pH dependence of the electroreduction of nitrate on Rh and Pt polycrystalline electrodes

2014 ◽  
Vol 50 (17) ◽  
pp. 2148-2151 ◽  
Author(s):  
Jian Yang ◽  
Paula Sebastian ◽  
Matteo Duca ◽  
Thijs Hoogenboom ◽  
Marc T. M. Koper

From a study of the electrocatalytic reduction of nitrate on Pt and Rh electrodes over a wide pH range, HNO3 is suggested as the only reducible species in nitrate reduction on Pt, whereas both HNO3 and the nitrate anion are reducible on Rh.

1990 ◽  
Vol 95 (6) ◽  
pp. 1183-1204 ◽  
Author(s):  
J E Raftos ◽  
B T Bulliman ◽  
P W Kuchel

When erythrocytes are suspended in a solution of known composition the resultant values of such basic cell parameters as volume and pH are difficult to predict. To facilitate such predictions, we developed a mathematical model describing the passive transmembrane distribution of permeant species; three simultaneous equations were produced. Certain essential data required for the model were determined experimentally; these included the pH dependence of the charge on the hemoglobin molecule and the variation of the osmotic coefficient of hemoglobin with cell volume. Finally, cells were added to various solutions, and then titrated to produce a wide pH range (pH 6-8). We measured the resultant cell volume, cellular and extracellular pH using both conventional and 31P NMR methods. The expected equilibrium values of these electrochemical parameters were also calculated by solving (numerically) the three model equations. The accuracy of the model simulations was evaluated by direct comparison of calculated and experimentally determined values.


1998 ◽  
Vol 335 (2) ◽  
pp. 357-368 ◽  
Author(s):  
Sarah E. J. FAWCETT ◽  
David DAVIS ◽  
Jacques L. BRETON ◽  
Andrew J. THOMSON ◽  
Fraser A. ARMSTRONG

Reactions of the [3Fe-4S] cluster and various metallated [M3Fe-4S] adducts co-ordinated in the ferredoxin from the hyperthermophile Pyrococcus furiosus have been studied by protein-film voltammetry, bulk-solution voltammetry, solution kinetics and magnetic CD (MCD). The [3Fe-4S] cluster exhibits two couples, [3Fe-4S]+/0 and [3Fe-4S]0/2-. Film voltammetry is possible over a wide pH range (2–8), revealing that the [3Fe-4S]+/0 couple shows a complex pH dependence with pKred1 = 2.8, pKox = 4.9 and pKred2 = 6.7. From MCD, pKred1 corresponds with protonation of [3Fe-4S]0 to give a spectroscopically distinct species, as reported for ferredoxins from Azotobacterand Sulfolobus. The status of the disulphide/disulphydryl entity makes no significant difference to the data (given for the -S-S- form). Formation of the hyper-reduced [3Fe-4S]2- state is observed, requiring 3H+ for the overall 3e- reduction of [3Fe-4S]+, the change therefore being electroneutral. By comparison with the ferredoxin from Desulfovibrio africanus, uptake of Fe(II) and other M(II) by [3Fe-4S]0 to give [M3Fe-4S] clusters is slow (t1/2 > 10 min at room temperature, slower still if the protein is adsorbed on the electrode), whereas reaction with Tl(I) to produce [Tl3Fe-4S] is very rapid (t1/2 ≪ 1 s), suggesting that co-ordination of Tl does not require reorganization of the protein structure. Rates of formation of [3Fe-4S] from [M3Fe-4S] adducts increase sharply at high potentials, showing that metal release involves a labile ‘super-oxidized ’ [M3Fe-4S]3+ state.


1991 ◽  
Vol 56 (12) ◽  
pp. 2791-2799 ◽  
Author(s):  
Juan A. Squella ◽  
Luis J. Nuñez-Vergara ◽  
Hernan Rodríguez ◽  
Amelia Márquez ◽  
Jose M. Rodríguez-Mellado ◽  
...  

Five N-p-phenyl substituted benzamidines were studied by DC and DP polarography in a wide pH range. Coulometric results show that the overall processes are four-electron reductions. Logarithmic analysis of the waves indicate that the process are irreversible. The influence of the pH on the polarographic parameters was also studied. A UV spectrophotometric study was performed in the pH range 2-13. In basic media some variations in the absorption bands were observed due to the dissociation of the amidine group. A determination of the pK values was made by deconvolution of the spectra. Correlations of both the electrochemical parameters and spectrophotometric pK values with the Hammett substituent constants were obtained.


1989 ◽  
Vol 54 (1) ◽  
pp. 64-69 ◽  
Author(s):  
Roland Meier ◽  
Gerhard Werner ◽  
Matthias Otto

Electrochemical oxidation of [V(IV)O(nta)(H2O)]- (H3nta nitrilotriacetic acid) was studied in aqueous solution by means of cyclic voltammetry, differential pulse polarography, and current sampled DC polarography on mercury as electrode material. In the pH-range under study (5.5-9.0) the corresponding V(V) complex is produced by one-electron oxidation of the parent V(IV) species. The oxidation product is stable within the time scale of cyclic voltammetry. The evaluation of the pH-dependence of the half-wave potentials leads to a pKa value for [V(IV)O(nta)(H2O)]- which is in a good agreement with previous determinations. The measured value for E1/2 is very close to the formal potential E0 calculated via the Nernst equation on the basis of known literature values for log Kox and log Kred, the complex stability constants for the oxidized and reduced form, respectively.


Author(s):  
Manoj Kumar Panjwani ◽  
Qing Wang ◽  
Yueming Ma ◽  
Yuxuan Lin ◽  
Feng Xiao ◽  
...  

The development of a heterogeneous Fenton-like catalyst, possessing high degradation efficiency in a wide pH range, is crucial for wastewater treatment. The Fe-Mn-SiO2 catalyst was designed, and prepared by a...


Nanomaterials ◽  
2021 ◽  
Vol 11 (3) ◽  
pp. 662 ◽  
Author(s):  
Guangsheng Liu ◽  
Kunyapat Thummavichai ◽  
Xuefeng Lv ◽  
Wenting Chen ◽  
Tingjun Lin ◽  
...  

Molybdenum disulfide (MoS2) has been universally demonstrated to be an effective electrocatalytic catalyst for hydrogen evolution reaction (HER). However, the low conductivity, few active sites and poor stability of MoS2-based electrocatalysts hinder its hydrogen evolution performance in a wide pH range. The introduction of other metal phases and carbon materials can create rich interfaces and defects to enhance the activity and stability of the catalyst. Herein, a new defect-rich heterogeneous ternary nanocomposite consisted of MoS2, NiS and reduced graphene oxide (rGO) are synthesized using ultrathin αNi(OH)2 nanowires as the nickel source. The MoS2/rGO/NiS-5 of optimal formulation in 0.5 M H2SO4, 1.0 M KOH and 1.0 M PBS only requires 152, 169 and 209 mV of overpotential to achieve a current density of 10 mA cm−2 (denoted as η10), respectively. The excellent HER performance of the MoS2/rGO/NiS-5 electrocatalyst can be ascribed to the synergistic effect of abundant heterogeneous interfaces in MoS2/rGO/NiS, expanded interlayer spacings, and the addition of high conductivity graphene oxide. The method reported here can provide a new idea for catalyst with Ni-Mo heterojunction, pH-universal and inexpensive hydrogen evolution reaction electrocatalyst.


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