Selective reactivity of an electrocatalytically generated catalyst-hydride intermediate toward the hydrogen evolution reaction (HER) or reduction of CO(2) is key for a CO(2) reduction electrocatalyst. Under appropriate conditions, Et(4)N[Fe(4)N(CO)(12)] (Et(4)N-1) is a catalyst for the HER or for CO(2) conversion at -1.25 V vs SCE using a glassy carbon electrode.

The development of efficient hydrogen evolving electrocatalysts that operate near neutral pH in aqueous solution remains of significant interest. A series of low-valent iron clusters have been investigated to provide insight into the structure-function relationships affecting their ability to promote formation of cluster-hydride intermediates and to promote electrocatalytic hydrogen evolution from water. Each of the metal carbonyl anions, [Fe4N(CO)12](-) (1(-)), [Fe4C(CO)12](2-) (2(2-)), [Fe5C(CO)15](2-) (3(2-)), and [Fe6C(CO)18](2-) (4(2-)) were isolated as their sodium salt to provide the necessary solubility in water. At pH 5 and -1.25 V vs SCE the clusters afford hydrogen with Faradaic efficiencies ranging from 53-98%. pH dependent cyclic voltammetry measurements provide insight into catalytic intermediates. Both of the butterfly shaped clusters, 1(-) and 2(2-), stabilize protonated adducts and are effective catalysts. Initial reduction of butterfly shaped 1(-) is pH-independent and subsequently, successive protonation events afford H1(-), and then hydrogen. In contrast, butterfly shaped 2(2-) undergoes two successive proton coupled electron transfer events to form H22(2-) which then liberates hydrogen. The higher nuclearity clusters, 3(2-) and 4(2-), do not display the same ability to associate with protons, and accordingly, they produce hydrogen less efficiently.

The hole transport polymer poly (3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) derives many of its favorable properties from a PSS-rich interfacial layer that forms spontaneously during coating. Since PEDOT:PSS is only usable as a blend it is not possible to study PEDOT:PSS without this interfacial layer. Through the use of the self-doped polymer sulfonated poly(thiophene-3-[2-(2-methoxyethoxy) ethoxy]-2,5-diyl) (S-P3MEET) and a polyfluorinated ionomer (PFI) it is possible to compare transparent conducting organic films with and without interfacial layers and to understand their function. Using neutron reflectometry, we show that PFI preferentially segregates at the top surface of the film during coating and forms a thermally-stable surface layer. Because of this distribution we find that even small amounts of PFI increase the electron work function of the hole transport layer. We also find that annealing at 150 C and above reduces the work function compared to samples heated at lower temperatures. Using near edge X-ray absorption fine structure spectroscopy and gas chromatography we show that this reduction in work function is due to S-P3MEET being doped by PFI. Organic photovoltaic devices with S-P3MEET/PFI hole transport layers yield higher power conversion efficiency than devices with pure S-P3MEET or PEDOT:PSS hole transport layers. Additionally, devices with a doped interface layer of S-P3MEET/PFI show superior performance to those with un-doped S-P3MEET.

Poly(3,4-ethylenedioxythiophene)-poly(styrenesulphonate) (PEDOT:PSS) is the most used organic hole injecting or hole transporting material. The hole carrying matrix PEDOT is highly doped by the acidic dopant PSS. When coated onto a substrate, PEDOT:PSS makes a highly uniform conductive layer and a thin (<5 nm) overlayer of PSS covers the air interface. Semiconducting polymer layers for organic photovoltaics or light emitting diodes are coated on top. In this article, we demonstrate that the PSS layer will mix with almost all conjugated polymers upon thermal annealing. Depending on the Fermi energy of the polymer an electrochemical reaction can take place, p-type doping the polymer at the interface between the PEDOT:PSS and the semiconducting polymer. We use chemical and spectroscopic analysis to characterize the polymer/PSS interlayer. We show that the stable and insoluble interlayer has a great effect on the charge injection and extraction from the interface. Finally we demonstrate and electronically model organic photovoltaic devices that are fabricated using these mixed interlayers.