An excess of elemental sulfur is generated annually from hydrodesulfurization in petroleum refining processes; however, it has a limited number of uses, of which one example is the production of sulfuric acid. Despite this excess, the development of synthetic and processing methods to convert elemental sulfur into useful chemical substances has not been investigated widely. Here we report a facile method (termed 'inverse vulcanization') to prepare chemically stable and processable polymeric materials through the direct copolymerization of elemental sulfur with vinylic monomers. This methodology enabled the modification of sulfur into processable copolymer forms with tunable thermomechanical properties, which leads to well-defined sulfur-rich micropatterned films created by imprint lithography. We also demonstrate that these copolymers exhibit comparable electrochemical properties to elemental sulfur and could serve as the active material in Li-S batteries, exhibiting high specific capacity (823 mA h g(-1) at 100 cycles) and enhanced capacity retention.

Polymers for IR imaging: The preparation of high refractive index polymers (n = 1.75 to 1.86) via the inverse vulcanization of elemental sulfur is reported. High quality imaging in the near (1.5 μm) and mid-IR (3-5 μm) regions using high refractive index polymeric lenses from these sulfur materials was demonstrated.

Sulfur-rich copolymers based on poly(sulfurrandom-1,3-diisopropenylbenzene) (poly(S-r-DIB)) were synthesized via inverse vulcanization to create cathode materials for lithium−sulfur battery applications. These materials exhibit enhanced capacity retention (1005 mAh/g at 100 cycles) and battery lifetimes over 500 cycles at a C/10 rate. These poly(Sr-DIB) copolymers represent a new class of polymeric electrode materials that exhibit one of the highest charge capacities reported, particularly after extended charge− discharge cycling in Li−S batteries.

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We compare the near-surface composition and electroactivity of commercial indium tin oxide (ITO) thin films, activated by plasma cleaning or etching with strong haloacids, with ITO films that have been freshly deposited in high vacuum, before and after exposure to the atmosphere or water vapor. Conductive-tip AFM, X-ray photoelectron spectroscopy (XPS), and the electrochemistry of probe molecules in solution were used to compare the relative degrees of electroactivity and the near-surface composition of these materials. Brief etching of commercial ITO samples with concentrated HCl or HI significantly enhances the electrical activity of these oxides as revealed by C-AFM. XPS was used to compare the composition of these activated surfaces, focusing on the intrinsically asymmetric O 1s line shape. Energy-loss processes associated with photoemission from the tin-doped, oxygen-deficient oxides complicate the interpretation of the O 1s spectra. O 1s spectra from the stoichiometric indium oxide lattice are accompanied by higher-binding-energy peaks associated with hydroxylated forms of the oxide (and in some cases carbonaceous impurities) and overlapping photoemission associated with energy-loss processes. Characterization of freshly sputter-deposited indium oxide (IO) and ITO films, transferred under high vacuum to the surface analysis environment, allowed us to differentiate the contributions of tin doping and oxygen-vacancy doping to the O 1s line shape, relative to higher-binding-energy O 1s components associated with hydroxyl species and carbonaceous impurities. Using these approaches, we determined that acid activation and O2 plasma etching create an ITO surface that is still covered with an average of one to two monolayers of hydroxide. Both of these activation treatments lead to significantly higher rates of electron transfer to solution probe molecules, such as dimethyferrocene in acetonitrile. Solution electron-transfer events appear to occur at no more than 4x10(7) electroactive sites per cm2 (each with diameters of ca. 50-200 nm) (i.e., a small fraction of the geometric area of the electrode). Electron-transfer rates correlate with the near-surface tin dopant concentration, suggesting that these electroactive sites arise from near-surface tin enrichment.