Fabrication of Large-Area Metal-on-Carbon Catalytic Condensers for Programmable Catalysis.

Catalytic condensers stabilize charge on either side of a high-k dielectric film to modulate the electronic states of a catalytic layer for the electronic control of surface reactions. Here, carbon sputtering provided for fast, large-scale fabrication of metal-carbon catalytic condensers required for industrial application. Carbon films were sputtered on HfO2 dielectric/p-type Si with different thicknesses (1, 3, 6, and 10 nm), and the enhancement of conductance and capacitance of carbon films was observed upon increasing the carbon thickness following thermal treatment at 400 °C. After Pt deposition on the carbon films, the Pt catalytic condenser exhibited a high capacitance of ∼210 nF/cm2 that was maintained at a frequency ∼1000 Hz, satisfying the requirement for a dynamic catalyst to implement catalytic resonance. Temperature-programmed desorption of carbon monoxide yielded CO desorption peaks that shifted in temperature with the varying potential applied to the condenser (-6 or +6 V), indicating a shift in the binding energy of carbon monoxide on the Pt condenser surface. A substantial increase in capacitance (∼2000 nF/cm2) of the Pt-on-carbon devices was observed at elevated temperatures of 400 °C that can modulate ∼10% of charge per metal atom when 10 V potential was applied. A large catalytic condenser of 42 cm2 area Pt/C/HfO2/Si exhibited a high capacitance of 9393 nF with a low leakage current/capacitive current ratio (<0.1), demonstrating the practicality and versatility of the facile, large-scale fabrication method for metal-carbon catalytic condensers.

Platinum Graphene Catalytic Condenser for Millisecond Programmable Metal Surfaces.

Accelerating catalytic chemistry and tuning surface reactions require precise control of the electron density of metal atoms. In this work, nanoclusters of platinum were supported on a graphene sheet within a catalytic condenser device that facilitated electron or hole accumulation in the platinum active sites with negative or positive applied potential, respectively. The catalytic condenser was fabricated by depositing on top of a p-type Si wafer an amorphous HfO2 dielectric (70 nm), on which was placed the active layer of 2-4 nm platinum nanoclusters on graphene. A potential of ±6 V applied to the Pt/graphene layer relative to the silicon electrode moved electrons into or out of the active sites of Pt, attaining charge densities more than 1% of an electron or hole per surface Pt atom. At a level of charge condensation of ±10% of an electron per surface atom, the binding energy of carbon monoxide to a Pt(111) surface was computed via density functional theory to change 24 kJ mol-1 (0.25 eV), which was consistent with the range of carbon monoxide binding energies determined from temperature-programmed desorption (ΔBECO of 20 ± 1 kJ mol-1 or 0.19 eV) and equilibrium surface coverage measurements (ΔBECO of 14 ± 1 kJ mol-1 or 0.14 eV). Impedance spectroscopy indicated that Pt/graphene condensers with potentials oscillating at 3000 Hz exhibited negligible loss in capacitance and charge accumulation, enabling programmable surface conditions at amplitudes and frequencies necessary to achieve catalytic resonance.

Measurement of Three Transport Coefficients and the Thermodynamic Factor in Block Copolymer Electrolytes with Different Morphologies.

The design and engineering of composite materials is one strategy to satisfy the materials needs of systems with multiple orthogonal property requirements. In the case of rechargeable batteries with lithium metal anodes, the system requires a separator with fast lithium ion transport and good mechanical strength. In this work, we focus on the system polystyrene-block-poly(ethylene oxide) (SEO) with bis(trifluoromethane)sulfonimide lithium salt (LiTFSI). Ion transport occurs in the salt-containing poly(ethylene oxide)-rich domains. Mechanical rigidity arises due to the glassy nature of polystyrene (PS). If we assume that the salt does not interact with the PS-rich domains, we can describe ion transport in the electrolyte by three transport parameters (ionic conductivity, κ, salt diffusion coefficient, D, and cation transference number, t+0) and a thermodynamic factor, Tf. By systematically varying the volume fraction of the conducting phase, ϕc between 0.29 and 1.0, and chain length, N between 80 and 8000, we elucidate the role of morphology on ion transport. We find that κ is the strongest function of morphology, varying by three full orders of magnitude, while D is a weaker function of morphology. To calculate t+0 and Tf, we measure the current fraction, ρ+, and the open circuit potential, U, of concentration cells. We find that ρ+ and U follow universal trends as a function of salt concentration, regardless of chain length, morphology, or ϕc, allowing us to calculate t+0 for any SEO/LiTFSI or PEO/LiTFSI mixture when κ and D are known. The framework developed in this paper enables predicting the performance of any block copolymer electrolyte in a rechargeable battery.