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Many breakthrough advances that are often at the cutting edge of technological development take place at synchrotron facilities. In the case of IR spectroscopy, the last decade has seen important developments in infrared instrumentation incorporated to and developed at synchrotron facilities to take advantages of the characteristics of the bright synchrotron source. In this feature article we describe the origin and nature of synchrotron infrared microspectroscopy, highlighting some of the key developments that will make a future impact in the study of macromolecular materials, and illustrating several applications in the area of polymer science. [ABSTRACT FROM AUTHOR]

With a view to the development of new sustainable and functional adhesives, two Diels–Alder (DA) adducts are incorporated as a third component into the curing process of solvent-based and solvent-free polyurethanes in this study. The influence of the nature and content of the DA molecules on the retro-DA (rDA) reaction and its reversibility and cyclability is investigated. It is demonstrated that the bonding/debonding properties of the adhesives are mainly controlled by the concentration of the DA adducts, with a minimum thermoreversible bond (TB) content required that depends on the system and the total ratio between all the diols in the formulation. For the solvent-based system, rDA/DA reversibility can be repeated up to ~20 times without deterioration, in contrast to the solvent-free system where a gradual loss in the DA network reconstruction efficiency is observed. Despite this limitation, the solvent-free system presents clear advantages from an environmental point of view. The changes observed in the physical properties of these new thermoreversible adhesives are of great relevance for recycling strategies and, in particular, their potential for separating multilayered film packaging materials in order to recycle the individual polymer films involved. [ABSTRACT FROM AUTHOR]

Given the pressing climate and sustainability challenges, shifting industrial processes towards environmentally friendly practices is imperative. Among various strategies, the generation of green, flexible materials combined with efficient reutilization of biomass stands out. This review provides a comprehensive analysis of the hydrothermal carbonization (HTC) process as a sustainable approach for developing carbonaceous materials from biomass. Key parameters influencing hydrochar preparation are examined, along with the mechanisms governing hydrochar formation and pore development. Then, this review explores the application of hydrochars in supercapacitors, offering a novel comparative analysis of the electrochemical performance of various biomass-based electrodes, considering parameters such as capacitance, stability, and textural properties. Biomass-based hydrochars emerge as a promising alternative to traditional carbonaceous materials, with potential for further enhancement through the incorporation of extrinsic nanoparticles like graphene, carbon nanotubes, nanodiamonds and metal oxides. Of particular interest is the relatively unexplored use of transition metal dichalcogenides (TMDCs), with preliminary findings demonstrating highly competitive capacitances of up to 360 F/g when combined with hydrochars. This exceptional electrochemical performance, coupled with unique material properties, positions these biomass-based hydrochars interesting candidates to advance the energy industry towards a greener and more sustainable future. [ABSTRACT FROM AUTHOR]

The thermal stability and degradation, near-to-surface mechanical properties, and scratch resistance and damage mechanism of poly(etheretherketone) (PEEK)/reduced graphene oxide (RGO) nanocomposite coatings are analyzed and discussed in terms of their nanosheet content and microstructure. Although RGO modified the thermal stability and degradation of the polymeric matrix, for instance, by slightly reducing the onset degradation temperature, its addition was not a limiting factor in the PEEK processing. Respecting the microstructural features induced by the nanosheets, the nanocomposite coatings were found to exhibit (i) a partially exfoliated and large-scale co-continuous morphology related to RGO nanosheets whose basal planes were mainly aligned with the coating surface, (ii) a dendritic morphology of PEEK domains related to transcrystallinity, (iii) and irregular domains associated with the deposition of PEEK particles wrapped by the nanosheets. The changes provoked by RGO in the morphology and PEEK crystalline phase influenced the near-to-surface mechanical properties, scratch resistance, and scratch damage mechanism of the nanocomposite coatings. Within this context, the interlayer strength between the nanosheets in the large-scale co-continuous morphology and PEEK transcrystallinity had an important effect. Furthermore, the random-bumpy surface texture formed by the irregular PEEK domains together with the conformal cracking damage mechanism was decisive in the scratch response of the PEEK/RGO nanocomposite coatings. The comprehensive characterization carried out in this work concludes that PEEK/RGO electrophoretic coatings are suitable for a variety of applications requiring tribo-mechanical resistance. [ABSTRACT FROM AUTHOR]

