Enhanced Electrocatalysis on Copper Nanostructures: Role of the Oxidation State in Sulfite Oxidation.

The influence of surface morphology and the oxidation state on the electrocatalytic activity of nanostructured electrodes is well recognized, yet disentangling their individual roles in specific reactions remains challenging. Here, we investigated the electrooxidation of sulfite ions in an alkaline environment using cyclic voltammetry on copper oxide nanostructured electrodes with different oxidation states and morphologies but with similar active areas. To this aim, we synthesized nanostructured Cu films made of nanoparticles or nanorods on top of glassy carbon electrodes. Our findings showed an enhanced sensitivity and a lower detection threshold when utilizing Cu(I) over Cu(II). Density functional theory-based thermochemical analysis revealed the underlying oxidation mechanism, indicating that while the energy gain associated with the process is comparable for both oxide surfaces, the desorption energy barrier for the resulting sulfate molecules is three times higher on Cu(II). This becomes the limiting step of the reaction kinetics and diminishes the overall electrooxidation efficiency. Our proposed mechanism relies on the tautomerization of hydroxyl groups confined on the surface of Cu-based electrodes. This mechanism might be applicable to electrochemical reactions involving other sulfur compounds that hold technological significance.

Hydrogen-Induced Reduction Improves the Photoelectrocatalytic Performance of Titania.

One of the main challenges to expand the use of titanium dioxide (titania) as a photocatalyst is related to its large band gap energy and the lack of an atomic scale description of the reduction mechanisms that may tailor the photocatalytic properties. We show that rutile TiO2 single crystals annealed in the presence of atomic hydrogen experience a strong reduction and structural rearrangement, yielding a material that exhibits enhanced light absorption, which extends from the ultraviolet to the near-infrared (NIR) spectral range, and improved photoelectrocatalytic performance. We demonstrate that both magnitudes behave oppositely: heavy/mild plasma reduction treatments lead to large/negligible spectral absorption changes and poor/enhanced (×10) photoelectrocatalytic performance, as judged from the higher photocurrent. To correlate the photoelectrochemical performance with the atomic and chemical structures of the hydrogen-reduced materials, we have modeled the process with in situ scanning tunneling microscopy measurements, which allow us to determine the initial stages of oxygen desorption and the desorption/diffusion of Ti atoms from the surface. This multiscale study opens a door toward improved materials for diverse applications such as more efficient rutile TiO2-based photoelectrocatalysts, green photothermal absorbers for solar energy applications, or NIR-sensing materials.

Harnessing two-dimensional nanomaterials for diagnosis and therapy in neurodegenerative diseases: Advances, challenges and prospects.

Neurodegenerative diseases (NDDs) are specific brain disorders characterized by the progressive deterioration of different motor activities as well as several cognitive functions. Current conventional therapeutic options for NDDs are limited in addressing underlying causes, delivering drugs to specific neuronal targets, and promoting tissue repair following brain injury. Due to the paucity of plausible theranostic options for NDDs, nanobiotechnology has emerged as a promising field, offering an interdisciplinary approach to create nanomaterials with high diagnostic and therapeutic efficacy for these diseases. Recently, two-dimensional nanomaterials (2D-NMs) have gained significant attention in biomedical and pharmaceutical applications due to their precise drug-loading capabilities, controlled release mechanisms, enhanced stability, improved biodegradability, and reduced cell toxicity. Although various studies have explored the diagnostic and therapeutic potential of different nanomaterials in NDDs, there is a lack of comprehensive review addressing the theranostic applications of 2D-NMs in these neuronal disorders. Therefore, this concise review aims to provide a state-of-the-art understanding of the need for these ultrathin 2D-NMs and their potential applications in biosensing and bioimaging, targeted drug delivery, tissue engineering, and regenerative medicine for NDDs.

Electrochemical sensor based on the synergy between Cucurbit[8]uril and 2D-MoS2 for enhanced melatonin quantification.

