The infrared spectral performance of the N x O y species observed on oxide surfaces [N2O, NO−, NO, (NO)2, N2O3, NO+, NO2 − (different nitro and nitrito anions), NO2, N2O4, N2O5, NO2, and NO3 − (bridged, bidentate, and monodentate nitrates)] is considered. The spectra of related compounds (N2, H-, and C-containing nitrogen oxo species, C─N species, NH x species) are also briefly discussed. Some guidelines for spectral identification of N x O y adspecies are proposed and the transformation of the nitrogen oxo species on catalyst surfaces are regarded.

Identification of Neutral and Charged N x O y Surface Species by IR Spectroscopy

Automotive catalytic converters: current status and some perspectives

Fluorine has received great attention in all fields of science. “Small atom with a big ego” was the title of the Symposium at the ACS meeting in San Francisco in 2000, where a number of the current scientific and industrial aspects of fluorine chemistry made possible by the small size and high electronegativity of the atom were discussed. This small atom has provided mankind with significant benefits in special products such as poly(tetrafluroethylene) (PTFE), freon, fluoro-liquid crystals, optical fiber, pharmaceutical and agrochemical compounds, and so on, all of which have their own unique properties that are otherwise difficult to obtain.1 For instance, at present, up to 30% of agrochemicals and 10% of pharmaceuticals currently used contain fluorine atoms. Therefore, organic fluorine compounds have received a great deal of interest and attention from the scientists involved in diverse fields of science and technology. Now, not only C-F bond formation but also selective C-F bond activation have become current subjects of active investigation from the viewpoint of effective synthesis of fluoroorganic compounds. The former is highlighted by designing a sophisticated fluorinating reagent for regioand stereocontrolled fluorination and developing versatile multifunctional and easily prepared building blocks. C-F bond formation has been treated extensively in several reviews2 and books.3 The latter is a subject that has been less explored but would be promising for selective defluorination of aliphatic fluorides, cross-coupling with aryl fluorides, and * To whom correspondence should be addressed. Phone: 81-78-803-5799. Fax: 81-78-803-5799. E-mail: amii@kobe-u.ac.jp and uneyamak@cc.okayamau.ac.jp. † Kobe University. ‡ Okayama University. Chem. Rev. 2009, 109, 2119–2183 2119

C-F bond activation in organic synthesis.

Research on the selective reduction of NOx with hydrocarbons under lean-burn conditions using non-zeolitic oxides and platinum group metal (PGM) catalysts has been critically reviewed. Alumina and silver-promoted alumina catalysts have been described in detail with particular emphasis on an analysis of the various reaction mechanisms that have been put forward in the literature. The influence of the nature of the reducing agent, and the preparation and structure of the catalysts have also been discussed and rationalised for several other oxide systems. It is concluded for non-zeolitic oxides that species that are strongly adsorbed on the surface, such as nitrates/nitrites and acetates, could be key intermediates in the formation of various reduced and oxidised species of nitrogen, the further reaction of which leads eventually to the formation of molecular nitrogen. For the platinum group metal catalysts, the different mechanisms that have been proposed in the literature have been critically assessed. It is concluded that although there is indirect, mainly spectroscopic, evidence for various reaction intermediates on the catalyst surface, it is difficult to confirm that any of these are involved in a critical mechanistic step because of a lack of a direct quantitative correlation between infrared and kinetic measurements. A simple mechanism which involves the dissociation of NO on a reduced metal surface to give N(ads) and O(ads), with subsequent desorption of N2 and N2O and removal of O(ads) by the reductant can explain many of the results with the platinum group metal catalysts, although an additional contribution from organo-nitro-type species may contribute to the overall NOx reduction activity with these catalysts. It is concluded, after the investigation of hundreds of catalyst formulations, that many of the fundamental questions relating to lean deNOx reactions have been addressed and the main boundary conditions have been established. It seems clear that catalysts with sufficient activity, selectivity or stability to satisfy the demanding conditions that appertain in automotive applications are still far away. The rapidly growing interest in NOx storage systems reflects this situation, and it now seems to be the case that acceptable direct NOx reduction catalysts may be very difficult to find for lean-burn applications.

A review of the selective reduction of NOx, with hydrocarbons under lean-burn conditions with non-zeolitic oxide and platinum group metal catalysts

Metal-mediated reductive hydrodehalogenation of organic halides.

