Effects of Mesoporosity and Conductivity of Hierarchically Porous Carbon Supports on the Deposition of Pt Nanoparticles and Their Performance as Electrocatalysts for Oxygen Reduction Reaction in Alkaline Media.

The structural characteristics of supports, such as surface area and type of porosity, affect the deposition of electrocatalysts and greatly influence their electrochemical performance in fuel cells. In this work, we use a series of high surface area hierarchical porous carbons (HPCs) with defined mesoporosity as model supports to study the deposition mechanism of Pt nanoparticles. The resulting electrocatalysts are characterized by several analytical techniques, and their electrochemical performance is compared to a state-of-the-art, commercial Pt/C system. Despite the similar chemical composition and surface area of the supports, as well as similar amounts of Pt precursor used, the size of the deposited Pt nanoparticles varies, and it is inversely proportional to the mesopore size of the system. In addition, we show that an increase in the size of the catalyst particles can increase the specific activity of the oxygen reduction reaction. We also report on our efforts to improve the overall performance of the above electrocatalyst systems and show that increasing the electronic conductivity of the carbon support by the addition of highly conductive graphene sheets improves the overall performance of an alkaline fuel cell.

Probing the Interfacial Properties of Oil-Water Interfaces Decorated with Ionizable, pH Responsive Silica Nanoparticles.

Particle-stabilized emulsions (Pickering emulsions) have recently attracted significant attention in scientific studies and for technological applications. The interest stems from the ease of directly assembling the particles at interfaces and modulating the interfacial properties. In this paper, we demonstrate the formation of stable, practical emulsions leveraging the assembly of ionizable, pH responsive silica nanoparticles, surface-functionalized by a mixture of silanes containing amine/ammonium groups, which renders them positively charged. Using pH as the trigger, the assembly and the behavior of the emulsion are controlled by modulating the charges of the functional groups of the nanoparticle and the oil (crude oil). In addition to their tunable charge, the particular combination of silane coupling agents leads to stable particle dispersions, which is critical for practical applications. Atomic force microscopy and interfacial tension (IFT) measurements are used to monitor the assembly, which is controlled by both the electrostatic interactions between the particles and oil and the interparticle interactions, both of which are modulated by pH. Under acidic conditions, when the surfaces of the oil and the nanoparticles (NPs) are positively charged, the NPs are not attracted at the interface and there is no significant reduction in the IFT. In contrast, under basic conditions in which the oil carries a high negative charge and the amine groups on the silica are deprotonated while still positively charged because of the ammonium groups, the NPs assemble at the interface in a closely packed configuration yielding a jammed state with a high dilatational modulus. As a result, two oil droplets do not coalesce even when pushed against each other and the emulsion stability improves significantly. The study provides new insights into the directed assembly of nanoparticles at fluid interfaces relevant to several applications, including environmental remediation, catalysis, drug delivery, food technology, and oil recovery.

Electrocatalysis in Alkaline Media and Alkaline Membrane-Based Energy Technologies.

Hydrogen energy-based electrochemical energy conversion technologies offer the promise of enabling a transition of the global energy landscape from fossil fuels to renewable energy. Here, we present a comprehensive review of the fundamentals of electrocatalysis in alkaline media and applications in alkaline-based energy technologies, particularly alkaline fuel cells and water electrolyzers. Anion exchange (alkaline) membrane fuel cells (AEMFCs) enable the use of nonprecious electrocatalysts for the sluggish oxygen reduction reaction (ORR), relative to proton exchange membrane fuel cells (PEMFCs), which require Pt-based electrocatalysts. However, the hydrogen oxidation reaction (HOR) kinetics is significantly slower in alkaline media than in acidic media. Understanding these phenomena requires applying theoretical and experimental methods to unravel molecular-level thermodynamics and kinetics of hydrogen and oxygen electrocatalysis and, particularly, the proton-coupled electron transfer (PCET) process that takes place in a proton-deficient alkaline media. Extensive electrochemical and spectroscopic studies, on single-crystal Pt and metal oxides, have contributed to the development of activity descriptors, as well as the identification of the nature of active sites, and the rate-determining steps of the HOR and ORR. Among these, the structure and reactivity of interfacial water serve as key potential and pH-dependent kinetic factors that are helping elucidate the origins of the HOR and ORR activity differences in acids and bases. Additionally, deliberately modulating and controlling catalyst-support interactions have provided valuable insights for enhancing catalyst accessibility and durability during operation. The design and synthesis of highly conductive and durable alkaline membranes/ionomers have enabled AEMFCs to reach initial performance metrics equal to or higher than those of PEMFCs. We emphasize the importance of using membrane electrode assemblies (MEAs) to integrate the often separately pursued/optimized electrocatalyst/support and membranes/ionomer components. Operando/in situ methods, at multiscales, and ab initio simulations provide a mechanistic understanding of electron, ion, and mass transport at catalyst/ionomer/membrane interfaces and the necessary guidance to achieve fuel cell operation in air over thousands of hours. We hope that this Review will serve as a roadmap for advancing the scientific understanding of the fundamental factors governing electrochemical energy conversion in alkaline media with the ultimate goal of achieving ultralow Pt or precious-metal-free high-performance and durable alkaline fuel cells and related technologies.

