Highly selective supported gold catalyst for CO-driven reduction of furfural in aqueous media

The reductive transformation of furfural （FAL） into furfuryl alcohol （FOL） is an attractive route for the use of renewable bio‐sources but it suffers from the heavy use of H2. We describe here a highly efficient reduction protocol for converting aqueous FAL to FOL. A single phase rutile TiO2 support with a gold catalyst （Au/TiO2‐R） that used CO/H2O as the hydrogen source catalyze this reduction efficiently under mild conditions. By eliminating the consumption of fossil fuel‐derived H2, our pro‐cess has the benefit afforded by using CO as a convenient and cost competitive reducing reagent.

In situ IR, pulse reaction and TPD-ITD study of catalytic performance of room-temperature carbon monoxide oxidation on supported gold catalysts

With in situ IR, two different CO adsorption bands were detected on various chemical state gold catalysts. One band is attributed to the linear CO on an oxidized gold catalyst(2100 cm -1 ), the other one is ascribed to the bridged CO on metallic gold (2085 cm -1 ). CO pulse reaction showed that Au/Fe 2O 3 catalyst had a room temperature activity even in the presence of moisture. The produced CO 2 was detained and more easily desorbed from supported gold catalyst than support oxide. TPD IDT results indicated that the O - 2 superoxide ions are the possible active oxygen species.

THE SUPPORTED GOLD CATALYSTS FOR CLOSED CYCLE CO_2 LASER

Sealed-off carbon dioxide lasers encounter problem of dissociation of CO2, Which causes the output power to fall. Reformation of CO2 is therefore essential for long life CO2 lasers. Au/Fe2O3 and Au/NiFe2O4 are promising candidates for this application.

Recent development of supported monometallic gold as heterogeneous catalyst for selective liquid phase hydrogenation reactions

The great potential of gold catalysts for chemical conversions in both industrial and environmental concerns has attracted increasing interest in many fields of research.Gold nanoparticles supported by metal oxides with high surface area have been recognized as highly efficient and effective green heterogeneous catalyst even at room temperature under normal reaction conditions,in gas and liquid phase reactions.In the present review,we discuss the recent development of heterogeneous,supported monometallic gold catalysts for organic transformations emphasizing mainly liquid phase hydrogenation reactions.Discussions on the catalytic synthesis procedures and the promoting effect of other noble metals are omitted since they are already worked out.Applications of heterogeneous,supported monometallic catalysts for chemoselective hydrogenations in liquid phase are studied including potential articles during the period 2000–2013.

Interfacial charge effects of supported-metal-cluster heterostructures on azo hydrogenation catalyzation

The impact of interfacial charge on catalytic performance of supported-metal-cluster(SMC)heterostructures remains unclear,hindering efforts to develop high-performance SMC catalysts.Herein we systematically investigated interfacial charge effects of SMCs using a model system of graphene-supported gold-nanoclusters(AuNCs/rGO)for azo hydrogenation.Three types of SMCs with different interfacial charges were synthesized by anchoring electropositive 2-aminoethanethiol(CSH),amphoteric cysteine(Cys),and electronegative 3-mercaptopropionic-acid(MPA)onto AuNCs/rGO,respectively.All three SMCs exhibited high and selective catalytic activity to azo-hydrogenation in four representative azo dyes.The catalytic activity of Cys@AuNCs/rGO was lower than that of CSH@AuNCs/rGO but higher than that of MPA@AuNCs/rGO.However,the cyclic stability of Cys@AuNCs/rGO was inferior to that of both CSH@AuNCs/rGO and MPA@AuNCs/rGO.Further mechanistic studies revealed that amino ligands modified CSH@AuNCs and Cys@AuNCs agglomerated into large-size gold nanoparticles on rGO surface during catalytic reaction under NaBH_(4) action,leading to reduced efficiency and cyclic stability.Conversely,non-amino ligand modified MPA@AuNCs only partially detached from rGO surface without agglomeration,resulting in better cyclic stability.Protection of amino groups in ligands such as modifying-NH_(3)^(+)group in Cys into imine to form N-isobutyryl-L-cysteine(NIBC)substantially improved the cyclic stability while maintaining the high activity in the NIBC@AuNCs/rGO catalyst system.Our work provides an approach for developing a highly-active and stable SMC heterostructure catalyst via manipulating interfacial charges in SMC.

Effective removal of the protective ligands from Au nanoclusters by ambient pressure nonthermal plasma treatment for CO oxidation

We used a dielectric barrier discharge(DBD)plasma technique to eliminate the protective ligand of ZnAl-hydrotalcite-supported gold nanoclusters.We used X-ray powder diffraction,ultraviolet-visible spectrophotometry,thermogravimetric analysis,and high angle annular dark-field-scanning transmission electron microscopy characterization to show that the samples pretreated with/without DBD-plasma displayed different performances in CO oxidation.The enhanced activity was obtained on the plasma-treated samples,implying that the protective ligand was effectively removed via the plasma technique.The crystal structure of the plasma-treated samples changed markedly,suggesting that the plasma treatment could not only break the chemical bond between the gold and the protective agent but could also decompose the interlayer ions over the hydrotalcite support.The particle sizes of the gold after DBD-plasma treatment implied that it was a good way to control the size of the gold nanoparticles under mild conditions.

