Guangsheng Guo

Controlled Generation of Uniform Spherical LaMnO3, LaCoO3, Mn2O3, and Co3O4 Nanoparticles and Their High Catalytic Performance for Carbon Monoxide and Toluene Oxidation

Uniform hollow spherical rhombohedral LaMO3 and solid spherical cubic MOx (M = Mn and Co) NPs were fabricated using the PMMA-templating strategy. Hollow spherical LaMO3 and solid spherical MOx NPs possessed surface areas of 21-33 and 21-24 m(2)/g, respectively. There were larger amounts of surface-adsorbed oxygen species and better low-temperature reducibility on/of the hollow spherical LaMO3 samples than on/of the solid spherical MOx samples. Hollow spherical LaMO3 and solid spherical MOx samples outperformed their nanosized counterparts for oxidation of CO and toluene, with the best catalytic activity being achieved over the solid spherical Co3O4 sample for CO oxidation (T50% = 81 °C and T90% = 109 °C) at space velocity = 10,000 mL/(g h) and the hollow spherical LaCoO3 sample for toluene oxidation (T50% = 220 °C and T90% = 237 °C) at space velocity = 20,000 mL/(g h). It is concluded that the higher surface areas and oxygen adspecies concentrations and better low-temperature reducibility are responsible for the excellent catalytic performance of the hollow spherical LaCoO3 and solid spherical Co3O4 NPs. We believe that the PMMA-templating strategy provides an effective route to prepare uniform perovskite-type oxide and transition-metal oxide NPs.

Preparation and high catalytic performance of Au/3DOM Mn2O3 for the oxidation of carbon monoxide and toluene.

Three-dimensionally ordered macroporous (3DOM) Mn2O3 and its supported gold (xAu/3DOM Mn2O3, x=1.9-7.5wt%) nanocatalysts were prepared using the polymethyl methacrylate-templating and polyvinyl alcohol-protected reduction methods, respectively. The 3DOM Mn2O3 and xAu/3DOM Mn2O3 samples exhibited a surface area of 34-38m(2)/g. The Au nanoparticles (NPs) with a size of 3.0-3.5nm were uniformly dispersed on the skeletons of 3DOM Mn2O3. The 5.8Au/3DOM Mn2O3 sample performed the best, giving the T90% (the temperature required for a conversion of 90%) of -15°C at space velocity (SV)=20,000mL/(gh) for CO oxidation and 244°C at SV=40,000mL/(gh) for toluene oxidation. The apparent activation energies (30 and 54kJ/mol) over 5.8Au/3DOM Mn2O3 were much lower than those (80 and 95kJ/mol) over 3DOM Mn2O3 for CO and toluene oxidation, respectively. The effects of SV, water vapor, CO2, and SO2 on catalytic activity were also examined. It is concluded that the excellent catalytic performance of 5.8Au/3DOM Mn2O3 was associated with its high oxygen adspecies concentration, good low-temperature reducibility, and strong interaction between Au NPs and 3DOM Mn2O3 as well as high-quality porous architecture.

Ultralow Loading of Silver Nanoparticles on Mn2O3 Nanowires Derived with Molten Salts: A High-Efficiency Catalyst for the Oxidative Removal of Toluene

Using a mixture of NaNO3 and NaF as molten salt and MnSO4 and AgNO3 as metal precursors, 0.13 wt % Ag/Mn2O3 nanowires (0.13Ag/Mn2O3-ms) were fabricated after calcination at 420 °C for 2 h. Compared to the counterparts derived via the impregnation and poly(vinyl alcohol)-protected reduction routes as well as the bulk Mn2O3-supported silver catalyst, 0.13Ag/Mn2O3-ms exhibited a much higher catalytic activity for toluene oxidation. At a toluene/oxygen molar ratio of 1/400 and a space velocity of 40,000 mL/(g h), toluene could be completely oxidized into CO2 and H2O at 220 °C over the 0.13Ag/Mn2O3-ms catalyst. Furthermore, the toluene consumption rate per gram of noble metal over 0.13Ag/Mn2O3-ms was dozens of times as high as that over the supported Au or AuPd alloy catalysts reported in our previous works. It is concluded that the excellent catalytic activity of 0.13Ag/Mn2O3-ms was associated with its high dispersion of silver nanoparticles on the surface of Mn2O3 nanowires and good low-temperature reducibility. Due to high efficiency, good stability, low cost, and convenient preparation, 0.13Ag/Mn2O3-ms is a promising catalyst for the practical removal of volatile organic compounds.

