Molecular Connectors Boosting the Performance of MoS2 Cathodes in Zinc-Ion Batteries.

Zinc-ion batteries (ZIBs) are promising energy storage systems due to high energy density, low-cost, and abundant availability of zinc as a raw material. However, the greatest challenge in ZIBs research is lack of suitable cathode materials that can reversibly intercalate Zn2+ ions. 2D layered materials, especially MoS2 -based, attract tremendous interest due to large surface area and ability to intercalate/deintercalate ions. Unfortunately, pristine MoS2 obtained by traditional protocols such as chemical exfoliation or hydrothermal/solvothermal methods exhibits limited electronic conductivity and poor chemical stability upon charge/discharge cycling. Here, a novel molecular strategy to boost the electrochemical performance of MoS2 cathode materials for aqueous ZIBs is reported. The use of dithiolated conjugated molecular pillars, that is, 4,4'-biphenyldithiols, enables to heal defects and crosslink the MoS2 nanosheets, yielding covalently bridged networks (MoS2 -SH2) with improved ionic and electronic conductivity and electrochemical performance. In particular, MoS2 -SH2 electrodes display high specific capacity of 271.3 mAh g-1 at 0.1 A g-1 , high energy density of 279 Wh kg-1 , and high power density of 12.3 kW kg-1 . With its outstanding rate capability (capacity of 148.1 mAh g-1 at 10 A g-1 ) and stability (capacity of 179 mAh g-1 after 1000 cycles), MoS2 -SH2 electrodes outperform other MoS2 -based electrodes in ZIBs.

Supramolecular Engineering of Cathode Materials for Aqueous Zinc-ion Energy Storage Devices: Novel Benzothiadiazole Functionalized Two-Dimensional Olefin-Linked COFs.

Two-dimensional covalent organic frameworks (COFs) have emerged as promising materials for energy storage applications exhibiting enhanced electrochemical performance. While most of the reported organic cathode materials for zinc-ion batteries use carbonyl groups as electrochemically-active sites, their high hydrophilicity in aqueous electrolytes represents a critical drawback. Herein, we report a novel and structurally robust olefin-linked COF-TMT-BT synthesized via the aldol condensation between 2,4,6-trimethyl-1,3,5-triazine (TMT) and 4,4'-(benzothiadiazole-4,7-diyl)dibenzaldehyde (BT), where benzothiadiazole units are explored as novel electrochemically-active groups. Our COF-TMT-BT exhibits an outstanding Zn2+ storage capability, delivering a state-of-the-art capacity of 283.5 mAh g-1 at 0.1 A g-1 . Computational and experimental analyses reveal that the charge-storage mechanism in COF-TMT-BT electrodes is based on the supramolecularly engineered and reversible Zn2+ coordination by the benzothiadiazole units.

New Anderson-Based Polyoxometalate Covalent Organic Frameworks as Electrodes for Energy Storage Boosted Through Keto-Enol Tautomerization.

The unique electrochemical properties of polyoxometalates (POMs) render them ideal components for the fabrication of next-generation high-performance energy storage systems. However, their practical applications have been hindered by their high solubility in common electrolytes. This problem can be overcome by the effective hybridization of POMs with other materials. Here we present the design and synthesis of two novel polyoxometalate-covalent organic frameworks (POCOF) via one-pot solvothermal strategy between an amino-functionalized Anderson-type POM and a trialdehyde-based building unit. We show that structural and functional complexity can be enriched by adding hydroxyl groups in the 2,4,6 position to the benzene-1,3,5-tricarbaldehyde allowing to exploit for the first time in POCOFs the keto-enol tautomerization as additional feature to impart greater chemical stability to the COFs and enhanced properties leading to large specific surface area (347 m2 /g) and superior electrochemical performance of the POCOF-1 electrodes, when compared with POCOF-2 electrodes that possess only imine-type linkage and with pristine POM electrodes. Specifically, POCOF-1 electrodes display remarkable specific, areal, and volumetric capacitance (125 F/g, 248 mF/cm2 and 41.9 mF/cm3 , respectively) at a current density of 0.5 A/g, a maximum energy density (56.2 Wh/kg), a maximum power density (3.7 kW/kg) and an outstanding cyclability (90 % capacitance retention after 5000 cycles).

