http://www1.udel.edu/chem/polenova/PDF/Polyoxometalates/POMs_Catalysis_NMR_ChemRev1998.pdf

Catalysis by Heteropoly Acids and Multicomponent Polyoxometalates in Liquid-Phase Reactions

ion. The oxidative addition mechanism was originally proposed22i because of the lack of a strong rate dependence on polar factors and on the acidity of the medium. Later, however, the electrophilic substitution mechanism also was proposed. Recently, the oxidative addition mechanism was confirmed by investigations into the decomposition and protonolysis of alkylplatinum complexes, which are the reverse of alkane activation. There are two routes which operate in the decomposition of the dimethylplatinum(IV) complex Cs2Pt(CH3)2Cl4. The first route leads to chloride-induced reductive elimination and produces methyl chloride and methane. The second route leads to the formation of ethane. There is strong kinetic evidence that the ethane is produced by the decomposition of an ethylhydridoplatinum(IV) complex formed from the initial dimethylplatinum(IV) complex. In D2O-DCl, the ethane which is formed contains several D atoms and has practically the same multiple exchange parameter and distribution as does an ethane which has undergone platinum(II)-catalyzed H-D exchange with D2O. Moreover, ethyl chloride is formed competitively with H-D exchange in the presence of platinum(IV). From the principle of microscopic reversibility it follows that the same ethylhydridoplatinum(IV) complex is the intermediate in the reaction of ethane with platinum(II). Important results were obtained by Labinger and Bercaw62c in the investigation of the protonolysis mechanism of several alkylplatinum(II) complexes at low temperatures. These reactions are important because they could model the microscopic reverse of C-H activation by platinum(II) complexes. Alkylhydridoplatinum(IV) complexes were observed as intermediates in certain cases, such as when the complex (tmeda)Pt(CH2Ph)Cl or (tmeda)PtMe2 (tmeda ) N,N,N′,N′-tetramethylenediamine) was treated with HCl in CD2Cl2 or CD3OD, respectively. In some cases H-D exchange took place between the methyl groups on platinum and the, CD3OD prior to methane loss. On the basis of the kinetic results, a common mechanism was proposed to operate in all the reactions: (1) protonation of Pt(II) to generate an alkylhydridoplatinum(IV) intermediate, (2) dissociation of solvent or chloride to generate a cationic, fivecoordinate platinum(IV) species, (3) reductive C-H bond formation, producing a platinum(II) alkane σ-complex, and (4) loss of the alkane either through an associative or dissociative substitution pathway. These results implicate the presence of both alkane σ-complexes and alkylhydridoplatinum(IV) complexes as intermediates in the Pt(II)-induced C-H activation reactions. Thus, the first step in the alkane activation reaction is formation of a σ-complex with the alkane, which then undergoes oxidative addition to produce an alkylhydrido complex. Reversible interconversion of these intermediates, together with reversible deprotonation of the alkylhydridoplatinum(IV) complexes, leads to multiple H-D exchange

Activation of c-h bonds by metal complexes

UV-Visible ار راد ن .د TiO2 ( تیفرظ راون مان هب نورتکلا یاراد یژرنا زارت لماش VB و ) رگید زارت ی یژرنا اب ( ییاناسر راون مان هب نورتکلا زا یلاخ و رتلااب VB یم ) .دشاب ت ود نیا نیب یژرنا توافت یژرنا فاکش زار ، پگ دناب هدیمان یم .دوش هک ینامز زا نورتکلا لاقتنا VB هب VB یم ماجنا دریگ ، TiO2 اب ودح یژرنا بذج د ev 2 / 3 ، نورتکلا تفج کی دیلوت یم هرفح .دیامن و نورتکلا هرفح ی نا اب هدش دیلوت یم کرتشم حطس هب لاقت ثعاب دناوت شنکاو ماجنا اه یی ددرگ . TiO2 دربراک ،دراد یدایز یاه هلمج زا یم ناوت اوه یگدولآ هیفصت یارب (CO2) و بآ و ... نآ زا هدافتسا درک .

