Single atom hot-spots at Au-Pd nanoalloys for electrocatalytic H2O2 production

A novel strategy to direct the oxygen reduction reaction to preferentially produce H(2)O(2) is formulated and evaluated. The approach combines the inertness of Au nanoparticles toward oxidation, with the improved O(2) sticking probability of isolated transition metal "guest" atoms embedded in the Au "host". DFT modeling was employed to screen for the best alloy candidates. Modeling indicates that isolated alloying atoms of Pd, Pt, or Rh placed within the Au surface should enhance the H(2)O(2) production relative to pure Au. Consequently, Au(1-x)Pd(x) nanoalloys with variable Pd content supported on Vulcan XC-72 were prepared to investigate the predicted selectivity toward H(2)O(2) production for Au alloyed with Pd. It is demonstrated that increasing the Pd concentration to 8% leads to an increase of the electrocatalytic H(2)O(2) production selectivity up to nearly 95%, when the nanoparticles are placed in an environment compatible with that of a proton exchange membrane. Further increase of Pd content leads to a drop in H(2)O(2) selectivity, to below 10% for x = 0.5. It is proposed that the enhancement in H(2)O(2) selectivity is caused by the presence of individual surface Pd atoms surrounded by gold, whereas surface ensembles of contiguous Pd atoms support H(2)O formation. The results are discussed in the context of exergonic electrocatalytic H(2)O(2) synthesis in Polymer Electrolyte Fuel Cells for the simultaneous cogeneration of chemicals and electricity, the latter a credit to production costs.     

Anionic polymerization initiators containing protected functional groups. II

An organolithium reagent substituted with a primary amine-protecting group [i.e.,? N(TMS)₂] has been prepared and used to polymerize 1,3-butadiene and isoprene. A method is described for converting the resulting? N(TMS)₂-containing polydienes into? NH₂-containing polymers. Both ? N(TMS)₂- and ? NH₂-terminated polydienes have been characterized with regard to microstructure, M _n, and M _w/M _n data, as well as qualitative and quantitative end-group analyses. The described preparative procedures represent a convenient route to the elusive primary amine-terminated polydienes.     

Effect of alkoxides on chain termination and chain transfer of sodium-catalyzed polybutadiene

The reaction of butadiene with n-butylsodium or metal alkoxide-modified n-butylsodium was studied. A loss of “live ends” was observed when the polymerization of butadiene-1,3 with n-butylsodium was conducted in hexane solvent. This occurs, presumably, by elimination of NaH or Na metal in the allylic system. Similar results were obtained when the polymerization was carried out in the presence of sodium-tert-butoxide-modified n-butylsodium. However, the modification of n-butylsodium by lithium or potassium tert-butoxide in the butadiene-1,3 polymerization showed no loss of live ends for a period of two weeks. The results and an explanation are discussed.     

Metalation of unsaturated polymers by using activated organolithium compounds and the formation of graft copolymers. II

Polybutadiene was successfully metalated by use of tert-butyllithium activated with alkoxides of Group I metals without chain degradation. The metalated polymer was grafted with styrene and 1,3-butadiene to give novel graft copolymers of varying microstructure. This metalating system was found to be highly efficient; however, its catalyst effectiveness is less than that of organolithium-TMEDA metalation agent.     

Anionic polymerization initiators containing protected functional groups and functionally terminated diene polymers

Organolithium reagents substituted with hydroxyl-carrying mixed acetals (i.e., tetra-hydropyranyl and α-ethoxyethyl ethers) have been prepared in high yields and used to polymerize 1,3-butadiene to various acetal-terminated polybutadiene polymers. A method is described for converting acetal-containing polymers into hydroxyl-containing polymers. The polybutadienes have been characterized with regard to endgroup types, quantitative functionalities, molecular weights, molecular weight distributions, and microstructures. Dihydroxyl terminated polymers are prepared anionically in the absence of gel. Such materials are more suitable from the standpoint of f (OH) and M?_w/M?_n for chain extension studies than are prepolymers prepared by radical methods.     

