The surface chemistry of the atomic layer deposition of metal thin films.

In this perspective we discuss the progress made in the mechanistic studies of the surface chemistry associated with the atomic layer deposition (ALD) of metal films and the usefulness of that knowledge for the optimization of existing film growth processes and for the design of new ones. Our focus is on the deposition of late transition metals. We start by introducing some of the main surface-sensitive techniques and approaches used in this research. We comment on the general nature of the metallorganic complexes used as precursors for these depositions, and the uniqueness that solid surfaces and the absence of liquid solvents bring to the ALD chemistry and differentiate it from what is known from metalorganic chemistry in solution. We then delve into the adsorption and thermal chemistry of those precursors, highlighting the complex and stepwise nature of the decomposition of the organic ligands that usually ensued upon their thermal activation. We discuss the criteria relevant for the selection of co-reactants to be used on the second half of the ALD cycle, with emphasis on the redox chemistry often associated with the growth of metallic films starting from complexes with metal cations. Additional considerations include the nature of the substrate and the final structural and chemical properties of the growing films, which we indicate rarely retain the homogeneous 2D structure often aimed for. We end with some general conclusions and personal thoughts about the future of this field.

Remote Activation of H-H Bonds by Platinum in Dilute Alloy Catalysts.

With heterogeneous catalysts, chemical promotion takes place at their surfaces. Even in the case of single-atom alloys, where small quantities of a reactive metal are dispersed within the main host, it is assumed that both elements are exposed and available to bond with the reactants. Here, we show, on the basis of in situ X-ray absorption spectroscopy data, that in alloy catalysts made from Pt highly diluted in Cu the Pt atoms are located at the inner interface between the metal nanoparticles and the silica support instead. Kinetic experiments indicated that these catalysts still display better selectivity for the hydrogenation of unsaturated aldehydes to unsaturated alcohols than the pure metals. Density functional theory calculations corroborated the stability of Pt at the metal-support interface and explained the catalytic performance as being due to a remote lowering of the activation barrier for the dissociation of H2 at Cu sites by the internal Pt atoms.

Redox Properties of TiO2 Thin Films Grown on Mesoporous Silica by Atomic Layer Deposition.

The redox properties of titania films grown by ALD on SBA-15, a silica-based mesoporous material, were characterized as a function of thickness (that is, the number of ALD cycles used). 29Si CP/MAS NMR helped to identify the nature of the surface species that form in the initial stages of deposition, and infrared absorption spectroscopy was used to follow the transition from silica to titania surfaces. The reducibility of the titania sites by CO and H2 was studied ex situ using EPR and in situ with ambient-pressure XPS. It was determined that the titania ALD films are amorphous and easier to reduce than crystalline titania and that the reduction is reversible. A transition in the nature of the surface was also observed, with unique mixed Si-O-Ti sites forming during the first few ALD cycles and a more typical titania surface progressively developing as the film grows in thickness.

In situ identification of surface sites in Cu-Pt bimetallic catalysts: Gas-induced metal segregation.

The effect of gases on the surface composition of Cu-Pt bimetallic catalysts has been tested by in situ infrared (IR) and x-ray absorption spectroscopies. Diffusion of Pt atoms within the Cu-Pt nanoparticles was observed both in vacuum and under gaseous atmospheres. Vacuum IR spectra of CO adsorbed on CuPtx/SBA-15 catalysts (x = 0-∞) at 125 K showed no bonding on Pt regardless of Pt content, but reversible Pt segregation to the surface was seen with the high-Pt-content (x ≥ 0.2) samples upon heating to 225 K. In situ IR spectra in CO atmospheres also highlighted the reversible segregation of Pt to the surface and its diffusion back into the bulk when cycling the temperature from 295 to 495 K and back, most evidently for diluted single-atom alloy catalysts (x ≤ 0.01). Similar behavior was possibly observed under H2 using small amounts of CO as a probe molecule. In situ x-ray absorption near-edge structure data obtained for CuPt0.2/SBA-15 under both CO and He pointed to the metallic nature of the Pt atoms irrespective of gas or temperature, but analysis of the extended x-ray absorption fine structure identified a change in coordination environment around the Pt atoms, from a (Pt-Cu):(Pt-Pt) coordination number ratio of ∼6:6 at or below 445 K to 8:4 at 495 K. The main conclusion is that Cu-Pt bimetallic catalysts are dynamic, with the composition of their surfaces being dependent on temperature in gaseous environments.