Advanced Nanoarchitectures for Solar Photocatalytic Applications

Ordered mesoporous materials in catalysis

The open literature concerning chemical and mechanistic aspects of the selective catalytic reduction of NO by ammonia (SCR process) on metal oxide catalysts is reviewed. Catalytic systems based on supported V2O5 (including the industrial TiO2-supported V2O5–WO3 and/or V2O5–MoO3 catalysts) and catalysts containing Fe2O3, CuO, MnOx and CrOx are considered. The results of spectroscopic studies of the adsorbed surface species, adsorption–desorption measurements, flow reactor and kinetic experiments are analyzed. The proposed reaction mechanisms are described and critically discussed. Points of convergence and of disagreement are underlined.

Chemical and mechanistic aspects of the selective catalytic reduction of NOx by ammonia over oxide catalysts: A review

When an SnO 2 element is impregnated with an aqueous solution of metal nitrate or acetate by coating with a brush and calcining at 773 K for 5 h, the element shows sensitivity to ppm-levels of CO 2 . Among the elements, the La 2 O 3 -loaded SnO 2 element is found to show promising sensing properties to CO 2 in dry air at 673 K, i.e., rather high sensitivity and quick response. The sensing properties depend on the operation temperature and the amount of La 2 O 3 loaded: the respective optima are 673 K and 4.2 wt.%. The sensitivity monotonically increases with the concentration of CO 2 in the range 0–2080 ppm.

CO2-sensing characteristics of SnO2 element modified by La2O3

Study of metal oxide catalysts by temperature programmed desorption. 2. Chemisorption of oxygen on copper(II) ion-exchanged Y-type zeolites

Synthesis of [PW9O37{Fe3-xNix(OAc)3}](9+x)− (x = predominantly 1 ) and oxidation catalysis by the catalyst precursor

Selective aldol reactions of acetals on mesoporous silica catalyst

Direct decomposition and selective reduction of nitrogen monoxide over copper ion-exchanged zeolite catalysts are proposed as new methods for removal of NO. The copper ion-exchanged ZSM-5 zeolite (Cu-Z) was the most active catalyst for decomposition of NO. The activity of Cu-Z zeolites increased with increase in the exchange level. The zeolites with copper ion-excange levels of 100% or more, which could be prepared by repeating ion exchange of the ZSM-5 zeolite using aqueous copper(II) acetate solution or addition of ammonia into the aqueous copper(II) nitrate solution, showed significantly high activity even in the presence of oxygen and at high GHSV region. It was clarified concerning Cu-Z, by using IR, ESR, phosphorescence, TPD, and CO adsorption measurements that (1) the Cu2+ ions exchanged into zeolite were reduced to Cu+ and/or Cu+-Cu+ through evacuation at elevated temperature, (2) after exposure to oxygen at 773K and subsequent evacuation, about 40% copper ions in zeolite existed as Cu+ ions, (3) the NO- species formed by adsorption of NO on Cu+ would be an intermediate in the NO decomposition, and (4) redox cycle of Cu+_??_Cu2+ in the zeolite is probably a key step to achieve the decomposition reaction. Selective reduction of NO by hydrocarbon in the presence of oxygen was first found by the authors and Cu-Z was remarkably effective for NO removal at temperatures as low as 523-673K. The activity for this selective reduction in NO+C3H6+O2 system was not poisoned very much by addition of SO2. The conversion into N2 was changed to 85% (773K) in the presence of SO2, from 100% in the absence of SO2, which is in contrast with the fact that the catalytic activity for direct decomposition NO was completely lost on adding the same amount of SO2. Furthermore, the reduction rate over Cu-Z at 573K was higher than those over H-zeolite and alumina catalysts at 723 and 773K, respectively, which have been reported to be active, after findings by the authors.

Masakazu Iwamoto

Papers

CO2-sensing characteristics of SnO2 element modified by La2O3

Study of metal oxide catalysts by temperature programmed desorption. 2. Chemisorption of oxygen on copper(II) ion-exchanged Y-type zeolites

Synthesis of [PW9O37{Fe3-xNix(OAc)3}](9+x)− (x = predominantly 1 ) and oxidation catalysis by the catalyst precursor

Selective aldol reactions of acetals on mesoporous silica catalyst

Removal of Nitrogen Monoxide over Copper Ion-exchanged Zeolite Catalysts