Investigation of platinum-based nanoparticles on boron-doped diamond substrate for applications in electrocatalysis

The search of new energy sources has motivated during the last few years numerous research projects due to environmental, economical and political reasons. One of the main subjects of these works is the development of fuel cells. Within this framework the Direct Alcohol Fuel Cell (DAFC), mainly fed with methanol or ethanol, has received great attention. However one of the major limitations of the DAFC is the electrocatalysis of fuel oxidation; the electrocatalyst (dispersed Pt-based particles) is indeed readily poisoned by adsorbed intermediates, hence decreasing the fuel cell efficiency. Consequently the electrocatalysis of methanol and ethanol oxidation on different types of Pt-based nanoparticles, deposited on synthetic boron-doped diamond (BDD) thin film, has been studied during this thesis. This substrate has been chosen due to its outstanding properties of chemical inertness, illustrated by a very low capacitive current. In the first part of this thesis, electrodeposited Pt particles on BDD have been studied. Electrodeposition of Pt particles has been carried out both on bare BDD and on diamond pre-modified with gold nanoparticles deposited via a thermal decomposition technique. In both cases it was established that Pt particles were electrodeposited following a progressive mechanism during which formation of new nuclei and growth of primary nuclei simultaneously occur. The electrocatalytic activity of electrodeposited particles was also studied, and it was shown that the presence of Au particles together with Pt particles does not influence markedly the electrocatalytic behaviour of the later ones. Preliminary calcination of the co-deposit results in a dramatic decrease of its electrocatalytic activity, presumably due to the formation of a core (Pt)–shell (Au) structure less capable of alcohols dehydrogenation. Finally electrodeposition of Pt on BDD leads to particles of diameter in the 150-700 nm domain with very large size distribution. Obviously such particles are not consistent with the definition of nanoparticles in catalysis and electrocatalysis. In a second part of this work, Pt-based nanoparticles synthesized via the microemulsion method have been investigated once deposited on a diamond substrate. Attention has been mainly focused on Pt, Pt/Ru and Pt/Sn nanoparticles. All the synthesized nanoparticles are in the 2-5 nm size range with narrow size distribution. Moreover the compositions of bimetallic particles were very close to those expected. The electrocatalytic behaviour of bimetallic Pt-based nanoparticles toward both methanol and ethanol electrooxidation has been investigated. Bimetallic nanoparticles are more efficient than pure Pt, and it was shown that Pt/Ru nanoparticles were more indicated for electrocatalysis of methanol oxidation whereas Pt/Sn were more efficient in the case of electrocatalysis of ethanol oxidation. Both cooperative and electronic effects are involved in the enhancement of the electrocatalytic activity of bimetallic nanoparticles, and Pt-rich nanoparticles are the most efficient ones due to their superior alcohols adsorption properties. However the electronic effect is not of same nature in Pt/Ru than in Pt/Sn (Pt/Ru nanoparticles are alloyed ones, on the contrary of Pt/Sn), and this may explain the probable activation of the ethanol C-C bond scission by Pt/Sn electrocatalysts. Due to the different action modes of Pt/Ru and Pt/Sn electrocatalysts, a ternary Pt/Ru/Sn sample has also been synthesized by the microemulsion technique. This ternary electrocatalyst has exhibited very good activity toward methanol electrooxidation whereas that toward ethanol electrooxidation was significantly lower. It is believed that the electronic effect mainly occurs between Sn and Ru components of the sample, creating a new state of adsorbed oxygenated species that should be of higher mobility and reactivity than on bimetallic surfaces. In addition, a model for methanol electrooxidation at Pt/M (M = Ru, Sn...) surfaces has been developed in order to generalise the obtained results. The concepts and theories of heterogeneous catalysis have been extended to the specific case of this electrochemical reaction involving adsorbed intermediates. The donor-acceptor theory of heterogeneous catalysis has been more particularly considered and adapted, and within this framework Pt has been considered as the acceptor whereas Sn was regarded as the donor. The development of this model has made the establishment of a relation between the measured current to the applied potential possible in a number of real limiting cases. Validity and limitations to the proposed model has in due course been discussed in view of the obtained results

The Impact of the Brain-Derived Neurotrophic Factor Gene on Trauma and Spatial Processing.

