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 molecularlevel 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 highperformance and durable alkaline fuel cells and related technologies.

A new two dimensional (2D) material-germanane-has been synthesised recently with promising electrical and optical properties. In this paper we report the first realisation of germanane fieldeffect transistors fabricated from multilayer single crystal flakes. Our germanane devices show transport in both electron and hole doped regimes with on/off current ratio of up to 10 5 (10 4 ) and carrier mobilities of 150 cm 2 (V • s) −1 (70 cm 2 (V • s) −1 ) at 77 K (room temperature). A significant enhancement of the device conductivity under illumination with 650 nm red laser is observed. Our results reveal ambipolar transport properties of germanane with great potential for (opto)electronics applications. LETTER RECEIVED

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.

Multifunctional pillared materials are synthesized by the intercalation of cage‐shaped adamantylamine (ADMA) molecules into the interlayer space of graphite oxide (GO) and aluminosilicate clays. The physicochemical and structural properties of these hybrids, determined by X‐ray diffraction (XRD), Fourier transform infrared (FTIR), Raman and X‐ray photoemission (XPS) spectroscopies and transmission electron microscopy (TEM) show that they can serve as tunable hydrophobic/hydrophilic and stereospecific nanotemplates. Thus, in ADMA‐pillared clay hybrids, the phyllomorphous clay provides a hydrophilic nanoenvironment where the local hydrophobicity is modulated by the presence of ADMA moieties. On the other hand, in the ADMA‐GO hybrid, both the aromatic rings of GO sheets and the ADMA molecules define a hydrophobic nanoenvironment where sp3‐oxo moieties (epoxy, hydroxyl and carboxyl groups), present on GO, modulate hydrophilicity. As test applications, these pillared nanostructures are capable of selective/stereospecific trapping of small chlorophenols or can act as cytotoxic agents.

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.

Germanane (GeH), ag ermanium analogue of graphane,h as 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,p hotovoltaics,a nd photocatalysis.U pt on ow,t he synthesis of GeH has been conducted by substituting Ca by H in a b-CaGe 2 layered Zintl phase through topochemical deintercalation in aqueous HCl. This reaction is generally slow and takes place over 6t o1 4days. The new and facile protocol presented here allows to synthesize GeH at room temperature in as ignificantly shorter time (a few minutes), which renders this method highly attractive for technological applications.T he GeH produced with this method is highly pure and has aband gap (E g)close to 1.4 eV,alower value than that reported for germanane synthesized using HCl, whichi s promising for incorporation of GeH in solar cells.

A new class of hybrid materials based on carbon nanotubes (CNT) rooted on smectite clays (SWy) was synthesized by catalytic chemical vapor deposition (CCVD) method, and studied to be introduced in a perfluorosulfonic acid (Nafion) membrane. Side-wall chemical oxidation and organo-functionalization of the CNT was performed using organic ester molecules containing hydrophilic groups (−RSO3H). SWy–CNT nanoadditives were incorporated in the polymer by solution-precipitation method producing highly homogeneous nanocomposite membranes with outstanding mechanical properties. Materials were characterized by a combination of techniques (TGA, Raman, FT-IR, SEM, TEM, and DMA), while a deep investigation on the water transport properties was performed by NMR methods (PFG and relaxation times). Membranes containing SWy–oxCNT–RSO3H nanoadditives are able to guarantee a very high proton diffusion in “quasi-anhydrous” conditions. Proton mobility is ensured by a correct network created from the long nanotubes (well distributed through the clay nanoplatelets) appropriately functionalized with acid groups. Remarkable are the electrochemical results: the best membrane reaches conductivities of 7 × 10–2 S cm–1 at 120 °C and 30% RH, 1 order of magnitude higher than pristine polymer, and a rather high value in the current panorama of the PEMFCs.

Fluorographene, at wo-dimensional derivativeo f graphene, is an excellent starting materialf or the synthesis of graphene derivatives. In this work, ao ne-step, substratefree method for the asymmetricf unctionalization of fluorographene layers with hydroxyl groups by af acile nucleophilic substitution reactioni sr eported. Such ac hemical modification occurs in ab iphasic 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.T he reported experimental route paves the way for two-dimensional bifacial graphene templates, thus broadening the application potential of graphene materials.