Hydrogen peroxide is a powerful oxidant that finds application in several areas, but most particularly in the treatment of industrial wastewaters. The aim of the present study was to investigate the ...effects of applied potential and electrolyte flow conditions on the in situ generation of hydrogen peroxide in an electrochemical flow-by reactor with a gas diffusion electrode (GDE). The electrolyses were performed in an aqueous acidic medium using a GDE constructed with conductive black graphite and polytetrafluoroethylene (80:20 w/w). Under laminar flow conditions (flow rate = 50 L/h), hydrogen peroxide was formed in a maximum yield of 414 mg/L after 2 h at −2.25 V vs Pt //Ag/AgCl (global rate constant = 3.1 mg/(L min); energy consumption = 22.1 kWh/kg). Under turbulent flow (300 L/h), the maximum yield obtained was 294 mg/L after 2 h at −1.75 V vs Pt//Ag/AgCl (global rate constant = 2.5 mg/(L min); energy consumption = 30.1 kWh/kg).
In this work, we present a computational investigation on the photoexcitation of indigo carmine (IC). Physical insights regarding IC photoexcitation and photolysis were obtained from a fundamental ...perspective through quantum chemistry computations. Density functional theory (DFT) was used to investigate the ground state while its time-dependent formalism (TD-DFT) was used for probing excited state properties, such as vertical excitation energies, generalized oscillator strengths (GOS), and structures. All the computations were undertaken using two different approaches: M06-2X/6-311+G(d,p) and CAM-B3LYP/6-311+G(d,p), in water. Results determined using both methods are in systematic agreement. For instance, the first singlet excited state was found at 2.28 eV (with GOS = 0.4730) and 2.19 eV (GOS = 0.4695) at the TD-DFT/CAM-B3LYP/6-311+G(d,p) and TD-DFT/M06-2X/6-311+G(d,p) levels of theory, respectively. Excellent agreement was observed between the computed and the corresponding experimental UV-Vis spectra. Moreover, results suggest IC undergoes photodecomposition through excited state chemical reaction rather than via a direct photolysis path. To the best of our knowledge, this work is the first to tackle the photoexcitation, and its potential connections to photodegradation, of IC from a fundamental chemical perspective, being presented with expectations to motivate further studies.
Bisphenol A (BPA) is an environmental endocrine disrupting chemical, which can lead to various adverse health effects. Aiming to develop effective tools for the detection of BPA, this work reports a ...low cost and stable film based on casein (CAS) and Carbon Black (CB). The proposed material (CAS‐CB) showed structures of CAS surrounded by CB agglomerates observed by Scanning Electron Microscopy while Fourier Transform Infrared Spectroscopy analysis illustrated characteristic bands of casein. Cyclic Voltammetry (CV) and linear sweep voltammetry (LSV) were used to investigate the electrochemical behavior of BPA using the CAS‐CB. Under optimal conditions, LSV detection presented a limit of detection of 0.25 μmol L−1 in a linear range from 0.49 to 24 μmol L−1. Additionally, the working electrode (GC) modified by the proposed film (CAS‐CB) was applied for BPA sensing in environmental and milk samples. The results showed recoveries between 95.4 to 114 % attesting the efficiency of this new material, which has simplicity in the preparation, high conductivity, and adsorption capability.
This study reports the use of carbon‐supported IrRh/C electrocatalysts with different iridium‐to‐rhodium atomic ratios (0 : 100, 50 : 50, 70 : 30, 90 : 10, and 100 : 0) for ammonia electro‐oxidation ...(AmER) in alkaline media. The materials prepared by using the sodium borohydride method showed a mean diameter of 4.5, 4.8, 4.2, and 4.5 nm for Ir/C, Ir90Rh10/C, Ir70Rh30/C, and Ir50Rh50/C, respectively. According to electrochemical and fuel cell experiments, the Ir50Rh50/C catalyst was the most promising towards AmER. This catalyst, which consisted predominantly of the metallic Ir/Rh phases, showed a 500 % higher current density and 55 % higher maximum power than that obtained for Ir/C. After 8 h galvanostatic electrolysis, 93 % of initial ammonia was degraded when using Ir50Rh50/C, whereas it was only 70 % with Ir/C. The high activity of the Ir50Rh50/C is attributed to a synergic effect of two metals at this iridium‐to‐rhodium ratio, which enhances the kinetics of AmER contributing towards ammonia dehydrogenation at lower potentials.
Fuel for thought: Carbon‐supported IrRh nanoparticles (IrRh/C) with different iridium‐to‐rhodium atomic ratios (0 : 100, 50 : 50, 70 : 30, 90 : 10, and 100 : 0) are synthesized, and their catalytic activity towards ammonia electro‐oxidation is evaluated. IrRh/C is then further evaluated in a direct ammonia fuel cell.