The combination of polyethylene terephthalate (PET), one of the most used polymers in the textile industry, with graphene, one of the most outstanding conductive materials in recent years, represents a promising strategy for the preparation of conductive textiles. This study focuses on the preparation of mechanically stable and conductive polymer textiles and describes the preparation of PET/graphene fibers by the dry-jet wet-spinning method from nanocomposite solutions in trifluoroacetic acid. Nanoindentation results show that the addition of a small amount of graphene (2 wt.%) to the glassy PET fibers produces a significant modulus and hardness enhancement (≈10%) that can be partly attributed to the intrinsic mechanical properties of graphene but also to the promotion of crystallinity. Higher graphene loadings up to 5 wt.% are found to produce additional mechanical improvements up to ≈20% that can be merely attributed to the superior properties of the filler. Moreover, the nanocomposite fibers display an electrical conductivity percolation threshold over 2 wt.% approaching ≈0.2 S/cm for the largest graphene loading. Finally, bending tests on the nanocomposite fibers show that the good electrical conductivity can be preserved under cyclic mechanical loading. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Laboratory astrochemistry aims at simulating, in the laboratory, some of the chemical and physical processes that operate in different regions of the universe. Amongst the diverse astrochemical problems that can be addressed in the laboratory, the evolution of cosmic dust grains in different regions of the interstellar medium (ISM) and its role in the formation of new chemical species through catalytic processes present significant interest. In particular, the dark clouds of the ISM dust grains are coated by icy mantles and it is thought that the ice–dust interaction plays a crucial role in the development of the chemical complexity observed in space. Here, we present a new ultra-high vacuum experimental station devoted to simulating the complex conditions of the coldest regions of the ISM. The INFRA-ICE machine can be operated as a standing alone setup or incorporated in a larger experimental station called Stardust, which is dedicated to simulate the formation of cosmic dust in evolved stars. As such, INFRA-ICE expands the capabilities of Stardust allowing the simulation of the complete journey of cosmic dust in space, from its formation in asymptotic giant branch stars to its processing and interaction with icy mantles in molecular clouds. To demonstrate some of the capabilities of INFRA-ICE, we present selected results on the ultraviolet photochemistry of undecane (C11H24) at 14 K. Aliphatics are part of the carbonaceous cosmic dust, and recently, aliphatics and short n-alkanes have been detected in situ in the comet 67P/Churyumov–Gerasimenko. [ABSTRACT FROM AUTHOR]

Graphene has recently become one of the preferred conductive materials for smart textiles. The most widely employed strategy to integrate graphene into textiles consists of coating the surface of the target substrate. However, this approach presents limitations related to the preparation of the coating material and its performance during work. Herein we introduce a new concept for the coating of conductive carbon-based materials on textiles by using a nanocomposite ink composed of graphene and an elastomer, in a low boiling point solvent. It allows coating large areas of textiles in a short time and the covering layer presents good elasticity making it durable under strong mechanical deformation. In addition, the apolar nature of the coating confers washing resistance to the textiles. Furthermore, the approach is broad in scope as the coating behaves similarly on both synthetic (Nylon, polyester, acrylic) or natural (cotton, cellulose) textiles. Image 1 [ABSTRACT FROM AUTHOR]

Abstract: 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. [ABSTRACT FROM AUTHOR]

Abstract: 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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Hazardous reactive dyes can cause serious environmental problems, as they are difficult to remove from water using conventional adsorbents due to their large molecular sizes and bulky structures. Sustainable mesoporous carbons derived from alginic acid demonstrated promising adsorbent capacity for several representative industrial bulky reactive dye molecules that account for almost 30% of the global textile dye market: Procion Yellow H-XEL (PY), Remazol Black (RB), Procion Crimson H-XEL (PC) and Procion Navy H-XEL (PN). These new adsorbents showed high mesoporosity (>90%) and large pore diameters (>20 nm) facilitating more straightforward and efficient adsorption and desorption processes when compared with predominately microporous activated carbon (AC), Norit, of similar surface chemistry, or with Silica gel (Sgel) that shows good mesoporosity but is hydrophilic. Their adsorption capacity was also significantly higher than that of both AC and Sgel, verifying suitability for bulky dye elimination from wastewater. Adsorption kinetic studies showed a best fit with the Elovich model, indicating a heterogeneous surface adsorption process. The adsorption isotherm data was best represented via the Toth model for almost all adsorbent/dye systems (R 2 ≥ 0.98), validating the results of the Elovich model whereby the adsorbent is structurally heterogenous with multilayer dye coverage. From thermodynamic analysis, the derived parameters of Δ G (−11.6 ∼ −6.2 kJ/mol), Δ H and Δ S demonstrate a spontaneous, enthalpy controlled adsorption process that was exothermic for RB (−10.0 kJ/mol) and PC (−23.9 kJ/mol) and endothermic for PY (3.9 kJ/mol) and PN (13.2 kJ/mol). Overall these alginic acid based mesoporous carbons are cost-effective, sustainable and efficient alternatives to current predominantly microporous adsorbent systems. [ABSTRACT FROM AUTHOR]

