, yielding Au-COOH. Au-COOH decomposition involves proton transfer to water and was suggested to be rate determining. These results provide a unified explanation to disparate literature results, clearly defining the mechanistic roles of water, support OH groups, and the metal-support interface.

Why Au and Cu Are More Selective Than Pt for Preferential Oxidation of CO at Low Temperature

Self-consistent, periodic density functional theory (DFT) calculations and micro-kinetic modeling are used to compare selectivity for the preferential oxidation of CO (PROX) with respect to H2 based on studies of elementary reaction steps on the (111) facet of Au, Cu and Pt. The first step of H oxidation (OH formation) has a higher activation barrier than the second step (H2O formation) on all three metal surfaces, indicating that OH formation competes with CO oxidation for the removal of trace amounts of CO from a typical reformate gas. The activation energy barrier for CO oxidation is found to be 0.18eV on Au(111), 0.82eV on Cu(111) and 0.96eV on Pt(111), whereas the barrier for OH formation is 0.90, 1.28 and 0.83eV respectively. A micro-kinetic model based on the DFT results shows that trends in the selectivity of these metals at different temperatures is due to (i) differences in the rate constants of the competitive CO and H oxidation reactions, and (ii) differences in the CO and H surface coverages. Our results explain why Au and Cu are more selective PROX catalysts compared to Pt at low temperatures. At higher temperatures, Pt and Cu lose some of their selectivity to CO oxidation, whereas the selectivity on Au decreases substantially primarily because of the significantly weaker CO adsorption.

Interlayer-Expanded Molybdenum Disulfide Nanocomposites for Electrochemical Magnesium Storage

Mg rechargeable batteries (MgRBs) represent a safe and high-energy battery technology but suffer from the lack of suitable cathode materials due to the slow solid-state diffusion of the highly polarizing divalent Mg ion. Previous methods improve performance at the cost of incompatibility with anode/electrolyte and drastic decrease in volumetric energy density. Herein we report interlayer expansion as a general and effective atomic-level lattice engineering approach to transform inactive intercalation hosts into efficient Mg storage materials without introducing adverse side effects. As a proof-of-concept we have combined theory, synthesis, electrochemical measurement, and kinetic analysis to improve Mg diffusion behavior in MoS2, which is a poor Mg transporting material in its pristine form. First-principles simulations suggest that expanded interlayer spacing allows for fast Mg diffusion because of weakened Mg-host interactions. Experimentally, the expansion was realized by inserting a controlled amount of poly(ethylene oxide) into the lattice of MoS2 to increase the interlayer distance from 0.62 nm to up to 1.45 nm. The expansion boosts Mg diffusivity by 2 orders of magnitude, effectively enabling the otherwise barely active MoS2 to approach its theoretical storage capacity as well as to achieve one of the highest rate capabilities among Mg-intercalation materials. The interlayer expansion approach can be leveraged to a wide range of host materials for the storage of various ions, leading to novel intercalation chemistry and opening up new opportunities for the development of advanced materials for next-generation energy storage.

Water-mediated proton hopping on an iron oxide surface

Water-Assisted Proton Diffusion Proton diffusion on metal oxide surfaces can play an important role in many catalytic processes. The presence of water is thought to accelerate proton diffusion. Merte et al. (p. 889) used high-speed, high-resolution scanning tunneling microscopy to study proton diffusion on an iron oxide. On oxygen-terminated FeO monolayer films formed on Pt, molecular water accelerated proton diffusion. Density function theory calculations implicated a H3O+ transition state in the diffusion process. The presence of adsorbed water enhances proton diffusion, likely through a hydronium ion transition state. The diffusion of hydrogen atoms across solid oxide surfaces is often assumed to be accelerated by the presence of water molecules. Here we present a high-resolution, high-speed scanning tunneling microscopy (STM) study of the diffusion of H atoms on an FeO thin film. STM movies directly reveal a water-mediated hydrogen diffusion mechanism on the oxide surface at temperatures between 100 and 300 kelvin. Density functional theory calculations and isotope-exchange experiments confirm the STM observations, and a proton-transfer mechanism that proceeds via an H3O+-like transition state is revealed. This mechanism differs from that observed previously for rutile TiO2(110), where water dissociation is a key step in proton diffusion.

Lattice strain effects on CO oxidation on Pt(111)

Surface strain plays a major role in determining the rate limiting step and catalytic activity of platinum for CO oxidation.

