Jacek B. Jasinski

Structural Evolution of Zeolitic Imidazolate Framework-8

We report the structural evolution of zeolitic imidazolate framework-8 (ZIF-8) as a function of time at room temperature. We have identified the different stages of ZIF-8 formation (nucleation, crystallization, growth, and stationary periods) and elucidated its kinetics of transformation. We hypothesize that the observed semicrystalline-to-crystalline transformation may take place via solution- and solid-mediated mechanisms, as suggested by the observed phase transformation evolution and Avramis kinetics, respectively. A fundamental understanding of ZIF-8 structural evolution as demonstrated in this study should facilitate the preparation of functional metal-organic framework phases with controlled crystal size and extent of crystallinity.

Fluorescence Manipulation by Gold Nanoparticles: From Complete Quenching to Extensive Enhancement

BackgroundWhen a fluorophore is placed in the vicinity of a metal nanoparticle possessing a strong plasmon field, its fluorescence emission may change extensively. Our study is to better understand this phenomenon and predict the extent of quenching and/or enhancement of fluorescence, to beneficially utilize it in molecular sensing/imaging.ResultsPlasmon field intensities on/around gold nanoparticles (GNPs) with various diameters were theoretically computed with respect to the distance from the GNP surface. The field intensity decreased rapidly with the distance from the surface and the rate of decrease was greater for the particle with a smaller diameter. Using the plasmon field strength obtained, the level of fluorescence alternation by the field was theoretically estimated. For experimental studies, 10 nm GNPs were coated with polymer layer(s) of known thicknesses. Cypate, a near infrared fluorophore, was placed on the outermost layer of the polymer coated GNPs, artificially separated from the GNP at known distances, and its fluorescence levels were observed. The fluorescence of Cypate on the particle surface was quenched almost completely and, at approximately 5 nm from the surface, it was enhanced ~17 times. The level decreased thereafter. Theoretically computed fluorescence levels of the Cypate placed at various distances from a 10 nm GNP were compared with the experimental data. The trend of the resulting fluorescence was similar. The experimental results, however, showed greater enhancement than the theoretical estimates, in general. The distance from the GNP surface that showed the maximum enhancement in the experiment was greater than the one theoretically predicted, probably due to the difference in the two systems.ConclusionsFactors affecting the fluorescence of a fluorophore placed near a GNP are the GNP size, coating material on GNP, wavelengths of the incident light and emitted light and intrinsic quantum yield of the fluorophore. Experimentally, we were able to quench and enhance the fluorescence of Cypate, by changing the distance between the fluorophore and GNP. This ability of artificially controlling fluorescence can be beneficially used in developing contrast agents for highly sensitive and specific optical sensing and imaging.

Surface properties of SnO2nanowires for enhanced performance with dye-sensitized solar cells

Our recent studies showed that nanowire based DSSCs exhibited over 250 mV higher open circuit potentials (VOC) compared to those using nanoparticles. In this study, the electron transport and surface properties of nanowires and nanoparticles are investigated to understand the reasons for the observed higher photovoltages with NW based solar cells. It was seen that, in addition to slow recombination kinetics, the lower work function of SnO2nanowires compared to the nanoparticle counterparts also significantly contributes to the high VOC observed for the nanowire based DSSCs.

Hydrogen reactivity of palladium nanoparticles coated with mixed monolayers of alkyl thiols and alkyl amines for sensing and catalysis applications.

Palladium monolayer-protected clusters (MPCs) coated with octylamines (C8NH(2)), hexanethiolates (C6S), and mixed monolayers of C8NH(2) and C6S exhibit significantly different reactivities with hydrogen gas, depending on the relative amounts of the two ligands coating the Pd nanoparticle surface, as determined by UV-vis spectroscopy of Pd MPCs in solution and electronic measurements of films of Pd MPCs as a function of exposure time to hydrogen. The average estimated composition of the ~3.0 nm diameter Pd MPCs was Pd(919)(C6S)(192) or Pd(919)(C8NH(2))(177-x)(C6S)(x), where x was varied to be 0, 3, 10, 16, 32, or 81 by the synthesis of pure C8NH(2) Pd MPCs and subsequent liquid-phase place exchange with a varied amount of C6SH. When x = 0-10, the Pd MPCs react strongly with H(2), leading to aggregated particles in solution and large irreversible changes in the morphology of films accompanied by an increase in film conductivity by 2-5 orders of magnitude. Pd(919)(C6S)(192) MPCs are stable against significant aggregation in solution and do not exhibit large film morphology changes, but they are also not highly reactive to H(2), as determined by minimal changes in the optical properties of solutions and the small, irreversible changes in the conductivity of films in the presence of H(2). Finally, when x is 32 and 81, the Pd MPCs are fairly stable, exhibit minimal aggregation or morphology changes, and readily react with H(2) based on the significant, reversible changes in film conductivity in the presence of H(2). Pd MPCs with mixed monolayers have the benefit of high H(2) reactivity while maintaining the structural stability necessary for sensing and catalysis applications.