We present the development of an electrochemical sensor towards melatonin determination based on the synergistic effect between MoS2 nanosheets and cucurbit[8]uril. For the sensor construction cucurbit[8]uril suspensions were prepared in water, and MoS2 nanosheets were obtained by liquid exfoliation in ethanol:water. The sensing platform was topographically characterized by Atomic Force Microscopy. Electrochemical Impedance Spectroscopy experiments allowed us to study the charge transfer process during melatonin oxidation. Moreover, stoichiometry of the resulting complex has also been determined. After the optimization of the sensor construction and the experimental variables involved in the Differential Pulse Voltammetric response of melatonin, detection limit of 3.80 × 10-7 M, relative errors minor than 3.8% and relative standard deviation lower than 4.4% were obtained. The proposed sensor has been successfully applied to melatonin determination in pharmaceutical and biological samples as human urine and serum, with very good recoveries ranging from 90 to 102%.

Two-Dimensional Self-Assembly Driven by Intermolecular Hydrogen Bonding in Benzodi-7-azaindole Molecules on Au(111).

The control of molecular structures at the nanoscale plays a critical role in the development of materials and applications. The adsorption of a polyheteroaromatic molecule with hydrogen bond donor and acceptor sites integrated in the conjugated structure itself, namely, benzodi-7-azaindole (BDAI), has been studied on Au(111). Intermolecular hydrogen bonding determines the formation of highly organized linear structures where surface chirality, resulting from the 2D confinement of the centrosymmetric molecules, is observed. Moreover, the structural features of the BDAI molecule lead to the formation of two differentiated arrangements with extended brick-wall and herringbone packing. A comprehensive experimental study that combines scanning tunneling microscopy, high-resolution X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, and density functional theory theoretical calculations has been performed to fully characterize the 2D hydrogen-bonded domains and the on-surface thermal stability of the physisorbed material.

Unveiling the Collaborative Effect at the Cucurbit [8] uril-MoS2 Hybrid Interface for Electrochemical Melatonin Determination.

Invited for the cover of this issue are two collaborating groups: one at the Universidad Autónoma de Madrid and the other at the Instituto de Ciencia de Materiales de Madrid. The image depicts Cucurbit[8]uril adsorbed on a transition metal dichalcogenide surface letting the cavity open for complex formation with melatonin and allowing efficient electrochemical sensing. Read the full text of the article at 10.1002/chem.202203244.

On-surface synthesis of metal-organic frameworks: the critical role of the reaction conditions.

Two different metal-organic frameworks with either a honeycomb or Kagome structure were grown on Cu(111) using para-aminophenol molecules and native surface adatoms. Although both frameworks are made up from the same chemical species, they are structurally different emphasizing the critical role being played by the reaction conditions during their growth. This work highlights the importance of the balance between thermodynamics and kinetics in the final structure of surface-supported metal-organic networks.

Unveiling the Collaborative Effect at the Cucurbit[8]uril-MoS2 Hybrid Interface for Electrochemical Melatonin Determination.

Host-guest interactions are of paramount importance in supramolecular chemistry and in a wide range of applications. Particularly well known is the ability of cucurbit[n]urils (CB[n]) to selectively host small molecules. We show that the charge transfer and complexation capabilities of CB[n] are retained on the surface of 2D transition metal dichalcogenides (TMDs), allowing the development of efficient electrochemical sensing platforms. We unveil the mechanisms of host-guest recognition between the MoS2 -CB[8] hybrid interface and melatonin (MLT), an important molecular regulator of vital constants in vertebrates. We find that CB[8] on MoS2 organizes the receptor portals perpendicularly to the surface, facilitating MLT complexation. This advantageous adsorption geometry is specific to TMDs and favours MLT electro-oxidation, as opposed to other 2D platforms like graphene, where one receptor portal is closed. This study rationalises the cooperative interaction in 2D hybrid systems to improve the efficiency and selectivity of electrochemical sensing platforms.

On-Surface Thermal Stability of a Graphenic Structure Incorporating a Tropone Moiety.

