Thomas E. Mallouk

Electric-field assisted assembly and alignment of metallic nanowires

This letter describes an electric-field assisted assembly technique used to position individual nanowires suspended in a dielectric medium between two electrodes defined lithographically on a SiO2 substrate. During the assembly process, the forces that induce alignment are a result of nanowire polarization in the applied alternating electric field. This alignment approach has facilitated rapid electrical characterization of 350- and 70-nm-diameter Au nanowires, which had room-temperature resistivities of approximately 2.9 and 4.5×10−6 Ω cm.

Photoassisted Overall Water Splitting in a Visible Light-Absorbing Dye-Sensitized Photoelectrochemical Cell

Iridium oxide nanoparticles stabilized by a heteroleptic ruthenium tris(bipyridyl) dye were used as sensitizers in photoelectrochemical cells consisting of a nanocrystalline anatase anode and a Pt cathode. The dye coordinated the IrO(2) x nH(2)O nanoparticles through a malonate group and the porous TiO(2) electrode through phosphonate groups. Under visible illumination (lambda > 410 nm) in pH 5.75 aqueous buffer, oxygen was generated at anode potentials positive of -325 mV vs Ag/AgCl and hydrogen was generated at the cathode. The internal quantum yield for photocurrent generation was ca. 0.9%. Steady-state luminescence and time-resolved flash photolysis/transient absorbance experiments were done to measure the rates of forward and back electron transfer. The low quantum yield for overall water splitting in this system can be attributed to slow electron transfer (approximately 2.2 ms) from IrO(2) x nH(2)O to the oxidized dye. Forward electron transfer does not compete effectively with the back electron transfer reaction from TiO(2) to the oxidized dye, which occurred on a time scale of 0.37 ms.

Transition metal dichalcogenides and beyond: synthesis, properties, and applications of single- and few-layer nanosheets.

CONSPECTUS: In the wake of the discovery of the remarkable electronic and physical properties of graphene, a vibrant research area on two-dimensional (2D) layered materials has emerged during the past decade. Transition metal dichalcogenides (TMDs) represent an alternative group of 2D layered materials that differ from the semimetallic character of graphene. They exhibit diverse properties that depend on their composition and can be semiconductors (e.g., MoS2, WS2), semimetals (e.g., WTe2, TiSe2), true metals (e.g., NbS2, VSe2), and superconductors (e.g., NbSe2, TaS2). The properties of TMDs can also be tailored according to the crystalline structure and the number and stacking sequence of layers in their crystals and thin films. For example, 2H-MoS2 is semiconducting, whereas 1T-MoS2 is metallic. Bulk 2H-MoS2 possesses an indirect band gap, but when 2H-MoS2 is exfoliated into monolayers, it exhibits direct electronic and optical band gaps, which leads to enhanced photoluminescence. Therefore, it is important to learn to control the growth of 2D TMD structures in order to exploit their properties in energy conversion and storage, catalysis, sensing, memory devices, and other applications. In this Account, we first introduce the history and structural basics of TMDs. We then briefly introduce the Raman fingerprints of TMDs of different layer numbers. Then, we summarize our progress on the controlled synthesis of 2D layered materials using wet chemical approaches, chemical exfoliation, and chemical vapor deposition (CVD). It is now possible to control the number of layers when synthesizing these materials, and novel van der Waals heterostructures (e.g., MoS2/graphene, WSe2/graphene, hBN/graphene) have recently been successfully assembled. Finally, the unique optical, electrical, photovoltaic, and catalytic properties of few-layered TMDs are summarized and discussed. In particular, their enhanced photoluminescence (PL), photosensing, photovoltaic conversion, and hydrogen evolution reaction (HER) catalysis are discussed in detail. Finally, challenges along each direction are described. For instance, how to grow perfect single crystalline monolayer TMDs without the presence of grain boundaries and dislocations is still an open question. Moreover, the morphology and crystal structure control of few-layered TMDs still requires further research. For wet chemical approaches and chemical exfoliation methods, it is still a significant challenge to control the lateral growth of TMDs without expansion in the c-axis direction. In fact, there is plenty of room in the 2D world beyond graphene. We envisage that with increasing progress in the controlled synthesis of these systems the unusual properties of mono- and few-layered TMDs and TMD heterostructures will be unveiled.

