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Brewe, Dale L.

Publications and source records attributed to Brewe, Dale L..

Intervening Oxygen Enabled Magnetic Moment Modulation in Spinel Nanostructures

Oxygen vacancies and lattice oxygen on the surface of nanoparticles play crucial roles in the magnetism of transition metal oxides. A fundamental understanding of the interactions between the 2p orbitals of oxygen anions and the 3d orbitals of metal cations is of immense interest for applications due to specific electronic, magnetic, and chemical properties. The spinel nanostructures Co 3 O 4 ,Fe 3 O 4 , and CoFe 2 O 4 present a unique model to alter coordination and bonding due to d electrons and oxygen 2p states. We performed complementary experimental techniques and corresponding model calculations to show that the overall net magnetism differs significantly between the O 2 -rich and -deficient environments. It was found that in monometallic spinel oxides (e.g., Co 3 O 4 and Fe 3 O 4 ), the changes in the spin moment are relatively small (~0.08μ B per formula unit) compared to those in the bimetallic spinel oxide CoFe 2 O 4 (~0.40 μ B per formula unit). Finally, our study illustrates that the O 2 -rich/deficient conditions alter the exchange of O h sites and adjust the metal ion moments so as to impact the overall magnetism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrical and structural properties of VO 2 in an electric field

We examined the electrical and local structural properties of a VO 2 film at different electric fields using electrical resistance and x-ray absorption fine structure (XAFS) measurements at the V K edge in the temperature range of 30–100 °C. The T c value of the metal-to-insulator transition (MIT) during both heating and cooling decreases with electric field. When the electric field exceeds a certain value, the MIT becomes sharper due to Joule heating. Furthermore, the MIT, the structural phase transition (SPT), and the pre-edge peak transition of the VO 2 do not congruently occur at a uniform temperature. A metallic VO 2 is observed in only the rutile (or M2) symmetry. An electric field induces a substantial amount of conduction electrons in insulating VO 2 . Simultaneously measured resistance and XAFS reveal that Joule heating caused by an external electric field significantly affects the MIT and SPT of VO 2 .

36 MATERIALS SCIENCE↗

Conversion of cellulose to high-yield glucose in water over sulfonated mesoporous carbon fibers with optimized acidity

The hydrolysis of cellulose to high-yield glucose in water remains challenging owing to the limited acidity and substrate contact of sulfonated carbons. In this study, we report a unique sulfonated mesoporous carbon fiber with optimized acidity prepared by the pyrolysis of FeCl 3 -impregnated wipe fibers followed by acid treatment. The Bronsted acidity (especially for SO 3 H) was produced by sulfonation of the magnetic carbon fiber intermediate, while Lewis acidity originated from small Fe 3 O 4 nanoparticles and the remaining defects. The balanced Bronsted and Lewis acidity combined with hydrophilic functionalities was simultaneously tailored by varying the Fe/wipe fiber (WF) feed ratio and pyrolysis temperature to change the porous structure of the final catalysts. The elaborately fabricated MCF-SO 3 H-20-500 (20% Fe/WF feed ratio and pyrolysis at 500 degrees C) delivered 66.0% glucose yield as cellulose was completely converted. This is the highest glucose yield achieved by the hydrolysis of untreated cellulose in water over a sulfonated carbon catalyst. The optimized Bronsted and Lewis acidity was mainly responsible for the controlled conversion of cellulose to glucose, while the rich hydrophilic functionalities and superior mesoporous structure of the catalyst facilitated contact to cellulose and mass transfer. This investigation will open new avenues to design high-performance carbon sulfoacid catalysts toward cellulose hydrolysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