Hybrid Photoelectrocatalytic TiO2-Co3O4/Co(OH)2 Materials Prepared from Bio-Based Surfactants for Water Splitting.

The development of new photoanode materials for hydrogen production and water treatment is in full progress. In this context, hybrid TiO2-Co3O4/Co(OH)2 photoanodes prepared using the sol-gel method using biosurfactants are currently being developed by our group. The combination of TiO2 with a cobalt-based compound significantly enhances the visible absorption and electrochemical performance of thin films, which is mainly due to an increase in the specific surface area and a decrease in the charge transfer resistance on the surface of the thin films. The formation of these composites allows for a 30-fold increase in the current density when compared to cobalt-free materials, with the best TiO2-CoN0.5 sample achieving a current of 1.570 mA.cm-2 and a theoretical H2 production rate of 0.3 µmol.min-1.cm-2 under xenon illumination.

Asymmetric Solvent-Annealed Triblock Terpolymer Thick Films Topped by a Hexagonal Perforated Lamellar Nanostructure.

Asymmetric and nanostructured polystyrene-block-poly(2-vinyl pyridine)-block-poly(ethylene oxide) (PS-b-P2VP-b-PEO or SVEO, S:V:EO ≈ 56:34:10, 79.5 kg mol-1 ) thick films blended with 20 wt% of a short PS homopolymer (hPS, 10.5 kg mol-1 ) are achieved by combining the non-solvent induced phase separation (NIPS) process with a solvent vapor annealing (SVA) treatment. Here, the NIPS step allows for the formation of a highly-permeable sponge-like substructure topped by a dense thin layer exhibiting poorly-ordered nanopores while the subsequent SVA treatment enables to reconstruct the material top surface into a porous monolayer of well-ordered hexagonal perforated lamellae (HPL). This optimized film architecture generated by NIPS-SVA shows a water permeability of 860 L h-1 m-2 bar-1 , which is roughly two times higher than the flux measured through NIPS made PS-b-P2VP-b-PEO/hPS materials having poorly-ordered nanopores. The post-SVA treatment is also revealed as a powerful tool to tailor the thickness of the nanostructure formed within the blended material because monoliths entirely composed of a HPL phase are produced by increasing the time of exposure to a chloroform stream. The water flux of such PS-b-P2VP-b-PEO/hPS monoliths is found to be an order of magnitude lower than that of their asymmetric film homologues.

Coaxial nanofibers of nickel/gadolinium oxide/nickel oxide as highly effective electrocatalysts for hydrogen evolution reaction.

Cost-effective, active and stable electrocatalysts are crucial for hydrogen production via electrocatalytic water splitting. Here, we describe the preparation of novel nanofibers (NF) made of Ni/Gd2O3/NiO heterostructures by electrospinning. The fabricated materials showed high electrocatalytic performance for hydrogen evolution reaction (HER) with onset potential values of 89 mV, which are very close to those of platinum (Pt). NiO chemical and electronic properties were successfully optimized in Ni/Gd2O3/NiO coaxial heterostructures; NiO NFs doped with Gd3+ significantly enhanced its electrical conductivity and promoted HER reaction kinetics. These NFs offer the distinct advantages of long-term durability and readiness for hydrogen production via HER, and also better performance than benchmark Pt catalysts. The successful fabrication of these metal oxide NFs and nanostructures may represent a new approach for the rational synthesis of efficient HER catalysts.

Atomic layer deposition of Pd nanoparticles on self-supported carbon-Ni/NiO-Pd nanofiber electrodes for electrochemical hydrogen and oxygen evolution reactions.

The most critical challenge in hydrogen fuel production is to develop efficient, eco-friendly, low-cost electrocatalysts for water splitting. In this study, self-supported carbon nanofiber (CNF) electrodes decorated with nickel/nickel oxide (Ni/NiO) and palladium (Pd) nanoparticles (NPs) were prepared by combining electrospinning, peroxidation, and thermal carbonation with atomic layer deposition (ALD), and then employed for hydrogen evolution and oxygen evolution reactions (HER/OER). The best CNF-Ni/NiO-Pd electrode displayed the lowest overpotential (63 mV and 1.6 V at j = 10 mA cm-2), a remarkably small Tafel slope (72 and 272 mV dec-1), and consequent exchange current density (1.15 and 22.4 mA cm-2) during HER and OER, respectively. The high chemical stability and improved electrocatalytic performance of the prepared electrodes can be explained by CNF functionalization via Ni/NiO NP encapsulation, the formation of graphitic layers that cover and protect the Ni/NiO NPs from corrosion, and ALD of Pd NPs at the surface of the self-supported CNF-Ni/NiO electrodes.

Plasma membranes modified by plasma treatment or deposition as solid electrolytes for potential application in solid alkaline fuel cells.

In the highly competitive market of fuel cells, solid alkaline fuel cells using liquid fuel (such as cheap, non-toxic and non-valorized glycerol) and not requiring noble metal as catalyst seem quite promising. One of the main hurdles for emergence of such a technology is the development of a hydroxide-conducting membrane characterized by both high conductivity and low fuel permeability. Plasma treatments can enable to positively tune the main fuel cell membrane requirements. In this work, commercial ADP-Morgane® fluorinated polymer membranes and a new brand of cross-linked poly(aryl-ether) polymer membranes, named AMELI-32®, both containing quaternary ammonium functionalities, have been modified by argon plasma treatment or triallylamine-based plasma deposit. Under the concomitant etching/cross-linking/oxidation effects inherent to the plasma modification, transport properties (ionic exchange capacity, water uptake, ionic conductivity and fuel retention) of membranes have been improved. Consequently, using plasma modified ADP-Morgane® membrane as electrolyte in a solid alkaline fuel cell operating with glycerol as fuel has allowed increasing the maximum power density by a factor 3 when compared to the untreated membrane.