Selective Ion Sensing in Artificial Sweat Using Low-Cost Reduced Graphene Oxide Liquid-Gated Plastic Transistors.

Health monitoring is experiencing a radical shift from clinic-based to point-of-care and wearable technologies, and a variety of nanomaterials and transducers have been employed for this purpose. 2D materials (2DMs) hold enormous potential for novel electronics, yet they struggle to meet the requirements of wearable technologies. Here, aiming to foster the development of 2DM-based wearable technologies, reduced graphene oxide (rGO)-based liquid-gated transistors (LGTs) for cation sensing in artificial sweat endowed with distinguished performance and great potential for scalable manufacturing is reported. Laser micromachining is employed to produce flexible transistor test patterns employing rGO as the electronic transducer. Analyte selectivity is achieved by functionalizing the transistor channel with ion-selective membranes (ISMs) via a simple casting method. Real-time monitoring of K+ and Na+ in artificial sweat is carried out employing a gate voltage pulsed stimulus to take advantage of the fast responsivity of rGO. The sensors show excellent selectivity toward the target analyte, low working voltages (<0.5 V), fast (5-15 s), linear response at a wide range of concentrations (10 µm to 100 mm), and sensitivities of 1 µA/decade. The reported strategy is an important step forward toward the development of wearable sensors based on 2DMs for future health monitoring technologies.

Chemical sensing with Au and Ag nanoparticles.

Noble metal nanoparticles (NPs) are ideal scaffolds for the fabrication of sensing devices because of their high surface-to-volume ratio combined with their unique optical and electrical properties which are extremely sensitive to changes in the environment. Such characteristics guarantee high sensitivity in sensing processes. Metal NPs can be decorated with ad hoc molecular building blocks which can act as receptors of specific analytes. By pursuing this strategy, and by taking full advantage of the specificity of supramolecular recognition events, highly selective sensing devices can be fabricated. Besides, noble metal NPs can also be a pivotal element for the fabrication of chemical nose/tongue sensors to target complex mixtures of analytes. This review highlights the most enlightening strategies developed during the last decade, towards the fabrication of chemical sensors with either optical or electrical readout combining high sensitivity and selectivity, along with fast response and full reversibility, with special attention to approaches that enable efficient environmental and health monitoring.

Highly Sensitive Strain Sensors Based on Molecules-Gold Nanoparticles Networks for High-Resolution Human Pulse Analysis.

High-performance flexible strain sensors are key components for the next generation of wearable health monitoring devices. Here, the authors have fabricated a novel strain sensor based on gold nanoparticles (AuNPs) interconnected by flexible and responsive molecular linkers. The combination of conductive AuNPs (25 nm in diameter) with tetra(ethylene glycol) dithiol (SH-TEG-SH) linkers yields a covalent 3D network which can be directly deposited onto prepatterned flexible supports exposing interdigitated Au electrodes. The electrically insulating nature of the linkers effectively defines the tunneling modulated charge transfer through the AuNPs network. When compressive/tensile strain is applied, the molecular linkers adopt a compressed/stretched conformation thus decreasing/increasing the interparticle distance, ultimately yielding an exponential increase/decrease of the tunneling current when voltage is applied. The strain sensor displays state-of-the-art performances including a highly sensitive response to both tensile and compressive strain, as quantified by a high gauge factor (GF≈126) combined with other superior sensing properties like high flexibility, short response time (16.1 ms), and good robustness (>2000 cycles). Finally, the applicability of the device for health monitoring is demonstrated: high-resolution artery pulse waves are acquired by placing the strain sensor onto the skin allowing the extraction of important physical parameters for human-health assessment.

Universal Fabrication of Highly Efficient Plasmonic Thin-Films for Label-Free SERS Detection.