The influence of genes and the environment on the development of Post-Traumatic Stress Disorder (PTSD) continues to motivate neuropsychological research, with one consistent focus being the Brain-Derived Neurotrophic Factor (BDNF) gene, given its impact on the integrity of the hippocampal memory system. Research into human navigation also considers the BDNF gene in relation to hippocampal dependent spatial processing. This speculative paper brings together trauma and spatial processing for the first time and presents exploratory research into their interactions with BDNF. We propose that quantifying the impact of BDNF on trauma and spatial processing is critical and may well explain individual differences in clinical trauma treatment outcomes and in navigation performance. Research has already shown that the BDNF gene influences PTSD severity and prevalence as well as navigation behaviour. However, more data are required to demonstrate the precise hippocampal dependent processing mechanisms behind these influences in different populations and environmental conditions. This paper provides insight from recent studies and calls for further research into the relationship between allocentric processing, trauma processing and BDNF. We argue that research into these neural mechanisms could transform PTSD clinical practice and professional support for individuals in trauma-exposing occupations such as emergency response, law enforcement and the military

A novel method for the preparation of bi-metallic (Pt-Au) nanoparticles on boron doped diamond (BDD) substrate: application to the oxygen reduction reaction

A novel method was developed to synthesize bi-metallic nanoparticles (Au-Pt) on boron-doped diamond (BDD) substrate. This method consisted of (a) deposition of a small amount of gold (equivalent to a few monolayers) by sputtering on the BDD surface, (b) heat treatment of the obtained sample at 600°C in air, resulting in the formation of stable nanoparticles on BDD (Au/BDD electrode), (c) electrodeposition of Pt on the Au/BDD surface occurring preferentially on the Au nanoparticles, and finally (d) heat treatment at 400°C to enhance the interaction between Au and Pt. The ratio between Au and Pt nanoparticles can be modified by modifying the amount of electrodeposited Pt and was estimated using cyclic voltammetry. These Pt-Au/BDD composite electrodes were used to study oxygen reduction using both potential sweep (cyclic voltammetry) and hydrodynamic (turbine electrochemical cell) method

Deposition of clusters and nanoparticles onto boron-doped diamond electrodes for electrocatalysis

Metal and metal oxide particles and nanoparticles, differing from each other by their nature and synthesis technique, were deposited onto boron-doped diamond (BDD) thin film electrodes. The applicability in electrocatalysis of thermally decomposed IrO2 and Au nanoparticles, electrodeposited Pt particles, dendrimer-encapsulated Pt nanoparticles (Pt DENs) and microemulsion-synthesized Pt/Ru nanoparticles was studied, once deposited on BDD substrate. In all cases, the electrochemical response of the composite electrodes could be solely attributed to the supported particles. All the particles, with the exception of Pt DENs, exhibited electrocatalytic activity. Pt DENs inactivity has been attributed to insufficient removal of the dendrimer polymer matrix. It was concluded that the BDD electrode is a suitable substrate for the electrochemical investigation of supported catalytic nanoparticle

Deposition of tin oxide, iridium and iridium oxide films by metal-organic chemical vapor deposition for electrochemical wastewater treatment

In this research, the specific electrodes were prepared by metal-organic chemical vapor deposition (MOCVD) in a hot-wall CVD reactor with the presence of O2 under reduced pressure. The Ir protective layer was deposited by using (Methylcyclopentadienyl) (1,5-cyclooctadiene) iridium (I), (MeCp)Ir(COD), as precursor. Tetraethyltin (TET) was used as precursor for the deposition of SnO2 active layer. The optimum condition for Ir film deposition was at 300 °C, 125 of O2/(MeCp)Ir(COD) molar ratio and 12 Torr of total pressure. While that of SnO2 active layer was at 380 °C, 1200 of O2/TET molar ratio and 15 Torr of total pressure. The prepared SnO2/Ir/Ti electrodes were tested for anodic oxidation of organic pollutant in a simple three-electrode electrochemical reactor using oxalic acid as model solution. The electrochemical experiments indicate that more than 80% of organic pollutant was removed after 2.1 Ah/L of charge has been applied. The kinetic investigation gives a two-step process for organic pollutant degradation, the kinetic was zero-order and first-order with respect to TOC of model solution for high and low TOC concentrations, respectively

The Recognizability and Localizability of Auditory Alarms: Setting Global Medical Device Standards.

