Hydrogen chemisorption on supported platinum, gold, and platinum-gold-alloy catalysts

Alloyed catalysts receive considerable attention, because of their unique catalytic properties; they often show higher selectivity, activity, and stability compared to the pure metal particles. To provide insights in the origins of these features, we report the structure and the interaction of hydrogen with each of the metals in an intimately mixed platinum-gold catalyst and compare these characteristics to those in the single metal particles. X-Ray absorption spectroscopy (XAS) and electron microscopy analysis showed that the structure of the mixed particle differed from the single metal particles. The interaction of platinum with hydrogen is stronger than the H-Au interaction and the adsorption sites were different. EXAFS analysis showed that the structure of the platinum clusters changes with increasing hydrogen coverage, observed as a relaxation of the contracted Pt-Pt distance and an increase in the Pt-Pt coordination number. No such changes were observed for gold clusters. Well-mixed PtAu-alloy clusters, with a bulk Au-to-Pt ratio of two, supported on SiO(2), adsorb hydrogen on both platinum and gold atoms, which indicates that gold cannot be regarded as an inert metal. The heat of adsorption on the platinum ensembles does not decrease upon alloying; the weakening of the overall hydrogen adsorption strength when alloying platinum with gold is an ensemble-size effect.     

Influence of the macroscopic distribution of platinum in PtHFAU catalysts on their activity for n-hexane isomerization

The macroscopic distribution of platinum in extrudates of bifunctional PtHFAU/Al₂O₃ catalysts is shown to have a significant effect on their activity, stability and selectivity in n-hexane transformation under hydrogen pressure. The best catalysts are those for which platinum is homogeneously dispersed. n-Hexane transformation is proposed as a model reaction for estimating the macroscopic distribution of platinum in industrial catalyst pellets.     

Superior Electron‐Transport Ability of π‐Conjugated Redox Molecular Wires Prepared by the Stepwise Coordination Method on a Surface

Electronic conductivity of molecular wires is a critical fundamental issue in molecular electronics. π‐Conjugated redox molecular wires with the superior long‐range electron‐transport ability could be constructed on a gold surface through the stepwise ligand–metal coordination method. The β^d value, indicating the degree of decrease in the electron‐transfer rate constant with distance along the molecular wire between the electrode and the redox active species at the terminal of the wire, were 0.008–0.07 Å^?1 and 0.002–0.004 Å^?1 for molecular wires of bis(terpyridine)iron and bis(terpyridine)cobalt complex oligomers, respectively. The influences on β^d by the chemical structure of molecular wires and the terminal redox units, temperature, electric field, and electrolyte concentration were clarified. The results indicate that facile sequential electron hopping between neighboring metal–complex units within the wire is responsible for the high electron‐transport ability.     

Gas Diffusion Electrodes for Use in an Amperometric Enzyme Biosensor

The preparation of gas diffusion electrodes and their use in an amperometric enzyme biosensor for the direct detection of a gaseous analyte is described. The gas diffusion electrodes are prepared by covering a PTFE membrane (thickness 250 μm, pore size 2 μm, porosity 35%) with gold, platinum, or a graphite/PTFE mixture. Gold and platinum are deposited by e‐beam sputtering, whereas the graphite/PTFE layer is prepared by vacuum filtration of a respective aqueous suspension. These gas diffusion electrodes are exemplarily implemented as working electrodes in an amperometric biosensor for gaseous formaldehyde containing NAD‐dependent formaldehyde dehydrogenase from P. putida [EC. 1.2.1.46] as enzyme and 1,2‐naphthoquinone‐4‐sulfonic acid as electrochemical mediator. The resulting sensors are compared with regard to background current, signal noise, linear range, sensitivity, and detection limit. In this respect, sensors with gold or graphite/PTFE covered membranes outclass ones with platinum for this particular analyte and sensor configuration.     

