Photoelectrochemical oxidation of glycerol on hematite: thermal effects, in situ FTIR and long-term HPLC product analysis

Photoelectrochemical (PEC) oxidation of biomass is a profitable approach to produce hydrogen by substituting the water oxidation reaction in the electrolyzers’ photoanodes. Among the biomass-derived molecules, glycerol is an interesting alternative to water since its standard thermodynamic potential is considerably lower than that of water and because it is widely produced in the biodiesel industry. Herein, we performed a fundamental study of the PEC oxidation of glycerol on hematite. In situ FTIR experiments and long-term electrolysis followed by HPLC analysis revealed C1, C2 and C3 oxidation products showing the low selectivity of the reaction under these conditions. We explained this lack of selectivity by an electrooxidation mechanism involving highly reactive radicals as intermediates. [Figure not available: see fulltext.]

Bi-modified Pt Electrodes toward Glycerol Electrooxidation in Alkaline Solution: Effects on Activity and Selectivity

Herein we investigate the effect of irreversibly adsorbed bismuth on polycrystalline platinum (Ptp) on the electrooxidation of glycerol in alkaline media by combining electrochemical, spectroscopic (in situ FTIR), and analytical (HPLC on line) techniques. We found that the activity of Ptp increases by about 5-fold when the optimal quantity of Bi ions is added to the solution. Besides, the adatom strongly impacts the reaction products by suppressing the pathways with C–C bond breaking, hindering the formation of CO (and other unknown intermediates) and enhancing the production of glycerate. Different from the results in acid media for Ptp-Bi systems where Bi blocks the oxidation pathway through the primary carbon, glycerate is the main product in alkaline media, and dihydroxyacetone is either produced in extremely low quantities or not produced. Besides, comparing our results with those in acid media, the peak current recorded at 1 mV·s–1 in this work was 1 order of magnitude higher. These results show the strong impact of the pH in the reaction rate and selectivity.Financial support from the Brazilian agencies: PSF and JLB thanks FAPESP (grants: 2016/01365-0) and Shell and the strategic importance of the support given by ANP (Brazil’s National Oil, Natural Gas and Biofuels Agency) through the R&D levy regulation. MBCS thanks PRP-FAEPEX and RAV and VYY thanks SAE-Unicamp for their scholarships. J.S-G. acknowledges financial support from VITC (Vicerrectorado de Investigación y Transferencia de Conocimiento) of the University of Alicante (UATALENTO16-02)

Weak gauge principle and electric charge quantization

Starting from a weak gauge principle we give a new and critical revision of the argument leading to charge quantization on arbitrary spacetimes. The main differences of our approach with respect to previous works appear on spacetimes with non trivial torsion elements on its second integral cohomology group. We show that in these spacetimes there can be topologically non-trivial configurations of charged fields which do not imply charge quantization. However, the existence of a non-exact electromagnetic field always implies the quantization of charges. Another consequence of the theory for spacetimes with torsion is the fact that it gives rise to two natural quantization units that could be identified with the electric quantization unit (realized inside the quarks) and with the electron charge. In this framework the color charge can have a topological origin, with the number of colors being related to the order of the torsion subgroup. Finally, we discuss the possibility that the quantization of charge may be due to a weak non-exact component of the electromagnetic field extended over cosmological scales.Comment: Latex2e, 24 pages, no figure

Electrooxidation of C-4 polyols on platinum single- crystals: a computational and electrochemical study

Many polyols are abundant and cheap molecules highly spread in the biomass. These molecules have an enormous potential to be used in electrochemical devices to generate energy and/or value-added molecules. The electrooxidation of polyols can produce different substances of interest in the chemical industry concomitantly to high purity hydrogen in electrolyzers. The cost in the production of all these chemicals depends, among other factors, on the develop of more active and selective catalysts. However, in order to search for these materials using computational experiments, it is mandatory to have a better understanding of the fundamental aspect of the reactions, which permit to base the search on the adsorption energies of one or more key reaction intermediates. To contribute to this task, we performed (spectro)-electrochemical and computational experiments to study the electrooxidation of C-4 polyols. We show that the electrooxidation of polyols does not depend on the relative orientation of their OH groups. Besides, using Pt single crystals, we demonstrate that the trend for the oxidation of the primary carbon (relative to the secondary) increases in the order Pt(111) < Pt(100) < Pt(110) and that this result can be extended to polyols with longer carbon chains. Finally, computational experiments permit us to rationalize these trends looking at the relative stability of double dehydrogenated intermediates on the Pt basal planes.Catalysis and Surface Chemistr

