Seed-Mediated Electrodeposition of Silver Nanowires and Nanorods.

Here, we compare the amount and morphology of silver (Ag) nanostructures electrodeposited at varied potentials and times in the presence of cetyltrimethylammonium bromide (CTAB) onto glass/indium tin oxide (glass/ITO) electrodes functionalized with mercaptopropyltrimethoxysilane (MPTMS) and coated or not coated with 4 nm average diameter Au nanoparticle (Au NP) seeds. There is a significantly larger amount of Ag deposited on the seeded electrode surface compared to that in the nonseeded electrode at potentials of -150 to -300 mV (vs Ag/AgCl) since the Au NP seeds act as catalysts for Ag deposition. At more negative overpotentials of -400 to -500 mV, the amount of Ag deposited on both electrodes is similar because the deposition kinetics are fast enough on glass/ITO that the Au seed catalyst does not make as big of a difference. Ag nanorods (NRs) and nanowires (NWs) form on the seeded surfaces, especially at more positive potentials, where deposition primarily occurs on the Au seed catalysts. Deposition of Ag onto the Au seeds appears as a separate peak in the voltammetry. This procedure mimics the seed-mediated growth of Ag NRs observed in solution in the presence of CTAB using ascorbic acid as a reducing agent. The yield, length, and aspect ratio of the Ag NRs/NWs depend on the deposition time and potential with the average length ranging from 300 nm to 3 µm for times of 30-120 min and potentials of -150 to -200 mV. The electrochemical seed-mediated growth of Ag NRs/NWs across electrode gaps could find use for resistive and surface-enhanced Raman-based sensing and molecular electronic applications.

Electrochemical Analysis of the Thermal Stability of 0.9-4.1 nm Diameter Gold Nanoclusters.

Here we report the thermal properties of weakly stabilized 0.9, 1.6, and 4.1 nm Au nanoparticles (NPs)/nanoclusters (NCs) attached to indium-tin-oxide- or fluorine-doped-tin-oxide-coated glass electrodes (glass/ITO or glass/FTO). The peak oxidation potential (Ep) for Au measured by anodic stripping voltammetry (ASV) is indicative of the NP/NC size. Heating leads to a positive shift in Ep due to an increase in NP/NC size from thermal ripening. The size transition temperature (Tt) decreases with decreasing NP/NC size following the order of 4.1 nm (509 °C) > 1.6 nm (132 °C) > 0.9 nm (90 °C/109 °C, two transitions) as compared to the bulk melting point (Tm,b) for Au of 1064 °C. The Tt generally agrees with models describing the size-dependent melting point of Au NPs (Tm,NP) for 4.1 and 1.6 nm diameter Au NPs but is higher than the models for 0.9 nm Au NCs. Scanning electron microscopy (SEM) and UV-vis size analysis confirm the electrochemical results. The thermal stability of electrode-supported metal NPs/NCs is important for their effective use in catalysis, sensing, nanoelectronics, photovoltaics, and other applications.

Electrophoretic Deposition of Hybrid Calcium Alginate-Gold Nanoparticle Hydrogel Films via Catalyzed Electrooxidation of Hydroquinone.

The electrophoretic deposition (EPD) of hybrid alginate (Alg)-Au nanoparticle (NP) films results from the localized pH drop at the electrode surface due to oxidation of hydroquinone (HQ) catalyzed by 4 and 15 nm diameter citrate-coated gold NPs (cit-Au NPs). The localized pH drop at the electrode leads to neutralization of both Alg and cit, leading to EPD of both Alg and cit-Au NPs simultaneously. Post-treatment of the film with Ca2+ solution leads to hybrid Ca-Alg-Au NP hydrogel films. The EPD of Alg in the presence of 4 nm cit-Au NPs occurs at ∼0.8 V (vs Ag/AgCl) as compared to ∼1.0 V in the presence of 15 nm cit-Au NPs and ∼1.4 V in the absence of cit-Au NPs. This is due to the higher catalytic activity of 4 nm cit-Au NPs compared to 15 nm cit-Au NPs for the oxidation of HQ. UV-vis spectra of Ca-Alg-Au NP hydrogel films show absorbance features for both Ca-Alg and Au NPs entrapped within the hydrogel. As the concentration of Au NPs in the EPD solution increases, the Ca-Alg absorbance and localized surface plasmon resonance (LSPR) peak of the Au NPs increases, confirming the role of the Au NPs as a catalyst for EPD of Alg. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectra of the Ca-Alg-Au NP hydrogel films show characteristic peaks for Ca-Alg and protonated alginic acid groups. The hydrogel thickness is greater with cit-Au NPs compared to without cit-Au NPs at constant EPD potential and time. Forming Ca-Alg and hybrid Ca-Alg-Au NP hydrogel films at low potentials has potential applications in electrochemical and optical sensor development, catalysis, and biological studies.

