Whether or not the active sites for the oxygen reduction reaction (ORR) in electrocatalysts based on carbon-supported transition-metal complexes are metal-centered has become controversial, especially for heat-treated materials. Some have proposed that the transition metal only serves to form highly active sites based on nitrogen and carbon. Here, we examine the oxygen reduction activity of carbon-supported iron(II) phthalocyanine (FePc) before and after pyrolysis at 800 °C and a carbon-supported copper(II) complex with 3,5-diamino-1,2,4-triazole (CuDAT) in the presence of several anions and small-molecule poisons, including fluoride, azide, thiocyanate, ethanethiol, and cyanide. CuDAT is poisoned in a manner consistent with a Cu-based active site. Although FePc and pyrolyzed FePc are remarkably resilient to most poisons, they are poisoned by cyanide, indicative of Fe-based active sites.

It is important to understand the buried interfacial structures containing epoxy underfills as such structures determine the interfacial adhesion properties. Weak adhesion or delamination at such interfaces leads to failure of microelectronic devices. Sum frequency generation (SFG) vibrational spectroscopy was used to examine buried interfaces at polymer/model epoxy and polymer/commercial epoxy resins (used as underfills in flip chip devices) at the molecular level. We investigated a model epoxy: bisphenol A digylcidyl ether (BADGE) at the interfaces of poly (ethylene terephthalate) (PET) before and after curing. Furthermore, small amounts of different silanes including (3-glycidoxypropyl) trimethoxysilane (γ-GPS), (3-Aminopropyl)trimethoxysilane (ATMS), Octadecyltrimethoxysilane (OTMS(18C)), and Octyltrimethoxysilane (OTMS(8C)) were mixed with BADGE. Silane influences on the polymer/epoxy interfacial structures were studied. SFG was also used to study molecular interfacial structures between polymers and two commercial epoxy resins. The interfacial structures probed by SFG were correlated to the adhesion strengths measured for corresponding interfaces. The results indicated that a small amount of silane molecules added to epoxy could substantially change the polymer/epoxy interfacial structure, greatly affecting the adhesion strength at the interface. It was found that ordered methyl groups at the interface lead to weak adhesion, and disordered interfaces lead to strong adhesion.

In this research, a variety of analytical techniques including sum frequency generation vibrational spectroscopy (SFG), coherent anti-Stokes Raman spectroscopy (CARS), and X-ray photoelectron spectroscopy (XPS) have been employed to investigate the surface and bulk structures of phthalate plasticized poly(vinyl chloride) (PVC) at the molecular level. Two types of phthalate molecules with different chain lengths, diethyl phthalate (DEP) and dibutyl phthalate (DBP), mixed with PVC in various weight ratios were examined to verify their different surface and bulk behaviors. The effects of oxygen and argon plasma treatment on PVC/DBP and PVC/DEP hybrid films were investigated on both the surface and bulk of films using SFG and CARS to evaluate the different plasticizer migration processes. Without plasma treatment, SFG results indicated that more plasticizers segregate to the surface at higher plasticizer bulk concentrations. SFG studies also demonstrated the presence of phthalates on the surface even at very low bulk concentration (5 wt %). Additionally, the results gathered from SFG, CARS, and XPS experiments suggested that the PVC/DEP system was unstable, and DEP molecules could leach out from the PVC under low vacuum after several minutes. In contrast, the PVC/DBP system was more stable; the migration process of DBP out of PVC could be effectively suppressed after oxygen plasma treatment. XPS results indicated the increase of C═O/C-O groups and decrease of C-Cl functionalities on the polymer surface after oxygen plasma treatment. The XPS results also suggested that exposure to argon plasma induced chemical bond breaking and formation of cross-linking or unsaturated groups with chain scission on the surface. Finally, our results indicate the potential risk of using DEP molecules in PVC since DEP can easily leach out from the polymeric bulk.

Using a combination of Fourier transform infrared (FTIR) spectroscopy and physics-based degradation models, we find that the early aging of small molecular weight organic photovoltaic (OPV) cells is due to photochemical degradation of the C60acceptor layer.