Formation and aging of incipient thin film wax-oil gels

A fundamental study of the deposition and aging of a thin incipient wax-oil gel that is formed during the flow of waxy oils in cooled pipes was performed. The solubility of high molecular weight paraffins in naphthenic, aromatic or paraffinic solvents is very low and decreases rapidly with decreasing temperature. This property of the paraffins leads to the formation of gels of complex morphology that deposit on the cold walls of the subsea pipelines during the flow of waxy crudes. This deposition reduces the pipe diameter and decreases the flow capacity of the pipe. These wax-oil gels contain a large fraction of oil trapped in a 3-D network structure of the wax crystals that behaves as a porous medium. After the incipient gel is formed, wax molecules continue to diffuse into this structure, thereby increasing its wax content. A model system of wax and oil mixture was used to understand the aging process of the wax-oil gels, which hardens the wax deposit with time. To understand the physics of the aging process for incipient thin-film deposits, a series of laboratory flow loop experiments was performed. The aging process was a counterdiffusion phenomenon with a critical carbon number above which wax molecules diffuse into the gel deposit and below which oil molecules diffuse out of the deposit. The aging rate of the gel deposit depends on the oil flow rate and the wall temperature. A mathematical model developed predicted the growth and wax content of the gel deposit on externally cooled pipe walls. The theory agreed with experiments excellently for thin gels.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/34241/1/690460517_ftp.pd

Morphological evolution of thick wax deposits during aging

The presence of waxes in crude oil can lead to the formation of wax deposits on the walls of cold subsea pipelines, which restricts flow and can lead to plugging of the pipelines. This problem has recently become more significant as the production wells move further offshore causing the oil to be cooled below the cloud point before reaching shore. Wax deposition was studied in the laboratory under conditions simulating the deposition in a subsea pipeline. Wax deposition is initiated by the precipitation of wax directly on the pipe wall and the formation of a network of' wax crystals (wax-oil gel) with significant amounts of oil trapped in it. Radial diffusion of the wax molecules from the bulk solution to the gel deposit causes it to simultaneously grow and age with time. The wax molecules diffusing into the gel deposit precipitate near the interface resulting in a faster aging rate of the deposit new the interface than that near the wall. This nonuniform aging of the wax deposit causes the evolution of complex morphologies of the wax deposits. The diffusion of wax molecules into the gel matrix was analyzed theoretically during the growth of the wax deposit. This mathematical model predicted the radial variation of the morphology of the wax deposit observed in the laboratory flow loop experiments along with the deposit thickness as a function of time.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/34242/1/690470103_ftp.pd

A cluster randomised trial, cost-effectiveness analysis and psychosocial evaluation of insulin pump therapy compared with multiple injections during flexible intensive insulin therapy for type 1 diabetes: the REPOSE Trial.

