Tunable Solid Acid Catalyst Thin Films Prepared by Atomic Layer Deposition.

Solid acid catalysts, including zeolites and amorphous silica-aluminas (ASAs), are industrially important materials widely used in the fuel and petrochemical industries. The versatility of zeolites is due to the Brønsted acidity of the bridging hydroxyl and shape selectivity that can be tailored during and after synthesis. This is in contrast to amorphous silica-alumina, where tailoring acidity is a major challenge as the Brønsted acid structure in ASA is still debated. In both cases, however, the pore size and acidity cannot be tuned independently, and this is particularly limiting in the application of biomass conversion, where zeolite pores are too small for the molecules of interest. Herein, we present a method using atomic layer deposition (ALD) to prepare thin films of solid acid materials where the ratio of Brønsted to Lewis acid sites can be tuned precisely. This capability, combined with the sub-nm pore size control afforded by ALD yields a powerful and flexible method for synthesizing solid acid catalysts inside virtually any mesoporous host. We demonstrate the utility of these materials in two acid-catalyzed reactions relevant to biomass conversion: (1) Meerwein-Ponndorf-Verley-Oppenauer (MPVO) reaction and dehydration of fructose and (2) cascade reaction of glucose to 5-hydroxymethylfurfural. Finally, we propose a plausible structure for the Brønsted acid sites in our materials based on infrared spectroscopy and solid-state nuclear magnetic resonance measurements and density functional theory calculations and argue that this same structure might apply to conventional ASAs as well.

Directly Formed Alucone on Lithium Metal for High-Performance Li Batteries and Li-S Batteries with High Sulfur Mass Loading.

Lithium metal is considered the "holy grail" of next-generation battery anodes. However, severe parasitic reactions at the lithium-electrolyte interface deplete the liquid electrolyte and the uncontrolled formation of high surface area and dendritic lithium during cycling causes rapid capacity fading and battery failure. Engineering a dendrite-free lithium metal anode is therefore critical for the development of long-life batteries using lithium anodes. In this study, we deposit a conformal, organic/inorganic hybrid coating, for the first time, directly on lithium metal using molecular layer deposition (MLD) to alleviate these problems. This hybrid organic/inorganic film with high cross-linking structure can stabilize lithium against dendrite growth and minimize side reactions, as indicated by scanning electron microscopy. We discovered that the alucone coating yielded several times longer cycle life at high current rates compared to the uncoated lithium and achieved a steady Coulombic efficiency of 99.5%, demonstrating that the highly cross-linking structured material with great mechanical properties and good flexibility can effectively suppress dendrite formation. The protected Li was further evaluated in lithium-sulfur (Li-S) batteries with a high sulfur mass loading of ∼5 mg/cm2. After 140 cycles at a high current rate of ∼1 mA/cm2, alucone-coated Li-S batteries delivered a capacity of 657.7 mAh/g, 39.5% better than that of a bare lithium-sulfur battery. These findings suggest that flexible coating with high cross-linking structure by MLD is effective to enable lithium protection and offers a very promising avenue for improved performance in the real applications of Li-S batteries.

Water Oxidation by Size-Selected Co27 Clusters Supported on Fe2 O3.

The complexity of the water oxidation reaction makes understanding the role of individual catalytic sites critical to improving the process. Here, size-selected 27-atom cobalt clusters (Co27 ) deposited on hematite (Fe2 O3 ) anodes were tested for water oxidation activity. The uniformity of these anodes allows measurement of the activity of catalytic sites of well-defined nuclearity and known density. Grazing incidence X-ray absorption near-edge spectroscopy (GIXANES) characterization of the anodes before and after electrochemical cycling demonstrates that these Co27 clusters are stable to dissolution even in the harsh water oxidation electrochemical environment. They are also stable under illumination at the equivalent of 0.4 suns irradiation. The clusters show turnover rates for water oxidation that are comparable or higher than those reported for Pd- and Co-based materials or for hematite. The support for the Co27 clusters is Fe2 O3 grown by atomic layer deposition on a Si chip. We have chosen to deposit a Fe2 O3 layer that is only a few unit cells thick (2 nm), to remove complications related to exciton diffusion. We find that the electrocatalytic and the photoelectrocatalytic activity of the Co27 /Fe2 O3 material is significantly improved when the samples are annealed (with the clusters already deposited). Given that the support is thin and that the cluster deposition density is equivalent to approximately 5 % of an atomic monolayer, we suggest that annealing may significantly improve the exciton diffusion from the support to the catalytic moiety.