Effect of Metal Nanoparticle Aggregate Structure on the Thermodynamics of Oxidative Dissolution.

Here, we compare the electrochemical oxidation potential of 15 nm diameter citrate-stabilized Au NPs aggregated by acid (low pH) to those aggregated by tetrakis(hydroxymethyl) phosphonium chloride (THPC). For acid-induced aggregation, the solution changes to a blue-violet color, the localized surface plasmon resonance (LSPR) band of Au NPs at 520 nm decreases along with an increase in absorbance at higher wavelengths (600-800 nm), and the peak oxidation potential (Ep) in anodic stripping voltammetry (ASV) obtained in bromide has a positive shift by as large as 200 mV. For THPC-induced aggregation (Au/THPC mole ratio = 62.5), the solution changes to a blue color as the LSPR band at 520 nm decreases and a new distinct peak at 700 nm appears, but the Ep does not exhibit a positive shift. Scanning transmission electron microscopy (STEM) images reveal that acid-induced aggregates are three-dimensional with strongly fused Au NP-Au NP contacts, while THPC-induced aggregates are linear or two-dimensional with ∼1 nm separation between Au NPs. The surface area-to-volume ratio (SA/V) decreases for acid-aggregated Au NPs due to strong Au NP-Au NP contacts, which leads to lower surface free energy and a higher Ep. The SA/V does not change for THPC-aggregated Au NPs since space remains between them and their SA is fully accessible. These findings show that metal NP oxidative stability, as determined by ASV, is highly sensitive to the details of the aggregate structure.

Reversing the Thermodynamics of Galvanic Replacement Reactions by Decreasing the Size of Gold Nanoparticles.

Here, we describe the surprising reactivity between surface-attached (a) 0.9, 1.6, and 4.1 nm diameter weakly stabilized Au nanoparticles (NPs) and aqueous 1.0 × 10-4 M Ag+ solution, and (b) 1.6 and 4.1 nm diameter weakly stabilized Au NPs and aqueous 1.0 × 10-5 M PtCl42-, which are considered to be antigalvanic replacement (AGR) reactions because they are not thermodynamically favorable for bulk-sized Au under these conditions. Anodic Stripping Voltammetry (ASV) and Scanning Transmission Electron Microscopy with Energy-Dispersive X-ray Spectroscopy (STEM-EDS) mapping provide quantitation of the extent of Ag and Pt replacement as a function of Au NP diameter. The extent of the reaction increases as the Au NP size decreases. The percentage of Ag in the AuAg alloy following AGR based on ASV is 17.8 ± 0.6% for 4.1 nm diameter Au NPs, 87.2 ± 2.9% for 1.6 nm Au NPs, and an unprecedented full 100% Ag for 0.9 nm diameter Au NPs. STEM-EDS mapping shows very close agreement with the ASV-determined compositions. In the case of PtCl42-, STEM-EDS mapping shows AuPt alloy NPs with 3.9 ± 1.3% and 41.1 ± 8.7% Pt following replacement with 4.1 and 1.6 nm diameter Au NPs, respectively, consistent with qualitative changes to the ASV. The size-dependent AGR correlates well with the negative shift in the standard potential (E0) for Au oxidation with decreasing NP size.

Size-Selective Electrophoretic Deposition of Gold Nanoparticles Mediated by Hydroquinone Oxidation.

