Ranjith K. Ramachandran

The spectro-kinetic characterization of complex catalytic materials, i.e. relating the observed reaction kinetics to spectroscopic descriptors of the catalyst state, presents a fundamental challenge with a potentially significant impact on various chemical technologies. We propose to reconcile the kinetic characteristics available from temporal analysis of products (TAP) pulse-response kinetic experiments with the spectroscopic data available from ambient pressure X-ray photoelectron spectroscopy (AP-XPS), using atomic layer deposition (ALD) to synthesize multicomponent model surfaces on 2D and 3D supports. The accumulated surface exposure to a key reactant (total number of collisions) is used as a common scale within which the results from the two techniques can be rigorously compared for microscopically-equivalent surfaces. This approach is illustrated by proof-of-principle TAP and AP-XPS experiments with PtIn/MgO/SiO₂ catalysts for alkane dehydrogenation at 800 K. Similarly to industrially-relevant Pt-based bimetallic catalysts on high-surface area supports, the initial period of coke accumulation on the surface resulted in gradually decreased conversion and increased selectivity towards propylene. We were able to monitor the process of coke deposition with both AP-XPS and TAP. The evolution of the C 1s photoelectron spectra is aligned on the common exposure scale with the evolution of the coke amounts deposited per Pt site during a multi-pulse TAP experiment. Moreover, TAP provided quantitative kinetic descriptors of propane consumption and product mean residence time within this common exposure scale. The challenges and opportunities presented by this novel tandem methodology are discussed in the context of catalysis research.

The N ₂ incorporation into an atomically-thin In ₂ O ₃ film at Au/In ₂ O ₃ –TiO ₂ heterointerfaces enabled the synergistic improvement of the long-term plasticity (LTP) of artificial metal oxide optical synapses.

We report the phase and size-controlled synthesis of Fe–Pt nanoalloys, prepared via a two-step synthesis procedure. The first step is the deposition of bilayers consisting of iron oxide and Pt films of desired thicknesses using atomic layer deposition, followed by a temperature-programmed reduction treatment of the film under H ₂ /N ₂ atmosphere. This method enables the phase pure synthesis of all three Fe–Pt alloy phases, namely Fe ₃ Pt, FePt, and FePt ₃ , as revealed by in situ x-ray diffraction and x-ray fluorescence measurements. It is also demonstrated that by changing the total thickness of the bilayers while keeping the Pt/(Pt + Fe) atomic ratio constant, the size of the resulting bimetallic nanoparticles can be tuned, as confirmed by scanning electron microscopic measurements.

The increasing interest in atomic layer deposition (ALD) of Pt for the controlled synthesis of supported nanoparticles for catalysis demands an in-depth understanding of the nucleation controlled growth behaviour. We present an in situ investigation of Pt ALD on planar Si substrates, with native SiO₂, by means of X-ray fluorescence (XRF) and grazing incidence small-angle X-ray scattering (GISAXS), using a custom-built synchrotron-compatible high-vacuum ALD setup and focusing on the thermal Pt ALD process, comprising (methylcyclopentadienyl)trimethylplatinum (MeCpPtMe₃) and O₂ gas at 300 °C. The evolution in key scattering features provides insights into the growth kinetics of Pt deposits from small nuclei to isolated islands and coalesced worm-like structures. An analysis approach is introduced to extract dynamic information on the average real space parameters, such as Pt cluster shape, size, and spacing. The results indicate a nucleation stage, followed by a diffusion-mediated particle growth regime that is marked by a decrease in average areal density and the formation of laterally elongated Pt clusters. Growth of the Pt nanoparticles is thus not only governed by the adsorption of Pt precursor molecules from the gas-phase and subsequent combustion of the ligands, but is largely determined by adsorption of migrating Pt species on the surface and diffusion-driven particle coalescence. Moreover, the influence of the Pt precursor dose on the particle nucleation and growth is investigated. It is found that the precursor dose influences the deposition rate (number of Pt atoms per cycle), while the particle morphology for a specific Pt loading is independent of the precursor dose used in the ALD process. Our results prove that combining in situ GISAXS and XRF provides an excellent experimental strategy to obtain new fundamental insights about the role of deposition parameters on the morphology of Pt ALD depositions. This knowledge is vital to improve control over the Pt nucleation stage and enable efficient synthesis of supported nanocatalysts.

Supported Pt nanoparticle stabilization via Atomic Layer Deposition overcoating with Al₂O₃ has been proved to prevent particle coarsening during thermal annealing for widely spaced nanoparticles while ensuring surface accessibility for applications.

Atomic layer deposition (ALD) of noble metals is an attractive technology potentially applied in nanoelectronics and catalysis. Unlike the combustion-like mechanism shown by other noble metal ALD processes, the main palladium (Pd) ALD process using palladium(II)hexafluoroacetylacetonate [Pd(hfac)2] as precursor is based on true reducing surface chemistry. In this work, a thorough investigation of plasma-enhanced Pd ALD is carried out by employing this precursor with different plasmas (H2*, NH3*, O2*) and plasma sequences (H2* + O2*, O2* + H2*) as co-reactants at varying temperatures, providing insights in the co-reactant and temperature dependence of the Pd growth per cycle (GPC). At all temperatures, films grown with only reducing co-reactants contain a large amount of carbon, while an additional O2* in the co-reactant sequence helps to obtain Pd films with much lower impurity concentrations. Remarkably, in situ XRD and SEM show an abrupt release of the carbon impurities during annealing at moderate temperatures in different atmospheres. In vacuo XPS measurements reveal the remaining species on the as-deposited surface after every exposure. Links are established between the particular surface termination prior to the precursor pulse and the observed differences in GPC, highlighting hydrogen as the key growth facilitator and carbon and oxygen as growth inhibitors. The increase in GPC with temperature for ALD sequences with H2* or NH3* prior to the precursor pulse is explained by an increase in the amount of hydrogen species that reside on the Pd surface which are available for reaction with the Pd(hfac)2 precursor.

Atomic layer deposition (ALD) is a vacuum technology for the deposition of a small number of atoms on surfaces. Its use in catalysis is growing. Here, we explored the use of ALD for introducing acid and metal sites in zeolites for performing bifunctional catalysis. Plasma-enhanced ALD involving cyclic exposure of a sample to tris(2,2,6,6-tetramethyl-3,5-heptanedionato)gallium (Ga(TMHD)₃) vapor and O₂ plasma (Ga-ALD) was used for introducing acid sites. Interestingly, Ga-ALD was found to cause preferential deposition of Pt nanoparticles via incipient wetness impregnation on the edges of COK-14 crystal plates, in contrast to previously published results on Al-ALD. Benefiting from the optimum proximity between the Ga acid and Pt metal sites, it is shown here that Ga-ALD is a way to introduce sufficient acidity into all-silica zeolite COK-14 for obtaining bifunctional catalytic behavior. Hydrogenation–dehydrogenation activity in bifunctional catalysts is typically provided by trace amounts of platinum dispersed on the zeolite. Pt-ALD was applied for finely dispersing platinum on ZSM-5 zeolite. Pt-ALD involved alternating exposure to the trimethyl(methylcyclopentadienyl)platinum(IV) (MeCpPtMe₃) precursor and ozone. The Pt-ALD method proved to be an efficient way to uniformly disperse ultra-small Pt nanoparticles onto the zeolite. The bifunctional catalytic behavior of ALD-functionalized zeolites was confirmed in the hydroconversion of the n-decane model molecule.