Efficient hydrogen evolution in transition metal dichalcogenides via a simple one-step hydrazine reaction.

Hydrogen evolution reaction is catalysed efficiently with precious metals, such as platinum; however, transition metal dichalcogenides have recently emerged as a promising class of materials for electrocatalysis, but these materials still have low activity and durability when compared with precious metals. Here we report a simple one-step scalable approach, where MoOx/MoS2 core-shell nanowires and molybdenum disulfide sheets are exposed to dilute aqueous hydrazine at room temperature, which results in marked improvement in electrocatalytic performance. The nanowires exhibit ∼100 mV improvement in overpotential following exposure to dilute hydrazine, while also showing a 10-fold increase in current density and a significant change in Tafel slope. In situ electrical, gate-dependent measurements and spectroscopic investigations reveal that hydrazine acts as an electron dopant in molybdenum disulfide, increasing its conductivity, while also reducing the MoOx core in the core-shell nanowires, which leads to improved electrocatalytic performance.

Photoelectrochemical activity of as-grown, α-Fe2O3 nanowire array electrodes for water splitting.

Undoped hematite nanowire arrays grown using plasma oxidation of iron foils show significant photoactivity (~0.38 mA cm(-2) at 1.5 V versus reversible hydrogen electrode in 1 M KOH). In contrast, thermally oxidized nanowire arrays grown on iron exhibit no photoactivity due to the formation of a thick (>7 μm Fe(1-x)O) interfacial layer. An atmospheric plasma oxidation process required only a few minutes to synthesize hematite nanowire arrays with a 1–5 μm interfacial layer of magnetite between the nanowire arrays and the iron substrate. An amorphous oxide surface layer on hematite nanowires, if present, is shown to decrease the resulting photoactivity of as-synthesized, plasma grown nanowire arrays. The photocurrent onset potential is improved after removing the amorphous surface on the nanowires using an acid etch. A two-step method involving high temperature nucleation followed by growth at low temperature is shown to produce a highly dense and uniform coverage of nanowire arrays.

Iron Sulfide (FeS) Nanotubes Using Sulfurization of Hematite Nanowires

We report the phase transformation of hematite (α-Fe2O3) single crystal nanowires to crystalline FeS nanotubes using sulfurization with H2S gas at relatively low temperatures. Characterization indicates that phase pure hexagonal FeS nanotubes were formed. Time-series sulfurization experiments suggest epitaxial growth of FeS as a shell layer on hematite. This is the first report of hollow, crystalline FeS nanotubes with NiAs structure and also on the Kirkendall effect in solid-gas reactions with nanowires involving sulfurization.

Decarboxylation of oleic acid over Pt catalysts supported on small-pore zeolites and hydrotalcite

The catalytic decarboxylation and further conversions of oleic acid to paraffins, branched and aromatic hydrocarbons over Pt supported on small pore zeolites and hydrotalcite are demonstrated. The influence of the support, platinum source, and reaction temperature on the decarboxylation of oleic acid was investigated. An increase in reaction temperature increased the degree of decarboxylation and selectivity to heptadecane. Pt-SAPO-34 was a very effective catalyst. In addition to a high degree of decarboxylation, Pt-SAPO-34 displayed a high selectivity to heptadecane and dodecylbenzene among the products. Branched isomers, cracked (mostly <C17) paraffins, alkenes such as undecene and dodecene, and carboxylic acids such as nonanoic acid and decanoic acid were observed as side products. The further isomerization of the initially formed linear heptadecane (by decarboxylation of oleic acid) to branched isomers is suppressed in the narrow pores of SAPO-34 due to restricted transition state shape selectivity limitations in the pore system of SAPO-34. Catalyst acidity, dispersion of Pt and the pore diameter of the support played crucial roles in determining product selectivity.

Tungsten oxide-coated copper oxide nanowire arrays for enhanced activity and durability with photoelectrochemical water splitting

The deposition of crystalline CuWO4 and WO3 layers on copper oxide nanowire arrays resulted in a five-fold improvement of the photocurrent density (∼1.7 mA cm−2 at −0.1 V vs. RHE) over titania-coated copper oxide NW arrays. The deposition of WO3 or CuWO4 reduced the CuO phase impurities in Cu2O. The improvement in the phase purity of the nanowire arrays led to a considerable enhancement in the resulting photoactivity. These protective coatings have been shown to play a dual role of marginally extending the durability of the electrode and promoting charge separation.

Alkyne/Alkene/Allene‐Induced Disproportionation of Cationic Gold(I) Catalyst

The first detailed experimental study of the deactivation of cationic gold was conducted, and the influence of each component in the reaction system (substrate, counterion, solvent) on the decay process was examined. It was found that a substrate (alkyne/allene/alkene)-induced disproportionation of gold(I) may play a key role in the decay process. Our mechanism is supported by kinetic, XPS, voltammetry studies, and high-resolution ESI-MS data.