Recent Advances in Preferential Oxidation of CO in H2 Over Gold Catalysts

Recent studies have revealed that supported gold catalysts exhibit comparable or superior catalytic performance relative to platinum group metals, especially at low temperatures, in the preferential oxidation of CO under excess H₂ (CO-PROX). Complete conversion of CO with good selectivity of O₂ for CO₂ and highly stable catalyst performance in the presence of CO₂ and H₂O are considered to be essential for the successful development of CO-PROX catalysts for application in polymer electrolyte membrane fuel cells. The performance of supported gold catalysts in the CO-PROX reaction has been shown to be dependent on the characteristics of gold (size, oxidation state, and its interaction with other metal/oxides), nature of the support (size, composition, preparation method, presence of promoters, and doping with other metal ions), and reaction conditions (temperature and feed composition). Complete CO conversion has been achieved in the presence of certain gold catalysts below 100 °C. The unresolved issues in CO-PROX include the undesired oxidation of H₂, detrimental effects of CO₂ and/or H₂O, and long-term stability of the catalysts. To address these issues, the catalytic activity of gold supported on simple oxides such as TiO₂, CeO₂, Al₂O₃, and Fe₂O₃ has been improved dramatically by the addition of promoters, alteration of the gold-oxide support interface, and modification of the oxide supports. Recently, nanoporous gold has also been recognized to be promising for this reaction. This review highlights recent developments of unsupported and supported gold catalysts for the CO-PROX reaction.     

Conical tungsten tips as substrates for the preparation of ultramicroelectrodes

Here we describe a simple method to prepare voltammetric microelectrodes using tungsten wires as a substrate. Tungsten wires have a high tensile modulus and enable the fabrication of electrodes that have small dimensions overall while retaining rigidity. In this work, 125 microm tungsten wires with a conical tip were employed. For the preparation of gold or platinum ultramicroelectrodes, commercial tungsten microelectrodes, completely insulated except at the tip, were used as substrates. Following removal of oxides from the exposed tungsten, platinum or gold was electroplated, yielding surfaces with an electroactive area of between 1 x 10-6 and 2 x 10-6 cm2. Carbon surfaces on the etched tip of tungsten microwires were prepared by coating with photoresist followed by pyrolysis. The entire electrode was then insulated with Epoxylite except the tip, yielding an exposed carbon surface with an area of around 4 x 10-6 to 6 x 10-6 cm2. All three types of ultramicroelectrodes fabricated on the tungsten wire had similar electrochemical behavior to electrodes fabricated from wires or fibers insulated with glass tubes.     

Self-organization of surfactant-metal-ion complex nanofibers on graphite surfaces and their application to fibrously concentrated platinum nanoparticle formation

We report the fabrication of self-organized surfactant nanofibers containing platinum ions on a highly oriented pyrolytic graphite (HOPG) surface from mixed solutions of hexadecyltrimethylammonium hydroxide (C16TAOH) and hydrogen hexachloroplatinate (IV) (H2PtCl6). The fibrous surfactant self-assembly was stable in air, even after being soaked in water, in contrast to surfactant hemicylindrical micelles, which are stable only at graphite/solution interfaces. The results show that the graphite surface served as an essential template for the specific formation of fibrous surfactant self-assemblies. In addition, when surfactant nanofibers containing metal ions were treated with hydrazine, platinum nanoparticles concentrated in the nanofibers formed on the HOPG surface. We also prepared surfactant nanofibers containing gold ions on HOPG surfaces and formed gold nanoparticles in the nanofibers.     

Attachment of Nanoparticles to Pyrolytic Graphite Electrode and Its Application for the Direct Electrochemistry and Electrocatalytic Behavior of Catalase

Abstract

A highly hydrophilic, nontoxic, and conductive effect of colloidal gold nanoparticles (GNP) and multi-walled carbon nanotubes (MWCNT) on pyrolytic graphite electrode has been demonstrated. The direct electron transfer of catalase (CAT) was achieved based on the immobilization of MWCNT/CAT-GNP on a pyrolytic graphite electrode by a Nafion film. The immobilized catalase displayed a pair of well-defined and nearly reversible redox peaks in 0.1 M phosphate buffer solution (PBS) (pH 6.98). The dependence of E°′on solution pH indicated that the direct electron transfer reaction of catalase was a single-electron-transfer coupled with single-proton-transfer reaction process. The immobilized catalase maintained its biological activity, showing a surface controlled electrode process with an apparent heterogeneous electron transfer rate constant (k _s) of 1.387±0.1 s^?1 and charge-transfer coefficient (α) of 0.49, and displayed electrocatalytic activity in the electrocatalytic reduction of hydrogen peroxide. Therefore, the resulting modified electrode can be used as a biosensor for detecting hydrogen peroxide.     