Finite-Size Effects in O and CO Adsorption for the Late Transition Metals

Gold is known to become significantly more catalytically active as its particle size is reduced, and other catalysts are also known to exhibit finite-size effects. To understand the trends related to finite-size effects, we have used density functional theory to study adsorption of representative adsorbates, CO and O, on the late transition metals Co, Ni, Cu, Ir, Pd, Ag, Rh, Pt and Au. We studied adsorption energies and geometries on 13-atom clusters and compared them to the fcc(111) and fcc(211) crystal facets. In all cases, adsorbates were found to bind significantly more strongly to the 13-atom clusters than to the extended surfaces. The binding strength of both adsorbates were found to correlate very strongly with the average coordination number of the metal atoms to which the adsorbate binds, indicating that the finite-size effects in bonding are not specific to gold.

Epitaxial Growth of ZSM-5@Silicalite-1: A Core–Shell Zeolite Designed with Passivated Surface Acidity

The design of materials with spatially controlled chemical composition has potential advantages for wide-reaching applications that span energy to medicine. Here, we present a method for preparing a core-shell aluminosilicate zeolite with continuous translational symmetry of nanopores and an epitaxial shell of tunable thickness that passivates Brønsted acid sites associated with framework Al on exterior surfaces. For this study, we selected the commercially relevant MFI framework type and prepared core-shell particles consisting of an aluminosilicate core (ZSM-5) and a siliceous shell (silicalite-1). Transmission electron microscopy and gas adsorption studies confirmed that silicalite-1 forms an epitaxial layer on ZSM-5 crystals without blocking pore openings. Scanning electron microscopy and dynamic light scattering were used in combination to confirm that the shell thickness can be tailored with nanometer resolution (e.g., 5-20 nm). X-ray photoelectron spectroscopy and temperature-programmed desorption measurements revealed the presence of a siliceous shell, while probe reactions using molecules that were either too large or adequately sized to access MFI pores confirmed the uniform shell coverage. The synthesis of ZSM-5@silicalite-1 offers a pathway for tailoring the physicochemical properties of MFI-type materials, notably in the area of catalysis, where surface passivation can enhance product selectivity without sacrificing catalyst activity. The method described herein may prove to be a general platform for zeolite core-shell design with potentially broader applicability to other porous materials.

Trends in Hydrodesulfurization Catalysis Based on Realistic Surface Models

Trends in hydrodesulfurization (HDS) activity are investigated on the basis of surface properties calculated by density functional theory for a series of HDS catalysts. It is shown that approximately linear correlations exist between HS group binding energies and activation barriers of key elementary reactions in HDS of thiophene. These linear correlations are used to develop a simple kinetic model, which qualitatively describes experimental trends in activity. The kinetic model identifies the HS-binding energy as a descriptor of HDS activity. This insight contributes to understanding the effect of promotion and structure–activity relationships.Graphical Abstract

CO-Induced Embedding of Pt Adatoms in a Partially Reduced FeOx Film on Pt(111)

The reduction of a single-layer FeO film grown on Pt(111) by CO at elevated pressures and temperatures has been studied through an interplay of scanning tunneling microscopy, ambient-pressure X-ray photoelectron spectroscopy, and density functional theory calculations. Exposure of the FeO thin film to CO at pressures between 1 and 30 Torr and temperatures between 500 and 530 K leads to formation of a honeycomb-structured Fe(3)O(2) film with hollow sites occupied by single Pt atoms extracted from the substrate surface. The formation of these adatoms is driven by an increase in CO adsorption energy. In addition, the structure incorporates undercoordinated Fe centers, which are proposed to have substantial effects on the catalytic properties of the surface.

Synergistic Effects in Bimetallic Palladium–Copper Catalysts Improve Selectivity in Oxygenate Coupling Reactions

Condensation reactions such as Guerbet and aldol are important since they allow for C-C bond formation and give higher molecular weight oxygenates. An initial study identified Pd-supported on hydrotalcite as an active catalyst for the transformation, although this catalyst showed extensive undesirable decarbonylation. A catalyst containing Pd and Cu in a 3:1 ratio dramatically decreased decarbonylation, while preserving the high catalytic rates seen with Pd-based catalysts. A combination of XRD, EXAFS, TEM, and CO chemisorption and TPD revealed the formation of CuPd bimetallic nanoparticles with a Cu-enriched surface. Finally, density functional theory studies suggest that the surface segregation of Cu atoms in the bimetallic alloy catalyst produces Cu sites with increased reactivity, while the Pd sites responsible for unselective decarbonylation pathways are selectively poisoned by CO.