One-Step, Facile and Ultrafast Synthesis of Phase- and Size-Controlled Pt–Bi Intermetallic Nanocatalysts through Continuous-Flow Microfluidics

Ordered intermetallic nanomaterials are of considerable interest for fuel cell applications because of their unique electronic and structural properties. The synthesis of intermetallic compounds generally requires the use of high temperatures and multiple-step processes. The development of techniques for rapid phase- and size-controlled synthesis remains a formidable challenge. The intermetallic compound Pt1Bi2 is a promising candidate catalyst for direct methanol fuel cells because of its high catalytic activity and excellent methanol tolerance. In this work, we explored a one-step, facile and ultrafast phase- and size-controlled process for synthesizing ordered Pt-Bi intermetallic nanoparticles (NPs) within seconds in microfluidic reactors. Single-phase Pt1Bi1 and Pt1Bi2 intermetallic NPs were prepared by tuning the reaction temperature, and size control was achieved by modifying the solvents and the length of the reaction channel. The as-prepared Pt-Bi intermetallic NPs exhibited excellent methanol tolerance capacity and high electrocatalytic activity. Other intermetallic nanomaterials, such as Pt3Fe intermetallic nanowires with a diameter of 8.6 nm and Pt1Sn1 intermetallic nanowires with a diameter of 6.3 nm, were also successfully synthesized using this method, thus demonstrating its feasibility and generality.

Charge Tunable Zwitterionic Polyampholyte Layers Formed in Cyclic Olefin Copolymer Microchannels through Photochemical Graft Polymerization

Zwitterionic layers immobilized on various surfaces exhibit ideal biocompatibility and antifouling capability, but direct immobilization of zwitterionic molecules provides limited choice of surface charges. In this paper, the formation of charge tunable zwitterionic polyampholyte layers onto the surface of microfluidic channels of cyclic olefin copolymer by photochemical graft polymerization of mixed acrylic monomers, [2-(acryloyloxy) ethyl] trimethyl ammonium chloride and 2-acrylamido-2-methyl-1-propanesulfonic, under UV illumination was reported. With this method, surface charge of the resulting modification layers could be tailored through the initial monomer ratio and reaction conditions. The incorporation of both monomers into the grafted layers was confirmed by X-ray photoelectron spectroscopy (XPS) and attenuated total reflection Fourier transform infrared (ATR-FTIR). The results indicate that the modified layers are hydrophilic with contact angles of 33.0-44.3°, and the isoelectric points of the modified layers can be tuned from <3 to >9 simply by adjusting the monomer ratios. Elimination of the nonspecific adsorption of proteins on the zwitterionic layers thus formed was proved by fluorescent microscopy and streaming potential measurement. The uniformity of the modified layers was verified through a comparison of electrophoresis inside the modified and native microchannels. A whole blood coagulation time measurement was performed to show its applicability.

High-resolution hydrodynamic chromatographic separation of large DNA using narrow, bare open capillaries: a rapid and economical alternative technology to pulsed-field gel electrophoresis?

A high-resolution, rapid, and economical hydrodynamic chromatographic (HDC) method for large DNA separations in free solution was developed using narrow (5 μm diameter), bare open capillaries. Size-based separation was achieved in a chromatographic format with larger DNA molecules being eluting faster than smaller ones. Lambda DNA Mono Cut Mix was baseline-separated with the percentage resolutions generally less than 9.0% for all DNA fragments (1.5 to 48.5 kbp) tested in this work. High efficiencies were achieved for large DNA from this chromatographic technique, and the number of theoretical plates reached 3.6 × 10(5) plates for the longest (48.5 kbp) and 3.7 × 10(5) plates for the shortest (1.5 kbp) fragments. HDC parameters and performances were also discussed. The method was further applied for fractionating large DNA fragments from real-world samples (SacII digested Arabidopsis plant bacterial artificial chromosome (BAC) DNA and PmeI digested Rice BAC DNA) to demonstrate its feasibility for BAC DNA finger printing. Rapid separation of PmeI digested Rice BAC DNA covering from 0.44 to 119.041 kbp was achieved in less than 26 min. All DNA fragments of these samples were baseline separated in narrow bare open capillaries, while the smallest fragment (0.44 kbp) was missing in pulsed-field gel electrophoresis (PFGE) separation mode. It is demonstrated that narrow bare open capillary chromatography can realize a rapid separation for a wide size range of DNA mixtures that contain both small and large DNA fragments in a single run.