Hydrogen oxidation reaction on platinum nanoparticles: Transition between mechanistic routes

The present work reports for the first time results which demonstrate that the hydrogen oxidation reaction on platinum nanoparticles supported on gold and glassy carbon substrates displays a transition between the Tafel–Volmer route, which dominates at low overpotentials, and the Heyrovsky–Volmer route, predominant at high overpotentials.     

Bio-sensing using recessed gold-filled capillary amperometric electrodes

A novel recessed electrode is reported for amperometric detection of hydrogen peroxide and via glucose oxidase for the detection of glucose. The electrode utilised electrodeposited platinum over a gold wire surface, which proved to be an effective peroxide-detecting surface. Compared with a traditional exposed electrode surface, the recessed tip facilitated an extended linear range for glucose from 4 to over 14 mM. Bio-fouling, as assessed by exposure to bovine serum albumin, was also significantly reduced. Though response time at the recess was increased, it was within an acceptable range for physiological monitoring. Moreover, the recess enabled precise measurement of the hydrogen peroxide diffusion coefficient; this was based on a bipartite expression for the transient amperometric current at the recessed structure following a step change in ambient hydrogen peroxide concentration. An important aspect of the diffusion measurement was the curve fitting routine used to map on to the theoretical response curve.     

氯化钠溶液中铜丝尺寸效应对腐蚀行为的影响

为了研究半径变化对铜丝腐蚀行为的影响, 通过极化曲线和交流阻抗测试方法研究了半径为0.04-0.82 mm的铜丝在自然通气的0.5 mol·L-1 NaCl(pH=7.4)溶液中的腐蚀行为. 结果表明, 当铜丝半径小于氧的扩散层厚度(0.56 mm)时, 随着半径减少, 非线性扩散的存在加速了电化学反应的传质过程, 其影响由慢到快迅速增大, 使得受扩散过程控制的阴、阳极反应速率增大, 铜丝的腐蚀电流密度显著增加. 对铂丝、不锈钢丝的氧阴极还原反应过程研究也得到了类似的反应特征. 上述现象表明铜丝腐蚀行为的尺寸效应具有一定的普遍性.     

Gold(III) Alkyne Complexes: Bonding and Reaction Pathways

The synthesis and characterization of hitherto hypothetical Au^III π‐alkyne complexes is reported. Bonding and stability depend strongly on the trans effect and steric factors. Bonding characteristics shed light on the reasons for the very different stabilities between the classical alkyne complexes of Pt^II and their drastically more reactive Au^III congeners. Lack of back‐bonding facilitates alkyne slippage, which is energetically less costly for gold than for platinum and explains the propensity of gold to facilitate C−C bond formation. Cycloaddition followed by aryl migration and reductive deprotonation is presented as a new reaction sequence in gold chemistry.     

The Electrochemical Detection of Arsenic(III) at a Silver Electrode

A study of three electrode substrates namely gold, platinum and silver, for arsenic detection via anodic stripping voltammetry is reported. Hitherto it has been accepted that gold is the most suitable metallic surface for use in this context, as suggested by Forsberg and co‐workers (Forsberg, G.; O'Laughlin, J. W.; Megargle, R. G. Anal. Chem. 1975, 47, 1586.). We revisit these experiments and find that by switching from hydrochloric acid to nitric acid the oxidation of silver that had previously masked the arsenic stripping signal at this surface is shifted considerably enough to allow a clear, analytically reliable As(III) stripping signal to be detected. In contrast to silver and gold platinum is found to have poor performance as an electrode substrate for arsenic detection. Using ASV a LOD of 6.3×10^?7 M is found for As(III) detection at a silver electrode, similar to that which we have previously reported at a gold electrode (A. O. Simm, C. E. Banks and R. G. Compton. Electroanalysis, 2005, 17, 335.) The use of ultrasound was then investigated to further reduce the LOD, which was found to be 1.4×10^?8 M. Apart from reduced cost of silver it also has an added advantage over gold in that it has a higher hydrogen reduction overvoltage enabling a 100 mV more negative deposition potential to be used before the onset of hydrogen evolution when compared to a gold electrode.     