The development of novel, highly efficient, reliable, and robust surface enhanced Raman scattering (SERS) substrates containing a large number of hot spots with programmed size, geometry, and density is extremely interesting since it allows the sensing of numerous (bio-)chemical species. Herein, an extremely reliable, easy to fabricate, and label-free SERS sensing platform based on metal nanoparticles (NPs) thin-film is developed by the layer-by-layer growth mediated by polyelectrolytes. A systematic study of the effect of NP composition and size, as well as the number of deposition steps on the substrate's performance, is accomplished by monitoring the SERS enhancement of 1-naphtalenethiol (532 nm excitation). Distinct evidence of the key role played by the interlayer (poly(diallyldimethylammonium chloride) (PDDA) or PDDA-functionalized graphene oxide (GO@PDDA)) on the overall SERS efficiency of the plasmonic platforms is provided, revealing in the latter the formation of more uniform hot spots by regulating the interparticle distances to 5 ± 1 nm. The SERS platform efficiency is demonstrated via its high analytical enhancement factor (≈106 ) and the detection of a prototypical substance(tamoxifen), both in Milli-Q water and in a real matrix, viz. tap water, opening perspectives towards the use of plasmonic platforms for future high-performance sensing applications.

Detection and imaging of quorum sensing in Pseudomonas aeruginosa biofilm communities by surface-enhanced resonance Raman scattering.

Most bacteria in nature exist as biofilms, which support intercellular signalling processes such as quorum sensing (QS), a cell-to-cell communication mechanism that allows bacteria to monitor and respond to cell density and changes in the environment. As QS and biofilms are involved in the ability of bacteria to cause disease, there is a need for the development of methods for the non-invasive analysis of QS in natural bacterial populations. Here, by using surface-enhanced resonance Raman scattering spectroscopy, we report rationally designed nanostructured plasmonic substrates for the in situ, label-free detection of a QS signalling metabolite in growing Pseudomonas aeruginosa biofilms and microcolonies. The in situ, non-invasive plasmonic imaging of QS in biofilms provides a powerful analytical approach for studying intercellular communication on the basis of secreted molecules as signals.

Au@pNIPAM SERRS Tags for Multiplex Immunophenotyping Cellular Receptors and Imaging Tumor Cells.

Detection technologies employing optically encoded particles have gained much interest toward clinical diagnostics and drug discovery, but the portfolio of available systems is still limited. The fabrication and characterization of highly stable surface-enhanced resonance Raman scattering (SERRS)-encoded colloids for the identification and imaging of proteins expressed in cells are reported. These plasmonic nanostructures are made of gold octahedra coated with poly(N-isopropylacrylamide) microgels and can be readily encoded with Raman active dyes while retaining high colloidal stability in biofluids. A layer-by-layer polyelectrolyte coating is used to seal the outer surface of the encoded particles and to provide a reactive surface for covalent conjugation with antibodies. The targeted multiplexing capabilities of the SERRS tags are demonstrated by the simultaneous detection and imaging of three tumor-associated surface biomarkers: epidermal growth factor receptor (EGFR), epithelial cell adhesion molecule (EpCAM), and homing cell adhesion molecule (CD44) by SERRS spectroscopy. The plasmonic microgels are able to discriminate tumor A431 (EGFR+/EpCAM+/CD44+) and nontumor 3T3 2.2 (EGFR-/EpCAM-/CD44+) cells while cocultured in vitro.

Metal nanoparticles and supramolecular macrocycles: a tale of synergy.

In this minireview, we summarize current research dealing with the combination of noble-metal nanoparticles and different families of supramolecular macrocycles (cyclodextrins, cucurbit[n]urils, calixarenes, and pillar[n]arenes). We intended to select relevant publications on the synthesis of noble-metal nanoparticles with macrocycles acting as capping agents or/and reducing agents, as well as on the post-synthetic metal-nanoparticle modification with macrocycles. We also discuss strategies in which supramolecular chemistry is applied to direct the self-assembly of nanoparticles and formation of polymer composites. We finally describe the main applications of these materials in various fields.

Pillar[5]arene-mediated synthesis of gold nanoparticles: size control and sensing capabilities.

