Electrocatalytic hydrogen generation using tripod containing pyrazolylborate-based copper(ii), nickel(ii), and iron(iii) complexes loaded on a glassy carbon electrode.

Three transition metal complexes (MC) namely, [TpMeMeCuCl(H2O)] (CuC), [TpMeMeNiCl] (NiC), and [TpMeMeFeCl2(H2O)] (FeC) {TpMeMe = tris(3,5-dimethylpyrazolyl)borate} were synthesized and structurally characterized. The three complexes CuC, NiC, and FeC-modified glassy carbon (GC) were examined as molecular electrocatalysts for the hydrogen evolution reaction (HER) in alkaline solution (0.1 M KOH). Various GC-MC electrodes were prepared by loading different amounts (ca. 0.2-0.8 mg cm-2) of each metal complex on GC electrodes. These electrodes were used as cathodes in aqueous alkaline solutions (0.1 M KOH) to efficiently generate H2 employing various electrochemical techniques. The three metal complexes' HER catalytic activity was assessed using cathodic polarization studies. The charge-transfer kinetics of the HER at the (GC-MC)/OH- interface at a given overpotential were also studied using the electrochemical impedance spectroscopy (EIS) technique. The electrocatalyst's stability and long-term durability tests were performed employing cyclic voltammetry (repetitive cycling up to 5000 cycles) and 48 h of chronoamperometry measurements. The catalytic evolution of hydrogen on the three studied MC surfaces was further assessed using density functional theory (DFT) simulations. The GC-CuC catalysts revealed the highest HER electrocatalytic activity, which increased with the catalyst loading density. With a low HER onset potential (E HER) of -25 mV vs. RHE and a high exchange current density of 0.7 mA cm-2, the best performing electrocatalyst, GC-CuC (0.8 mg cm-2), showed significant HER catalytic performance. Furthermore, the best performing electrocatalyst required an overpotential value of 120 mV to generate a current density of 10 mA cm-2 and featured a Tafel slope value of -112 mV dec-1. These HER electrochemical kinetic parameters were comparable to those measured here for the commercial Pt/C under the same operating conditions (-10 mV vs. RHE, 0.88 mA cm-2, 108 mV dec-1, and 110 mV to yield a current density of 10 mA cm-2), as well as the most active molecular electrocatalysts for H2 generation from aqueous alkaline electrolytes. Density functional theory (DFT) simulations were used to investigate the nature of metal complex activities in relation to hydrogen adsorption. The molecular electrostatic surface potential (MESP) of the metal complexes was determined to assess the putative binding sites of the H atoms to the metal complex.

Correction: Electrocatalytic hydrogen generation using tripod containing pyrazolylborate-based copper(ii), nickel(ii), and iron(iii) complexes loaded on a glassy carbon electrode.

[This corrects the article DOI: 10.1039/D1RA08530A.].

The Influence of Microstructure on the Passive Layer Chemistry and Corrosion Resistance for Some Titanium-Based Alloys.

The effect of microstructure and chemistry on the kinetics of passive layer growth and passivity breakdown of some Ti-based alloys, namely Ti-6Al-4V, Ti-6Al-7Nb and TC21 alloys, was studied. The rate of pitting corrosion was evaluated using cyclic polarization measurements. Chronoamperometry was applied to assess the passive layer growth kinetics and breakdown. Microstructure influence on the uniform corrosion rate of these alloys was also investigated employing dynamic electrochemical impedance spectroscopy (DEIS). Corrosion studies were performed in 0.9% NaCl solution at 37 °C, and the obtained results were compared with ultrapure Ti (99.99%). The different phases of the microstructure were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Chemical composition and chemistry of the corroded surfaces were studied using X-ray photoelectron spectroscopy (XPS) analysis. For all studied alloys, the microstructure consisted of α matrix, which was strengthened by ß phase. The highest and the lowest values of the ß phase's volume fraction were recorded for TC21 and Ti-Al-Nb alloys, respectively. The susceptibility of the investigated alloys toward pitting corrosion was enhanced following the sequence: Ti-6Al-7Nb < Ti-6Al-4V << TC21. Ti-6Al-7Nb alloy recorded the lowest pitting corrosion resistance (Rpit) among studied alloys, approaching that of pure Ti. The obvious changes in the microstructure of these alloys, together with XPS findings, were adopted to interpret the pronounced variation in the corrosion behavior of these materials.

Optimisation of the composition of a screen-printed acrylate polymer enzyme layer with respect to an improved selectivity and stability of enzyme electrodes.

Glucose oxidase (GOD) was immobilized on screen-printed platinum electrodes by entrapment in a screen printable paste polymerized by irradiation with UV-light. The influences of different additives, in particular polymers and graphite, on the sensitivity and stability of the sensor and the permeability of the enzyme layer for a possible electrochemical interferent were investigated. The chosen additives were Gafquat 755N, poly-L-lysine, bovine serum albumin (BSA), sodium dodecylsulfate (SDS), polyethylene glycol (PEG), Nafion and graphite. All additives led to increases of glucose signals, i.e. improved the sensitivity of glucose detection with Gafquat 755N, poly-L-lysine, SDS and graphite showing the strongest influences with increases by a factor 4, 6.5, 5 and 10, respectively. Ascorbic acid was used as a model interferent showing the influence of the enzyme layer composition on the selectivity of the sensor. The addition of Gafquat 755N or poly-L-lysine led to higher signals not only for glucose, but also for ascorbic acid. SDS addition already reduced the influence of ascorbic acid, which was almost completely eliminated when Nafion (5%) and PEG (10%) were added. A comparable beneficial effect on the selectivity of the sensors was also observed for the addition of 0.5% graphite. Thus, the enzyme electrodes with PEG, Nafion or graphite as additives in the enzyme layer were applied to glucose determinations in food samples and samples obtained from E. coli cultivations.