Anionic polymerization to high vinyl polybutadiene

1,3-Butadiene was polymerized anionically to polybutadiene which contained up to 100% 1,2-addition product. The atactic 100% 1,2-polybutadiene was prepared with n-butyllithium modified with bis piperidino ethane. The polymerization was done in hexane solvent at ?5 to +20°C polymerization temperature.     

Temperature and concentration effects on polar-modified alkyllithium polymerizations and copolymerizations

Addition of polar modifiers to alkyllithium-initiated homopolymerizations of butadiene causes substantial changes in the microstructure of the polymers produced. These changes are shown to depend not only on the concentration of modifier, but also on the polymerization temperature. The combined effects of modifier concentration and reaction temperature have been considered, and a method is presented for quickly determining the proper conditions for preparation of a polybutadiene of any 1,2-microstructure within a range of 10–80%. It is also shown that in anionic polar-modified copolymerizations of butadiene–styrene, the reaction temperature is again critical. Within a certain concentration range of modifier, the temperature will influence the rate of styrene incorporation or the randomness of styrene units in the resulting copolymers.     

Microstructure of polybutadiene catalyzed by alkali metal tert-butoxides and n-butylsodium. II.

A polybutadiene of high molecular weight was prepared in hydrocarbon solvent by using n-BuNa–tert-BuOM (M = Li, K) as a polymerization initiator. The microstructure of this polymer varied from 35 to 76% of 1,2 content, depending on the type of modifiers. The kinetics of polymerization was not studied, primarily due to the heterogeneous nature of the catalyst. However, other variables, such as the catalyst concentration and temperature, have been studied. The results and mechanistic implications are discussed.     

Study of free volume in high-vinyl polybutadiene/cis-polyisoprene blends using positron annihilation spectroscopy

High-Vinyl Polybutadiene (HVBD)/cis-Polyisoprene (CPI) blends were characterized by Differential Scanning Calorimetry (DSC) and Positron Annihilation Lifetime Spectroscopy (PALS). A single DSC glass transition temperature T_g is observed, whose composition dependence strongly deviates from additivity, and shows an apparent cusp when the weight fraction of HVBD ≈ 0.75. The free-volume hole size, V_h, and the scaled fractional free volume, h_ps/C, = I₃V_h were determined by PALS from the orthopositronium (o-Ps) intensities, I₃, and lifetimes, τ₃, over a temperature range encompassing T_g and the temperature at which “positronium bubble” formation occurs. In the glass, V_h and h_ps/C are smaller for CPI than for HVBD, but the thermal expansion coefficient for hole volume, α_f, is larger in the melt for CPI than for HVBD; thus, an iso-hole volume temperature occurs in these blends at T_iso ≈ −34°C. Above and below T_iso, V_h and h_ps/C each show a negative departure from additivity. A quantitative interpretation of the cusp in the composition dependence of T_g can be obtained, via a modified analysis of Kovacs, using free-volume quantities from PALS, with the ratio of scaling constants C_CPI/C_HVBD as an adjustable parameter. At high temperatures, the positron bubble size is smaller in CPI than in HVBD. This agrees with the observation that the thermal expansivity of hole volume, and, hence the internal pressure are larger in the equilibrium melt of CPI. The effect of e⁺-irradiation on the o-Ps intensity was investigated. I₃ decreases more rapidly in the melt as T → T_g, and then more slowly in the glass, suggesting that the effect is due to trapping of radical or ionic species which inhibit o-Ps formation. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 861–871, 1998     

Nonquiescent relaxation in entangled polymer liquids after step shear

Large step shear experiments revealed through particle tracking velocimetry that entangled polymeric liquids display either internal macroscopic movements upon shear cessation or rupturelike behavior during shear. Visible inhomogeneous motions were detected in five samples with the number of entanglements per chain ranging from 20 to 130 at amplitudes of step strain as low as 135%.