Germanane Monolayer Films as Antibacterial Coatings.

Germanane (GeH), a graphane analogue, has attracted significant interest because of its optoelectronic properties; however, the environmental and biological effects of GeH have scarcely been investigated so far. Here we report a facile approach based on the Langmuir-Schaefer deposition to produce homogeneous and dense GeH monolayer films on various substrates. In view of possible applications and to extend the use of GeH to unexplored fields, we investigated its antibacterial activity for the first time and found that this promising 2D structure exhibits remarkable antibacterial activity against both Gram-negative and Gram-positive bacterial strains.

Synthesis of 2D Germanane (GeH): a New, Fast, and Facile Approach.

Germanane (GeH), a germanium analogue of graphane, has recently attracted considerable interest because its remarkable combination of properties makes it an extremely suitable candidate to be used as 2D material for field effect devices, photovoltaics, and photocatalysis. Up to now, the synthesis of GeH has been conducted by substituting Ca by H in a ß-CaGe2 layered Zintl phase through topochemical deintercalation in aqueous HCl. This reaction is generally slow and takes place over 6 to 14 days. The new and facile protocol presented here allows to synthesize GeH at room temperature in a significantly shorter time (a few minutes), which renders this method highly attractive for technological applications. The GeH produced with this method is highly pure and has a band gap (Eg ) close to 1.4 eV, a lower value than that reported for germanane synthesized using HCl, which is promising for incorporation of GeH in solar cells.

Fabrication of highly ordered Cu2+/Fe3+ decorated polyhedral oligomeric silsesquioxane hybrids: How metal coordination influences structure.

Incorporation of isolated metal centers into well-organized nanostructures is a promising route in the development of the next generation of chemical, magnetic and electronic devices. In this work, a layer-by-layer protocol to grow highly ordered thin films of metal-decorated organic-inorganic cage-like polyhedral oligomeric silsesquioxane (POSS) is introduced. The key strategy is to use metal ions (Cu2+ or Fe3+) as linker for the amino-functionalized cage-like POSS, which are self-assembled between arachidic acid layers during Langmuir-Schaefer deposition. The Langmuir-Schaefer films are examined by X-ray photoelectron spectroscopy, X-ray diffraction, grazing incidence wide-angle X-ray scattering and extended X-ray absorption fine structure in order to understand how the coordination of metal ions influences the structure in the course of the layer-by-layer formation of the films.

Tunable one-step double functionalization of graphene based on fluorographene chemistry.

Double functionalized graphene derivatives were synthetized by a one-pot reaction of fluorographene with organometallic nucleophiles. Their nucleophilicity governed the preference for grafting and was utilized for tuning the functionalization. This approach paves the way toward the facile, up-scalable and controllable multifunctionalization of graphene.

One-Step Synthesis of Janus Fluorographene Derivatives.

Fluorographene, a two-dimensional derivative of graphene, is an excellent starting material for the synthesis of graphene derivatives. In this work, a one-step, substrate-free method for the asymmetric functionalization of fluorographene layers with hydroxyl groups by a facile nucleophilic substitution reaction is reported. Such a chemical modification occurs in a biphasic aqueous-organic system under mild conditions, leading to Janus graphene nanosheets functionalized by hydroxyl groups on one side and retaining fluorine atoms on the other. The reported experimental route paves the way for two-dimensional bifacial graphene templates, thus broadening the application potential of graphene materials.

Insertion of Iron Decorated Organic-Inorganic Cage-Like Polyhedral Oligomeric Silsesquioxanes between Clay Platelets by Langmuir Schaefer Deposition.

Tuning the architecture of multilayer nanostructures by exploiting the properties of their constituents is a versatile way to develop multifunctional films. Herein, we report a bottom-up approach for the fabrication of highly ordered hybrid films consisting of dimethyldioctadecylammonium (DODA), iron decorated polyhedral oligomeric silsesquioxanes (POSS), and montmorillonite clay platelets. Clay platelets provided the template where Fe/POSS moieties were grafted by the use of the surfactant. Driven by the iron ions present, DODA adopted a staggered arrangement, which is essential to realize the controllable layer-by-layer growth of the film. The elemental composition of the film was studied by X-ray photoelectron spectroscopy and X-ray reflectivity confirmed the existence of smooth interfaces between the different layers.

