and Perspectives Sophie Carenco,†,‡,§,∥,⊥ David Portehault,*,†,‡,§ Ced́ric Boissier̀e,†,‡,§ Nicolas Meźailles, and Cleḿent Sanchez*,†,‡,§ †Chimie de la Matier̀e Condenseé de Paris, UPMC Univ Paris 06, UMR 7574, Colleg̀e de France, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France ‡Chimie de la Matier̀e Condenseé de Paris, CNRS, UMR 77574, Colleg̀e de France, 11 Place Marcellin Berthelot, 75231 Paris Cedex 05, France Chimie de la Matier̀e Condenseé de Paris, Colleg̀e de France, 11 Place Marcellin Berthelot, 75231 Paris Cedex 05, France Laboratory Heteroelements and Coordination, Chemistry Department, Ecole Polytechnique, CNRS-UMR 7653, Palaiseau, France

Nanoscaled metal borides and phosphides: recent developments and perspectives

Here we report that photostability and photoactivity of WO3 for water oxidation can be simultaneously enhanced by controlled introduction of oxygen vacancies into WO3 in hydrogen atmosphere at elevated temperatures. In comparison to pristine WO3, the hydrogen-treated WO3 nanoflakes show an order of magnitude enhanced photocurrent, and more importantly, exhibit extraordinary stability for water oxidation without loss of photoactivity for at least seven hours. The enhanced photostability is attributed to the formation of substoichiometric WO3−x after hydrogen treatment, which is highly resistive to the re-oxidation and peroxo-species induced dissolution. This work constitutes the first example where WO3 can be stabilized for water oxidation in neutral medium without the need for oxygen evolution catalysts. The demonstration of electrochemically stable WO3 could open up new opportunities for WO3 based photoelectrochemical and photocatalytic applications.

Hydrogen-treated WO3 nanoflakes show enhanced photostability

Tribology of electroless nickel coatings – A review

Hydrogen storage alloys are of particular interest as a novel group in functional materials owing to their potential and practical applications in Ni/MH rechargeable batteries. This review is devoted to the specific alloy families developed for high-energy and high-power Ni/MH batteries in the last decades, especially for EV, HEV and PHEV applications. The scope of the work encompasses principles of Ni/MH batteries, electrochemical hydrogen storage thermodynamics and kinetics, prerequisites for hydrogen storage electrode alloys and recent advances in hydrogen storage electrode alloys. Rare earth AB5-type alloys, Ti- and Zr-based AB2-type alloys, Mg-based amorphous/nanocrystalline alloys, rare earth-Mg–Ni-based alloys and Ti–V-based alloys are highlighted. Additionally, the challenges met in developing advanced hydrogen storage alloys for Ni/MH rechargeable batteries are pointed out and some research directions are suggested.

Advanced hydrogen storage alloys for Ni/MH rechargeable batteries

Photoelectrochemical (PEC) water splitting represents an environmentally friendly and sustainable method to obtain hydrogen fuel. Semiconductor materials as the central components in PEC water splitting cells have decisive influences on the device's solar-to-hydrogen conversion efficiency. Among semiconductors, metal oxides have received a lot of attention due to their outstanding (photo)-electrochemical stability, low cost, favorable band edge positions and wide distribution of bandgaps. In the past decades, significant processes have been made in developing metal oxide nanomaterials for PEC water splitting. In this review, the recent progress using metal oxides as photoelectrodes and co-catalysts for PEC water splitting is summarized. Their performance, limitations and potentials are also discussed. Last, the key challenges and opportunities in the development and implementation of metal oxide nanomaterials for PEC water splitting are discussed.

Progress in Developing Metal Oxide Nanomaterials for Photoelectrochemical Water Splitting

The effect of borohydride, thallium acetate, ethylenediamine and sodium hydroxide concentrations, and the coating bath temperature on both the coating rate and boron content of the electroless Ni–B films was investigated systematically. The Ni–B coating rate increased with the increase in thallium acetate and sodium hydroxide concentrations, but it was not very sensitive to the borohydride concentration. Below 90 g L − 1 ethylenediamine concentration the coating efficiency was significantly low and above this value as the ethylenediamine concentration increased the coating rate decreased slightly. Below 85 °C the coating rate was very low and above this temperature it was insensitive to the bath temperature. The boron content of Ni–B film increased with the increase in the borohydride concentration and the bath temperature, and decreased with the increase in thallium acetate and ethylenediamine concentrations. Up to 50 g L − 1 sodium hydroxide concentration, the boron content of the film increased and above this concentration it was insensitive to the sodium hydroxide concentration. As the boron content of Ni–B film increased, both the corrosion resistance and microhardness of Ni–B film increased. Heat treatment brought significant improvement in the microhardness but the corrosion resistance of Ni–B film was observed to decrease due to the disappearance of the amorphous characteristics of the as-deposited Ni–B film and the formation of the Ni–B compound phases.

Effect of coating bath composition on the properties of electroless nickel–boron films

Analysis of the electrochemical reaction behavior of alloy AZ91 by EIS technique in H3PO4/KOH buffered K2SO4 solutions

Potentiodynamic and potentiostatic polarization, and the rotating disk electrode technique, were used to study the anodic behavior of tungsten (W) in a broad pH range (0.5-13.5) in H 3 PO 4 /KOH buffered solution. Surface oxides were found to play a prominent role in the anodic oxidation and dissolution of tungsten. Five distinct pH regimes and the corresponding reaction mechanisms were identified. Below pH I (region A) H + -assisted dissolution was the main dissolution pathway. As the pH increased, the role of H diminished and at pH 2.6 (region B), which was identified as the point of zero charge (pzc) of the surface tungsten oxide, dissolution was mainly H 2 O-assisted. The dissolution was observed to be OH -assisted above the pzc. The reaction order for OH was one between pH 4.5 and 6.5 (region C). The reaction order became zero at pH 8 (region D). This observation was attributed to the pH-independent dissolution of the hydrated oxide phase. Above pH 10, OH dependence of the anodic current commenced and at around pH 12.5 (region E) the reaction order for OH - became one.

https://iopscience.iop.org/article/10.1149/1.1471544/pdf

Effect of pH on the Anodic Behavior of Tungsten

Potentiostatic polarization and rotating disk electrode techniques were used to obtain the rate constant for the dissolution of electrochemically-formed (at 1 V) WO3 on tungsten (W) in acidic solutions. The corresponding rate constant for the chemical dissolution of WO3(s) powder was found by measuring the dissolved tungsten concentration as a function of time and pH. The chemical dissolution experiments supported the view that the rate-determining step in the anodic reaction of W in acidic solution is the chemical dissolution of WO3(s) formed on the metal surface. Zeta potential measurements gave the isoelectric point (iep) of the WO3(s) powder as pH 1.5, a value that was somewhat smaller than the point of zero charge (pzc) of WO3(s) formed on W metal (pH 2.5). This difference was attributed to the highly hydrated nature of the oxide film formed on W metal in aqueous systems.

Mustafa Anik

Papers

Effect of coating bath composition on the properties of electroless nickel–boron films

Analysis of the electrochemical reaction behavior of alloy AZ91 by EIS technique in H3PO4/KOH buffered K2SO4 solutions

Effect of pH on the Anodic Behavior of Tungsten

Dissolution kinetics of WO3 in acidic solutions

Development of the high performance magnesium based hydrogen storage alloy