Alcohol to water catalyzed by Pt nanoparticles: an experimental and computational approach

Dehouche, F.; Archirel, Pierre; Remita, Hynd; Brodie–Linder, Nancy; Traverse, A.

doi:10.1039/c2ra20533e

Cited by 9 publications

(17 citation statements)

References 49 publications

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“…The absorption bands were consistent with those of the square planar complex of Pt(acac) 2 in ethanol and dichloromethane. 43,44 Thus, Pt(acac) 2 was considered to dissolve in TMHATFSA without changing its coordination environment. Figure 2 shows the cyclic voltammograms (CVs) of a GC electrode in TMHATFSA containing 5 mM Pt(acac) 2 at various temperatures up to 130 • C. Two distinct cathodic current peaks were observed around −1.7 and −2.7 V during the initial cathodic scan.…”

Section: Resultsmentioning

confidence: 99%

Electrochemical Behavior of Bis(acetylacetonato)platinum(II) Complex in an Amide-Type Ionic Liquid

Sultana

Tachikawa

Yoshii

et al. 2016

J. Electrochem. Soc.

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Electrochemical behavior of bis(acetylacetonato)platinum(II) (Pt(acac) 2 ) was investigated in an amide-type ionic liquid, trimethylhexylammonium bis(trifluoromethylsulfonyl)amide (TMHATFSA), at various temperatures. Ultraviolet visible spectroscopy revealed the existence of Pt(acac) 2 having square planar geometry in TMHATFSA. The electrochemical reduction of Pt(acac) 2 to Pt(0) was considered to occur with formation of some intermediate species of Pt by cyclic voltammetry. Potentiostatic cathodic reduction on a glassy carbon electrode in TMHATFSA containing Pt(acac) 2 at −1.7 V at 130 • C resulted in deposition of metallic Pt, which was confirmed by scanning electron microscopy and energy dispersive X-ray spectroscopy. In addition, formation of Pt nanoparticles dispersed in the ionic liquid after potentiostatic cathodic reduction was confirmed by transmission electron microscopy and electron diffraction. The sizes of the Pt nanoparticles were found to depend on the reduction potential.Platinum (Pt) has been known to be one of the important catalysts for various chemical and electrochemical reactions. Pt is well known to be used as the catalyst in water electrolysis, hydrogenation of hydrocarbon, fuel cell, and so on. The electrodeposition method has been proved to be useful for preparation of materials with controlled size and morphology. To date, efforts have been focused on preparation of Pt catalysts with high surface area to achieve high catalytic activity. Numerous studies on electrochemical behavior of Pt film and/or nanoparticles in aqueous solutions are available in the literature. [1][2][3][4][5][6][7][8] However, the previous attempts on electrodeposition of Pt in aqueous solutions were often accompanied with hydrogen evolution due to the high catalytic activity of Pt. The co-deposition of hydrogen during Pt electrodeposition leads to embrittlement of Pt. This necessitates the utilization of non-aqueous electrolytes including ionic liquids.Ionic liquids have drawn intensive interest as an alternative of molecular solvents due to their excellent properties, which include acceptable ionic conductivity, negligible vapor pressure, and less inflammability. Aprotic ionic liquids having wide electrochemical potential windows are expected to be the alternative media for deposition of metals compared with conventional organic electrolytes. 9,10 In addition, preparation of nanoparticles in ionic liquids has received increasing attention in recent years. 11-17 Among the ionic liquids, the chloroaluminate or chlorozincate ionic liquids have received special attention for metal electrodeposition. However, the application of these chlorometallate ionic liquids was limited due to their water sensitivity and co-deposition of Al or Zn during reduction of desired metals. Based on these issues, air and water stable bis(trifluoromethylsulfonyl)amide (TFSA − )-based ionic liquids have been considered promising media for electrodeposition of various metals and metal nanoparticles. 18-25 Electrodeposition of Pt and its allo...

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Section: Resultsmentioning

confidence: 99%

Electrochemical Behavior of Bis(acetylacetonato)platinum(II) Complex in an Amide-Type Ionic Liquid

Sultana

Tachikawa

Yoshii

et al. 2016

J. Electrochem. Soc.

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“…Precious metals are key catalysts that are invaluable to many industrial processes; notable examples include hydrogenation/dehydrogenation reactions, − low-temperature reduction of automobile pollutants, , and fuel cells. − Precious-metal nanoparticles deposited on various supports have attracted considerable interest because the as-prepared new functional materials have the desired properties of the support combined with the complementary and desired properties of the metal nanoparticles. − Halloysite nanotubes [Al 2 Si 2 O 5 (OH) 4 ·2H 2 O, HNTs] consist of a 1:1 layered aluminosilicate mineral that has a predominantly hollow tubular structure . They exhibit interesting features and offer potential application as supports for catalytic composites with markedly improved mechanical properties and stability, − attractive for technological applications.…”

Section: Introductionmentioning

confidence: 99%

Precious-Metal Nanoparticles Anchored onto Functionalized Halloysite Nanotubes

Zhang

Xie

Tang

et al. 2014

Ind. Eng. Chem. Res.