Vanadate Retention by Iron and Manganese Oxides.

Anthropogenic emissions of vanadium (V) into terrestrial and aquatic surface systems now match those of geogenic processes, and yet, the geochemistry of vanadium is poorly described in comparison to other comparable contaminants like arsenic. In oxic systems, V is present as an oxyanion with a +5 formal charge on the V center, typically described as H x VO4 (3-x)-, but also here as V(V). Iron (Fe) and manganese (Mn) (oxy)hydroxides represent key mineral phases in the cycling of V(V) at the solid-solution interface, and yet, fundamental descriptions of these surface-processes are not available. Here, we utilize extended X-ray absorption fine structure (EXAFS) and thermodynamic calculations to compare the surface complexation of V(V) by the common Fe and Mn mineral phases ferrihydrite, hematite, goethite, birnessite, and pyrolusite at pH 7. Inner-sphere V(V) complexes were detected on all phases, with mononuclear V(V) species dominating the adsorbed species distribution. Our results demonstrate that V(V) adsorption is exergonic for a variety of surfaces with differing amounts of terminal -OH groups and metal-O bond saturations, implicating the conjunctive role of varied mineral surfaces in controlling the mobility and fate of V(V) in terrestrial and aquatic systems.

Designing Sites in Heterogeneous Catalysis: Are We Reaching Selectivities Competitive With Those of Homogeneous Catalysts?

A critical review of different prominent nanotechnologies adapted to catalysis is provided, with focus on how they contribute to the improvement of selectivity in heterogeneous catalysis. Ways to modify catalytic sites range from the use of the reversible or irreversible adsorption of molecular modifiers to the immobilization or tethering of homogeneous catalysts and the development of well-defined catalytic sites on solid surfaces. The latter covers methods for the dispersion of single-atom sites within solid supports as well as the use of complex nanostructures, and it includes the post-modification of materials via processes such as silylation and atomic layer deposition. All these methodologies exhibit both advantages and limitations, but all offer new avenues for the design of catalysts for specific applications. Because of the high cost of most nanotechnologies and the fact that the resulting materials may exhibit limited thermal or chemical stability, they may be best aimed at improving the selective synthesis of high value-added chemicals, to be incorporated in organic synthesis schemes, but other applications are being explored as well to address problems in energy production, for instance, and to design greener chemical processes. The details of each of these approaches are discussed, and representative examples are provided. We conclude with some general remarks on the future of this field.

Adsorption of crotonaldehyde on metal surfaces: Cu vs Pt.

The thermal chemistry of crotonaldehyde on the surface of a polished polycrystalline copper disk was characterized by temperature-programmed desorption (TPD) and reflection-absorption infrared spectroscopy (RAIRS) and contrasted with previous data obtained on a Pt(111) single crystal substrate. A clear difference in the adsorption mode was identified between the two surfaces, highlighted by the prevalence of RAIRS peaks for the C=C bond on Cu vs for C=O on Pt. Adsorption was also determined to be much weaker on Cu vs Pt, with an adsorption energy on the former ranging from -50 kJ/mol to -65 kJ/mol depending on the surface coverage. The experimental data were complemented by extensive quantum mechanics calculations using density functional theory (DFT) to determine the most stable adsorption configurations on both metals. It was established that crotonaldehyde adsorption on Cu occurs via the oxygen atom in the carbonyl group, in a mono-coordinated fashion, whereas on Pt multi-coordination is preferred, centered around the C=C bond. The contrasting surface adsorption modes seen on these two metals are discussed in terms of the possible relevance to selectivity in single-atom alloy hydrogenation catalysis.

Nucleation and Initial Stages of Growth during the Atomic Layer Deposition of Titanium Oxide on Mesoporous Silica.

