Catalytic Micromotors and Micropumps and their Collective Behavior

Open Access
Author:
Ibele, Michael Edward
Graduate Program:
Chemistry
Degree:
Doctor of Philosophy
Document Type:
Dissertation
Date of Defense:
August 13, 2010
Committee Members:
  • Ayusman Sen, Dissertation Advisor
  • Ayusman Sen, Committee Chair
  • Christine Dolan Keating, Committee Member
  • Thomas E Mallouk, Committee Member
  • Jeffrey M Catchmark, Committee Member
Keywords:
  • colloids
  • nanoparticles
  • silver chloride
  • oscillating reaction
  • nanomotors
Abstract:
The overarching goal which initiated this research was the desire to learn how to synthesize artificial micrometer- and nanometer-sized objects which have the ability to move autonomously in solution, and to be able to understand, predict, and control their movements. In the natural world, such motion is common. Bacteria, for instance, use flagella, cilia, or other mechanisms to chemotax to nutrient-rich regions of their environments. However, at the outset of this research, only a few simple examples of artificially powered motions on the microscale had been reported in the literature. This dissertation discusses the evolution of artificial catalytic micromotors and micropumps from the initial bimetallic-microrod design, which catalyzed the decomposition of hydrogen peroxide (H2O2), to the current state of the field, in which particle motion can also be powered by hydrazine-derived fuels or by ultraviolet light. Analyses of these new motors are presented, with particular emphasis given to the motor-motor interactions which occur in solution and which give rise to collective behavior in dense populations of the motors. The first artificial autonomous micromotor ever synthesized consisted of a bimetallic microrod with spatially segregated gold and platinum segments. When placed in aqueous solutions containing H2O2, this microrod decomposed the H2O2 asymmetrically on its two metallic surfaces and powered its own motion through solution via self-electrophoresis. In this dissertation, it is shown that a similar self-electrophoretic mechanism is at play in a micropump system comprised of spatially segregated, lithographically patterned, palladium and gold features, which operates in solutions of either hydrazine (N2H4) or N,N-dimethylhydrazine [(CH3)2N(NH3)]. While this new electrophoretic system is interesting from a theoretical standpoint, N2H4 is highly toxic, and the decision was made to move on to other more environmentally friendly systems. The bulk of this dissertation therefore details experiments performed on silver chloride (AgCl) particles, a newly discovered autonomous micromotor system, discovered by the author, which exhibits collective behaviors that have never before been seen in wholly artificial microscale systems. When placed in deionized water and illuminated with ultraviolet (UV) light, these colloids decompose into protons, chloride ions, oxygen gas, and silver metal. The difference in the diffusion constants of the two ions creates an electric field in solution which powers the motion of the particles. Over time, the ion gradients of nearby particles overlap and collective behavior of the particles is observed. Modeling of this phenomenon was performed using the programming language NetLogo. Over time, silver metal plates out onto the particle surface and ultimately poisons the reaction. For this reason, it was decided to add H2O2 to the system in an attempt to oxidize away the silver metal byproduct and regenerate a fresh AgCl surface. Surprisingly, the UV-induced decomposition reaction and the peroxide-related oxidation reaction appear to occur via oscillatory kinetics. As a result, the AgCl colloids are seen to exhibit oscillatory motion: switching between periods where they quickly traverse several body lengths over the course of about a second and times during which they are attached to the underlying glass slide and are therefore immobile. In high density populations of these oscillators, the oscillating reactions of individual particles synchronize, resulting in waves of particle motion which traverse the system. Because this system exhibits non-linear oscillatory kinetics, it was possible to begin the oscillations starting with a different set of reactants, namely silver metal, chloride ions, and H2O2. This allowed for the measurement of the electrical current associated with the reaction, as silver electrodes can be easily prepared. Finally, this dissertation concludes with a discussion of a somewhat unrelated project: the template synthesis of flexible nanowires, in which the silver sections of bimetallic nanorods are replaced with carbonaceous impurities or poly(allylamine hydrochloride).