Study of <Emphasis Type="Italic">n</Emphasis>-hexane isomerization on Pt/SO<Subscript>4</Subscript>/ZrO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts: Effect of the state of platinum on catalytic and adsorption properties

The state of surface Pt atoms in the Pt/SO₄/ZrO₂/Al₂O₃ catalyst and the effect of the state of platinum on its adsorption and catalytic properties in the reaction of n-hexane isomerization were studied. The Pt-X/Al₂O₃ alumina-platinum catalysts modified with various halogens (X = Br, Cl, and F) and their mechanical mixtures with the SO₄/ZrO₂/Al₂O₃ superacid catalyst were used in this study. With the use of IR spectroscopy (CO_ads), oxygen chemisorption, and oxygen-hydrogen titration, it was found that ionic platinum species were present on the reduced form of the catalysts. These species can adsorb to three hydrogen atoms per each surface platinum atom. The specific properties of ionic platinum manifested themselves in the formation of a hydride form of adsorbed hydrogen. It is believed that the catalytic activity and operational stability of the superacid system based on sulfated zirconium dioxide were due to the participation of ionic and metallic platinum in the activation of hydrogen for the reaction of n-hexane isomerization.     

Graphite‐Supported Gold Nanoparticles as Efficient Catalyst for Aerobic Oxidation of Benzylic Amines to Imines and N‐Substituted 1,2,3,4‐Tetrahydroisoquinolines to Amides: Synthetic Applications and Mechanistic Study

Selective oxidation of amines using oxygen as terminal oxidant is an important area in green chemistry. In this work, we describe the use of graphite‐supported gold nanoparticles (AuNPs/C) to catalyze aerobic oxidation of cyclic and acyclic benzylic amines to the corresponding imines with moderate‐to‐excellent substrate conversions (43–100 %) and product yields (66–99 %) (19 examples). Oxidation of N‐substituted 1,2,3,4‐tetrahydroisoquinolines in the presence of aqueous NaHCO₃ solution gave the corresponding amides in good yields (83–93 %) with high selectivity (up to amide/enamide=93:4) (6 examples). The same protocol can be applied to the synthesis of benzimidazoles from the reaction of o‐phenylenediamines with benzaldehydes under aerobic conditions (8 examples). By simple centrifugation, AuNPs/C can be recovered and reused for ten consecutive runs for the oxidation of dibenzylamine to N‐benzylidene(phenyl)methanamine without significant loss of catalytic activity and selectivity. This protocol “AuNPs/C+O₂” can be scaled to the gram scale, and 8.9 g (84 % isolated yield) of 3,4‐dihydroisoquinoline can be obtained from the oxidation of 10 g 1,2,3,4‐tetrahydroisoquinoline in a one‐pot reaction. Based on the results of kinetic studies, radical traps experiment, and Hammett plot, a mechanism involving the hydrogen‐transfer reaction from amine to metal and oxidation of M‐H is proposed.     

Determination of trace amounts of gold in waste water by graphite furnace atomic-absorption spectrophotometry with preconcentration on trioctylphosphine oxide chemically modified tungsten wire matrix

Preconcentration on a trioctylphosphine oxide (TOPO) chemically modified tungsten wire matrix followed by graphite furnace atomic-absorption spectrophotometry measurement is described for the determination of trace gold in waste water. The TOPO modified tungsten wire matrix, after accumulating the gold, is placed in a graphite cup for direct atomization and measurement. Under the selected conditions, the absorbance is proportional to the concentration of gold over the range 0.4-18 ng/ml and the detection limit is 0.2 ng/ml. This method is sensitive and convenient. It has been applied to some waste waters with satisfactory results.     