Turning down the heat: design and mechanism in solid-state synthesis.

Solid-state compounds have historically been prepared through high-temperature solid-solid reactions. New mechanistic understanding of these reactions suggests possible routes to metastable compositions and structures as well as to thermodynamically stable, low-temperature phases that decompose at higher temperatures. Intermediate-temperature synthetic techniques, including flux and hydrothermal methods, as well as low-temperature intercalation and coordination reactions, have recently been developed and have been used to prepare unprecedented materials with interesting electronic, optical, and catalytic properties. The trend in modern solid-state synthesis resembles increasingly the approach used in small-molecule chemistry, in the sense that attention to reaction mechanism and the use of molecular building blocks result in an ability to prepare new materials of designed structure.

Orthogonal Self-Assembly on Colloidal Gold-Platinum Nanorods

±COOAr, m to ±CH2O±, m to ArCOO± and m to ±OOCAr), 7.25±7.32 (m, 4 Ar±H, o to ±CH2O± and o to ArCOO±), 6.96±7.04 (m, 4 Ar±H, o to ±OCH2(CH2)11± and o to ±OOCAr), 4.20 (t, 2H, ArOCH2CH2O±), 4.05 (t, 2 H, ArOCH2(CH2)10±, J=6.6 Hz), 3.54±4.00 (m, 68 H, ±CH2O±), 3.37 (s, 3 H, CH3O±), 1.77±1.85 (m, 2 H, ±CH2(CH2)9±), 1.14±1.47 (m, 18 H, ±CH2(CH2)9±), 0.87 (t, 3 H, CH3(CH2)11±, J=6.8 Hz). C-NMR (62.5 MHz, CDCl3) d 165.6, 165.4 164.0, 159.6, 151.0, 150.9, 146.4, 138.7, 138.4, 132.7, 131.2, 128.8, 128.6, 128.5, 127.9, 127.1, 122.6, 122.5, 121.9, 115.5, 114.7, 72.3, 71.3, 71.1, 71.0, 68.8, 68.0, 59.4, 32.3, 30.04, 29.99, 29.97, 29.8, 29.5, 26.4, 23.7, 23.1, 14.5: Anal. calcd for C79H116O23: C, 66.18; H, 8.15. Found: C, 66.72, H, 8.33. MW/Mn=1.03 (gel permeation chromatography).

Controlled synthesis and transfer of large-area WS2 sheets: from single layer to few layers.

The isolation of few-layered transition metal dichalcogenides has mainly been performed by mechanical and chemical exfoliation with very low yields. In this account, a controlled thermal reduction-sulfurization method is used to synthesize large-area (~1 cm(2)) WS2 sheets with thicknesses ranging from monolayers to a few layers. During synthesis, WOx thin films are first deposited on Si/SiO2 substrates, which are then sulfurized (under vacuum) at high temperatures (750-950 °C). An efficient route to transfer the synthesized WS2 films onto different substrates such as quartz and transmission electron microscopy (TEM) grids has been satisfactorily developed using concentrated HF. Samples with different thicknesses have been analyzed by Raman spectroscopy and TEM, and their photoluminescence properties have been evaluated. We demonstrated the presence of single-, bi-, and few-layered WS2 on as-grown samples. It is well known that the electronic structure of these materials is very sensitive to the number of layers, ranging from indirect band gap semiconductor in the bulk phase to direct band gap semiconductor in monolayers. This method has also proved successful in the synthesis of heterogeneous systems of MoS2 and WS2 layers, thus shedding light on the controlled production of heterolayered devices from transition metal chalcogenides.

