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.

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.

Construction of Multi-Stimuli Responsive Highly Porous Switchable Frameworks by In Situ Solid-State Generation of Spiropyran Switches.

Stimuli-responsive molecular systems support within permanently porous materials offer the opportunity to host dynamic functions in multifunctional smart materials. However, the construction of highly porous frameworks featuring external-stimuli responsiveness, for example by light excitation, is still in its infancy. Here a general strategy is presented to construct spiropyran-functionalized highly porous switchable aromatic frameworks by modular and high-precision anchoring of molecular hooks and an innovative in situ solid-state grafting approach. Three spiropyran-grafted frameworks bearing distinct functional groups exhibiting various stimuli-responsiveness are generated by two-step post-solid-state synthesis of a parent indole-based material. The quantitative transformation and preservation of high porosity are demonstrated by spectroscopic and gas adsorption techniques. For the first time, a highly efficient strategy is provided to construct multi-stimuli-responsive, yet structurally robust, spiropyran materials with high pore capacity which is proved essential for the reversible and quantitative isomerization in the bulk as demonstrated by solid-state NMR spectroscopy. The overall strategy allows to construct dynamic materials that undergoes reversible transformation of spiropyran to zwitterionic merocyanine, by chemical and physical stimulation, showing potential for pH active control, responsive gas uptake and release, contaminant removal, and water harvesting.

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.

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.

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.

Controlling the Formation of Electroactive Graphene-Based Cementitious Composites: Towards Structural Health Monitoring of Civil Structures.

The development of composites combining multiple components each one imparting a specific function to the ensemble is highly sought after for disruptive applications in chemistry and materials science, with a particular importance for the realization of smart structures. Here, we report on the development of an unprecedented multifunctional cementitious composite incorporating reduced graphene oxide (rGO). By design, this material features significantly enhanced electrical properties while retaining the excellent cement's hydration and microstructure. The multiscale investigation on the chemical and physical properties of the dispersion made it possible to establish an efficient preparation protocol for rGO aqueous dispersion as well as rGO-based cementitious composites using a commercial poly(carboxylate ether)-based superplasticizer. The conduction mechanisms within the matrix of rGO containing mortars were unraveled by electrochemical impedance spectroscopy revealing conductive paths originating from bulk cement matrix and rGO nanosheets in composites with rGO loadings as low as 0.075 wt. %. For this rGO loading, we observed the reduction of the resistivity of bulk cement mortar layers from 18.3 MΩ cm to 2.8 MΩ cm. Moreover, the addition of 0.2 wt. % of rGO resulted in the formation of rGO conductive paths with the resistivity of 51.1 kΩ cm. These findings represent a major step forward towards the practical application of graphene-based materials in structural health monitoring of concrete structures.

Dynamic Cages-Towards Nanostructured Smart Materials.

The interest in capsular assemblies such as dynamic organic and coordination cages has blossomed over the last decade. Given their chemical and structural variability, these systems have found applications in diverse fields of research, including energy conversion and storage, catalysis, separation, molecular recognition, and live-cell imaging. In the exploration of the potential of these discrete architectures, they are increasingly being employed in the formation of more complex systems and smart materials. This Review highlights the most promising pathways to overcome common drawbacks of cage systems (stability, recovery) and discusses the most promising strategies for their hybridization with systems featuring various dimensionalities. Following the description of the most recent advances in the fabrication of zero to three-dimensional cage-based systems, this Review will provide the reader with the structure-dependent relationship between the employed cages and the properties of the materials.

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).

High Selectivity and Sensitivity in Chemiresistive Sensing of Co(II) Ions with Liquid-Phase Exfoliated Functionalized MoS2 : A Supramolecular Approach.

