Junjun Shan

Efficient removal of pathogenic bacteria and viruses by multifunctional amine-modified magnetic nanoparticles

A novel amine-functionalized magnetic Fe3O4-SiO2-NH2 nanoparticle was prepared by layer-by-layer method and used for rapid removal of both pathogenic bacteria and viruses from water. The nanoparticles were characterized by TEM, EDS, XRD, XPS, FT-IR, BET surface analysis, magnetic property tests and zeta-potential measurements, respectively, which demonstrated its well-defined core-shell structures and strong magnetic responsivity. Pathogenic bacteria and viruses are often needed to be removed conveniently because of a lot of co-existing conditions. The amine-modified nanoparticles we prepared were attractive for capturing a wide range of pathogens including not only bacteriophage f2 and virus (Poliovirus-1), but also various bacteria such as S. aureus, E. coli O157:H7, P. aeruginosa, Salmonella, and B. subtilis. Using as-prepared amine-functionalized MNPs as absorbent, the nonspecific removal efficiency of E. coli O157:H7 or virus was more than 97.39%, while it is only 29.8% with Fe3O4-SiO2 particles. From joint removal test of bacteria and virus, there are over 95.03% harmful E. coli O157:H7 that can be removed from mixed solution with polyclonal anti-E. coli O157:H7 antibody modified nanoparticles. Moreover, the synergy effective mechanism has also been suggested.

Restructuring transition metal oxide nanorods for 100% selectivity in reduction of nitric oxide with carbon monoxide.

Transition metal oxide is one of the main categories of heterogeneous catalysts. They exhibit multiple phases and oxidation states. Typically, they are prepared and/or synthesized in solution or by vapor deposition. Here we report that a controlled reaction, in a gaseous environment, after synthesis can restructure the as-synthesized transition metal oxide nanorods into a new catalytic phase. Co3O4 nanorods with a preferentially exposed (110) surface can be restructured into nonstoichiometric CoO1-x nanorods. Structure and surface chemistry during the process were tracked with ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and environmental transmission electron microscopy (E-TEM). The restructured nanorods are highly active in reducing NO with CO, with 100% selectivity for the formation of N2 in temperatures of 250-520 °C. AP-XPS and E-TEM studies revealed the nonstoichiometric CoO1-x nanorods with a rock-salt structure as the active phase responsible for the 100% selectivity. This study suggests a route to generate new oxide catalysts.

Conversion of Methane to Methanol with a Bent Mono(μ-oxo)dinickel Anchored on the Internal Surfaces of Micropores

The oxidation of methane to methanol is a pathway to utilizing this relatively abundant, inexpensive energy resource. Here we report a new catalyst, bent mono(μ-oxo)dinickel anchored on an internal surface of micropores,which is active for direct oxidation. It is synthesized from the direct loading of a nickel precursor to the internal surface of micropores of ZSM5 following activation in O2. Ni 2p3/2 of this bent mono(μ-oxo)dinickel species formed on the internal surface of ZSM5 exhibits a unique photoemission feature, which distinguishes the mono(μ-oxo)dinickel from NiO nanoparticles. The formation of the mono(μ-oxo)dinickel species was confirmed with X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). This mono(μ-oxo)dinickel species is active for the direct oxidation of methane to methanol under the mild condition of a temperature as low as 150 °C in CH4 at 1 bar. In-situ studies using UV-vis, XANES, and EXAFS suggest that this bent mono(μ-oxo)dinickel species is the active site for the direct oxidation of methane to methanol. The energy barrier of this direct oxidation of methane is 83.2 kJ/mol.

Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts

An efficient and direct method of catalytic conversion of methane to liquid methanol and other oxygenates would be of considerable practical value. However, it remains an unsolved problem in catalysis, as typically it involves expensive or corrosive oxidants or reaction media that are not amenable to commercialization. Although methane can be directly converted to methanol using molecular oxygen under mild conditions in the gas phase, the process is either stoichiometric (and therefore requires a water extraction step) or is too slow and low-yielding to be practical. Methane could, in principle, also be transformed through direct oxidative carbonylation to acetic acid, which is commercially obtained through methane steam reforming, methanol synthesis, and subsequent methanol carbonylation on homogeneous catalysts. However, an effective catalyst for the direct carbonylation of methane to acetic acid, which might enable the economical small-scale utilization of natural gas that is currently flared or stranded, has not yet been reported. Here we show that mononuclear rhodium species, anchored on a zeolite or titanium dioxide support suspended in aqueous solution, catalyse the direct conversion of methane to methanol and acetic acid, using oxygen and carbon monoxide under mild conditions. We find that the two products form through independent pathways, which allows us to tune the conversion: three-hour-long batch-reactor tests conducted at 150 degrees Celsius, using either the zeolite-supported or the titanium-dioxide-supported catalyst, yield around 22,000 micromoles of acetic acid per gram of catalyst, or around 230 micromoles of methanol per gram of catalyst, respectively, with selectivities of 60–100 per cent. We anticipate that these unusually high activities, despite still being too low for commercial application, may guide the development of optimized catalysts and practical processes for the direct conversion of methane to methanol, acetic acid and other useful chemicals.