Catalytic performance enhancement by alloying Pd with Pt on ordered mesoporous manganese oxide for methane combustion

Ordered mesoporous Mn 2 O 3 (meso-Mn 2 O 3 ) and meso-Mn 2 O 3 -supported Pd, Pt, and Pd-Pt alloy x (Pd y Pt)/meso-Mn 2 O 3 ; x =(0.10-1.50) wt%; Pd/Pt molar ratio ( y )=4.9-5.1 nanocatalysts were prepared using KIT-6-templated and poly(vinyl alcohol)-protected reduction methods, respectively. The meso-Mn 2 O 3 had a high surface area, i.e., 106 m 2 /g, and a cubic crystal structure. Noble-metal nanoparticles (NPs) of size 2.1-2.8 nm were uniformly dispersed on the meso-Mn 2 O 3 surfaces. Al-loying Pd with Pt enhanced the catalytic activity in methane combustion; 1.41(Pd 5.1 Pt)/meso-Mn 2 O 3 gave the best performance; T 10% , T 50% , and T 90% (the temperatures required for achieving methane conversions of 10%, 50%, and 90%) were 265, 345, and 425℃, respectively, at a space velocity of 20000 mL/(g·h). The effects of SO 2 , CO 2 , H 2 O, and NO on methane combustion over 1.41(Pd 5.1 Pt)/meso-Mn 2 O 3 were also examined. We conclude that the good catalytic performance of 1.41(Pd 5.1 Pt)/meso-Mn 2 O 3 is associated with its high-quality porous structure, high adsorbed oxy-gen species concentration, good low-temperature reducibility, and strong interactions between Pd-Pt alloy NPs and the meso-Mn 2 O 3 support.

Synthesis and characterization of a novel binuclear iron phthalocyanine/reduced graphene oxide nanocomposite for non-precious electrocatalyst for oxygen reduction

Binuclear iron phthalocyanine/reduced graphene oxide (bi-FePc/RGO) nanocomposite with good electrocatalytic activity for ORR in alkaline medium was prepared in one step. High angle annular dark field image scanning transmission electron microscopy (HAADF-STEM) and energy dispersive X-ray spectroscopy element mapping results show bi-FePc was uniformly distributed on RGO. An obvious cathodic peak located at about −0.23 V (vs. SCE) in CV and an onset potential of −0.004 V (vs. SCE) in LSV indicate the as-prepared bi-FePc/RGO nanocomposite possesses high activity which is closed to Pt/C for ORR. The ORR on bi-FePc/RGO nanocomposite follows four-electron transfer pathway in alkaline medium. Compared with Pt/C, there is only a slight decrease (about 0.02 V vs. SCE) for bi-FePc/RGO nanocomposite when the methanol exists. The excellent activity and methanol tolerance in alkaline solutions proves that bi-FePc/RGO nanocomposite could be considered as a promising cathode catalyst for alkaline fuel cells.

Anomalous enhancement of fluorescence of carbon dots through lanthanum doping and potential application in intracellular imaging of ferric ion

An anomalous enhancement of fluorescence of carbon dots (CDs) was observed via lanthanum (La) doping. La-doped CDs (La-CDs) were prepared through microwave pyrolysis within 4 min. With La3+ doping, the emission band shifted from blue to green although La3+ is non-fluorescent. The quantum yield and fluorescence lifetime improved by about 20% and 35%, respectively. All experiment results indicate that La3+ doping is an effective way to tune fluorescence and improve the performance of CDs. Another unique attribute of La-CDs is high sensitivity to Fe3+. The La-CD-based fluorescence probe was established and used for sensitive and selective detection of Fe3+ with a limit of detection of 91 nmol/L. The proposed fluorescence probe also was successfully employed to visualize intracellular Fe3+ in live HeLa cells through cell imaging. It was also shown that yttrium exhibited the same fluorescence enhancement effect as La. The results may provide a new route for preparing CDs with special properties.

Influence of elution conditions on DNA transport behavior in free solution by hydrodynamic chromatography

We have previously developed bare narrow-bore capillary chromatography. In this work, high-performance DNA separation was realized for a size range of 10–800 base pairs (bp) utilizing bare narrow-bore capillary chromatography with 750 nm-radius capillaries. Separation behavior of double-stranded DNA (dsDNA) fragments was investigated over a range of eluent concentrations and elution pressures. DNA molecules were hydrodynamically separated in a size-dependent manner in free solution without any sieving matrices, with the longer fragments being eluted out from the capillary earlier. It was found that the eluent concentration variously influenced the transport behavior for different-sized DNA fragments depending upon the configuration of DNA molecules and the association of counterions. Ionic strength of the solutions strongly impacted DNA persistence length. Enhanced elution pressure could shorten analysis time with a slight loss in resolution. Excellent efficiency of two million theoretical plates per meter was achieved, which indicates the enormous potential of bare narrow-bore capillary chromatography for the analysis of DNA fragments. These findings would be useful in understanding the transport behavior of DNA fragments in confined dimensions for chromatography in free solution.