Here we describe the size-selective, hydroquinone (HQ)-mediated electrophoretic deposition of 4 and 15 nm diameter citrate-stabilized Au nanoparticles (NPs) onto a glass/indium-tin-oxide (ITO) electrode. Protons liberated from HQ during electrochemical oxidation at the Au NP surface during collisions with the glass/ITO electrode lead to Au NP deposition through neutralization of the citrate stabilizer surrounding the Au NPs, protonation of the glass/ITO electrode, or some combination of the two. Interestingly, the 4 nm Au NPs deposit at about 300-400 mV more negative potential than that of 15 nm diameter Au NPs because of faster HQ oxidation kinetics at the 4 nm NPs, leading to lower overpotentials. This allows for selective deposition of the 4 nm Au NPs over 15 nm Au NPs in a solution containing a mixture of the two by controlling the electrode potential. Controlled pH experiments indicate that significant NP deposition occurs on glass/ITO at a pH of ∼3, giving insight into the local pH needed from HQ oxidation in order to deposit the Au NPs. Experiments performed at different ionic strengths confirm that migration is a major mode of mass transport of the NPs to the glass/ITO. Long deposition times lead to films of densely packed Au NPs that are mostly free from NP-NP contact, indicating that some electrostatic repulsion between the NPs remains during the deposition. This simple method of Au NP deposition may find use for separation of Au NPs and electrode device preparation for a variety of sensor and electrocatalysis applications.

Effect of Size, Coverage, and Dispersity on the Potential-Controlled Ostwald Ripening of Metal Nanoparticles.

Here, we describe the size-dependent, electrochemically controlled Ostwald ripening of 1.6, 4, and 15 nm-diameter Au nanoparticles (NPs) attached to (3-aminopropyl)triethoxysilane (APTES)-modified glass/indium-tin-oxide electrodes. Holding the Au NP-coated electrodes at a constant negative potential of the dissolution potential in a bromide-containing electrolyte led to electrochemical Ostwald ripening of the different-sized Au NPs. The relative increase in the diameter of the NPs (Dfinal/Dinitial) during electrochemical Ostwald ripening increases with decreasing NP size, increasing applied potential, increasing NP population size dispersity, and increasing NP coverage on the electrodes. Monitoring the average size of the Au NPs as a function of time at a controlled potential allows the measurement of the Ostwald ripening rate. Anodic stripping voltammetry and electrochemical determination of the surface area-to-volume ratio provide fast and convenient size analysis for many different samples and conditions, with consistent sizes from scanning electron microscopy images for some samples. It is important to better understand electrochemical Ostwald ripening, especially under potential control, since it is a major process that occurs during the synthesis of metal NPs and leads to detrimental size instability during electrochemical applications.

Detection of influenza virus by electrochemical surface plasmon resonance under potential modulation.

In this study we report the development of a novel viral pathogen immunosensor technology based on the electrochemical modulation of the optical signal from a surface plasmon wave interacting with a redox dye reporter. The device is formed by incorporating a sandwich immunoassay onto the surface of a plasmonic device mounted in a micro-electrochemical flow cell, where it is functionalized with a monoclonal antibody aimed to a specific target pathogen antigen. Once the target antigen is bound to the surface, it promotes the capturing of a secondary polyclonal antibody that has been conjugated with a redox-active methylene blue dye. The methylene blue displays a reversible change in the complex refractive index throughout a reduction-oxidation transition, which generates an optical signal that can be electrochemically modulated and detected at high sensitivity. For proof-of-principle measurements, we have targeted the hemagglutinin protein from the H5N1 avian influenza A virus to demonstrate the capabilities of our device for detection and quantification of a critical influenza antigen. Our experimental results of the EC-SPR-based immunosensor under potential modulation showed a 300 pM limit of detection for the H5N1 antigen.

Size Stability Study of Catalytically Active Sub-2 nm Diameter Gold Nanoparticles Synthesized with Weak Stabilizers.

Here we report on the very low size stability of electrocatalytically active 1.5 to 2.0 nm diameter tetrakis(hydroxymethyl)phosphonium chloride-stabilized Au nanoparticles (THPC Au2nm NPs) chemically attached to glass/indium tin oxide electrodes. The potential for oxidative dissolution of THPC Au2nm NPs in the presence of bromide is about 250 mV negative of 4 nm diameter citrate-stabilized Au NPs (Cit Au4nm NPs) and 450 mV negative of bulk Au, which provides us with an easy method to assess the size stability using anodic stripping voltammetry. The THPC Au2nm NPs show a strong CO2 reduction wave at about -0.40 V (vs RHE), which is nonexistent for the Cit Au4nm NPs or bulk Au. The THPC Au2nm NPs are also comparatively more electroactive for the hydrogen evolution reaction. In acid electrolyte, however, the potential for surface Au2O3 formation on THPC Au2nm NPs is significantly negative relative to bulk Au, and a single cycle through the surface oxide and reduction waves leads to an increase in the NP size to about 4 nm. Similarly, the THPC Au2nm NPs undergo Ostwald ripening in the presence of bromide within 5 min at potentials well before oxidation, which increases their size to 4-10 nm in diameter by 35 min. Exposure to ozone for only 1-2 min also causes the THPC Au2nm NPs to increase in size to about 4 nm. In comparison, Cit Au4nm NPs are stable under all of these conditions, requiring much longer times to change in size. These differences in reactivity and size stability are due to the different Au NP size. Sub-2 nm diameter NPs with weak stabilizers are potentially very useful for electrocatalysis, but their low oxidation potential and poor size stability are major issues of concern.

