Michelle Kidder

Characterization of Biochars Produced from Cornstovers for Soil Amendment

Through cation exchange capacity assay, nitrogen adsorption-desorption surface area measurements, scanning electron microscopic imaging, infrared spectra and elemental analyses, we characterized biochar materials produced from cornstover under two different pyrolysis conditions, fast pyrolysis at 450 °C and gasification at 700 °C. Our experimental results showed that the cation exchange capacity (CEC) of the fast-pyrolytic char is about twice as high as that of the gasification char as well as that of a standard soil sample. The CEC values correlate well with the increase in the ratios of the oxygen atoms to the carbon atoms (O:C ratios) in the biochar materials. The higher O:C ratio was consistent with the presence of more hydroxyl, carboxylate, and carbonyl groups in the fast pyrolysis char. These results show how control of biomass pyrolysis conditions can improve biochar properties for soil amendment and carbon sequestration. Since the CEC of the fast-pyrolytic cornstover char can be about double that of a standard soil sample, this type of biochar products would be suitable for improvement of soil properties such as CEC, and at the same time, can serve as a carbon sequestration agent.

Lab-in-a-Shell: Encapsulating Metal Clusters for Size Sieving Catalysis

Here we describe a lab-in-a-shell strategy for the preparation of multifunctional core-shell nanospheres consisting of a core of metal clusters and an outer microporous silica shell. Various metal clusters (e.g., Pd and Pt) were encapsulated and confined in the void space mediated by the entrapped polymer dots inside hollow silica nanospheres acting first as complexing agent for metal ions and additionally as encapsulator for clusters, limiting growth and suppressing the sintering. The Pd clusters encapsulated in hybrid core-shell structures exhibit exceptional size-selective catalysis in allylic oxidations of substrates with the same reactive site but different molecular size (cyclohexene ∼0.5 nm, cholesteryl acetate ∼1.91 nm). The solvent-free aerobic oxidation of diverse hydrocarbons and alcohols was further carried out to illustrate the benefits of such an architecture in catalysis. High activity, outstanding thermal stability and good recyclability were observed over the core-shell nanocatalyst.

Nonfunctionalized Polydimethyl Siloxane Superhydrophobic Surfaces Based on Hydrophobic−Hydrophilic Interactions

Superhydrophobic surfaces based on polydimethyl siloxane (PDMS) were fabricated using a 50:50 PDMS-poly(ethylene glycol) (PEG) blend. PDMS was mixed with PEG, and incomplete phase separation yielded a hierarchic structure. The phase-separated mixture was annealed at a temperature close to the crystallization temperature of the PEG. The PEG crystals were formed isothermally at the PDMS/PEG interface, leading to an engineered surface with PDMS spherulites. The resulting roughness of the surface was studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The PDMS spherulites, a few micrometers in diameter observed from SEM images, were found to have an undulated (rippled) surface with nanometer-sized features. The combination of micrometer- and nanometer-sized surface features created a fractal surface and increased the water contact angle (WCA) of PDMS more than 60°, resulting in a superhydrophobic PDMS surface with WCA of >160°. The active surface layer for the superhydrophobicity was approximately 100 μm thick, illustrating that the material had bulk superhydrophobicity compared to conventional fluorocarbon or fluorinated coated rough surfaces. Theoretical analysis of the fractal surface indicates that the constructed surface has a fractal dimension of 2.5, which corresponds to the Apollonian sphere packing.

Confinement effects on product selectivity in the pyrolysis of phenethyl phenyl ether in mesoporous silica

Pyrolysis of phenethyl phenyl ether confined in mesoporous silicas by covalent grafting results in significantly increased product selectivity compared with fluid phases.

Pyrolysis of Phenethyl Phenyl Ether Tethered in Mesoporous Silica. Effects of Confinement and Surface Spacer Molecules on Product Selectivity

There has been expanding interest in exploring porous metal oxides as a confining environment for organic molecules resulting in altered chemical and physical properties including chemical transformations. In this paper, we examine the pyrolysis behavior of phenethyl phenyl ether (PPE) confined in mesoporous silica by covalent tethers to the pore walls as a function of tether density and the presence of cotethered surface spacer molecules of varying structure (biphenyl, naphthyl, octyl, and hexadecyl). The PPE pyrolysis product selectivity, which is determined by two competitive free-radical pathways cycling through the two aliphatic radical intermediates (PhCH·CH(2)OPh and PhCH(2)CH·OPh), is shown to be significantly different from that measured in the liquid phase as well as for PPE tethered to the exterior surface of nonporous silica nanoparticles. Tailoring the pore surface with spacer molecules further alters the selectivity such that the PPE reaction channel involving a molecular rearrangement (O-C phenyl shift in PhCH(2)CH·OPh), which accounts for 25% of the products in the liquid phase, can be virtually eliminated under pore confinement conditions. The origin of this change in selectivity is discussed in the context of steric constraints on the rearrangement path inside the pores, surface and pore confinement effects, pore surface curvature, and hydrogen bonding of PPE with residual surface silanols supplemented by nitrogen physisorption data and molecular dynamics simulations.