We present a simple procedure for the synthesis of quasi-spherical Au nanoparticles in a wide size range mediated by macrocyclic host molecules, ammonium pillar[5]arene (AP[5]A). The strategy is based on a seeded growth process in which the water-soluble pillar[5]arene undergoes complexation of the Au salt through the ammonium groups, thereby avoiding Au nucleation, while acting as a stabilizer. The presence of the pillar[5]arene onto the Au nanoparticle particle surface is demonstrated by surface-enhanced Raman scattering (SERS) spectroscopy, and the most probable conformation of the molecule when adsorbed on the Au nanoparticles surface is suggested on the basis of theoretical calculations. In addition, we analyze the host-guest interactions of the AP[5]A with 2-naphthoic acid (2NA) by using (1)H NMR spectroscopy and the results are compared with theoretical calculations. Finally, the promising synergetic effects of combining supramolecular chemistry and metal nanoparticles are demonstrated through SERS detection in water of 2NA and a polycyclic aromatic hydrocarbon, pyrene (PYR).

Humidity Sensing with Supramolecular Nanostructures.

Precise monitoring of the humidity level is important for the living comfort and for many applications in various industrial sectors. Humidity sensors have thus become one among the most extensively studied and used chemical sensors by targeting a maximal device performance through the optimization of the components and working mechanism. Among different moisture-sensitive systems, supramolecular nanostructures are ideal active materials for the next generation of highly efficient humidity sensors. Their noncovalent nature guarantees fast response, high reversibility, and fast recovery time in the sensing event. Herein, the most enlightening recent strategies on the use of supramolecular nanostructures for humidity sensing are showcased. The key performance indicators in humidity sensing, including operation range, sensitivity, selectivity, response, and recovery speed are discussed as milestones for true practical applications. Some of the most remarkable examples of supramolecular-based humidity sensors are presented, by describing the finest sensing materials, the operating principles, and sensing mechanisms, the latter being based on the structural or charge-transport changes triggered by the interaction of the supramolecular nanostructures with the ambient humidity. Finally, the future directions, challenges, and opportunities for the development of humidity sensors with performance beyond the state of the art are discussed.

Boosting Zinc Hybrid Supercapacitor Performance via Thiol Functionalization of Graphene-Based Cathodes.

Zinc hybrid supercapacitors (Zn-HSCs) hold immense potential toward the next-generation energy storage systems, effectively spanning the divide between conventional lithium-ion batteries (LIBs) and supercapacitors. Unfortunately, the energy density of most of Zn-HSCs has not yet rivalled the levels observed in LIBs. The electrochemical performance of aqueous Zn-HSCs can be enhanced through the chemical functionalization of graphene-based cathode materials with thiol moieties as they will be highly suitable for favoring Zn2+ adsorption/desorption. Here, a single-step reaction is employed to synthesize thiol-functionalized reduced graphene oxide (rGOSH), incorporating both oxygen functional groups (OFGs) and thiol functionalities, as demonstrated by X-ray photoelectron spectroscopy (XPS) studies. Electrochemical analysis reveals that rGOSH cathodes exhibit a specific capacitance (540 F g-1) and specific capacity (139 mAh g-1) at 0.1 A g-1 as well as long-term stability, with over 92% capacitance retention after 10 000 cycles, outperforming chemically reduced graphene oxide (CrGO). Notably, rGOSH electrodes displayed an exceptional maximum energy density of 187.6 Wh kg-1 and power density of 48.6 kW kg-1. Overall, this study offers an unprecedented powerful strategy for the design and optimization of cathode materials, paving the way for efficient and sustainable energy storage solutions to meet the increasing demands of modern energy applications.

MOF (UiO-66-NH2)@COF (TFP-TABQ) hybrids via on-surface condensation reactions for sustainable energy storage.

Core-shell MOF@COF hybrids were synthesized via subsequent modification of MOF UiO-66-NH2 with 1,3,5-triformylphloroglucinol (TFP) and 2,3,5,6-tetraaminobenzoquinone (TABQ). The hybrids exhibited significant surface area (236 m2 g-1) and outstanding electrochemical performance (103 F g-1 at 0.5 A g-1), surpassing both COFs and MOFs, thereby showcasing the potential of on-surface condensation reactions for developing high-performance energy storage devices.