Size Determination of Metal Nanoparticles Based on Electrochemically Measured Surface-Area-to-Volume Ratios.

Here we report the electrochemical determination of the surface-area-to-volume ratio (SA/ V) of Au nanospheres (NSs) attached to electrode surfaces for size analysis. The SA is determined by electrochemically measuring the number of coulombs of charge passed during the reduction of surface Au2O3 following Au NS oxidation in HClO4, whereas V is determined by electrochemically measuring the coulombs of charge passed during the complete oxidative dissolution of all of the Au in the Au NSs in the presence of Br- to form aqueous soluble AuBr4-. Assuming a spherical geometry and taking into account the total number of Au NSs on the electrode surface, the SA/ V is theoretically equal to 3/radius. A plot of the electrochemically measured SA/ V versus 1/radius for five different-sized Au NSs is linear with a slope of 1.8 instead of the expected value of 3. Following attachment of the Au NSs to the electrode and ozone treatment, the plot of SA/ V versus 1/radius is linear with a slope of 3.5, and the size based on electrochemistry matches very closely with those measured by scanning electron microscopy. We believe the ozone cleans the Au NS surface, allowing a more accurate measurement of the SA.

Aggregation-Dependent Oxidation of Metal Nanoparticles.

Here we describe the effect of aggregation on the oxidation of citrate-stabilized Au nanoparticles (NPs) attached electrostatically to amine-functionalized glass/ITO electrodes. When the Au NPs are attached to the electrode from a solution with pH greater than ∼3.0, they are well-separated on the electrode and oxidize in bromide-containing electrolyte at 0.698, 0.757, and 0.943 V (vs Ag/AgCl) for 4, 15, and 50 nm diameter Au NPs, respectively, in line with their size-dependent oxidation behavior. In solutions below pH 3.0, the Au NPs aggregate in solution and attach to the electrode in the aggregated form. The solution UV-vis spectra and scanning electron microscopy images of the electrodes show clear evidence of aggregation. The oxidation potential for aggregated 4 and 15 nm diameter Au NPs shifts positive by a maximum of 230 and 180 mV, respectively. The magnitude of the shift depends on the extent of aggregation, which was controlled by the solution pH and time. NP aggregation leads to a significant reduction in the surface area-to-volume ratio, which is likely responsible for the positive shift in the oxidation potential. The oxidation potential does not shift at all for aggregated 50 nm diameter Au NPs.

Size-Dependent Electrophoretic Deposition of Catalytic Gold Nanoparticles.

Here we describe size-dependent electrophoretic deposition (EPD) of citrate-stabilized Au nanoparticles (NPs) onto indium-tin-oxide-coated glass (glass/ITO) electrodes as studied by linear sweep stripping voltammetry (LSSV) and scanning electron microscopy (SEM). LSSV allows both the determination of the Au NP coverage and NP size from the peak area and the peak potential, respectively. Two-electrode EPD in aqueous solutions of Au NPs plus H2O2 reveal that a minimum potential of 1.5 V is needed for significant deposition of 4 nm diameter Au NPs as opposed to 2.0 V for 33 nm diameter Au NPs. EPD at 0.4 V in a solution of Au NPs prepared with a short 5 min reaction time led to the successful capture of 1-2 nm diameter Au NPs with appreciable coverage. In all cases, deposition did not occur in the absence of H2O2. Three-electrode experiments with a real reference electrode revealed the same size selective deposition with potential and that the amount of Au deposited depends on the deposition time and H2O2 concentration. The deposition occurs indirectly by oxidation of H2O2, which liberates protons and neutralizes the citrate stabilizer, leading to precipitation of the Au NPs onto the glass/ITO electrode. Studies on pH stability show that larger Au NPs aggregate at lower pH compared to smaller Au NPs. More importantly, though, 4 nm diameter Au NPs are much more catalytic for H2O2 oxidation, which is the main reason for the size selective deposition.