Fabrication of transparent-conducting-oxide-coated inverse opals as mesostructured architectures for electrocatalysis applications: a case study with NiO.

Highly ordered, and conductive inverse opal arrays were made with silica and subsequently coated with tin-doped indium oxide (ITO) via atomic layer deposition (ALD). We demonstrate the utility of the resulting mesostructured electrodes by further coating them with nickel oxide via ALD. The NiO-coated arrays are capable of efficiently electrochemically evolving oxygen from water. These modular, crack-free, transparent, high surface area, and conducting structures show promise for many applications including electrocatalysis, photocatalysis, and dye-sensitized solar cells.

Toward atomically-precise synthesis of supported bimetallic nanoparticles using atomic layer deposition.

Multi-metallic nanoparticles constitute a new class of materials offering the opportunity to tune the properties via the composition, atomic ordering and size. In particular, supported bimetallic nanoparticles have generated intense interest in catalysis and electrocatalysis. However, traditional synthesis methods often lack precise control, yielding a mixture of monometallic and bimetallic particles with various compositions. Here we report a general strategy for synthesizing supported bimetallic nanoparticles by atomic layer deposition, where monometallic nanoparticle formation is avoided by selectively growing the secondary metal on the primary metal nanoparticle but not on the support; meanwhile, the size, composition and structure of the bimetallic nanoparticles are precisely controlled by tailoring the precursor pulse sequence. Such exquisite control is clearly demonstrated through in situ Fourier transform infrared spectroscopy of CO chemisorption by mapping the gradual atomic-scale evolution in the surface composition, and further confirmed using aberration-corrected scanning transmission electron microscopy.

Design and implementation of an integral wall-mounted quartz crystal microbalance for atomic layer deposition.

Quartz crystal microbalance (QCM) measurements have played a vital role in understanding and expediting new atomic layer deposition (ALD) processes; however, significant barriers remain to their routine use and accurate execution. In order to turn this exclusively in situ technique into a routine characterization method, an integral QCM fixture was developed. This new design is easily implemented on a variety of chemical vapor deposition (CVD) tools, allows rapid sample exchange, prevents backside deposition, and minimizes both the footprint and flow disturbance. Unlike previous QCM designs, the fast thermal equilibration enables tasks such as temperature-dependent studies and ex situ sample exchange, further highlighting the utility of this QCM design for day-to-day use. Finally, the in situ mapping of thin film growth rates across the ALD reactor was demonstrated in a popular commercial tool operating in both continuous and quasi-static ALD modes.

Polynucleotide adsorption to negatively charged surfaces in divalent salt solutions.

Polynucleotide adsorption to negatively charged surfaces via divalent ions is extensively used in the study of biological systems. We analyze here the adsorption mechanism via a self-consistent mean-field model that includes the pH effect on the surface-charge density and the interactions between divalent ions and surface groups. The adsorption is driven by the cooperative effect of divalent metal ion condensation along polynucleotides and their reaction with the surface groups. Although the apparent reaction constants are enhanced by the presence of polynucleotides, the difference between reaction constants of different divalent ions at the ideal condition explains why not all divalent cations mediate DNA adsorption onto anionic surfaces. Calculated divalent salt concentration and pH value variations on polynucleotide adsorption are consistent with atomic force microscope results. Here we use long-period x-ray standing waves to study the adsorption of mercurated-polyuridylic acid in a ZnCl2 aqueous solution onto a negatively charged hydroxyl-terminated silica surface. These in situ x-ray measurements, which simultaneously reveal the Hg and Zn distribution profiles along the surface normal direction, are in good agreement with our model. The model also provides the effects of polyelectrolyte line-charge density and monovalent salt on adsorption.

Comparative X-ray standing wave analysis of metal-phosphonate multilayer films of dodecane and porphyrin molecular square.

The nanoscale structures of multilayer metal-phosphonate thin films prepared via a layer-by-layer assembly process using Zr(4+) and 1,12-dodecanediylbis(phosphonic acid) (DDBPA) or porphyrin square bis(phosphonic acid) (PSBPA) were studied using specular X-ray reflectivity (XRR), X-ray fluorescence, and long-period X-ray standing wave (XSW) analysis. The films were prepared in 1, 2, 3, 4, 6, and 8 layer series on both Si(001) substrates for XRR and on 18.6 nm period Si/Mo layered-synthetic microstructure X-ray mirrors for XSW. After functionalizing the SiO(2) substrate surfaces with a monolayer film terminated with phosphonate groups, the organic multilayer films were assembled by alternating immersions in (a) aqueous solutions containing Zr(4+)or Hf(4+) (final metal layer only) cations and then (b) organic solvent solutions of PO(3)-R-PO(3)(4-), where R was DDBPA or PSBPA spacer molecule. The Hf(4+) cation served as the marker for the top surface of the films, whereas the Zr(4+) cation was present in all other layers. The PSBPA also contained Zn and Re atoms at its midline which served as heavy-atom markers for each layer. The long-period XSW generated by the 0th- (total external reflection) through 4th-order Bragg diffraction conditions made it possible to examine the Fourier transforms of the fluorescent atom distributions over a much larger q(z) range in reciprocal space which permitted simultaneous analysis of Hf, Zn/Re, and Zr atomic distributions.

