Local surface structure and composition control the hydrogen evolution reaction on iron nickel sulfides

In order to design more powerful electrocatalysts, developing our understanding of the role of the surface structure and composition of widely abundant bulk materials is crucial. This is particularly true in the search for alternative hydrogen evolution reaction (HER) catalysts to replace platinum. We report scanning electrochemical cell microscopy (SECCM) measurements of the (111)‐crystal planes of Fe4.5Ni4.5S8, a highly active HER catalyst. In combination with structural characterization methods, we show that this technique can reveal differences in activity arising from even the slightest compositional changes. By probing electrochemical properties at the nanoscale, in conjunction with complementary structural information, novel design principles are revealed for application to rational material synthesis

Proton-Coupled Reduction of the Catalytic [4Fe-4S] Cluster in [FeFe]-Hydrogenases

In nature, [FeFe]-hydrogenases catalyze the uptake and release of molecular hydrogen (H2) at a unique iron-sulfur cofactor. The absence of an electrochemical overpotential in the H2 release reaction makes [FeFe]-hydrogenases a prime example of efficient biocatalysis. However, the molecular details of hydrogen turnover are not yet fully understood. Herein, we characterize the initial one-electron reduction of [FeFe]-hydrogenases by infrared spectroscopy and electrochemistry and present evidence for proton- coupled electron transport during the formation of the reduced state Hred′. Charge compensation stabilizes the excess electron at the [4Fe-4S] cluster and maintains a conservative configuration of the diiron site. The role of Hred′ in hydrogen turnover and possible implications on the catalytic mechanism are discussed. We propose that regulation of the electronic properties in the periphery of metal cofactors is key to orchestrating multielectron processes

Printing in Three Dimensions with Graphene

Responsive graphene oxide sheets form non‐covalent networks with optimum rheological properties for 3D printing. These networks have shear thinning behavior and sufficiently high elastic shear modulus (G′) to build self‐supporting 3D structures by direct write assembly. Drying and thermal reduction leads to ultra‐light graphene‐only structures with restored conductivity and elastomeric behavior

Nanostructured biopolymer/few-layer graphene freestanding films with enhanced mechanical and electrical properties

In the present work, novel freestanding multilayered films based on chitosan (CHI), alginate (ALG), and functionalized few-layer graphene are developed through layer-by-layer assembly. First, functionalized few-layer graphene aqueous suspensions are prepared from graphite by a stabilizer-assisted liquid phase exfoliation process, using a pyrene derivative as stabilizer. Afterward, the films are produced and their physical, morphological, thermal, and mechanical properties are evaluated. Furthermore, their degradation and swelling profiles, as well as their biological behavior, are assessed. The incorporation of functionalized few-layer graphene results in films with a nanolayered structure, lower roughness than the control CHI/ALG films, and hydrophilic behavior. The mechanical characterization reveals an increase of the Young's modulus, ultimate tensile strength, and elongation at break due to the incorporation of the graphene derivative. A decrease in the electrical resistivity of the multilayered films is also observed. The biological assays reveal improved cytocompatibility toward L929 cells when functionalized few-layer graphene is incorporated in the CHI/ALG matrix. Therefore, these new graphene-reinforced multilayered films exhibit interesting properties and great potential for biomedical applications, particularly in wound healing and cardiac and bone tissue engineering.The authors acknowledge the Portuguese Foundation for Science and Technology (FCT) and the European program FEDER/COMPETE for the financial support through projects UID/Multi/50026/2013 and UID/CTM/50025/2013. This work was also financially supported by FCT through the scholarships SFRH/BPD/96797/2013 granted to Sofia G. Caridade, SFRH/BD/97606/2013 granted to Maria P. Sousa, and SFRH/BD/87214/2012 granted to Eunice Cunh

Pinacol Rearrangement and Direct Nucleophilic Substitution of Allylic Alcohols Promoted by Graphene Oxide and Graphene Oxide CO2H

Graphene oxide (GO) and carboxylic acid functionalized GO (GO–CO2H) have been found to efficiently promote the heterogeneous and environmentally friendly pinacol rearrangement of 1,2-diols and the direct nucleophilic substitution of allylic alcohols. In general, high yields and regioselectivities are obtained in both reactions using 20 wt % of catalyst loading and mild reaction conditions.Financial support from the University of Alicante (UAUSTI16-03, VIGROB-173), and Spanish Ministerio de Economía y Competitividad (CTQ2015-66624-P) is acknowledged

Glass, Gel, and Liquid Crystals: Arrested States of Graphene Oxide Aqueous Dispersions

Colloidal systems with competing interactions are known to exhibit a range of dynamically arrested states because of the systems' inability to reach its underlying equilibrium state due to intrinsic frustration. Graphene oxide (GO) aqueous dispersions constitute a class of 2D-anisotropic colloids with competing interactions long-range electrostatic repulsion, originating from ionized groups located on the rim of the sheets, and weak dispersive attractive interactions originating from the unoxidized graphitic domains. We show here that aqueous dispersions of GO exhibit a range of arrested states, encompassing fluid, glass, and gels that coexist with liquid-crystalline order with increasing volume fraction. These states can be accessed by varying the relative magnitudes of the repulsive and attractive forces. This can be realized by changing the ionic strength of the medium. We observe at low salt concentrations, where long-range electrostatic repulsion dominates, the formation of a repulsive Wigner glass, while at high salt concentrations, when attractive forces dominate, the formation of gels exhibits a nematic to columnar liquid-crystalline transition. The present work highlights how the chemical structure of GO hydrophilic ionizable groups and hydrophobic graphitic domains coexisting on a single sheet gives rise to a rich and complex array of arrested states