The selective catalytic reduction of nitric oxide with propene and oxygen-containing organic compounds over several alumina-supported metal catalysts was investigated. Alumina-supported silver catalysts showed high activities in the presence of water and excess oxygen, while water vapor significantly decreased the activities of alumina and Co/Al2O3 which were highly active in the absence of water. It was also found that oxygen-containing organic compounds such as ethanol and acetone were more effective than propene in reducing nitric oxide over Ag/Al2O3 in the presence of water and excess oxygen.

Alumina-supported silver catalysts for the selective reduction of nitric oxide with propene and oxygen-containing organic compounds

An exhaust gas cleaner constituted by a first catalyst comprising a first porous inorganic oxide supporting an Ag component, a W component and a Pt component and optionally a second catalyst comprising a second porous inorganic oxide supporting a Pt component alone or in combination with a W component. The Ag component may include Ag and compounds thereof, the Pt component of the first and second catalysts may include Pt, Pd, Ru, Rh, Ir and Au, and the W component of the first and second catalysts may include W, V, Mn, Mo, Nb and Ta. The W component effectively catalyze the reduction of nitrogen oxides by ammonia to enhance the removal efficiency of the exhaust gas cleaner.

Exhaust gas cleaner and method for cleaning exhaust gas

The involvement of the reaction of surface nitrate [NO3−(ads)] species with different reductants (C3H6, C2H5OH and CH3OH) in the selective catalytic reduction of nitrogen oxides (NOx) over a Ag/Al2O3 catalyst
 has been studied by in situ
 diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy and temperature-programmed
 desorption (TPD). When an NO/O2 mixture was exposed to a Ag/Al2O3 catalyst at 150 °C, three kinds of nitrate species (bridging, monodentate and bidentate) were observed by DRIFT. The thermal stability of the monodentate NO3−(ads) species was higher than that of the bridging and bidentate NO3−(ads)
 species, which was confirmed by DRIFT and TPD measurements. The monodentate NO3−(ads) species reacted effectively with C2H5OH and CH3OH in the presence of O2 to form surface isocyanate [NCO(ads)] species at 250 °C, whereas the bridging and bidentate NO3−(ads) species reacted minimally. All NO3−(ads) species were
 largely unreactive with C3H6 in the presence of O2 at temperatures below 250 °C. On the other hand, the order of reactivity in the reduction of NOx at temperatures below 350 °C was in good agreement with that of
 both the reactivity of the monodentate NO3−(ads) species and the ease of NCO(a) formation (C2H5OH>CH3OH>C3H6). Based on these findings, the involvement of the reactivity of NO3−(ads) species and the formation of
 NCO(ads) species in the selective reduction of NOx are discussed.

Selective catalytic reduction of NOx with CH3OH, C2H5OH and C3H6 in the presence of O2 over Ag/Al2O3 catalyst: Role of surface nitrate species

Catalytic hydrodehalogenation of aromatic halides was carried out in an alcohol solution containing base compounds in the presence of carbon-supported noble metal catalysts. It was found that dechlorination of 1,2,4-trichlorobenzene to benzene effectively occurred in a 2-propanol solution of a base compound such as NaOH or KOH in the presence of Rh/C or Pd/C at temperatures below 65°C. When deuorium-labeled 2-propanol, CD3CD(OD)CD3, was used as a solvent, 1,2,4-trichlorobenzene was dechlorinated to give benzene containing D atoms with high yield, indicating that the hydrodechlorination reaction includes hydrogen-transfer from 2-propanol to chlorobenzenes. Iodo-, bromo- and fluoro-benzenes were also readily dehalogenated in the catalytic system.

Hydrogen-transfer hydrodehalogenation of aromatic halides with alcohols in the presence of noble metal catalysts

The effect of water vapor and SO2 on the selective reduction of nitric oxide over alumina-supported Ag, In, Ga, Sn, and Zn catalysts has been investigated. Water vapor and SO2 had large effect on the reactivity of propene and on the reduction of NO over those catalysts.

Tatsuo Miyadera

Papers

Alumina-supported silver catalysts for the selective reduction of nitric oxide with propene and oxygen-containing organic compounds

Exhaust gas cleaner and method for cleaning exhaust gas

Selective catalytic reduction of NOx with CH3OH, C2H5OH and C3H6 in the presence of O2 over Ag/Al2O3 catalyst: Role of surface nitrate species

Hydrogen-transfer hydrodehalogenation of aromatic halides with alcohols in the presence of noble metal catalysts

Alumina-supported Catalysts for the Selective Reduction of Nitric Oxide by Propene