Chunjuan Zhang

Measuring fundamental properties in operating solid oxide electrochemical cells by using in situ X-ray photoelectron spectroscopy

Photoelectron spectroscopic measurements have the potential to provide detailed mechanistic insight by resolving chemical states, electrochemically active regions and local potentials or potential losses in operating solid oxide electrochemical cells (SOCs), such as fuel cells. However, high-vacuum requirements have limited X-ray photoelectron spectroscopy (XPS) analysis of electrochemical cells to ex situ investigations. Using a combination of ambient-pressure XPS and CeO(2-x)/YSZ/Pt single-chamber cells, we carry out in situ spectroscopy to probe oxidation states of all exposed surfaces in operational SOCs at 750 °C in 1 mbar reactant gases H(2) and H(2)O. Kinetic energy shifts of core-level photoelectron spectra provide a direct measure of the local surface potentials and a basis for calculating local overpotentials across exposed interfaces. The mixed ionic/electronic conducting CeO(2-x) electrodes undergo Ce(3+)/Ce(4+) oxidation-reduction changes with applied bias. The simultaneous measurements of local surface Ce oxidation states and electric potentials reveal the active ceria regions during H(2) electro-oxidation and H(2)O electrolysis. The active regions extend ~150 μm from the current collectors and are not limited by the three-phase-boundary interfaces associated with other SOC materials. The persistence of the Ce(3+)/Ce(4+) shifts in the ~150 μm active region suggests that the surface reaction kinetics and lateral electron transport on the thin ceria electrodes are co-limiting processes.

Mechanistic Studies of Water Electrolysis and Hydrogen Electro-Oxidation on High Temperature Ceria-Based Solid Oxide Electrochemical Cells

Through the use of ambient pressure X-ray photoelectron spectroscopy (APXPS) and a single-sided solid oxide electrochemical cell (SOC), we have studied the mechanism of electrocatalytic splitting of water (H2O + 2e(-) → H2 + O(2-)) and electro-oxidation of hydrogen (H2 + O(2-) → H2O + 2e(-)) at ∼700 °C in 0.5 Torr of H2/H2O on ceria (CeO2-x) electrodes. The experiments reveal a transient build-up of surface intermediates (OH(-) and Ce(3+)) and show the separation of charge at the gas-solid interface exclusively in the electrochemically active region of the SOC. During water electrolysis on ceria, the increase in surface potentials of the adsorbed OH(-) and incorporated O(2-) differ by 0.25 eV in the active regions. For hydrogen electro-oxidation on ceria, the surface concentrations of OH(-) and O(2-) shift significantly from their equilibrium values. These data suggest that the same charge transfer step (H2O + Ce(3+) <-> Ce(4+) + OH(-) + H(•)) is rate limiting in both the forward (water electrolysis) and reverse (H2 electro-oxidation) reactions. This separation of potentials reflects an induced surface dipole layer on the ceria surface and represents the effective electrochemical double layer at a gas-solid interface. The in situ XPS data and DFT calculations show that the chemical origin of the OH(-)/O(2-) potential separation resides in the reduced polarization of the Ce-OH bond due to the increase of Ce(3+) on the electrode surface. These results provide a graphical illustration of the electrochemically driven surface charge transfer processes under relevant and nonultrahigh vacuum conditions.

Quantized magnetoresistance in atomic-size contacts.

When the dimensions of a metallic conductor are reduced so that they become comparable to the de Broglie wavelengths of the conduction electrons, the absence of scattering results in ballistic electron transport and the conductance becomes quantized. In ferromagnetic metals, the spin angular momentum of the electrons results in spin-dependent conductance quantization and various unusual magnetoresistive phenomena. Theorists have predicted a related phenomenon known as ballistic anisotropic magnetoresistance (BAMR). Here we report the first experimental evidence for BAMR by observing a stepwise variation in the ballistic conductance of cobalt nanocontacts as the direction of an applied magnetic field is varied. Our results show that BAMR can be positive and negative, and exhibits symmetric and asymmetric angular dependences, consistent with theoretical predictions.

In situ magnetoresistance of Ni nanocontacts

Magnetoresistance properties of Ni nanocontacts in the ballistic quantum regime are investigated in situ during closure and opening of electrochemically grown planar electrodes. The magnitude of conductance change when sweeping the magnetic field is of the order of the quantum conductance e2/h for conductance values spanning 1–100 quanta. The relative orientation of electric current and applied magnetic field changes the magnetoresistance sign, with symmetry properties reminiscent of bulk anisotropy magnetoresistance. Ex situ investigations of samples of higher conductance values, of the order of 1000 quanta, unambiguously show the analogy with bulk anisotropy magnetoresistance.

Wet Synthesis and Characterization of MSe (M = Cd, Hg) Nanocrystallites at Room Temperature

Semiconductor selenides of MSe (M = Cd, Hg) nanocrystalline powders were synthesized through the reactions between metal chlorides and sodium selenosulfate in the ammoniacal aqueous solution at room temperature for 6-10 h. The samples were characterized by x-ray powder diffraction, transmission electron microscopy, electron diffraction, x-ray photoelectron spectroscopy, and elemental analysis. The average diameters of CdSe and HgSe nanocrystallites are 4 and 8 nm, respectively. The storage and an interesting phase transition under hydrothermal conditions have been presented. The absorption spectrum of the as-prepared samples exhibits obvious blue shift due to the size confinement.

Metal/Self-Assembled Monolayer/Metal Junctions for Magnetoelectronic Applications.

Abstract : Metal/organic self-assembled monolayer/metal junctions were investigated for junction areas 10(-2) to 10(2) microns squared. Several types and thickness of monolayers are investigated, and magnetic electrodes were made. Electroless deposition was used to make the top metal without disrupting the organic film. This deposition is activated with Pd clusters obtained by evaporation or by chemical reduction of a Pd-based catalyst. This method allows us to obtain a high yield of junctions that are not electrically shorted and are mechanically and electrically stable over a wide temperature range. Low-temperatures investigations reveal strong non-linearity in the IV curves and an increase of resistance with decreasing temperature. Zero bias anomalies observed at low temperatures are attributed to a Coulomb blockade associated with the Pd clusters