We synthesized uniform-sized nanorods of transition metal phosphides from the thermal decomposition of continuously delivered metal-phosphine complexes using a syringe pump. MnP nanorods with dimensions of 8 nm x 16 nm and 6 nm x 22 nm sized were synthesized by the thermal decomposition of Mn-TOP complex, which was prepared from the reaction of Mn(2)(CO)(10) and tri-n-octylphosphine (TOP), using a syringe pump with constant injection rates of 10 and 20 mL/h, respectively. When Co-TOP complex, which was prepared from the reaction of cobalt acetylacetonate and TOP, was reacted in a mixture solvent composed of octyl ether and hexadecylamine at 300 degrees C using a syringe pump, uniform 2.5 nm x 20 nm sized Co(2)P nanorods were generated. When cobaltocene was employed as a precursor, uniform Co(2)P nanorods with 5 nm x 15 nm were obtained. When Fe-TOP complex was added to trioctylphosphine oxide (TOPO) at 360 degrees C using a syringe pump and then allowed to age at 360 degrees C for 30 min, uniform-sized FeP nanorods with an average dimension of 12 nm x 500 nm were produced. Nickel phosphide (Ni(2)P) nanorods with 4 nm x 8 nm were synthesized successfully by thermally decomposing the Ni-TOP complex, which was synthesized by reacting acetylacetonate [Ni(acac)(2)] and TOP. We measured the magnetic properties of these nanorods, and some of the nanorods exhibited different magnetic characteristics compared to the bulk counterparts.

Magnetic nanoparticles that can be transported in subsurface reservoirs at high salinities and temperatures are expected to have a major impact on enhanced oil recovery, carbon dioxide sequestration, and electromagnetic imaging. Herein we report a rare example of steric stabilization of iron oxide (IO) nanoparticles (NPs) grafted with poly(2-acrylamido-2-methylpropanesulfonate-co-acrylic acid) (poly(AMPS-co-AA)) that not only display colloidal stability in standard American Petroleum Institute (API) brine (8% NaCl + 2% CaCl2 by weight) at 90 °C for 1 month but also resist undesirable adsorption on silica surfaces (0.4% monolayer NPs). Because the AMPS groups interacted weakly with Ca(2+), they were sufficiently well solvated to provide steric stabilization. The PAA groups, in contrast, enabled covalent grafting of the poly(AMPS-co-AA) chains to amine-functionalized IO NPs via formation of amide bonds and prevented polymer desorption even after a 40,000-fold dilution. The aforementioned methodology may be readily adapted to stabilize a variety of other functional inorganic and organic NPs at high salinities and temperatures.

We developed facile synthetic procedures to produce monodisperse palladium nanoparticles stabilized with various phosphine ligands by a better understanding of their coordination chemistry. Compared to small sized phosphines such as triphenylphosphine (TPP), trioctylphosphine (TOP) showed weaker coordination ability to palladium nanoparticles. This result was ascertained based on the 31 P NMR spectroscopic results of in situ generated molecular palladium complexes. Since TOP acts as a more efficient surfactant in the preparation of high quality monodisperse palladium nanoparticles than smaller sized phosphines, we conducted surfactant exchange reactions of TOP-stabilized palladium nanoparticles in order to produce monodisperse palladium nanoparticles stabilized with various other phosphines. These monodisperse nanoparticles include monodisperse Pd nanoparticles stabilized with chiral ligands and water-dispersable Pd nanoparticles.

Nanoparticles (diameter of approximately 5 to 50 nm) easily pass through typical pore throats in reservoirs, but physicochemical attraction between nanoparticles and pore walls may still lead to significant retention. We conducted an extensive series of nanoparticle-transport experiments in core plugs and in columns packed with crushed sedimentary rock, systematically varying flow rate, type of nanoparticle, injection-dispersion concentration, and porous-medium properties. Effluent-nanoparticle-concentration histories were measured with fine resolution in time, enabling the evaluation of nanoparticle adsorption in the columns during slug injection and post-flushes. We also applied this analysis to nanoparticle-transport experiments reported in the literature.Our analysis suggests that nanoparticles undergo both reversible and irreversible adsorption. Effluent-nanoparticle concentration reaches the injection concentration during slug injection, indicating the existence of an adsorption capacity. Experiments with a variety of nanoparticles and porous media yield a wide range of adsorption capacities (from 10 -5 to 10 1 mg/g for nanoparticles and rock, respectively) and also a wide range of proportions of reversible and irreversible adsorption. Reversible-and irreversible-adsorption sites are distinct and interact with nanoparticles independently. The adsorption capacities are typically much smaller than monolayer coverage. Their values depend not only on the type of nanoparticle and porous media, but also on the operating conditions, such as injection concentration and flow rate.