Development of Supported Bifunctional Electrocatalysts for Unitized Regenerative Fuel Cells

bUOP LLC, Des Plaines, Illinois 60017, USA Mixed metal catalysts containing Pt, Ir, Ru, Os, and Rh were synthesized on three different conductive oxide supports, Ebonex, which is a mixture of Ti4O7 and other phases, phase-pure microcrystalline Ti4O7 , and Ti0.9Nb0.1O2 , a doped rutile compound. Ebonex-supported catalysts were prepared as arrays and screened combinatorially for activity and stability as bifunctional oxygen reduction/water oxidation catalysts. The highest activity and stability was found in the Pt-Ru-Ir ternary region at compositions near Pt4Ru4Ir1 . X-ray near edge absorption spectra indicated a significant electronic interaction between the catalyst and the support, and a substantial increase in catalyst utilization was observed, even though the support surface areas were relatively low. Both Ebonex and Ti4O7 have short-lived electrochemical stability under conditions of oxygen evolution at 11.6 V vs. RHE in 0.5 M H2SO4 . Current at these supported catalysts gradually decreases, and the decrease is attributed to loss of electronic conductivity. Ebonex and Ti4O7 are also thermally oxidized in air at temperatures above 400°C. In contrast, Ti0.9Nb0.1O2 , which has a nondefective oxygen lattice, is quite resistant to electrochemical and thermal oxidation. Conditioning of Ti 0.9Nb0.1O2-supported Pt4Ru4Ir1 at positive potentials had little effect on the activity of the catalyst.

Autonomous Motion of Metallic Microrods Propelled by Ultrasound

Autonomously moving micro-objects, or micromotors, have attracted the attention of the scientific community over the past decade, but the incompatibility of phoretic motors with solutions of high ionic strength and the use of toxic fuels have limited their applications in biologically relevant media. In this letter we demonstrate that ultrasonic standing waves in the MHz frequency range can levitate, propel, rotate, align, and assemble metallic microrods (2 μm long and 330 nm diameter) in water as well as in solutions of high ionic strength. Metallic rods levitated to the midpoint plane of a cylindrical cell when the ultrasonic frequency was tuned to create a vertical standing wave. Fast axial motion of metallic microrods at ~200 μm/s was observed at the resonant frequency using continuous or pulsed ultrasound. Segmented metal rods (AuRu or AuPt) were propelled unidirectionally with one end (Ru or Pt, respectively) consistently forward. A self-acoustophoresis mechanism based on the shape asymmetry of the metallic rods is proposed to explain this axial propulsion. Metallic rods also aligned and self-assembled into long spinning chains, which in the case of bimetallic rods had a head-to-tail alternating structure. These chains formed ring or streak patterns in the levitation plane. The diameter or distance between streaks was roughly half the wavelength of the ultrasonic excitation. The ultrasonically driven movement of metallic rods was insensitive to the addition of salt to the solution, opening the possibility of driving and controlling metallic micromotors in biologically relevant media using ultrasound.

Rapid Charge Transport in Dye-Sensitized Solar Cells Made from Vertically Aligned Single-Crystal Rutile TiO2 Nanowires†

A rapid solvothermal approach was used to synthesize aligned 1D single-crystal rutile TiO(2) nanowire (NW) arrays on transparent conducting substrates as electrodes for dye-sensitized solar cells. The NW arrays showed a more than 200 times faster charge transport and a factor four lower defect state density than conventional rutile nanoparticle films.

Improving the efficiency of water splitting in dye-sensitized solar cells by using a biomimetic electron transfer mediator

Photoelectrochemical water splitting directly converts solar energy to chemical energy stored in hydrogen, a high energy density fuel. Although water splitting using semiconductor photoelectrodes has been studied for more than 40 years, it has only recently been demonstrated using dye-sensitized electrodes. The quantum yield for water splitting in these dye-based systems has, so far, been very low because the charge recombination reaction is faster than the catalytic four-electron oxidation of water to oxygen. We show here that the quantum yield is more than doubled by incorporating an electron transfer mediator that is mimetic of the tyrosine-histidine mediator in Photosystem II. The mediator molecule is covalently bound to the water oxidation catalyst, a colloidal iridium oxide particle, and is coadsorbed onto a porous titanium dioxide electrode with a Ruthenium polypyridyl sensitizer. As in the natural photosynthetic system, this molecule mediates electron transfer between a relatively slow metal oxide catalyst that oxidizes water on the millisecond timescale and a dye molecule that is oxidized in a fast light-induced electron transfer reaction. The presence of the mediator molecule in the system results in photoelectrochemical water splitting with an internal quantum efficiency of approximately 2.3% using blue light.