A chemical approach to the deposition of thin films on solid surfaces is highly desirable but prone to affect the final properties of the film. To better understand the origin of these complications, the initial stages of the atomic layer deposition of titania films on silica mesoporous materials were characterized. Adsorption-desorption measurements indicated that the films grow in a layer-by-layer fashion, as desired, but initially exhibit surprisingly low densities, about one-quarter of that of bulk titanium oxide. Electron microscopy, X-ray diffraction, UV/visible, and X-ray absorption spectroscopy data pointed to the amorphous nature of the first monolayers, and EXAFS and 29Si CP/MAS NMR results to an initial growth via the formation of individual tetrahedral Ti-oxide units on isolated Si-OH surface groups with unusually long Ti-O bonds. Density functional theory calculations were used to propose a mechanism where the film growth starts at the nucleation centers to form an open 2D structure.

Adsorption Site Regulation to Guide Atomic Design of Ni-Ga Catalysts for Acetylene Semi-Hydrogenation.

Atomic regulation of metal catalysts has emerged as an intriguing yet challenging strategy to boost product selectivity. Here, we report a density functional theory-guided atomic design strategy for the fabrication of a NiGa intermetallic catalyst with completely isolated Ni sites to optimize acetylene semi-hydrogenation processes. Such Ni sites show not only preferential acetylene π-adsorption, but also enhanced ethylene desorption. The characteristics of the Ni sites are confirmed by multiple characterization techniques, including aberration-corrected high-resolution scanning transmission electron microscopy and X-ray absorption spectrometry measurements. The superior performance is also confirmed experimentally against a Ni5 Ga3 intermetallic catalyst with partially isolated Ni sites and against a Ni catalyst with multi-atomic ensemble Ni sites. Accordingly, the NiGa intermetallic catalyst with the completely isolated Ni sites shows significantly enhanced selectivity to ethylene and suppressed coke formation.

Use of Au@Void@TiO2 yolk-shell nanostructures to probe the influence of oxide crystallinity on catalytic activity for low-temperature oxidations.

A series of Au@Void@TiO2 yolk-shell structures were synthesized and characterized, and their catalytic activity was tested for the oxidation of carbon monoxide. The target of this work was to evaluate the effects of (1) the crystallinity of the TiO2 shell and (2) the presence of titanate phases. Transmission electron microscopy and X-ray diffraction data show that increasing calcination temperatures, from 850 to 1250 K, leads to the formation of larger titania crystallites. These crystallites are typically in the form of anatase, but some rutile is also made at high temperatures. The general yolk-shell nanostructures retain their basic characteristics upon calcination and upon treatment with HCl (used to remove the titanate phases), but a few structural and chemical changes do take place: (1) the void-space diameter is reduced by approximately 10% when going from TCalc = 850 K to TCalc = 1250 K, a change that is accompanied by a decrease in the surface area (estimated from N2 adsorption-desorption isotherms); (2) the shell thickness remains unaffected by either calcination or HCl treatment; (3) the pore volume also remains approximately constant with increasing calcination temperature in the catalysts free of titanates but diminishes significantly in the samples with titanate phases; (4) the mesoporosity is minimal in all yolk-shell nanostructures but more noticeable with the pure TiO2 shells; (5) the titanates have high Na content (measured by X-ray photoelectron spectroscopy), but that Na is fully removed upon treatment with HCl; (6) no Ti3+ was detectable in any of the samples, but silica, together with C and (minor amounts of) N, was present in all; (7) all Au is in metallic form; (8) two temperature regimes were observed for the catalytic oxidation of CO, as reported for other similar samples in the past, an Arrhenius regime around or above room temperature, and a cryogenic range going to temperatures as low as 120 K; (9) the latter regime is only seen with the samples containing titanate phases; (10) the titanates seem to also aid in the oxidation at higher temperatures; and (11) in general, increasing titania crystallinity leads to a decrease the catalytic activity.

Porous LaFeO3 Prepared by an in Situ Carbon Templating Method for Catalytic Transfer Hydrogenation Reactions.

