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Item type:Publication, Access status: with files , Nanoporous Gold: from structure evolution to functional properties in catalysis and electrochemistry(2023-05-24); ; ; Nanoporous gold (NPG) is characterized by a bicontinuous network of nanometer-sized metallic struts and interconnected pores formed spontaneously by oxidative dissolution of the less noble element from gold alloys. The resulting material exhibits decent catalytic activity for low-temperature, aerobic total as well as partial oxidation reactions, the oxidative coupling of methanol to methyl formate being the prototypical example. This review not only provides a critical discussion of ways to tune the morphology and composition of this material and its implication for catalysis and electrocatalysis, but will also exemplarily review the current mechanistic understanding of the partial oxidation of methanol using information from quantum chemical studies, model studies on single-crystal surfaces, gas phase catalysis, aerobic liquid phase oxidation, and electrocatalysis. In this respect, a particular focus will be on mechanistic aspects not well understood, yet. Apart from the mechanistic aspects of catalysis, best practice examples with respect to material preparation and characterization will be discussed. These can improve the reproducibility of the materials property such as the catalytic activity and selectivity as well as the scope of reactions being identified as the main challenges for a broader application of NPG in target-oriented organic synthesis.Publicationtype: Review ArticleScopus© Citations 26 38 54 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: without files , Promoting Effect of the Residual Silver on the Electrocatalytic Oxidation of Methanol and Its Intermediates on Nanoporous GoldNanoporous gold (NPG) obtained by dealloying Ag75Au25 with an overall residual Ag content of less than 1% was investigated as an electrocatalyst for the oxidation of methanol, formaldehyde, and formate in aqueous 0.1 M NaOH solution. The NPG was used to fill cavity microelectrodes, which allowed the recording of well-resolved voltammetry from the porous material. NPG differs from polycrystalline Au (Au(poly)) by its microstructure and its residual Ag content and also behaves distinctly different than Au(poly). The residual Ag content is higher at the surface of the ligaments than in the bulk. By cycling the NPG electrodes in 0.1 M H2SO4, the surface concentration of Ag could be decreased. It could then be set to a defined value by underpotential deposition (UPD) of Ag. The surface structure, and specifically its evolution upon the removal of Ag from the surface, was analyzed by the characteristic voltammetric features of Pb UPD. The effect of Ag on the electrocatalytic methanol oxidation reaction (MOR) is different in different potential regions. Ag coverage shifts the onset of the methanol oxidation current to less positive potentials. In the range of the peak current density, only a defined low Ag concentration enhanced the MOR current density compared to the Ag-free NPG. The 1 0 0 and 1 1 1 facets contributed the largest current, as concluded from selective poisoning experiments. At a potential of 1.63 V vs RHE, Ag2O at the surface is oxidized to AgO. Those layers can oxidize methanol and formate to CO2. The oxidation of formaldehyde proceeds at a much higher reaction rate than the MOR and formate oxidation; the reaction leads to CO and CO2 depending on the applied potential. Given the high oxidation rate of formaldehyde, it would be immediately further oxidized should it be formed as an intermediate of MOR. This is an important difference to the methanol oxidation at Pt. The water oxidation that occurs at the same potential range in the methanol-free solution was suppressed during CO2 formation.Publicationtype: Journal Article30 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: without files , Nanoporous gold dealloyed from AuAg and AuCu: Comparison of structure and chemical composition© 2018 Properties of dealloyed nanoporous gold (npAu) in catalysis, sensing or actuation applications depend on its structure and chemical composition. NpAu is obtained by corrosion of alloys of gold and a less noble metal such as silver or copper. Structural parameters can be tuned by variations in the preparation process. Due to the large number of parameters that can be varied a direct comparison of results obtained with various samples is often difficult. In this report we compare structure and chemical composition of npAu dealloyed from AuAg and AuCu alloys keeping the number of different sample preparation parameters at a minimum.Publicationtype: Journal Article189 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: with files , Measurement of local crystal lattice strain variations in dealloyed nanoporous gold(Taylor & Francis, 2018-01-02); ; ; ; Reversible macroscopic length changes in nanoporous structures can be achieved by applying electric potentials or by exposing them to different gases or liquids. Thus, these materials are interesting candidates for applications as sensors or actuators. Macroscopic length changes originate from microscopic changes of crystal lattice parameters. In this report, we show spatially resolved measurements of crystal lattice strain in dealloyed nanoporous gold. The results confirm theory by indicating a compression of the lattice along the axis of cylindrically shaped ligaments and an expansion in radial direction. Furthermore, we show that curved npAu surfaces show inward relaxation of the surface layer. (Figure presented) IMPACT STATEMENT We show spatially resolved measurements of strain in nanoporous gold confirming theory: Crystal lattice is compressed along the axis of cylindrical ligaments and expanded in radial direction, surfaces relax inward.Publicationtype: Journal ArticleScopus© Citations 12 401 392 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: without files , A comparative study of alcohol oxidation over nanoporous gold in gas and liquid phase(Elsevier, 2017-08-02); ; ; ; The aerobic oxidation of methanol and ethanol in liquid phase is investigated using unsupported nanoporous gold (npAu) catalysts and compared to gas phase experiments. We pursue the question if this material is still suited as a type of model catalyst even under much more complex conditions in liquid phase. Indeed, npAu is an active catalyst for both liquid and gas phase oxidation of methanol and ethanol with O2 under mild conditions (starting at 40 °C). While in case of methanol solely the self coupling product (methyl formate) is detected, the more facile formation of the acetaldehyde in case of ethanol results in the formation of the free aldehyde (acetaldehyde) and the coupling product (ethyl acetate) in similar amounts. To further probe the surface chemistry, cross coupling reactions between both alcohols, as well as the acetaldehyde are performed. As observed also in gas phase experiments, the formation of the surface bonded aldehyde by β-H elimination of the alcoxy species is rate determining.Publicationtype: Journal Article207