Note: When clicking on a Digital Object Identifier (DOI) number, you will be taken to an external site maintained by the publisher.
Some full text articles may not yet be available without a charge during the embargo (administrative interval).
What is a DOI Number?
Some links on this page may take you to non-federal websites. Their policies may differ from this site.
-
The high bond dissociation energy of C–C σ-bonds presents a challenge to chemical conversions in organic synthesis, polymer degradation, and biomass conversion that require chemoselective C–C bond cleavage at room temperature. Dye-sensitized photoelectrochemical cells (DSPECs) incorporating molecular organic dyes could offer a means of using renewable solar energy to drive these types of energetically demanding chemoselective C–C bond cleavage reactions. This study reports the solar light-driven activation of a bicyclic aminoxyl mediator to achieve C–C bond cleavage in the aryl-ether linkage of a lignin model compound (LMC) at room temperature using a donor–π-conjugated bridge–acceptor (D–π–A) organic dye-based DSPEC system. Mesoporous TiO 2 photoanode surfaces modified with 5-[4-(diphenylamino)phenyl]thiophene-2-cyanoacrylic acid (DPTC) D–π–A organic dye were investigated along with a bicyclic aminoxyl radical mediator (9-azabicyclo[3,3,1]nonan-3-one-9-oxyl, KABNO) in solution with and without the presence of LMC. Photophysical studies of DPTC with KABNO showed intermolecular energy/electron transfer under 1 sun illumination (100 mW cm −2 ). Under illumination, the D–π–A type DPTC sensitized TiO 2 photoanodes facilitate the generation of the reactive oxoammonium species KABNO+ as a strong oxidizing agent, which is required to drive the oxidative C–C bond cleavage of LMC. The photoelectrochemical oxidative reaction in a complete DSPEC with KABNO afforded C–C bond cleavage products 2-(2-methoxyphenoxy)acrylaldehyde (94%) and 2,6-dimethoxy-1,4-benzoquinone (66%). This process provides a first report utilizing a D–π–A type organic dye in combination with a bicyclic nitroxyl radical mediator for heterogeneous photoelectrolytic oxidative cleavage of C–C σ-bonds, modeled on those found in lignin, at room temperature.more » « less
-
Using sunlight to produce hydrogen gas via photocatalytic water splitting is highly desirable for green energy harvesting and sustainability. In this work, Mn 2+ doped 1-dimensional (1D) CdS nanorods (NRs) with Pt tips ( i.e. , 1D Mn:CdS-Pt NRs) were synthesized for photocatalytic water splitting to generate hydrogen gas. The incorporation of Mn 2+ dopants inside the 1D CdS NRs with a significantly longer lifetime (∼ms) than that of host excitons (∼ns) facilitates charge separation; the electron transfer to metal Pt tips leads to enhanced photocatalytic activity in water splitting redox reactions. The as-synthesized Mn 2+ doped CdS NR-based photocatalyst generated an order of magnitude greater yield of hydrogen gas compared to the undoped CdS NR-based photocatalyst. The enhanced charge transport from the long lifetime excited state of Mn 2+ dopants in light harvesting semiconductor nanomaterials presents a new opportunity to increase the overall photocatalytic performance.more » « less
-
The all-solid-state battery is a promising alternative to conventional lithium-ion batteries that have reached the limit of their technological capabilities. The next-generation lithium-ion batteries are expected to be eco-friendly, long-lasting, and safe while demonstrating high energy density and providing ultrafast charging. These much-needed properties require significant efforts to uncover and utilize the chemical, morphological, and electrochemical properties of solid-state electrolytes and cathode nanocomposites. Here we report solid-state electrochemical cells based on lithium oxyhalide electrolyte that is produced by melt-casting. This method results in enhanced cathode/electrolyte interfaces that allow exceptionally high charging rates (>4000C) while maintaining the electrochemical stability of solid-state electrolyte in the presence of lithium metal anode and lithium iron phosphate-based cathode. The cells exhibit long cycle life (>1800 cycles at 100 °C) and offer a promising route to the next-generation all-solid-state battery technology.more » « less
An official website of the United States government

Full Text Available