Catalytic transfer hydrogenation is an attractive route for the synthesis of biomass-derived chemicals. However, development of efficient, low-cost, and stable catalysts for that reaction is still a challenge. Here, we report on the preparation and testing of a non-noble perovskite oxide (LaFeO3) catalyst synthesized by an in situ carbon templating method. We show that our catalyst is quite active and selective toward the hydrogenation of unsaturated organics. Compared to an analogous LaFeO3 catalyst prepared by a more traditional method, using citric acid, the new LaFeO3 exhibited a more porous structure, a La-enriched surface composition, and abundant oxygen vacancies, all characteristics that improve contact with the reactants. In the case of the conversion of furfural to furfuryl alcohol (FOL) using iso-propanol as hydrogen donor, the new LaFeO3 showed a furfural conversion of 90% and a selectivity to FOL of 94%, significantly higher than with the reference LaFeO3 prepared by the traditional sol-gel method (60 and 91%, respectively). Moreover, our new LaFeO3 catalyst can be recovered after a calcination treatment, with no appreciable changes in its structure or activity, a test that we repeated six times, and can promote the hydrogenation of other carbonyl compounds containing electron-withdrawing groups. A reaction mechanism is proposed in which metal cations are the adsorption sites for iso-propanol and oxygen vacancies are the adsorption sites for furfural, and where the conversion proceeds following an acid-base mechanism. We believe that the novel use of perovskites as catalysts for hydrogenation reactions reported here may be easily extendable to other processes, and that our carbon-templating synthetic approach offers a way to synthesize viable perovskite catalysts with high surface areas for optimized activity.

Gas-Phase Electron-Impact Activation of Atomic Layer Deposition (ALD) Precursors: MeCpPtMe3.

The use of gas-phase electron-impact activation of metalorganic complexes to facilitate atomic layer depositions (ALD) was tested for the case of (methylcyclopentadienyl)Pt(IV) trimethyl (MeCpPtMe3) on silicon oxide films. Uptake enhancements of more than 1 order of magnitude were calculated from X-ray photoelectron spectroscopy (XPS) data. On the basis of the measured C:Pt ratios, the surface species were estimated to mainly consist of MeCpPt moieties, likely because of the prevalent formation of [MeCpPtMe x- nH]+ ions after gas-phase ionization (as determined by mass spectrometry). Counterintuitively, more extensive adsorption was observed on thick SiO2 films than on the native thin SiO2 film that forms on Si(100) wafers, despite the former having virtually no surface OH groups. The adsorption of MeCpPt fragments on silicon oxide surfaces was determined by density functional theory (DFT) calculations to be highly exothermic and to favor attachment to Si-O-Si bridge sites.

Selectivity in Hydrogenation Catalysis with Unsaturated Aldehydes: Parallel versus Sequential Steps.

A high-flux molecular beam setup has been used to characterize the kinetics of the steady-state catalytic hydrogenation of unsaturated aldehydes, specifically of crotonaldehyde, promoted by platinum surfaces under single-collision conditions. Surprisingly, in addition to the hydrogenation of the individual single bonds, to yield the saturated aldehyde and the unsaturated alcohol, the formation of the saturated alcohol, the product of the hydrogenation of both C═C and C═O bonds, was detected as well. This indicates that the dual hydrogenation reaction is a primary pathway and not the result of secondary hydrogenation of the other products as commonly assumed. Moreover, an increase in the partial pressure of the reactant was found to shift the reaction selectivity from the saturated alcohol to the saturated aldehyde without significantly affecting the selectivity toward the production of the unsaturated alcohol. We explain these observations by proposing a mechanism involving the parallel formation of several monohydrogenated intermediates on the surface.

The Chemistry of Inorganic Precursors during the Chemical Deposition of Films on Solid Surfaces.