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Natural halloysite nanotubes (HNTs) were functionalized with a silane coupling agent with the aim of tuning the loading rate and dispersion of precious-metal nanoparticles. The samples were characterized by FTIR spectroscopy, TEM, and XPS. The results indicated that a large number of precious-metal nanoparticles were anchored on the surface of the silanized HNTs, with an average diameter of ∼3 nm. The functionalized HNTs contain a large number of functional groups (−NH 2 or −SH groups) that have one lone electron pair and can form a chemical bond complex with nanoparticles. Because of bond formation between the nanoparticles and the functional groups, most of the nanoparticles (NPs) are anchored by the functional groups, resulting in the formation of nanoparticle−functional group complexes. Bond formation between the nanoparticles and the functional groups was demonstrated, and furthermore, atomic-level interfaces for NPs anchored onto functionalized HNTs were depicted. The chemical immobilization of precious-metal nanoparticles onto silanized HNTs could avoid particle aggregation and movement, thus leading to a higher catalytic efficiency.

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“…The most exciting examples of catalytic properties of nanostructured materials have been demonstrated by using gold-based nanocages and nanoboxes . The noble-metal nanoparticles, in particular platinum, are efficiently used as a catalyst in many commercially important organic reactions such as cyclopropanation, cycloisomerization, H-D exchange, Suzuki coupling, hydrosilylation, and electron transfer reaction. − Recently, it has also been shown that Pt nanoparticles can degrade alcohol into water . The catalytic activity of these platinum nanoparticles have been reported to be highly dependent on the morphology, porosity, size distribution, and phase composition. − It has been reported that significant enhancement in the catalytic activity could be achieved when monodispersed platinum nanoparticles are linked into platinum nanowires .…”

Section: Introductionmentioning

confidence: 99%

“…7−13 Recently, it has also been shown that Pt nanoparticles can degrade alcohol into water. 14 The catalytic activity of these platinum nanoparticles have been reported to be highly dependent on the morphology, porosity, size distribution, and phase composition. 15−19 It has been reported that significant enhancement in the catalytic activity could be achieved when monodispersed platinum nanoparticles are linked into platinum nanowires.…”

Section: Introductionmentioning

confidence: 99%

Investigation into the Catalytic Activity of Porous Platinum Nanostructures

et al. 2013

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The catalytic activity of porous platinum nanostructures, viz. platinum nanonets (PtNNs) and platinum nanoballs (PtNBs), synthesized by radiolysis were studied using two model reactions (i) electron transfer reaction between hexacyanoferrate (III) and sodium thiosulfate and (ii) the reduction of p-nitrophenol by sodium borohydride to p-aminophenol. The kinetic investigations were carried out for the platinum nanostructure-catalyzed reactions at different temperatures. The pseudofirst-order rate constant for the electron transfer reaction between hexacyanoferrate (III) and sodium thiosulfate catalyzed by PtNNs and PtNBs at 293 K are (9.1 ± 0.7) × 10(-3) min(-1) and (16.9 ± 0.6) × 10(-3) min(-1), respectively. For the PtNN- and PtNB-catalyzed reduction of p-nitrophenol to p-aminophenol by sodium borohydride, the pseudofirst-order rate constant was (8.4 ± 0.3) × 10(-2) min(-1) and (12.6 ± 2.5) × 10(-2) min(-1), respectively. The accessible surface area of the PtNNs and PtNBs determined before the reaction are 99 and 110 m(2)/g, respectively. These nanostructures exhibit significantly higher catalytic activity, consistent with the largest accessible surface area reported so far for the solid platinum nanoparticles. The equilibrium of the reactants on the surface of the platinum nanostructures played an important role in the induction time (t0) observed in the reaction. A possible role of structural modifications of PtNBs catalyzed the reaction leading to change in the accessible surface area of PtNBs is being explored to explain the nonlinear behavior in the kinetic curve. The activation energy of the PtNN- and PtNB-catalyzed reduction of p-nitrophenol are 26 and 6.4 kJ/mol, respectively. These observations open up new challenges in the field of material science to design and synthesize platinum nanostructures which could withstand such reaction conditions.

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Alcohol to water catalyzed by Pt nanoparticles: an experimental and computational approach

Cited by 9 publications

References 49 publications

Electrochemical Behavior of Bis(acetylacetonato)platinum(II) Complex in an Amide-Type Ionic Liquid

Electrochemical Behavior of Bis(acetylacetonato)platinum(II) Complex in an Amide-Type Ionic Liquid

Precious-Metal Nanoparticles Anchored onto Functionalized Halloysite Nanotubes

Investigation into the Catalytic Activity of Porous Platinum Nanostructures

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