Atomic Layer Deposition (ALD) Synthesis and Raman Spectroscopy of Catalytic Systems

Nanobowl synthesis steps. Step 1: Prepare substrate with Al2O3 ALD. Step 2: Grow Pd nanoparticles with Pd ALD. Step 3: Add blocking agent. Step 4: Modify support and grow nanobowl wall. Step 5: Remove blocking agent.

Schematic of our new ALD system.

Atomic layer deposition (ALD) is a thin film growth technique capable of growing an expansive amount of materials including oxides, nitrides and metals.  ALD is widely used in the semiconductor industry and is beginning to expand as a new synthetic tool in catalysis. We are developing catalysts that mimic the shape and functionalization of enzymes, nature’s selective catalysts. One strategy to do this involves placing metal nanoparticle catalysts at the bottom of metal oxide bowls on the catalyst support.  Nanobowl catalysts have been synthesized using ALD and chemistry that protects the particles during bowl growth has been explored using DRIFTS (Fig. 1).  In the future hydrogenation catalysis will be preformed to evaluate the reactivity and selectivity. Recently, another ALD system was built with unique capabilities for the study of catalytic reactions (Fig. 2).  This ALD system will be able to monitor ALD surface reactions in-situ using SERS and quartz crystal microbalance. The reactor will be connected to a GC for in-situ catalytic studies. The GC is equipped with a Thermal Conductivity and Flame Ionization detector so both permanent gases and hydrocarbons can be detected. Possible catalytic systems of study are the epoxidation of olefins and plasmon-enhanced photocatalysis.

Ryan Hackler, 3rd year graduate student joint with Peter C. Stair
Cassie George, 6th year graduate student joint with Peter C. Stair

Recent Publications:

“Shape-selective sieving layers on an oxide catalyst surface,” C. Canlas , J. Lu , N. Ray , N. Grosso-Giordano, S.  Lee, J. Elam, R. Winans, P. Stair, R. Van Duyne, and J. Notestein,* Nature Chemistry, 4, 1030-1036 (2012).

“Synthesis Strategy for Protected Metal Nanoparticles,” N. A. Ray, R. P. Van Duyne, and P. C. Stair, J. Phys. Chem. C, 116, 7748-7756 (2012).

“Displacement of Hexanol by the Hexanoic Acid Over-oxidation Product in Alcohol Oxidation on a Model Supported Palladium Nanoparticle Catalyst,” A. Buchbinder, N. Ray, J.Lu, R. P. Van Duyne, P. C. Stair, E. Weitz, and F. Geiger, JACS. (2011).

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  • Professor Richard Van Duyne

    Additional Information

    Discoverer of Surface-enhanced Raman Spectroscopy (1977)
    Inventor of Nanosphere Lithography (1995) & Localized Surface Plasmon Resonance Spectroscopy (2000)

  • Group Members

    Professor Van Duyne has, in his career to date, advised a total of 87 graduate students and 47 postdoctoral fellows. Every year, Professor Van Duyne gives a talk to introduce new graduate students to our research. The 2017 seminar slides are available here.

  • News

    Professor Van Duyne was recently named a Vannevar Bush Faculty Fellow by the U.S. Department of Defense to conduct "high risk, high payoff" basic scientific research. Read more here