In this study, we report an electrochemical study based on nanocellulose (NC) and single-walled carbon nanohorns (SWCNH). SWCNH and NC ensure large surface area, good conductivity, high porosity and ...chemical stability, becoming attractive for electrodes. The materials were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR), Scanning Electron Micrograph (SEM), Transmission electron microscopy (TEM), dynamic light scattering (DLS) and zeta potential. Using XRD and FTIR it was possible to observe particular characteristics of NC and SWCNH. The presence of dahlia-like assemblies on the NC surface was observed by MEV and TEM. Then, we investigated the electrochemical behavior of NC-SWCNH, which showed the excellent results when it was used guanine and adenine, as proof of concept, by using cyclic and linear sweep voltammetry (LSV). LSV was also employed for simultaneous detection resulting in limits of detection of 1.7 × 10−7 mol L−1 and 1.4 × 10−6 mol L−1, for guanine and adenine, respectively. In addition, the proposed electrode was applied for determination of both bases in synthetic human serum and fish sperm. We demonstrate that it is possible to use NC, a renewable material, in conducting thin films with SWCNH, and due to simplicity in the preparation and high conductivity, this new thin film could be extended for others electrochemical purposes such as sensing and biosensing.
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This study reports the use of PtAu/C electrocatalysts with different atomic ratios (90:10, 70:30 and 50:50) supported on Vulcan XC 72 carbon and prepared by the sodium borohydride method toward ...formate electro-oxidation in alkaline media. The materials were characterized by X-ray diffraction, showing peaks characteristics of Pt and Au face-centered-cubic structures, and also by transmission electron micrographs that show the nanoparticles well dispersed on carbon and a mean particle size between 4 and 5 nm for all electrocatalysts. Electrochemical experiments show PtAu/C as promising catalysts toward formate oxidation, while single cell experiments reveal PtAu/C 90:10 as the best material since it provides a power density higher than Pt/C. The incorporation of Au could increase formate oxidation for more than one reason: (i) a facilitated rupture of C–H bond; (ii) the Au/oxide interface or (iii) by regenerating active sites.
PtAu/C electrocatalysts in different atomic ratios and supported on Vulcan XC 72 carbon were tested for ethanol electro-oxidation in alkaline media. The electrocatalysts were prepared using ...borohydride as reducing agent. PtAu/C X-ray diffraction (XRD) patterns showed peaks characteristic of Pt face-centered cubic (fcc) structure and carbon. PtAu/C (70:30) and (50:50) XRD patterns showed a shift to lower values of 2θ when compared to Pt/C, this way suggesting the formation of PtAu alloy. Transmission electron micrographs showed the nanoparticles with particle size between 4 and 6.5 nm for all PtAu/C electrocatalysts. Electrochemical characterization of the PtAu/C materials suggested the PtAu/C (50:50) as the most promising material for ethanol electro-oxidation while experiments in single fuel cell suggested PtAu/C (70:30). The discrepancy in the results obtained can be explained by the electrode construction since PtAu/C (50:50) yields a much thicker electrode than PtAu/C (70:30), due to the Pt load is the same. The best results obtained with PtAu/C electrocatalysts could be explained by the presence of Pt and Au in close contact (alloy) associated to the extend in the platinum lattice parameters since these properties could contribute to the C–C breaking bond.
•Effect of PtAu/C electrocatalysts toward the ethanol electro-oxidation reaction.•PtAu/C 50:50 showed the best result in electrochemical experiments.•PtAu/C 70:30 showed a power density 3 times higher than the one obtained using Pt/C.•Pt and Au in close contact (alloy) contribute to the C–C breaking bond.
PdAu/C electrocatalysts in different atomic ratios (90:10, 80:20, 70:30, and 50:50) supported on Vulcan XC72 carbon were evaluated toward formate oxidation in alkaline media. The materials were ...prepared by the borohydride process. X-ray diffraction (XRD) patterns of PdAu materials showed peak characteristic of Pd and Au face-centered-cubic (fcc) structures while transmission electron micrographs (TEM) showed the nanoparticles with particle size between 4 and 10 nm for all electrocatalysts. Experiments considering single cell suggested the PdAu/C (90:10) and PdAu/C (80:20) as promisors for formate oxidation. The best result obtained was attributed to the presence of Au in small quantities that contributes to the formate adsorption.
•Evaluation of PtAu/C catalysts by electrochemical experiments.•Effect of PtAu/C electrocatalysts in a direct ammonia fuel cell.•PtAu/C 70:30 showed a power density 60% higher than Pt/C.•PtAu/C 70:30 ...showed alloyed phase and lower Au-N energy adsorption.
PtAu/C electrocatalysts prepared by borohydride reduction method with different Pt:Au atomic ratios (50:50 and 70:30) were tested as work electrodes/anodes in electrochemical experiments and also using a direct ammonia fuel cell (DAFC). X-ray diffraction patterns showed the formation of PtAu alloy while transmission electron micrographs showed the particles sizes between 5.8 and 6.4nm. PtAu/C 70:30 presented the best results showing a current density about 20% higher when compared to Pt/C in voltammetry experiments and a power density about 60% higher than Pt/C using DAFC, while Au/C showed practically no activity in both experiments. The best results obtained with PtAu/C (70:30) could be explained by the electronic effect (PtAu alloy) associated with adsorbed hydroxyl species (AuOHads) and also the lower Au-N energy adsorption.
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