Catalysis for the valorization of exhaust carbon: from CO2 to chemicals, materials, and fuels. technological use of CO2.

A surface science perspective on TiO2 photocatalysis

Keywords: Fragmentation Chain-Transfer ; Self-Assembled Monolayers ; Walled Carbon Nanotubes ; Well-Defined Polymer ; Nitroxide-Mediated Polymerization ; Block-Copolymer Brushes ; Poly(Methyl Methacrylate) Brushes ; Transfer Raft Polymerization ; Quartz-Crystal Microbalance ; Poly(Acrylic Acid) Brushes Reference EPFL-REVIEW-148464doi:10.1021/cr900045aView record in Web of Science Record created on 2010-04-23, modified on 2017-05-10

Polymer Brushes via Surface-Initiated Controlled Radical Polymerization: Synthesis, Characterization, Properties, and Applications

Photoreduction of CO2 into sustainable and green solar fuels is generally believed to be an appealing solution to simultaneously overcome both environmental problems and energy crisis. The low selectivity of challenging multi-electron CO2 photoreduction reactions makes it one of the holy grails in heterogeneous photocatalysis. This Review highlights the important roles of cocatalysts in selective photocatalytic CO2 reduction into solar fuels using semiconductor catalysts. A special emphasis in this review is placed on the key role, design considerations and modification strategies of cocatalysts for CO2 photoreduction. Various cocatalysts, such as the biomimetic, metal-based, metal-free, and multifunctional ones, and their selectivity for CO2 photoreduction are summarized and discussed, along with the recent advances in this area. This Review provides useful information for the design of highly selective cocatalysts for photo(electro)reduction and electroreduction of CO2 and complements the existing reviews on various semiconductor photocatalysts.

Cocatalysts for Selective Photoreduction of CO2 into Solar Fuels.

Hydrogen has been hailed as a clean and sustainable alternative to finite fossil fuels in many energy systems. Water splitting is an important method for hydrogen production in high purity and large quantities. To accelerate the hydrogen evolution reaction (HER) rate, it is highly necessary to develop high efficiency catalysts and to select a proper electrolyte. Herein, the performances of non-noble metal-based carbon composites under various pH values (acid, alkaline and neutral media) for HER in terms of catalyst synthesis, structure and molecular design are systematically discussed. A detailed analysis of the structure-activity-pH correlations in the HER process gives an insight on the origin of the pH-dependence for HER, and provide guidance for future HER mechanism studies on non-noble metal-based carbon composites. Furthermore, this Review gives a fresh impetus to rational design of high-performance noble-metal-free composites catalysts and guide researchers to employ the established electrocatalysts in proper water electrolysis technologies.

Non-Noble Metal-based Carbon Composites in Hydrogen Evolution Reaction: Fundamentals to Applications.

Monomethylmercury (MeHg) in fish from freshwater, estuarine, and marine environments is a major global environmental issue. Mercury levels in biota are mainly controlled by the methylation of inorganic mercuric mercury (HgII) to MeHg in water, sediments, and soils. There is, however, a knowledge gap concerning the mechanisms and rates of methylation of specific geochemical HgII species. Such information is crucial for a better understanding of variations in MeHg concentrations among ecosystems and, in particular, for predicting the outcome of currently proposed measures to mitigate mercury emissions and reduce MeHg concentrations in fish. To fill this knowledge gap we propose an experimental approach using HgII isotope tracers, with defined and geochemically important adsorbed and solid HgII forms in sediments, to study MeHg formation. We report HgII methylation rate constants, km, in estuarine sediments which span over 2 orders of magnitude depending on chemical form of added tracer: metacinnabar (β-201H...

Mercury Methylation Rates for Geochemically Relevant HgII Species in Sediments

Finding an abundant and cost-effective electrocatalyst for the hydrogen evolu-tion reaction (HER) is crucial for a global production of hydrogen from water electrolysis. This work reports an except ...

Stabilizing Active Edge Sites in Semicrystalline Molybdenum Sulfide by Anchorage on Nitrogen‐Doped Carbon Nanotubes for Hydrogen Evolution Reaction

Nanostructured porous tungsten oxide materials were synthesized by the means of electrochemical etching (anodization) of tungsten foils in aqueous NaF electrolyte. Formation of the sub-micrometer size mesoporous particles has been achieved by infiltrating the pores with water. The obtained colloidal anodic tungsten oxide dispersions have been used to fabricate resistive WO3 gas sensors by drop casting the sub-micrometer size mesoporous particles between Pt electrodes on Si/SiO2 substrate followed by calcination at 400 °C in air for 2 h. The synthesized WO3 films show slightly nonlinear current–voltage characteristics with strong thermally activated carrier transport behavior measured at temperatures between −20 °C and 280 °C. Gas response measurements carried out in CO, H2, NO and O2 analytes (concentration from 1 to 640 ppm) in air as well as in Ar buffers (O2 only in Ar) exhibited a rapid change of sensor conductance for each gas and showed pronounced response towards H2 and NO in Ar and air, respectively. The response of the sensors was dependent on temperature and yielded highest values between 170 °C and 220 °C.

Gas sensors based on anodic tungsten oxide

The mechanism of adsorption of long-chain alkylamines at pH 6−7 onto quartz was studied using FTIR and XPS spectroscopy. The spectroscopic data were correlated with ζ potential and Hallimond flotation results. For the first time it was shown that (1) amine cation in the first monolayer is H-bonded with surface silanol group and this H-bond becomes stronger after the break in the adsorption characteristics (isotherm, ζ potential, floatability); (2) at the break the origin of the adsorbed amine species changes qualitatively, and along with alkylammonium ion attached to deprotonated silanol group, molecular amine appears at the surface and, as a result, monolayer thick patches of well-oriented and densely packed adsorbed amine species form rendering the surface highly hydrophobic; and (3) at higher amine concentration, bulk precipitation of molecular amine takes place. The counterion was found to influence both these steps. A model of successive two-dimensional and three-dimensional precipitation was suggest...

Andrey Shchukarev

Papers

Mercury Methylation Rates for Geochemically Relevant HgII Species in Sediments

Stabilizing Active Edge Sites in Semicrystalline Molybdenum Sulfide by Anchorage on Nitrogen‐Doped Carbon Nanotubes for Hydrogen Evolution Reaction

Gas sensors based on anodic tungsten oxide

Mechanism of Adsorption of Long-Chain Alkylamines on Silicates: A Spectroscopic Study. 2. Albite

XPS spectra and electronic structure of Group IA sulfates