Chemical sensing of water contamination by heavy metal ions is key as it represents a most severe environmental problem. Liquid-phase exfoliated two-dimensional (2D) transition metal dichalcogenides (TMDs) are suitable candidates for chemical sensing thanks to their high surface-to-volume ratio, sensitivity, unique electrical characteristics, and scalability. However, TMDs lack selectivity due to nonspecific analyte-nanosheet interactions. To overcome this drawback, defect engineering enables controlled functionalization of 2D TMDs. Here, ultrasensitive and selective sensors of cobalt(II) ions via the covalent functionalization of defect-rich MoS2 flakes with a specific receptor, 2,2':6',2″-terpyridine-4'-thiol is developed. A continuous network is assembled by healing of MoS2 sulfur vacancies in a tailored microfluidic approach, enabling high control over the assembly of thin and large hybrid films. The Co2+ cations complexation represents a powerful gauge for low concentrations of cationic species which can be best monitored in a chemiresisitive ion sensor, featuring a 1 pm limit of detection, sensing in a broad concentration range (1 pm - 1 µm) and sensitivity as high as 0.308 ± 0.010 lg([Co2+ ])-1 combined with a high selectivity towards Co2+ over K+ , Ca2+ , Mn2+ , Cu2+ , Cr3+ , and Fe3+ cations. This supramolecular approach based on highly specific recognition can be adapted for sensing other analytes through specific ad-hoc receptors.

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.

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.

Novel thiophene-based donor-acceptor scaffolds as cathodes for rechargeable aqueous zinc-ion hybrid supercapacitors.

Well-defined π-conjugated thiophene donor-acceptor molecules play an important role in different fields ranging from synthetic chemistry to materials science. Their chemical structure provides specific electronic and physicochemical properties, which can be further tuned by the introduction of functional groups. Herein, we design and synthesize two novel thiophene-based π-conjugated donor-acceptor molecules TDA-1 and TDA-2 through Aldol and Knoevenagel condensations. In our proof-of-concept study we report for the first time on the use of small organic molecules employed in aqueous zinc-ion hybrid supercapacitors (Zn-HSCs),which exhibit capacitance as high as 206.7 and 235.2 F g-1 for TDA-1, and TDA-2, respectively.

Schiff base capped gold nanoparticles for transition metal cation sensing in organic media.

We report a fast and ultrasensitive colorimetric method for the detection of transition metal ions (Fe3+, Cu2+, Ni2+) in a mixture of toluene-acetonitrile using Schiff base functionalized gold nanoparticles. We achieved limits of detection for the three metal ions at least two orders of magnitude lower than the EU recommended limits. Finally, our methodology was assessed for the determination of nickel in the organic waste of a relevant industrial reaction.

Boosting the electronic and catalytic properties of 2D semiconductors with supramolecular 2D hydrogen-bonded superlattices.

The electronic properties of two-dimensional semiconductors can be strongly modulated by interfacing them with atomically precise self-assembled molecular lattices, yielding hybrid van der Waals heterostructures (vdWHs). While proof-of-concepts exploited molecular assemblies held together by lateral unspecific van der Waals interactions, the use of 2D supramolecular networks relying on specific non-covalent forces is still unexplored. Herein, prototypical hydrogen-bonded 2D networks of cyanuric acid (CA) and melamine (M) are self-assembled onto MoS2 and WSe2 forming hybrid organic/inorganic vdWHs. The charge carrier density of monolayer MoS2 exhibits an exponential increase with the decreasing area occupied by the CA·M unit cell, in a cooperatively amplified process, reaching 2.7 × 1013 cm-2 and thereby demonstrating strong n-doping. When the 2D CA·M network is used as buffer layer, a stark enhancement in the catalytic activity of monolayer MoS2 for hydrogen evolution reactions is observed, outperforming the platinum (Pt) catalyst via gate modulation.

Quantum Capacitance through Molecular Infiltration of 7,7,8,8-Tetracyanoquinodimethane in Metal-Organic Framework/Covalent Organic Framework Hybrids.

Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have been extensively investigated during the last two decades. More recently, a family of hybrid materials (i.e., MOF@COF) has emerged as particularly appealing for gas separation and storage, catalysis, sensing, and drug delivery. MOF@COF hybrids combine the unique characteristics of both MOF and COF components and exhibit peculiar properties including high porosity and large surface area. In this work, we show that the infiltration of redox-active 7,7,8,8-tetracyanoquinodimethane (TCNQ) molecules into the pores of MOF@COF greatly improves the characteristics of the latter, thereby attaining high-performance energy storage devices. Density functional theory (DFT) calculations were employed to guide the design of a MOF@COF-TCNQ hybrid with the TCNQ functional units incorporated in the pores of MOF@COF. To demonstrate potential application of our hybrids, the as-synthesized MOF@COF-TCNQ hybrid has been employed as an active material in supercapacitors. Electrochemical energy storage analysis revealed outstanding supercapacitor performance, as evidenced by a specific areal capacitance of 78.36 mF cm-2 and a high stack volumetric energy density of 4.46 F cm-3, with a capacitance retention of 86.4% after 2000 cycles completed at 0.2 A cm-2. DFT calculation results strongly indicate that the high capacitance of MOF@COF-TCNQ has a quantum capacitance origin. Our liquid-phase infiltration protocol of MOF@COF hybrids with redox-active molecules represents a efficacious approach to design functional porous hybrids.

Harnessing selectivity in chemical sensing via supramolecular interactions: from functionalization of nanomaterials to device applications.

Chemical sensing is a strategic field of science and technology ultimately aiming at improving the quality of our lives and the sustainability of our Planet. Sensors bear a direct societal impact on well-being, which includes the quality and composition of the air we breathe, the water we drink, and the food we eat. Pristine low-dimensional materials are widely exploited as highly sensitive elements in chemical sensors, although they suffer from lack of intrinsic selectivity towards specific analytes. Here, we showcase the most recent strategies on the use of (supra)molecular interactions to harness the selectivity of suitably functionalized 0D, 1D, and 2D low-dimensional materials for chemical sensing. We discuss how the design and selection of receptors via machine learning and artificial intelligence hold a disruptive potential in chemical sensing, where selectivity is achieved by the design and high-throughput screening of large libraries of molecules exhibiting a set of affinity parameters that dictates the analyte specificity. We also discuss the importance of achieving selectivity along with other relevant characteristics in chemical sensing, such as high sensitivity, response speed, and reversibility, as milestones for true practical applications. Finally, for each distinct class of low-dimensional material, we present the most suitable functionalization strategies for their incorporation into efficient transducers for chemical sensing.

Solution-Processed Graphene-Nanographene van der Waals Heterostructures for Photodetectors with Efficient and Ultralong Charge Separation.

Sensitization of graphene with inorganic semiconducting nanostructures has been demonstrated as a powerful strategy to boost its optoelectronic performance. However, the limited tunability of optical properties and toxicity of metal cations in the inorganic sensitizers prohibits their widespread applications, and the in-depth understanding of the essential interfacial charge-transfer process within such hybrid systems remains elusive. Here, we design and develop high-quality nanographene (NG) dispersions with a large-scale production using high-shear mixing exfoliation. The physisorption of these NG molecules onto graphene gives rise to the formation of graphene-NG van der Waals heterostructures (VDWHs), characterized by strong interlayer coupling through π-π interactions. As a proof of concept, photodetectors fabricated on the basis of such VDWHs show ultrahigh responsivity up to 4.5 × 107 A/W and a specific detectivity reaching 4.6 × 1013 Jones, being competitive with the highest values obtained for graphene-based photodetectors. The outstanding device characteristics are attributed to the efficient transfer of photogenerated holes from NGs to graphene and the long-lived charge separation at graphene-NG interfaces (beyond 1 ns), as elucidated by ultrafast terahertz (THz) spectroscopy. These results demonstrate the great potential of such graphene-NG VDWHs as prototypical building blocks for high-performance, low-toxicity optoelectronics.

Self-Assembly of Functionalized Lipophilic Guanosines into Cation-Free Stacked Guanine-Quartets.

The hierarchical self-assembly of various lipophilic guanosines exposing either a phenyl or a ferrocenyl group in the C(8) position was investigated. In a solution, all the derivatives were found to self-assemble primarily into isolated guanine (G)-quartets. In spite of the apparent similar bulkiness of the two substituents, most of the derivatives form disordered structures in the solid state, whereas a specific 8-phenyl derivative self-assembles into an unprecedented, cation-free stacked G-quartet architecture.