Effects of preparation conditions of Au/FeO_x /Al_2O_3 catalysts prepared by a modified two-step method on the stability for CO oxidation

Composite oxide FeO x /Al 2 O 3 -supported gold catalysts were prepared by a modified two-step method. The effects of preparation conditions on the initial catalytic activity and long-time stability were studied for CO oxidation. XRD, XPS and in situ FTIR were employed to investigate the state of FeO x and the species on the catalyst surface. The results showed that Au/FeO x /Al 2 O 3 catalysts prepared by this method exhibited high activity and high stability in a wide pH value range. Calcination pretreatment was proved to be beneficial to improving the activity and stability. The beneficial effects of FeO x acting as a structural promoter could be ascribed to the ability to supply active oxygen species. As the precursor of FeO x , Fe（NO 3 ） 3 is superior to FeCl 3 for obtaining higher stability.

Study on Au/Al_2O_3 catalysts for low-temperature CO oxidation in situ FT-IR

Au/Al2O3 catalyst was prepared by a modified anion impregnation method and investigated with respect to its initial activity and stability for low-temperature CO oxidation.The activity changes of the catalyst were examined after separate treatment in CO＋O2 or CO2 ＋O2 .Furthermore,in situ FT-IR studies were performed to investigate the species on the surface when CO or CO＋O2 or CO2 ＋O2 was selected separately as adsorption gas.The results showed that Au/Al2O3 catalyst exhibited very high initial activity,but the catalytic activity was found to decrease gradually during CO oxidation with time on stream.And also,the activity of the catalyst declined after treatment in CO＋O2 or CO2 ＋O2 .The formation and accumulation of carbonate-like species during CO oxidation or treatment in CO＋O2 or CO2 ＋O2 might be mainly responsible for the activity decrease,which was reversible.

Concurrent catalytic removal of typical volatile organic compound mixtures over Au-Pd/α-MnO2 nanotubes

α-MnO2 nanotubes and their supported Au-Pd alloy nanocatalysts were prepared using hydrothermal and polyvinyl alcohol-protected reduction methods, respectively. Their catalytic activity for the oxidation of toluene/m-xylene, acetone/ethyl acetate, acetone/m-xylene and ethyl acetate/m-xylene mixtures was evaluated. It was found that the interaction between Au-Pd alloy nanoparticles and α-MnO2 nanotubes significantly improved the reactivity of lattice oxygen, and the 0.91 wt.% Au0.48 Pd/α-MnO2 nanotube catalyst outperformed the α-MnO2 nanotube catalyst in the oxidation of toluene, m-xylene, ethyl acetate and acetone. Over the0.91 wt.% Au0.48 Pd/α-MnO2 nanotube catalyst,（i） toluene oxidation was greatly inhibited in the toluene/m-xylene mixture, while m-xylene oxidation was not influenced;（ii） acetone and ethyl acetate oxidation suffered a minor impact in the acetone/ethyl acetate mixture; and（iii） m-xylene oxidation was enhanced whereas the oxidation of the oxygenated VOCs（volatile organic compounds） was suppressed in the acetone/m-xylene or ethyl acetate/m-xylene mixtures. The competitive adsorption of these typical VOCs on the catalyst surface induced an inhibitive effect on their oxidation, and increasing the temperature favored the oxidation of the VOCs. The mixed VOCs could be completely oxidized into CO2 and H2 O below 320°C at a space velocity of 40,000 m L/（g·hr）. The 0.91 wt.% Au0.48 Pd/α-MnO2 nanotube catalyst exhibited high catalytic stability as well as good tolerance to water vapor and CO2 in the oxidation of the VOC mixtures. Thus, the α-MnO2 nanotube-supported noble metal alloy catalysts hold promise for the efficient elimination of VOC mixtures.

Synthesis of hierarchical Polystyrene/Polyaniline@Au nanostructures of different surface states and studies of their catalytic properties

We synthesized hierarchical Polystyrene/Polyaniline@Au(PS/PANI@Au) catalysts through a seeded swelling polymerization and in-situ reduction procedure. PS/PANI@Au catalysts possess a core of PS as seed and template, a PANI shell with fibers and uniform gold nanoparticles on the surface. The configuration changes of the PANI chains resulting from the doping/ dedoping procedure led to various loading amounts of Au nanoparticles. Reduction of 4-nitrophenol was chosen as the probe reaction to evaluate the catalytic activity of supported Au nanocatalysts. The catalytic results indicated that dedoping treatment of the PS/PANI supports provides stronger coordinative ability to metal nanoparticles as well as more –N= groups, which results in a better catalytic performance towards the reduction of 4-nitrophenol.