On-surface synthesis, complementary to wet chemistry, has been demonstrated to be a valid approach for the synthesis of tailored graphenic nanostructures with atomic precision. Among the different existing strategies used to tune the optoelectronic and magnetic properties of these nanostructures, the introduction of non-hexagonal rings inducing out-of-plane distortions is a promising pathway that has been scarcely explored on surfaces. Here, we demonstrate that non-hexagonal rings, in the form of tropone (cycloheptatrienone) moieties, are thermally transformed into phenyl or cyclopentadienone moieties upon an unprecedented surface-mediated retro-Buchner-type reaction involving a decarbonylation or an intramolecular rearrangement of the CO unit, respectively.

Metal-catalyst-free gas-phase synthesis of long-chain hydrocarbons.

Development of sustainable processes for hydrocarbons synthesis is a fundamental challenge in chemistry since these are of unquestionable importance for the production of many essential synthetic chemicals, materials and carbon-based fuels. Current industrial processes rely on non-abundant metal catalysts, temperatures of hundreds of Celsius and pressures of tens of bars. We propose an alternative gas phase process under mild reaction conditions using only atomic carbon, molecular hydrogen and an inert carrier gas. We demonstrate that the presence of CH2 and H radicals leads to efficient C-C chain growth, producing micron-length fibres of unbranched alkanes with an average length distribution between C23-C33. Ab-initio calculations uncover a thermodynamically favourable methylene coupling process on the surface of carbonaceous nanoparticles, which is kinematically facilitated by a trap-and-release mechanism of the reactants and nanoparticles that is confirmed by a steady incompressible flow simulation. This work could lead to future alternative sustainable synthetic routes to critical alkane-based chemicals or fuels.

Role of the metal surface on the room temperature activation of the alcohol and amino groups of p-aminophenol.

We present a comparative study of the room-temperature adsorption of p-aminophenol (p-AP) molecules on three metal surfaces, namely Cu(110), Cu(111) and Pt(111). We show that the chemical nature and the structural symmetry of the substrate control the activation of the terminal molecular groups, which result in different arrangements of the interfacial molecular layer. To this aim, we have used in-situ STM images combined with synchrotron radiation high resolution XPS and NEXAFS spectra, and the results were simulated by DFT calculations. On copper, the interaction between the molecules and the surface is weaker on the (111) surface crystal plane than on the (110) one, favouring molecular diffusion and leading to larger ordered domains. We demonstrate that the p-AP molecule undergoes spontaneous dehydrogenation of the alcohol group to form phenoxy species on all the studied surfaces, however, this process is not complete on the less reactive surface, Cu(111). The Pt(111) surface exhibits stronger molecule-surface interaction, inducing a short-range ordered molecular arrangement that increases overtime. In addition, on the highly reactive Pt(111) surface other chemical processes are evidenced, such as the dehydrogenation of the amine group.

Chemically synthesized chevron-like graphene nanoribbons for electrochemical sensors development: determination of epinephrine.

We employ chevron-like graphene nanoribbons (GNRs) synthesized by a solution-based chemical route to develop a novel electrochemical sensor for determination of the neurotransmitter epinephrine (EPI). The sensor surface, a glassy carbon electrode modified with GNRs, is characterized by atomic force microscopy, scanning electron microscopy and Raman spectroscopy, which show that the electrode surface modification comprises of bi-dimensional multilayer-stacked GNRs that retain their molecular structure. The charge transfer process occurring at the electrode interface is evaluated by electrochemical impedance spectroscopy. The sensor is applied to the determination of EPI, employing as an analytical signal the reduction peak corresponding to the epinephrinechrome-leucoepinephrinechrome transition (E = - 0.25 V) instead of the oxidation peak usually employed in the literature (E = + 0.6 V) in order to minimize interferences. The results obtained demonstrate that chevron-like nanoribbons synthesized by solution methods exhibit reliable electrocatalytic activity for EPI determination. Using differential pulse voltammetry, we obtain a linear concentration range from 6.4 × 10-6 to 1.0 × 10-4 M and a detection limit of 2.1 × 10-6 M. The applicability of the sensor was evaluated by determining EPI in pharmaceutical samples with satisfactory results.