Size tunable elemental copper nanoparticles: extracellular synthesis by thermoanaerobic bacteria and capping molecules

Bimodal sized elemental copper (Cu) nanoparticles (NPs) were synthesized from inexpensive oxidized copper salts by an extracellular metal-reduction process using anaerobic Thermoanaerobacter sp. X513 bacteria in aqueous solution. The bacteria nucleate NPs outside of the cell, and they control the Cu2+ reduction rate to form uniform crystallites with an average diameter of 1.75 ± 0.46 μm after 3 days incubation. To control the size and enhance the air stability of Cu NPs, the reaction mixtures were supplemented with nitrilotriacetic acid as a chelator, and the surfactant capping agents oleic acid, oleylamine, ascorbic acid, or L-cysteine. Time-dependent UV-visible absorption measurements and XPS studies indicated well-suspended, bimodal colloidal Cu NPs (70–150 and 5–10 nm) with extended air-stability up to 300 min and stable Cu NP film surfaces with 14% oxidation after 20 days. FTIR spectroscopy suggested that these capping agents were effectively adsorbed on the NP surface providing oxidation resistance under aqueous and dry conditions. Compared to previously reported Cu NP syntheses, this biological process substantially reduced the requirement for hazardous organic solvents and chemical reducing agents, while reducing the levels of Cu oxide impurities in the product. This process was highly reproducible and scalable from 0.01 to 1 L batches.

CO2 Capture from Ambient Air by Crystallization with a Guanidine Sorbent

Carbon capture and storage is an important strategy for stabilizing the increasing concentration of atmospheric CO2 and the global temperature. A possible approach toward reversing this trend and decreasing the atmospheric CO2 concentration is to remove the CO2 directly from air (direct air capture). Herein we report a simple aqueous guanidine sorbent that captures CO2 from ambient air and binds it as a crystalline carbonate salt by guanidinium hydrogen bonding. The resulting solid has very low aqueous solubility (Ksp =1.0(4)×10-8 ), which facilitates its separation from solution by filtration. The bound CO2 can be released by relatively mild heating of the crystals at 80-120 °C, which regenerates the guanidine sorbent quantitatively. Thus, this crystallization-based approach to CO2 separation from air requires minimal energy and chemical input, and offers the prospect for low-cost direct air capture technologies.

Oxygenation of Biochar for Enhanced Cation Exchange Capacity

This chapter reports a technological concept for producing a partially oxygenated biochar material that possesses enhanced cation-exchanging property by reaction of a biochar source with one or more oxygenating compounds in such a manner that the biochar material homogeneously acquires oxygen-containing cation-exchanging groups. This concept is based on our recent experimental finding that the O:C atomic ratio in biochar material correlates with its cation-exchange capacity. The technology is directed at biochar compositions and soil formulations containing the partially oxygenated biochar materials for soil amendment and carbon sequestration.

Final Report: Investigation of Catalytic Pathways for Lignin Breakdown into Monomers and Fuels

Lignin is a biopolymer that comprises up to 35% of woody biomass by dry weight. It is currently underutilized compared to cellulose and hemicellulose, the other two primary components of woody biomass. Lignin has an irregular structure of methoxylated aromatic groups linked by a suite of ether and alkyl bonds which makes it difficult to degrade selectively. However, the aromatic components of lignin also make it promising as a base material for the production of aromatic fuel additives and cyclic chemical feed stocks such as styrene, benzene, and cyclohexanol. Our laboratory research focused on three methods to selectively cleave and deoxygenate purified lignin under mild conditions: acidolysis, hydrogenation and electrocatalysis. (1) Acidolysis using boron tribromide was undertaken in CH2Cl2 at room temperature. (2) Hydrogenation was carried out by dissolving lignin and a rhodium catalyst in 1:1 water:methoxyethanol under a 1 atm H2 environment. (3) Electrochemical conversion of lignin dissolved in a solution of 1M NaOH(aq) was carried out at a catalytic palladium cathode using hydrogen from the electrolysis of water. In all of the experiments, the lignin degradation products were identified and quantified by gas chromatography mass spectroscopy and flame ionization detection. Yields were low, but this may have reflected the difficulty in recovering the various fractions after conversion. Acidolysis resulted in under 1% yield of bromocyclohexanes. The homogeneous hydrogenation of lignin showed fragmentation into monomers, while the electrocatalytic hydrogenation showed production of polyaromatic hydrocarbons and substituted benzenes. In addition to the experiments, promising industrial scale pathways for the conversion of lignin were assessed. Three conversion methods were compared based on their material and energy inputs and proposed improvements using better catalyst and process technology. A variety of areas were noted as needing further experimental and theoretical effort to increase the feasibility of lignin conversion to fuels. In particular, the thermodynamics of hydrogen needed for the conversion of lignin played an important role in the feasibility of the process.

In situ capping for size control of monochalcogenide (ZnS, CdS and SnS) nanocrystals produced by anaerobic metal-reducing bacteria

Metal monochalcogenide quantum dot nanocrystals of ZnS, CdS and SnS were prepared by anaerobic, metal-reducing bacteria using in situ capping by oleic acid or oleylamine. The capping agent preferentially adsorbs on the surface of the nanocrystal, suppressing the growth process in the early stages, thus leading to production of nanocrystals with a diameter of less than 5 nm.