Employing a cylindrical single crystal in gas-surface dynamics

We describe the use of a polished, hollow cylindrical nickel single crystal to study effects of step edges on adsorption and desorption of gas phase molecules. The crystal is held in an ultra-high vacuum apparatus by a crystal holder that provides axial rotation about a [100] direction, and a crystal temperature range of 89 to 1100 K. A microchannel plate-based low energy electron diffraction/retarding field Auger electron spectrometer (AES) apparatus identifies surface structures present on the outer surface of the cylinder, while a separate double pass cylindrical mirror analyzer AES verifies surface cleanliness. A supersonic molecular beam, skimmed by a rectangular slot, impinges molecules on a narrow longitudinal strip of the surface. Here, we use the King and Wells technique to demonstrate how surface structure influences the dissociation probability of deuterium at various kinetic energies. Finally, we introduce spatially-resolved temperature programmed desorption from areas exposed to the supersonic molecular beam to show how surface structures influence desorption features.

Identification of Hydroxyl on Ni(111)

Hydroxyl (OH) is identified and characterized on the Ni(111) surface by high-resolution electron energy loss spectroscopy. We find clear evidence of stretching, bending, and translational modes that differ significantly from modes observed for H(2)O and O on Ni(111). Hydroxyl may be produced from water by two different methods. Annealing of water co-adsorbed with atomic oxygen at 85 K to above 170 K leads to the formation of OH with simultaneous desorption of excess water. Pure water layers treated in the same fashion show no dissociation. However, the exposure of pure water to 20 eV electrons at temperatures below 120 K produces OH in the presence of adsorbed H(2)O. In combination with temperature-programmed desorption studies, we show that the OH groups recombine between 180 and 240 K to form O and immediately desorbing H(2)O. The lack of influence of co-adsorbed H(2)O at 85 K on the O-H stretching mode indicates that OH does not participate in a hydrogen-bonding network.

Palladium–gold single atom alloy catalysts for liquid phase selective hydrogenation of 1-hexyne

Silica supported and unsupported PdAu single atom alloys (SAAs) were investigated for the selective hydrogenation of 1-hexyne to hexenes under mild conditions. The catalysts were prepared by adding a trace amount of Pd (0.4 at%) into the surface of pre-formed Au nanoparticles through a sequential reduction method. TEM and XRD analyses indicate the formation of PdAu nanoparticles and ATR-IR confirms the single atom dispersion of Pd in the Au matrix. In time-resolved batch reactor studies, we found that the Pd single atoms improved the hydrogenation activity of Au by nearly 10-fold but did not decrease the high selectivity to partial hydrogenation products. The enhanced reactivity is attributed to the Pd single atoms (isolated Pd atoms in the Au surface) facilitating molecular hydrogen dissociation leading to the availability of weakly bound atomic hydrogen on the otherwise inert gold surface. Higher than 85% selectivity to hexenes was observed, which is significantly greater than that of monometallic Pd catalysts. Model catalyst studies were conducted to investigate the formation and reactivity of the Pd/Au(111) SAAs. Scanning tunneling microscopy of Pd/Au(111) surfaces confirms the formation of PdAu single atom alloys at low Pd coverage with the Pd preferentially located in the vicinity of the herringbone elbows of the reconstructed Au(111) surface. Temperature-programmed desorption experiments confirm that single Pd atom sites dissociate hydrogen and bind both CO and H atoms more weakly as compared to extended Pd surfaces.

Sample Preparation and Analysis of Aggregated ‘Single Atom Alloy’ Nanoparticles by Atom Probe Tomography

1. Chemical Physics of Materials and Catalysis, Université libre de Bruxelles, 1050 Brussels, Belgium 2. John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge MA, USA 3. Department of Chemistry and Chemical Biology, Harvard University, Cambridge MA, USA 4. Center for Nanoscale Systems, Harvard University, Cambridge MA, USA 5. Department of Chemical and Biological Engineering, Tufts University, Medford MA, USA

Atomic-scale Characterization of Restructured PtCu Nanocubes

Bimetallic nanoparticles are of increasing interest due to the mutual influence of different neighboring atoms that leads to catalytic behavior different than that of a monometallic cluster[1]. The catalytic properties of these materials are dependent on the catalyst atoms at the edge and/or corner[2], i.e., surface of the nanoparticle. Motivated by previous studies [3,4] resulting to surface compositional change of bimetallic catalyst through metal segregation and reconstruction; post-synthesis reaction in the gas phase with ambient pressure x-ray photoelectron spectroscopy (AP-XPS) was used to tune the composition of two types of PtCu nanocubes(NCs) with different surfaces. Here we have used microscopy and spectroscopy techniques to provide direct evidence of atomic-scale elemental distributions within the NCs post-synthesis gas reactions.