On-Surface Driven Formal Michael Addition Produces m-Polyaniline Oligomers on Pt(111).

On-surface synthesis is emerging as a highly rational bottom-up methodology for the synthesis of molecular structures that are unattainable or complex to obtain by wet chemistry. Here, oligomers of meta-polyaniline, a known ferromagnetic polymer, were synthesized from para-aminophenol building-blocks via an unexpected and highly specific on-surface formal 1,4 Michael-type addition at the meta position, driven by the reduction of the aminophenol molecule. We rationalize this dehydrogenation and coupling reaction mechanism with a combination of in situ scanning tunneling and non-contact atomic force microscopies, high-resolution synchrotron-based X-ray photoemission spectroscopy and first-principles calculations. This study demonstrates the capability of surfaces to selectively modify local molecular conditions to redirect well-established synthetic routes, such as Michael coupling, towards the rational synthesis of new covalent nanostructures.

Prevalence of non-aromatic carbonaceous molecules in the inner regions of circumstellar envelopes.

Evolved stars are a foundry of chemical complexity, gas and dust that provides the building blocks of planets and life, and dust nucleation first occurs in their photosphere. Despite their importance, the circumstellar regions enveloping these stars remain hidden to many observations, thus dust formation processes are still poorly understood. Laboratory astrophysics provides complementary routes to unveil these chemical processes, but most experiments rely on combustion or plasma decomposition of molecular precursors under physical conditions far removed from those in space. We have built an ultra-high vacuum machine combining atomic gas aggregation with advanced in-situ characterization techniques to reproduce and characterize the bottom-up dust formation process. We show that carbonaceous dust analogues formed from low-pressure gas-phase condensation of C atoms in a hydrogen atmosphere, in a C/H2 ratio similar to that reported for evolved stars, leads to the formation of amorphous C nanograins and aliphatic C-clusters. Aromatic species or fullerenes do not form effectively under these conditions, raising implications for the revision of the chemical mechanisms taking place in circumstellar envelopes.

Fluorescence enhancement of fungicide thiabendazole by van der Waals interaction with transition metal dichalcogenide nanosheets for highly specific sensors.

Many molecules quench their fluorescence upon adsorption on surfaces. Herein we show that the interaction of thiabendazole, a widespread used fungicide of the benzimidazole family, with nanosheets of transition metal dichalcogenides, particularly of WS2, leads to a significant increase, more than a factor of 5, of the fluorescence yield. This surprising effect is rationalized by DFT calculations and found to be related to the inhibition of the intramolecular rotation between the benzimidazole and thiazole groups due to a bonding rigidization upon interaction with the MoS2 surface. This non-covalent adsorption leads to a redistribution of the molecular LUMO that blocks the non-radiative energy dissipation channel. This unusual behaviour does not operate either for other molecules of the same benzimidazole family or for other 2D materials (graphene or graphene oxide). Moreover, we found that a linear dependence of the emission with the concentration of thiabendazole in solution, which combined with the specificity of the process, allows the development of a highly sensitive and selective method towards thiabendazole determination that can be applied to real river water samples. An excellent detection limit of 2.7 nM, comparable to the best performing reported methods, is obtained with very good accuracy (Er ≤ 6.1%) and reproducibility (RSD ≤ 4.1%) in the concentration range assayed.

Versatile Graphene-Based Platform for Robust Nanobiohybrid Interfaces.

Technologically useful and robust graphene-based interfaces for devices require the introduction of highly selective, stable, and covalently bonded functionalities on the graphene surface, whilst essentially retaining the electronic properties of the pristine layer. This work demonstrates that highly controlled, ultrahigh vacuum covalent chemical functionalization of graphene sheets with a thiol-terminated molecule provides a robust and tunable platform for the development of hybrid nanostructures in different environments. We employ this facile strategy to covalently couple two representative systems of broad interest: metal nanoparticles, via S-metal bonds, and thiol-modified DNA aptamers, via disulfide bridges. Both systems, which have been characterized by a multitechnique approach, remain firmly anchored to the graphene surface even after several washing cycles. Atomic force microscopy images demonstrate that the conjugated aptamer retains the functionality required to recognize a target protein. This methodology opens a new route to the integration of high-quality graphene layers into diverse technological platforms, including plasmonics, optoelectronics, or biosensing. With respect to the latter, the viability of a thiol-functionalized chemical vapor deposition graphene-based solution-gated field-effect transistor array was assessed.

