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Timothy R Kline

Publications and source records attributed to Timothy R Kline.

7 recordsLinked to original sources

Catalytically driven colloidal patterning and transport.

We recently reported the convection and pattern formation of tracers caused by a catalytically generated electric field. The electric field arises due to the heterogeneous electrochemical reduction and oxidation of hydrogen peroxide (H2O2) on silver (Ag) and gold (Au), respectively.1 Here we describe an electrokinetic model, developed in conjunction with experiments, that explains the details of the convection and pattern formation phenomenon. The model also enables the measurement of reaction kinetic parameters that are otherwise difficult to obtain. This quantitative model serves as a platform for the modeling of other catalytic redox systems and systems with broken symmetries.

Journal Article↗

Bipolar electrochemical mechanism for the propulsion of catalytic nanomotors in hydrogen peroxide solutions.

Bimetallic nanorods are propelled in aqueous solutions by the catalytic decomposition of hydrogen peroxide to oxygen and water. Several mechanisms (interfacial tension gradients, bubble recoil, viscous Brownian ratchet, self-electrophoresis) have been proposed for the transduction of chemical to mechanical energy in this system. From Tafel plots of anodic and cathodic hydrogen peroxide reactions at various metal (Au, Pt, Rh, Ni, Ru, and Pd) ultramicroelectrodes, we determine the potential at which the anodic and cathodic reaction rates are equal for each metal. These measurements allow one to predict the direction of motion of all possible bimetallic combinations according to the bipolar electrochemical (or self-electrophoretic) mechanism. These predictions are consistent with the observed direction of motion in all cases studied, providing strong support for the mechanism. We also find that segmented nanorods with one Au end and one poly(pyrrole) end containing catalase, an enzyme that decomposes hydrogen peroxide nonelectrochemically, perform the overall catalytic reaction at a rate similar to that of nanorods containing Au and Pt segments. However, in this case there is no observed axial movement, again supporting the bipolar electrochemical propulsion mechanism for bimetallic nanorods.

Catalysis↗

Catalytically induced electrokinetics for motors and micropumps.

We have explored the role of electrokinetics in the spontaneous motion of platinum-gold nanorods suspended in hydrogen peroxide (H2O2) solutions that may arise from the bimetallic electrochemical decomposition of H2O2. The electrochemical decomposition pathway was confirmed by measuring the steady-state short-circuit current between platinum and gold interdigitated microelectrodes (IMEs) in the presence of H2O2. The resulting ion flux from platinum to gold implies an electric field in the surrounding solution that can be estimated from Ohm's Law. This catalytically generated electric field could in principle bring about electrokinetic effects that scale with the Helmholtz-Smoluchowski equation. Accordingly, we observed a linear relationship between bimetallic rod speed and the resistivity of the bulk solution. Previous observations relating a decrease in speed to an increase in ethanol concentration can be explained in terms of a decrease in current density caused by the presence of ethanol. Furthermore, we found that the catalytically generated electric field in the solution near a Pt/Au IME in the presence of H2O2 is capable of inducing electroosmotic fluid flow that can be switched on and off externally. We demonstrate that the velocity of the fluid flow in the plane of the IME is a function of the electric field, whether catalytically generated or applied from an external current source. Our findings indicate that the motion of PtAu nanorods in H2O2 is primarily due to a catalytically induced electrokinetic phenomenon and that other mechanisms, such as those related to interfacial tension gradients, play at best a minor role.

Catalysis↗

Template-grown metal nanowires.

The growth of metal nanowires using membranes as hard templates is reviewed. The method provides access to arrays of single-crystal metal nanowires and to quasi-one-dimensional metal nanostructures with controlled compositional variation along their length. Recent applications of these kinds of nanowires to problems in superconductivity, optical spectroscopy and sensing, and catalytic conversion of chemical to mechanical energy are reviewed.

Journal Article↗

Reversible pattern formation through photolysis.

We report a photolytic method to induce spatial and temporal patterning/deposition of particles at the micron scale on a time scale of seconds. Reversible pattern formation by negatively charged particles occur around micron-sized silver features on different substrates when exposed to UV light in the presence of aqueous hydrogen peroxide. Diffusiophoretic motion due to a spatially defined ion gradient accounts for our observations. Atomic force and optical microscopy, as well as conductivity measurements, support this hypothesis.

Journal Article↗

Catalytic micropumps: microscopic convective fluid flow and pattern formation.

As innovations continue to be made in the fields of microfluidics and the colloidal assembly, new strategies for moving particles and fluids may be needed. Heterogeneous catalysis provides means of locally converting the stored chemical energy of fuels to mechanical energy. We report an ambient temperature stationary "pump" that generates a proton concentration gradient through the bipolar electrochemical decomposition of hydrogen peroxide on patterned silver-gold surfaces. The resulting electric field drives convective fluid flow and pattern formation of colloidal tracer particles at the microscopic level by a combination of electroosmotic and electrophoretic forces.

Journal Article↗