Highly Conductive Metallic State and Strong Spin-Orbit Interaction in Annealed Germanane.

Similar to carbon, germanium exists in various structures such as three-dimensional crystalline germanium and germanene, a two-dimensional germanium atomic layer. Regarding the electronic properties, they are either semiconductors or Dirac semimetals. Here, we report a highly conductive metallic state in thermally annealed germanane (hydrogen-terminated germanene, GeH), which shows a resistivity of ∼10-7 Ω·m that is orders of magnitude lower than any other allotrope of germanium. By comparing the resistivity, Raman spectra, and thickness change measured by AFM, we suggest the highly conductive metallic state is associated with the dehydrogenation during heating, which likely transforms germanane thin flakes to multilayer germanene. In addition, weak antilocalization is observed, serving as solid evidence for strong spin-orbit interaction (SOI) in germanane/germanene. Our study opens a possible new route to investigate the electrical transport properties of germanane/germanene, and the large SOI might provide the essential ingredients to access their topological states predicted theoretically.

Thiophenol-Modified Fluorographene Derivatives for Nonlinear Optical Applications.

The synthesis and characterization of two thiophenol-modified fluorographene derivatives, namely methoxythiophenol-and dimethylaminothiophenol-modified fluorographenes, are reported, while their third-order nonlinear optical response were thoroughly investigated under both visible (532 nm) and infrared (1064 nm) with 35 ps and 4 ns laser pulses. The graphene derivatives were obtained by partial nucleophilic substitution/reduction of fluorographene by the corresponding organic thiophenols, and were fully characterized by techniques including infrared/Raman spectroscopy, X-ray photoelectron spectroscopy, atomic force spectroscopy, and high-resolution transmission microscopy. This type of modification resulted in graphenic structures where the attached thiol groups, sp2 domains, and the residual fluorine groups act as donors, π bridges, and acceptors, respectively. Both derivatives exhibited large nonlinear optical response compared to fluorographene, and have potential applications in optical limiting as an alternative to fullerenes.

Controlled deposition of fullerene derivatives within a graphene template by means of a modified Langmuir-Schaefer method.

The scientific and technological potential of graphene's includes the development of light, open 3D hybrid structures with high surface area, tunable pore size and aromatic functionalities. Towards this aim, we describe a scalable and low-cost bottom-up approach that combines self-assembly and Langmuir-Schaefer deposition for the production of fullerene-intercalated graphene oxide hybrids. This method uses graphene oxide (GO) nanosheets as template for the attachment of two types of fullerene derivatives (bromo-fullerenes, C60Br24 and fullerols, C60(OH)24) in a bi-dimensional arrangement, allowing a layer-by-layer growth with control at nanoscale. Our film preparation approach relies on a bottom-up process that includes the formation of a hybrid organo-graphene Langmuir film, which is transferred onto a substrate and then brought in contact with C60(OH)24 molecules in solution to induce self-assembly. In the case of grafting C60Br24 molecules into graphene a further modification of the GO platelets was performed by bringing the surface of the transferred GO Langmuir film in contact with a second amino surfactant solution. Repeating these deposition cycles, pillared structures were fabricated in thin films form. These fullerene-based hybrid thin films were characterized by Raman and X-ray photoelectron (XPS) spectroscopies, X-ray diffraction (XRD), Atomic Force Microscopy (AFM) and contact angle measurements.

Iron-substituted cubic silsesquioxane pillared clays: Synthesis, characterization and acid catalytic activity.

Novel pillared structures were developed from the intercalation of iron-substituted cubic silsesquioxanes in a sodium and an acid-activated montmorillonite nanoclay and evaluated as acid catalysts. Octameric cubic oligosiloxanes were formed upon controlled hydrolytic polycondensation of the corresponding monomer (a diamino-alkoxysilane) and reacted with iron cations to form complexes that were intercalated within the layered nanoclay matrices. Upon calcination iron oxide nanoparticles are formed which are located on the silica cubes (pillars) and on the surfaces of the clay platelets. Acid activation of the nanoclay was performed in order to increase the number of acid active sites in the pristine clay and thus increase its catalytic activity. A plethora of analytical techniques including X-ray diffraction, thermal analyses, Fourier transform infrared, electron paramagnetic resonance, Raman, Mössbauer and X-ray photoelectron spectroscopies and porosimetry measurements were used in order to follow the synthesis steps and to fully characterize the final catalysts. The resulting pillared clays exhibit a high specific area and show significant acid catalytic activity that was verified using the catalytic dehydration of isopropanol asa probe reaction.