Chemistry below graphene: decoupling epitaxial graphene from metals by potential-controlled electrochemical oxidation.

While high-quality defect-free epitaxial graphene can be efficiently grown on metal substrates, strong interaction with the supporting metal quenches its outstanding properties. Thus, protocols to transfer graphene to insulating substrates are obligatory, and these often severely impair graphene properties by the introduction of structural or chemical defects. Here we describe a simple and easily scalable general methodology to structurally and electronically decouple epitaxial graphene from Pt(111) and Ir(111) metal surfaces. A multi-technique characterization combined with ab-initio calculations was employed to fully explain the different steps involved in the process. It was shown that, after a controlled electrochemical oxidation process, a single-atom thick metal-hydroxide layer intercalates below graphene, decoupling it from the metal substrate. This decoupling process occurs without disrupting the morphology and electronic properties of graphene. The results suggest that suitably optimized electrochemical treatments may provide effective alternatives to current transfer protocols for graphene and other 2D materials on diverse metal surfaces.

On-Surface Bottom-Up Synthesis of Azine Derivatives Displaying Strong Acceptor Behavior.

On-surface synthesis is an emerging approach to obtain, in a single step, precisely defined chemical species that cannot be obtained by other synthetic routes. The control of the electronic structure of organic/metal interfaces is crucial for defining the performance of many optoelectronic devices. A facile on-surface chemistry route has now been used to synthesize the strong electron-acceptor organic molecule quinoneazine directly on a Cu(110) surface, via thermally activated covalent coupling of para-aminophenol precursors. The mechanism is described using a combination of in situ surface characterization techniques and theoretical methods. Owing to a strong surface-molecule interaction, the quinoneazine molecule accommodates 1.2 electrons at its carbonyl ends, inducing an intramolecular charge redistribution and leading to partial conjugation of the rings, conferring azo-character at the nitrogen sites.

Enantiopure distorted ribbon-shaped nanographene combining two-photon absorption-based upconversion and circularly polarized luminescence.

Herein we describe a distorted ribbon-shaped nanographene exhibiting unprecedented combination of optical properties in graphene-related materials, namely upconversion based on two-photon absorption (TPA-UC) together with circularly polarized luminescence (CPL). The compound is a graphene molecule of ca. 2 nm length and 1 nm width with edge defects that promote the distortion of the otherwise planar lattice. The edge defects are an aromatic saddle-shaped ketone unit and a [5]carbohelicene moiety. This system is shown to combine two-photon absorption and circularly polarized luminescence and a remarkably long emission lifetime of 21.5 ns. The [5]helicene is responsible for the chiroptical activity while the push-pull geometry and the extended network of sp2 carbons are factors favoring the nonlinear absorption. Electronic structure theoretical calculations support the interpretation of the results.

Highly selective covalent organic functionalization of epitaxial graphene.

Graphene functionalization with organics is expected to be an important step for the development of graphene-based materials with tailored electronic properties. However, its high chemical inertness makes difficult a controlled and selective covalent functionalization, and most of the works performed up to the date report electrostatic molecular adsorption or unruly functionalization. We show hereafter a mechanism for promoting highly specific covalent bonding of any amino-terminated molecule and a description of the operating processes. We show, by different experimental techniques and theoretical methods, that the excess of charge at carbon dangling-bonds formed on single-atomic vacancies at the graphene surface induces enhanced reactivity towards a selective oxidation of the amino group and subsequent integration of the nitrogen within the graphene network. Remarkably, functionalized surfaces retain the electronic properties of pristine graphene. This study opens the door for development of graphene-based interfaces, as nano-bio-hybrid composites, fabrication of dielectrics, plasmonics or spintronics.