The formation, characterization and application of starch-derived carbonaceous mesoporous materials (Starbon®) for the selective adsorption and recovery of critical metals (Au3+, Pt2+ and Pd2+) has been described. Starbon® successfully separated these critical metals from a mixture containing earth abundant elements (Ni2+, Cu2+ and Zn2+) with the consequent formation of metal nanoparticles. [ABSTRACT FROM AUTHOR]

Highlights: [•] Studies on multiscale fiber/thermoplastic/carbon nanotube composites are reviewed. [•] Their mechanical, thermal and electrical properties are comparatively analyzed. [•] Synergic effects between fillers on enhancing composite performance are described. [•] Challenges for future developments and potential applications are discussed. [ABSTRACT FROM AUTHOR]

Abstract: Polymer/inorganic nanoparticle nanocomposites have garnered considerable academic and industrial interest over recent decades in the development of advanced materials for a wide range of applications. In this respect, the dispersion of so-called inorganic fullerene-like (IF) nanoparticles, e.g., tungsten disulfide (IF-WS2) or molybdenum disulfide (IF-MoS2), into polymeric matrices is emerging as a new strategy. The surprising properties of these layered metal dichalcogenides such as high impact resistance and superior tribological behavior, attributed to their nanoscale size and hollow quasi-spherical shape, open up a wide variety of opportunities for applications of these inorganic compounds. The present work presents a detailed overview on research in the area of IF-based polymer nanocomposites, with special emphasis on the use of IF-WS2 nanoparticles as environmentally friendly reinforcing fillers. The incorporation of IF particles has been shown to be efficient for improving thermal, mechanical and tribological properties of various thermoplastic polymers, such as polypropylene, nylon-6, poly(phenylene sulfide), poly(ether ether ketone), where nanocomposites were fabricated by simple melt-processing routes without the need for modifiers or surfactants. This new family of nanocomposites exhibits similar or enhanced performance when compared with nanocomposites that incorporate carbon nanotubes, carbon nanofibers or nanoclays, but are substantially more cost-effective, efficient and environmentally satisfactory. Most recently, innovative approaches have been described that exploit synergistic effects to produce new materials with enhanced properties, including the combined use of micro- and nanoparticles such as IF-WS2/nucleating agent or IF-WS2/carbon fiber, as well as dual nanoparticle systems such as SWCNT/IF-WS2 where each nanoparticle has different characteristics. The structure–property relationships of these nanocomposites are discussed and potential applications proposed ranging from medicine to the aerospace, automotive and electronics industries. [Copyright &y& Elsevier]

• Synergistic effect between 2D WS 2 and diamond nanoparticles in electroanalysis. • Electrochemical sensor for the simultaneous analysis of food additives in real samples. • High selective Sunset Yellow determination because of a previous reduction step. We present the development of an electrochemical sensor towards the simultaneous analysis of a mixture of food additives: sunset yellow (SY) and quinoline yellow (QY) dyes. The sensor is based on the synergetic effect observed between diamond nanoparticles (DNPs) and WS 2 nanosheets obtained by liquid exfoliation. The prepared TMDs were characterized using Raman spectroscopy, X-Ray Diffraction (XRD) and Atomic Force Microscopy (AFM). The AFM characterization showed isolated WS 2 flakes with different lateral dimensions scattered over the flat background. The combination of WS 2 and DNPs allows resolution of the oxidation signals of the analytes, which overlap working with the bare glassy carbon (GC) electrode. The best electroanalytical response was obtained with a sensor containing both nanomaterials deposited employing the drop-casting method in a sequential manner, a first layer of WS 2 and a second layer of DNPs (GC/WS 2 /DNPs). Electrochemical impedance spectroscopy experiments showed that for the GC/WS 2 /DNPs system the charge transfer is clearly improved. Under optimized differential pulse voltammetry conditions, the GC/WS 2 /DNPs sensor allows the determination of SY at +100 mV and QY at +850 mV with detection limits of 0.086 and 3.4 μM respectively, with relative errors ≤ 8.40 % and a relative standard deviation ≤ 12.6 %. The proposed methodology was applied to the determination of SY and QY in commercial throat lozenge samples with very good recoveries on average: 93 %, for QY and 106 % for SY. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]