"Clickable" graphene nanoribbons for biosensor interfaces.

We report on the synthesis of "clickable" graphene nanoribbons (GNRs) and their application as a versatile interface for electrochemical biosensors. GNRs are successfully deposited on gold-coated working electrodes and serve as a platform for the covalent anchoring of a bioreceptor (i.e., a DNA aptamer), enabling selective and sensitive detection of Interleukin 6 (IL6). Moreover, when applied as the intermediate linker on reduced graphene oxide (rGO)-based field-effect transistors (FETs), the GNRs provide improved robustness compared to conventional aromatic bi-functional linker molecules. GNRs enable an orthogonal and covalent attachment of a recognition unit with a considerably higher probe density than previously established methods. Interestingly, we demonstrate that GNRs introduce photoluminescence (PL) when applied to rGO-based FETs, paving the way toward the simultaneous optical and electronic probing of the attached biointerface.

Li Promoting Long Afterglow Organic Light-Emitting Transistor for Memory Optocoupler Module.

The artificial brain is conceived as advanced intelligence technology, capable to emulate in-memory processes occurring in the human brain by integrating synaptic devices. Within this context, improving the functionality of synaptic transistors to increase information processing density in neuromorphic chips is a major challenge in this field. In this article, Li-ion migration promoting long afterglow organic light-emitting transistors, which display exceptional postsynaptic brightness of 7000 cd m-2 under low operational voltages of 10 V is presented. The postsynaptic current of 0.1 mA operating as a built-in threshold switch is implemented as a firing point in these devices. The setting-condition-triggered long afterglow is employed to drive the photoisomerization process of photochromic molecules that mimic neurotransmitter transfer in the human brain for realizing a key memory rule, that is, the transition from long-term memory to permanent memory. The combination of setting-condition-triggered long afterglow with photodiode amplifiers is also processed to emulate the human responding action after the setting-training process. Overall, the successful integration in neuromorphic computing comprising stimulus judgment, photon emission, transition, and encoding,  to emulate the complicated decision tree of the human brain is demonstrated.

Enhancing the Carrier Transport in Monolayer MoS2 through Interlayer Coupling with 2D Covalent Organic Frameworks.

The coupling of different 2D materials (2DMs) to form van der Waals heterostructures (vdWHs) is a powerful strategy for adjusting the electronic properties of 2D semiconductors, for applications in opto-electronics and quantum computing. 2D molybdenum disulfide (MoS2 ) represents an archetypical semiconducting, monolayer thick versatile platform for the generation of hybrid vdWH with tunable charge transport characteristics through its interfacing with molecules and assemblies thereof. However, the physisorption of (macro)molecules on 2D MoS2 yields hybrids possessing a limited thermal stability, thereby jeopardizing their technological applications. Herein, the rational design and optimized synthesis of 2D covalent organic frameworks (2D-COFs) for the generation of MoS2 /2D-COF vdWHs exhibiting strong interlayer coupling effects are reported. The high crystallinity of the 2D-COF films makes it possible to engineer an ultrastable periodic doping effect on MoS2 , boosting devices' field-effect mobility at room temperature. Such a performance increase can be attributed to the synergistic effect of the efficient interfacial electron transfer process and the pronounced suppression of MoS2 's lattice vibration. This proof-of-concept work validates an unprecedented approach for the efficient modulation of the electronic properties of 2D transition metal dichalcogenides toward high-performance (opto)electronics for CMOS digital circuits.

Tuning the electrical properties of graphene oxide through low-temperature thermal annealing.