Direct observation of cations and polynucleotides explains polyion adsorption to like-charged surfaces.

We show an experimental approach for directly observing the condensation of polynucleotides and their electrolyte counterions at a liquid/solid interface. X-ray standing waves (XSW) generated by Bragg diffraction from a d = 20 nm Si/Mo multilayer substrate are used to measure the distinct distribution profiles of the polyanions and simple cations along the surface normal direction with subnanometer resolution. The 1D spatial sensitivity of this approach is enhanced by observing the XSW induced fluorescence modulations over multiple orders of Bragg peaks. We study the interesting divalent cation driven adsorption of anionic polynucleotides to anionic surfaces by exposing a hydroxyl-terminated silica surface to an aqueous solution with ZnCl2 and mercurated poly-uridylic acid (a synthetic RNA molecule). The in situ long-period XSW measurements are used to follow the evolution of both the Zn and Hg distribution profiles during the adsorption process. The conditions and physical mechanisms that govern the observed divalent cation adsorption and subsequent polynucleotide adsorption to an anionic surface are explained by a thermodynamic model that incorporates nonlinear electrostatic effects.

X-ray nanoscale profiling of layer-by-layer assembled metal/organophosphonate films.

The nanoscale structure of multilayer metal/phosphonate thin films prepared via a layer-by-layer assembly process was studied using specular X-ray reflectivity (XRR), X-ray fluorescence (XRF), and long-period X-ray standing wave (XSW) analysis. After the SiO(2) X-ray mirror surfaces were functionalized with a monolayer film terminated with phosphonate groups, the organic multilayer films were assembled by alternating immersions in (a) aqueous solutions containing Zr(4+), Hf(4+), or Y(3+) cations and then (b) organic solvent solutions of PO(3)-R-PO(3), where R was a porphyrin or porphyrin-square spacer molecule. The different heavy metal cations provided X-ray fluorescence marker layers at different heights within the different multilayer assemblies. The XSW measurements used a 22 nm period Si/Mo multilayer mirror. The long-period XSW generated by the zeroth-order (total external reflection) through fourth-order Bragg diffraction conditions made it possible to examine the Fourier transforms of the fluorescent atom distributions over a much larger q(z)() range in reciprocal space than previously achieved.

X-ray studies of self-assembled organic monolayers grown on hydrogen-terminated Si(111).

The structure of self-assembled monolayers (SAMs) of undecylenic acid methyl ester (SAM-1) and undec-10-enoic acid 2-bromo-ethyl ester (SAM-2) grown on hydrogen-passivated Si(111) were studied by X-ray reflectivity (XRR), X-ray standing waves (XSW), X-ray fluorescence (XRF), atomic force microscopy, and X-ray photoelectron spectroscopy (XPS). The two different SAMs were grown by immersion of H-Si(111) substrates into the two different concentrated esters. UV irradiation during immersion was used to create Si dangling bond sites that act as initiators of the surface free-radical addition process that leads to film growth. The XRR structural analysis reveals that the molecules of SAM-1 and SAM-2 respectively have area densities corresponding to 50% and 57% of the density of Si(111) surface dangling bonds and produce films with less than 4 angstroms root-mean-square roughness that have layer thicknesses of 12.2 and 13.2 angstroms. Considering the molecular lengths, these thicknesses correspond to a 38 degrees and 23 degrees tilt angle for the respective molecules. For SAM-2/Si(111) samples, XRF analysis reveals a 0.58 monolayer (ML) Br total coverage. Single-crystal Bragg diffraction XSW analysis reveals (unexpectedly) that 0.48 ML of these Br atoms are at a Si(111) lattice position height that is identical to the T1 site that was previously found by XSW analysis for Br adsorbed onto Si(111) from a methanol solution and from ultrahigh vacuum. From the combined XPS, XRR, XRF, and XSW evidence, it is concluded that Br abstraction by reactive surface dangling bonds competes with olefin addition to the surface.