Surface Functionalization of g‐C3N4: Molecular‐Level Design of Noble‐Metal‐Free Hydrogen Evolution Photocatalysts

A stable noble‐metal‐free hydrogen evolution photocatalyst based on graphite carbon nitride (g‐C₃N₄) was developed by a molecular‐level design strategy. Surface functionalization was successfully conducted to introduce a single nickel active site onto the surface of the semiconducting g‐C₃N₄. This catalyst family (with less than 0.1 wt % of Ni) has been found to produce hydrogen with a rate near to the value obtained by using 3 wt % platinum as co‐catalyst. This new catalyst also exhibits very good stability under hydrogen evolution conditions, without any evidence of deactivation after 24 h.     

Large Enhancement of the Single-Molecular Conductance of a Molecular Wire through a Radical Substituent

The single-molecular conductance between two π-conjugated wires with and without a radical substituent has been compared. Specifically, methyl- and iminonitroxide-substituted 4-(biphenyl-4-yl)pyridine wires bound onto a porphyrin template were subjected to scanning tunneling microscopy (STM) apparent-height measurement at the interface between highly oriented pyrolytic graphite (HOPG) and octan-1-oic acid. Statistical analysis of the STM images revealed that the radical-substituted wire has 3.2±1.7-fold higher conductance than the methyl-substituted reference. Although density functional theory (DFT) calculation suggests that only 17 % of the SOMO is distributed on the wire moiety, the effect was significant. This study presents the potential of radical substituents to achieve high conductivity in molecular wires.     

Electrochemical Codeposition of Platinum and Molybdenum Oxides: Formation of Composite Films with Distinct Electrocatalytic Activity for Hydrogen Peroxide Detection

The electrochemical properties of gold electrode surfaces modified by molybdenum oxide films intercalated with platinum microparticles have been described. The incorporation of Pt microparticles at the oxide film was characterized by PIXE (particle induced X‐ray emission) spectroscopy. The modified electrode showed electrochemical activity at around ?0.5 V in 50 mmol L^?1 Na₂SO₄ supporting electrolyte (pH 3), corresponding to the reduction of protons at platinum sites and further transfer of hydrogen atoms to form reduced molybdenum oxides (bronzes). At 0.1 V, the MoO₃ / Pt electrode showed a better performance for hydrogen peroxide oxidation than on platinized gold electrodes. The solution pH has a marked effect on the voltammetric profile and best responses for hydrogen peroxide were obtained at the 5.0 to 6.0 pH range. The activation of the electrode by polarization at negative potentials was also studied and a mechanism by which more platinum sites are available as a consequence of this process was proposed. Calibration plots for hydrogen peroxide were highly linear (r=0.9989) in the 0.2 to 1.6 mmol L^?1 concentration range, with a relative standard deviation (RSD)<1%.     

Structures of Peptidic H‐wires at Mercury Surface: Molecular Dynamics Study

Biopolymer immobilization strategies, self‐assembly systems and adsorption phenomenon in general are crucial for the development of methods that work on the basis of the surface‐detection principle, including electrochemistry. A mechanistic view into the interaction of biopolymers with electrode surfaces is also important for studying fundamental and dynamic processes such as electron/proton transport. In this sense, the utilization of new approaches for investigating the interfacial behavior of immobilized biomolecular architectures is a permanent focus. Here we use a molecular dynamics (MD) approach to simulate the structural changes and metallic surface interactions of a model 21‐mer peptide of His (H) and Ala (A), A₃(HA₂)₆, a peptidic proton wire (H‐wire). This H‐wire was previously proposed for the electrochemical study of proton transfer at mercury electrodes (Langmuir, 2018, 34, 6997). The rigid solid mercury mono‐atomic layer (α‐mercury lattice model) was used systematically in all our simulations. The calculations were performed in a simulation box with 1, 16 and 32 H‐wire strands attached covalently to the mercury layer via the thiol group of a cysteinamide residue appended to the H‐wire C‐terminus. The internal alpha‐helical configuration of H‐wires was maintained by the presence of 2,2,2‐trifluoroethanol. It was shown that both the surface density of H‐wires and the protonation state of His residues play a decisive role in the structural stability and orientation of the peptide to the surface, whereas the applied voltage only has a mild effect on it, especially in case of 16 and 32 H‐wire strand configurations. The MD simulations presented here could be used for the further investigation of other peptides at metallic surfaces and for electrochemical analyses of structural changes of surface‐attached peptides that depend on their protonation states and other external factors.