BACKGROUND: Insulin is generally administered to people with type 1 diabetes mellitus (T1DM) using multiple daily injections (MDIs), but can also be delivered using infusion pumps. In the UK, pumps are recommended for patients with the greatest need and adult use is less than in comparable countries. Previous trials have been small, of short duration and have failed to control for training in insulin adjustment. OBJECTIVE: To assess the clinical effectiveness and cost-effectiveness of pump therapy compared with MDI for adults with T1DM, with both groups receiving equivalent structured training in flexible insulin therapy. DESIGN: Pragmatic, multicentre, open-label, parallel-group cluster randomised controlled trial, including economic and psychosocial evaluations. After participants were assigned a group training course, courses were randomly allocated in pairs to either pump or MDI. SETTING: Eight secondary care diabetes centres in the UK. PARTICIPANTS: Adults with T1DM for > 12 months, willing to undertake intensive insulin therapy, with no preference for pump or MDI, or a clinical indication for pumps. INTERVENTIONS: Pump or MDI structured training in flexible insulin therapy, followed up for 2 years. MDI participants used insulin analogues. Pump participants used a Medtronic Paradigm(®) Veo(TM) (Medtronic, Watford, UK) with insulin aspart (NovoRapid, Novo Nordisk, Gatwick, UK). MAIN OUTCOME MEASURES: Primary outcome - change in glycated haemoglobin (HbA1c) at 2 years in participants whose baseline HbA1c was ≥ 7.5% (58 mmol/mol). Key secondary outcome - proportion of participants with HbA1c ≤ 7.5% at 2 years. Other outcomes at 6, 12 and 24 months - moderate and severe hypoglycaemia; insulin dose; body weight; proteinuria; diabetic ketoacidosis; quality of life (QoL); fear of hypoglycaemia; treatment satisfaction; emotional well-being; qualitative interviews with participants and staff (2 weeks), and participants (6 months); and ICERs in trial and modelled estimates of cost-effectiveness. RESULTS: We randomised 46 courses comprising 317 participants: 267 attended a Dose Adjustment For Normal Eating course (132 pump; 135 MDI); 260 were included in the intention-to-treat analysis, of which 235 (119 pump; 116 MDI) had baseline HbA1c of ≥ 7.5%. HbA1c and severe hypoglycaemia improved in both groups. The drop in HbA1c% at 2 years was 0.85 on pump and 0.42 on MDI. The mean difference (MD) in HbA1c change at 2 years, at which the baseline HbA1c was ≥ 7.5%, was -0.24% [95% confidence interval (CI) -0.53% to 0.05%] in favour of the pump (p = 0.098). The per-protocol analysis showed a MD in change of -0.36% (95% CI -0.64% to -0.07%) favouring pumps (p = 0.015). Pumps were not cost-effective in the base case and all of the sensitivity analyses. The pump group had greater improvement in diabetes-specific QoL diet restrictions, daily hassle plus treatment satisfaction, statistically significant at 12 and 24 months and supported by qualitative interviews. LIMITATION: Blinding of pump therapy was not possible, although an objective primary outcome was used. CONCLUSION: Adding pump therapy to structured training in flexible insulin therapy did not significantly enhance glycaemic control or psychosocial outcomes in adults with T1DM. RESEARCH PRIORITY: To understand why few patients achieve a HbA1c of < 7.5%, particularly as glycaemic control is worse in the UK than in other European countries. TRIAL REGISTRATION: Current Controlled Trials ISRCTN61215213. FUNDING: This project was funded by the National Institute for Health Research (NIHR) Health Technology Assessment programme and will be published in full in Health Technology Assessment; Vol. 21, No. 20. See the NIHR Journals Library website for further project information

Study of the electrocatalytic activity of platinum-based catalysts supported on transition metal carbide for the oxygen reduction reaction in acid medium