The deposition of thin solid films is central to many industrial applications, and chemical vapor deposition (CVD) methods are particularly useful for this task. For one, the isotropic nature of the adsorption of chemical species affords even coverages on surfaces with rough topographies, an increasingly common requirement in microelectronics. Furthermore, by splitting the overall film-depositing reactions into two or more complementary and self-limiting steps, as it is done in atomic layer depositions (ALD), film thicknesses can be controlled down to the sub-monolayer level. Thanks to the availability of a vast array of inorganic and metalorganic precursors, CVD and ALD are quite versatile and can be engineered to deposit virtually any type of solid material. On the negative side, the surface chemistry that takes place in these processes is often complex, and can include undesirable side reactions leading to the incorporation of impurities in the growing films. Appropriate precursors and deposition conditions need to be chosen to minimize these problems, and that requires a proper understanding of the underlying surface chemistry. The precursors for CVD and ALD are often designed and chosen based on their known thermal chemistry from inorganic chemistry studies, taking advantage of the vast knowledge developed in that field over the years. Although a good first approximation, however, this approach can lead to wrong choices, because the reactions of these precursors at gas-solid interfaces can be quite different from what is seen in solution. For one, solvents often aid in the displacement of ligands in metalorganic compounds, providing the right dielectric environment, temporarily coordinating to the metal, or facilitating multiple ligand-complex interactions to increase reaction probabilities; these options are not available in the gas-solid reactions associated with CVD and ALD. Moreover, solid surfaces act as unique "ligands", if these reactions are to be viewed from the point of view of the metalorganic complexes used as precursors: they are bulky and rigid, can provide multiple binding sites for a single reaction, and can promote unique bonding modes, especially on metals, which have delocalized electronic structures. The differences between the molecular and surface chemistry of CVD and ALD precursors can result in significant variations in their reactivity, ultimately leading to unpredictable properties in the newly grown films. In this Account, we discuss some of the main similarities and differences in chemistry that CVD/ALD precursors follow on surfaces when contrasted against their known behavior in solution, with emphasis on our own work but also referencing other key contributions. Our approach is unique in that it combines expertise from the inorganic, surface science, and quantum-mechanics fields to better understand the mechanistic details of the chemistry of CVD and ALD processes and to identify new criteria to consider when designing CVD/ALD precursors.

High-Potential Metalless Nanocarbon Foam Supercapacitors Operating in Aqueous Electrolyte.

Light-weight graphite foam decorated with carbon nanotubes (dia. 20-50 nm) is utilized as an effective electrode without binders, conductive additives, or metallic current collectors for supercapacitors in aqueous electrolyte. Facile nitric acid treatment renders wide operating potentials, high specific capacitances and energy densities, and long lifespan over 10 000 cycles manifested as 164.5 and 111.8 F g-1 , 22.85 and 12.58 Wh kg-1 , 74.6% and 95.6% capacitance retention for 2 and 1.8 V, respectively. Overcharge protection is demonstrated by repetitive cycling between 2 and 2.5 V for 2000 cycles without catastrophic structural demolition or severe capacity fading. Graphite foam without metallic strut possessing low density (≈0.4-0.45 g cm-3 ) further reduces the total weight of the electrode. The thorough investigation of the specific capacitances and coulombic efficiencies versus potential windows and current densities provides insights into the selection of operation conditions for future practical devices.

Monte Carlo Simulations of the Uptake of Chiral Compounds on Solid Surfaces.

A Monte Carlo algorithm was developed and used to describe and explain previous experimental results associated with the kinetics of the uptake of chiral molecules on solid surfaces. The specific system simulated in this study is the adsorption of propylene oxide (PO) on Pt(111) surfaces. The surface was represented by a square lattice, and the time evolution of the adsorption, starting from a clean surface, was simulated via a number of sequential events chosen using a stochastic approach based on the so-called Master equation and derived from the formalism advanced by Gillespie. Two main assumptions were required to explain the experimental results: (1) that adsorption is assisted by previously adsorbed molecules, that is, that the probability for sticking is higher next to other adsorbates than on empty isolated sites, and (2) that the geometry adopted by the new adsorbate next to an old one is defined and different for homochiral versus heterochiral pairs. Our model was able to quantitatively reproduce the experimental data and to explain a number of important observations associated with the fact that the adsorbates are chiral, including the following: (1) the final PO saturation depends on the enantiocomposition of the gas phase, yielding a layer approximately 20% less dense with a racemic mixture than with enantiopure S-PO or R-PO; (2) the same changes in saturation coverages are seen if PO of different chirality are dosed sequentially; (3) the sticking probability is also higher with enantiopure adsorbates, at least in the initial stages of the uptake; (4) the sticking probability initially increases with increasing exposure, until reaching a maximum at about 20% of saturation; and (5) the adsorbed layers do not show any long-range ordering but display small linear clusters. It was also possible to reproduce the experimental observation that the addition of a prochiral molecule such as propylene (Py) to a surface dosed with a small amount of a chiral "seed" (PO) leads to an amplification of the initial enantioselectivity of that surface.