Surface Enhanced Raman Spectroscopy at Electrochemically Fabricated Silver Nanowire Junctions.

Here we describe enhanced Raman scattering at Au electrode 1 (E1)/Ag nanowire (NW)/4-aminothiophenol (4-ATP)/Au electrode 2 (E2) nanojunctions fabricated by combining self-assembly and metal electrodeposition at microgap electrodes (E1 and E2). In this method we assemble the 4-ATP on electrode E2 and electrodeposit Ag on the opposite electrode E1 of an Au interdigitated array (IDA) electrode device. The electrodeposited Ag grows in the form of NWs on E1 and makes nanoscale contact to E2 to form the junctions. The presence of the Ag NW leads to strong Raman scattering of the 4-ATP molecules within the nanojunction leading to estimated enhancement factors ranging from 10(3) to 10(6). Scanning electron microscopy (SEM) images provide insight into the morphology of the junctions. The magnitude of the Raman enhancement depends on the extent of contact between the Ag NW and the 4-ATP self-assembled monolayer (SAM). With this approach we could detect 4-ATP molecules diluted by a factor of 1000 with hexanethiol molecules within the junctions. Our approach is simple and fast with the potential to correlate electronic measurements of molecules with Raman spectroscopy data of the same molecules in a nanoscale junction for molecular electronics or chemiresistive sensing applications.

Regioselective plasmonic coupling in metamolecular analogs of benzene derivatives.

In analogy with benzene-derived molecular structures, we construct plasmonic metamolecules by attaching Au nanospheres to specific sites on a hexagonal Au nanoplate. We employ a ligand exchange strategy that allows regioselective control of nanosphere attachment and study resulting structures using correlated electron microscopy/optical spectroscopy at the single-metamolecule level. We find that plasmonic coupling within the resulting assembly is strongly dependent on the structure of the metamolecule, in particular the site of attachment of the nanosphere(s). We also uncover a synergy in the polarizing effect of multiple nanospheres attached to the nanoplate. Regioselective control of plasmonic properties demonstrated here enables the design of novel structure-dependent electromagnetic modes and applications in three-dimensional spatial nanosensors.

Effect of surface charge and electrode material on the size-dependent oxidation of surface-attached metal nanoparticles.

Here we report on the size-dependent oxidation of Au nanoparticles (NPs) electrodeposited directly on indium tin oxide-coated glass (glass/ITO) electrodes as compared to those chemically synthesized and electrostatically or drop-cast deposited onto aminopropyltriethoxysilane (APTES)-modified, mercaptopropyltrimethoxysilane (MPTMS)-modified, or unmodified glass/ITO electrodes. The peak oxidation potential (Ep) of 54 nm diameter Au NPs shifts by as much as 155 mV negative when deposited electrostatically on the highly positively charged glass/ITO/APTES surface and oxidized at low pH as compared to their oxidation on more neutral glass/ITO or glass/ITO/MPTMS surfaces at all pH's and on glass/ITO/APTES at neutral pH. Electrodeposited Au NPs on glass/ITO of similar size also oxidize at more positive potentials due to the neutral electrode surface charge. Ag NPs show a similar charge dependence on their Ep. Interestingly, the Ep value of Au and Ag NPs smaller than about 10 nm in diameter is independent of surface charge. The Ep of 9 nm diameter citrate-capped Ag NPs attached to Au, Pt, glassy carbon (GC), and glass/ITO electrodes electrostatically through short amine-terminated organic linkers depends on the electrode material, following the order (vs Ag/AgCl) of Au (384 ± 7 mV) ≈ Pt (373 ± 12 mV) > GC (351 ± 2 mV) > glass/ITO (339 ± 1 mV). The underlying electrode material affects the Ag NP Ep even though the NPs are not directly interacting with it. In addition to size, the electrode material and its surface charge have a strong influence on the oxidation potential of surface-confined metallic nanostructures.

Covalent modification of photoanodes for stable dye-sensitized solar cells.