During the last fifteen years, the reduction of electrically insulating graphene oxide (GO) through the elimination of oxygen containing functional groups and the restoration of sp2 conjugation yielding its conducting form, known as reduced graphene oxide (rGO), has been widely investigated as a scalable and low-cost method to produce materials featuring graphene-like characteristics. Among various protocols, thermal annealing represents an attractive green approach compatible with industrial processes. However, the high temperatures typically required to accomplish this process are energetically demanding and are incompatible with the use of plastic substrates often desired for flexible electronics applications. Here, we report a systematic study on the low-temperature annealing of GO by optimizing different annealing conditions, i.e., temperature, time, and reduction atmosphere. We show that the reduction is accompanied by structural changes of GO, which affect its electrochemical performance when used as an electrode material in supercapacitors. We demonstrate that thermally-reduced GO (TrGO) obtained under air or inert atmosphere at relatively low temperatures (<300 °C) exhibits low film resistivities (10-2-10-4 Ω m) combined with unaltered resistance after 2000 bending cycles when supported on plastic substrates. Moreover, it exhibits enhanced electrochemical characteristics with a specific capacitance of 208 F g-1 and a capacitance retention of >99% after 2000 cycles. The reported strategy is an important step forward toward the development of environmentally friendly TrGO for future electrical or electrochemical applications.

Covalently Functionalized MXenes for Highly Sensitive Humidity Sensors.

Transition metal carbides and nitrides (MXenes) are an emerging class of 2D materials, which are attracting ever-growing attention due to their remarkable physicochemical properties. The presence of various surface functional groups on MXenes' surface, e.g., F, O, OH, Cl, opens the possibility to tune their properties through chemical functionalization approaches. However, only a few methods have been explored for the covalent functionalization of MXenes and include diazonium salt grafting and silylation reactions. Here, an unprecedented two-step functionalization of Ti3 C2 Tx MXenes is reported, where (3-aminopropyl)triethoxysilane is covalently tethered to Ti3 C2 Tx and serves as an anchoring unit for subsequent attachment of various organic bromides via the formation of CN bonds. Thin films of Ti3 C2 Tx functionalized with linear chains possessing increased hydrophilicity are employed for the fabrication of chemiresistive humidity sensors. The devices exhibit a broad operation range (0-100% relative humidity), high sensitivity (0.777 or 3.035), a fast response/recovery time (0.24/0.40 s ΔH-1 , respectively), and high selectivity to water in the presence of saturated vapors of organic compounds. Importantly, our Ti3 C2 Tx -based sensors display the largest operating range and a sensitivity beyond the state of the art of MXenes-based humidity sensors. Such outstanding performance makes the sensors suitable for real-time monitoring applications.

A comparative investigation of the chemical reduction of graphene oxide for electrical engineering applications.

The presence of oxygen-containing functional groups on the basal plane and at the edges endows graphene oxide (GO) with an insulating nature, which makes it rather unsuitable for electronic applications. Fortunately, the reduction process makes it possible to restore the sp2 conjugation. Among various protocols, chemical reduction is appealing because of its compatibility with large-scale production. Nevertheless, despite the vast number of reported chemical protocols, their comparative assessment has not yet been the subject of an in-depth investigation, rendering the establishment of a structure-performance relationship impossible. We report a systematic study on the chemical reduction of GO by exploring different reducing agents (hydrazine hydrate, sodium borohydride, ascorbic acid (AA), and sodium dithionite) and reaction times (2 or 12 hours) in order to boost the performance of chemically reduced GO (CrGO) in electronics and in electrochemical applications. In this work, we provide evidence that the optimal reduction conditions should vary depending on the chosen application, whether it is for electrical or electrochemical purposes. CrGO exhibiting a good electrical conductivity (>1800 S m-1) can be obtained by using AA (12 hours of reaction), Na2S2O4 and N2H4 (independent of the reaction time). Conversely, CrGO displaying a superior electrochemical performance (specific capacitance of 211 F g-1, and capacitance retention >99.5% after 2000 cycles) can be obtained by using NaBH4 (12 hours of reaction). Finally, the compatibility of the different CrGOs with wearable and flexible electronics is also demonstrated using skin irritation tests. The strategy described represents a significant advancement towards the development of environmentally friendly CrGOs with ad hoc properties for advanced applications in electronics and energy storage.