Objective Four sets of eight audible alarms matching the functions specified in IEC 60601-1-8 were designed using known principles from auditory cognition with the intention that they would be more recognizable and localizable than those currently specified in the standard. Background The audible alarms associated with IEC 60601-1-8, a global medical device standard, are known to be difficult to learn and retain, and there have been many calls to update them. There are known principles of design and cognition that might form the basis of more readily recognizable alarms. There is also scope for improvement in the localizability of the existing alarms. Method Four alternative sets of alarms matched to the functions specified in IEC 60601-1-8 were tested for recognizability and localizability and compared with the alarms currently specified in the standard. Results With a single exception, all prototype sets of alarms outperformed the current IEC set on both recognizability and localizability. Within the prototype sets, auditory icons were the most easily recognized, but the other sets, using word rhythms and simple acoustic metaphors, were also more easily recognized than the current alarms. With the exception of one set, all prototype sets were also easier to localize. Conclusion Known auditory cognition and perception principles were successfully applied to an existing audible alarm problem. Application This work constitutes the first (benchmarking) phase of replacing the alarms currently specified in the standard. The design principles used for each set demonstrate the relative ease with which different alarm types can be recognized and localized

Transition numérique et pratiques de recherche et d’enseignement supérieur en agronomie, environnement, alimentation et sciences vétérinaires à l’horizon 2040.

Pour citer ce document:Barzman M. (Coord.), Gerphagnon M. (Coord.), Mora O. (Coord.),Aubin-Houzelstein G., Bénard A., Martin C., Baron G.L, Bouchet F., Dibie-Barthélémy J., Gibrat J.F., Hodson S., Lhoste E., Moulier-Boutang Y., Perrot S., Phung F., Pichot C., Siné M., Venin T. 2019. Transition numérique et pratiques de recherche et d’enseignement supérieur en agronomie, environnement, alimentation et sciences vétérinaires à l’horizon 2040.INRA, France, 161pagesTransition numérique et pratiques de recherche et d’enseignement supérieur en agronomie, environnement, alimentation et sciences vétérinaires à l’horizon 2040

What makes icons appealing? The role of processing fluency in predicting icon appeal in different task contexts.

Although icons appear on almost all interfaces, there is a paucity of research examining the determinants of icon appeal. The experiments reported here examined the icon characteristics determining appeal and the extent to which processing fluency - the subjective ease with which individuals process information - was used as a heuristic to guide appeal evaluations. Participants searched for, and identified, icons in displays. The initial appeal of icons was held constant while ease of processing was manipulated by systematically varying the complexity and familiarity of the icons presented and the type of task participants were asked to carry out. Processing fluency reliably influenced users' appeal ratings and appeared to be based on users' unconscious awareness of the ease with which they carried out experimental tasks

When the going gets tough the beautiful get going: aesthetic appeal facilitates task performance.

The current studies examined the effect of aesthetic appeal on performance. According to one hypothesis, appeal would lead to overall decrements or enhancements in performance [e.g. Sonderegger & Sauer, (Applied Ergonomics, 41, 403-410, 2010)]. Alternatively, appeal might influence performance only in problem situations, such as when the task is difficult [e.g. Norman, (2004)]. The predictions of these hypotheses were examined in the context of an icon search-and-localisation task. Icons were used because they are well-defined stimuli and pervasive to modern everyday life. When search was made difficult using visually complex stimuli (Experiment 1), or abstract and unfamiliar stimuli (Experiment 2), icons that were appealing were found more quickly than their unappealing counterparts. These findings show that in a low-level visual processing task, with demand characteristics related to appeal eliminated, appeal can influence performance, especially under duress