This paper describes the surface modification of TiO2 with 3-aminopropyltriethoxysilane (APTES) followed by covalent attachment of Ru-based N719 dye molecules to TiO2 through an amide linkage for use as photoanodes (PAs) in dye-sensitized solar cells (DSSCs). Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) confirms the surface chemistry between the TiO2 and dye. The photovoltaic efficiency of DSSCs with covalently linked dye is very similar (6-7%) to that of traditionally prepared DSSCs prepared by direct immersion when both have similar dye coverage. Importantly, the efficiency of PAs with covalently linked dye did not change after storage for more than 60 days in air, whereas the traditionally prepared PAs decreased dramatically after 1 day and lost most of their efficiency after a week. FTIR and UV-vis characterization of the dye suggests that covalent linkage improves stability by preventing the loss of the thiocyanato ligands and/or tetrabutylammonium cations on the dye. PAs with covalently linked dye are also more stable toward water, acid, heat, and UV light compared to traditionally prepared PAs and are more stable compared to other modified PAs with dye attached through electrostatic or hydrogen-bonding interactions.

Oxidation of highly unstable <4 nm diameter gold nanoparticles 850 mV negative of the bulk oxidation potential.

Here we describe the oxidation of <4 nm diameter Au nanoparticles (NPs) attached to indium tin oxide-coated glass electrodes in Br(-) and Cl(-) solution. Borohydride reduction of AuCl(4)(-) in the presence of hexanethiol or trisodium citrate (15 min) led to Au NPs <4 nm in diameter. After electrochemical and ozone removal of the hexanthiolate ligands from the thiol-coated Au NPs, Au oxidation peaks appeared in the range 0-400 mV vs Ag/AgCl (1 M KCl), which is 850-450 mV negative of the bulk Au oxidation peak near 850 mV. The oxidation potential of citrate-coated Au NPs is in the 300-500 mV range and those of 4 and 12 nm diameter Au NPs in the 660-780 mV range. The large negative shift in potential agrees with theory for NPs in the 1-2 nm diameter range. The oxidation potential of Au in Cl(-) solution is positive of that in Br(-) solution, but the difference decreases dramatically as the NP size decreases, showing less dependence on the halide for smaller NPs.

Chemiresistive sensing with chemically modified metal and alloy nanoparticles.

This review describes the use of chemically modified pure and alloyed metal nanoparticles for chemiresistive sensing applications. Chemically modified metal nanoparticles consist of a pure or alloyed metallic core with some type of chemical coating. Researchers have studied the electronic properties of 1D, 2D, and 3D assemblies of chemically modified metal nanoparticles, and even single individual nanoparticles. The interaction with the analyte alters the conductivity of the sensitive material, providing a signal to measure the analyte concentration. This review focuses on chemiresistive sensing of a wide variety of gas- and liquid-phase analytes with metal nanoparticles coated with organothiols, ions, polymers, surfactants, and biomolecules. Different strategies used to incorporate chemically modified nanoparticles into chemiresistive sensing devices are reviewed, focusing on the different types of metal and alloy compositions, coatings, methods of assembly, and analytes (vapors, gases, liquids, biological materials), along with other important factors.

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.

Electrochemical fabrication of metal/organic/metal junctions for molecular electronics and sensing applications.

A simple electrochemical approach was used for fabricating electrode/metal nanowire/(molecule or polymer)/electrode junctions for sensing or molecular electronics applications. The procedure for fabricating these molecule-based devices involves electropolymerization of phenol or chemisorption of alkanethiols on one set of electrodes (E1) and electrodeposition of Ag metal nano/microwires on a second electrode (E2) which is ∼5 µm away from E1. Under appropriate deposition conditions, Ag nanowires grow from E2 and cross over to E1, forming a E1/(molecule or polymer)/Ag nanowire (NW)/E2 junction. The junction resistance was controlled by (1) electrodepositing polyphenol of varied densities on E1 and (2) assembling alkanethiols of different chain lengths on E1. Ag NWs at high resistance E1/polyphenol/Ag NW/E2 junctions functionalized with Pd monolayer protected clusters (MPCs) responded fast and reversibly to H(2) concentrations as low as 0.11% in a nitrogen carrier gas by a resistance decrease, likely due to volume expansion of the Pd nanoparticles, demonstrating the use of these electrochemically fabricated junctions for gas sensing applications.