As células a combustível são dispositivos eletroquímicos que produzem energia elétrica limpa. Entretanto, o seu uso em larga escala ainda é limitado devido às enormes perdas de potencial que ocorrem no cátodo em função da lenta cinética da reação de redução de oxigênio (RRO). Portanto, é necessário o desenvolvimento de novos catalisadores que sejam viáveis comercialmente, apresentem alta atividade eletrocatalítica e grande estabilidade para esta reação. Neste trabalho, a RRO foi estuda em meio ácido em eletrocatalisadores à base de platina suportadas em carbetos de tungstênio (WC) e molibdênio (MoC) com diferentes estruturas cristalinas. Os carbetos foram preparados pelos métodos de decomposição térmica (MDT) e carburação (MC) e, subsequentemente, utilizados para a preparação dos catalisadores do tipo Pt-carbeto pelo método do ácido fórmico ou borohidreto de sódio. Estes materiais foram caracterizados por difração de raios-X (XRD), espectroscopia de energia dispersiva de raios-X (EDX), microscopia eletrônica de transmissão (TEM), espectroscopia de absorção de raios-X (XAS) in situ e espectroscopia de fotoelétrons excitados por raios-X (XPS). As medidas eletroquímicas foram realizadas em meio ácido usando a técnica de eletrodo disco-anel rotativo de camada fina. Os resultados de XRD, em conjunto com as medidas de TEM, indicaram que o MDT e MC fornecem carbetos com estruturas cúbicas (&beta;-WC1-x e &delta;-MoC) e hexagonais (&alpha;-WC e &alpha;-Mo2C) com tamanho de partícula < 2 nm e entre 10 e 40 nm, respectivamente. Os estudos eletroquímicos evidenciaram que os catalisadores Pt-carbeto/C apresentam diferenças de atividade específica (SA) e mássica (MA) para a RRO em função da estrutura e composição e que todos os catalisadores do tipo Pt-&beta;-WC1-x/C, Pt- &alpha;-Mo2C/C e Pt-&delta;-MoC/C e Pt2Ni- &alpha;-WC/C apresentam maior SA em comparação à Pt/C. A concentração de carbeto na matriz de carbono também influenciou significativamente os valores de SA, porém não há uma tendência clara que permita unificar um efeito comum para todos os catalisadores. Dentre todos estes catalisadores, o Pt-&beta;-WC1-x40/C e o Pt-&delta;-MoC40/C são 3,6 e 2,5 vezes mais ativos (SA) em comparação ao catalisador Pt/C. Também foi observado que a via predominante da RRO envolve cerca de 4 elétrons por molécula de oxigênio, com baixa produção de H2O2 em todos os casos. No caso dos materiais baseados em Pt-&beta;-WC1-x/C, análises de XANES in situ mostraram um pequeno aumento na ocupação da banda 5d da Pt, o que deve levar a uma interação Pt-OHx mais fraca, aumentando a cinética da RRO como observado. Além disso, os resultados de XPS evidenciam que a melhora na atividade específica está relacionada a um efeito sinérgico entre Pt ou Pt2Ni com as espécies do tipo WOx ou MoOx; exceto para os catalisadores de ligas Pt2Ni, para o qual os resultados de XPS indicaram a presença de WC na superfície do catalisador. Os testes de estabilidade mostraram que apesar do Pt/C ser mais ativo após 12.000 ciclos, o catalisador Pt-&alpha;-WC20/C é o mais estável em relação a sua AS, indicando que as interações benéficas das fases remanescente de Pt e WC/WOx são mantidas após o teste de durabilidade.Fuel cells are electrochemical devices that produce clean electrical energy. However, their use on large scale is still limited due to the enormous potential losses that occur at the cathode due the slow kinetics of the oxygen reduction reaction (ORR). Therefore, the development of new catalysts that are commercially viable, present high electrocatalytic activity and great stability for this reaction is still necessary. In this work, the ORR was studied in acid medium on platinum-based electrocatalysts supported on tungsten (WC) and molybdenum (MoC) carbides with different crystalline structures. Carbides were prepared by the thermal decomposition (TDM) and a carburizing (CM) methodes and, subsequently used for the preparation of the Pt-carbide type catalysts by the formic acid or sodium borohydride method. These materials were characterized by X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS). The electrochemical measurements were performed in acid medium using the thin-layer rotating disk-ring electrode technique. The results of XRD, together with those of TEM, indicate that the MDT and MC provide carbides with cubic (&beta;-WC1-x and &delta;-MoC) and hexagonal ( &alpha;-WC and &alpha;-Mo2C) structures with particle size < 2 nm and between 10 and 40 nm, respectively. The Pt-carbide/C catalysts exhibit differences in the specific activity (SA) and mass (MA) for the ORR as a function of structure and composition. All catalysts of the types Pt-&beta;-WC1-x/C, Pt- &alpha;-Mo2C/C, Pt-&delta;-MoC/C and Pt2Ni- &alpha;-WC/C presented higher SA as compared to Pt/C. The concentration of carbide in the carbon matrix significantly influence the SA, but no tendency was clearly found so to identify a common effect catalysts overall. Among all catalysts, Pt-&beta;-WC1-x40/C and Pt-&delta;-MoC40/C are 3.6 and 2.5 times more active (SA) compared to the Pt/C catalyst. It was also observed that the predominant ORR mechanism involve &cong; 4 electrons per oxygen molecule, and so with negligible production of H2O2. In the case of the materials based on Pt-&beta;-WC1-x/C, in situ XANES analyzes evidenced a small increase in the Pt 5d-band, occupancy leading to a weaker Pt-OHx interaction, increasing ORR kinetics as observed. In addition, XPS results show that the improvement in SA is related to a synergistic effect between Pt or Pt2Ni with WOx or MoOx species, except for the Pt2Ni alloy catalysts, for which the XPS results indicated the presence of some WC on the catalyst surface. Stability tests show that although Pt/C is more active after 12,000 cycles, the Pt-&alpha;-WC20/C catalyst is the most stable relative to its SA, indicating that the beneficial interactions of the remaining phases of Pt and WC/WOx are maintained after the durability test