Sustainable Photocatalytic Acylation of Transition Metal Dichalcogenides with Atom Economy.

Transition metal dichalcogenides (TMDs) are promising 2D nanomaterials for diverse applications, but their intrinsic chemical inertness hinders their modification. Herein, a novel approach is presented for the photocatalytic acylation of 2H-MoS2 and 2H-MoSe2, utilizing tetrabutyl ammonium decatungstate ((nBu4N)4W10O32) polyoxometalate complex as a catalyst and a conventional halogen lamp as a source of irradiation. By harnessing the semiconducting properties of TMDs, new avenues emerge for the functionalization of these materials. This novel photocatalytic protocol constitutes the first report on the chemical modification of 2D nanomaterials based on a catalytic protocol and applies to both aliphatic and aromatic substrates. The scope of the decatungstate-photocatalyzed acylation reaction of TMDs is explored by employing an alkyl and an aromatic aldehyde and the success of the methodology is confirmed by diverse spectroscopic, thermal, microscopy imaging, and redox techniques. This catalytic approach on modifying 2D nanomaterials introduces the principles of atom economy in a functionalization protocol for TMDs. It marks a transformative shift toward more sustainable and efficient methodologies in the realm of TMD modification and nanomaterial chemistry.

Carbon Dots Strongly Immobilized onto Carbon Nanohorns as Non-Metal Heterostructure with High Electrocatalytic Activity towards Protons Reduction in Hydrogen Evolution Reaction.

Highly performing, non-metal inexpensive electrocatalysts for the production of hydrogen via electrochemical water splitting are called for the replacement of current platinum-based ones. In order to speed up the electrocatalytic hydrogen evolution, abundant active sites but also efficient charge transfer is needed. In this context, 0D carbon dots (CDs) with large specific surface area, low cost, high conductivity, and rich functional groups emerge as promising non-metal electrocatalysts. Additionally, the use of conductive substrates provides an effective strategy to boost their electrocatalytic performance. Herein, the unique 3D superstructure of carbon nanohorns (CNHs), as well as without any metal content in their structure, is used to provide a conductive support of high porosity, large specific surface area, and good electrical conductivity, for the in situ growth and immobilization of CDs, via a simple hydrothermal method. The direct contact of CDs with the 3D conductive network of CNHs promotes charge transfer, accelerating hydrogen evolution. The all-carbon non-metal CDs/CNHs nanoensembleshows an onset potential close to the one of Pt/C, low charge transfer resistance, and excellent stability.

Covalently Modified Kevlar Fabric Incorporating Graphene Oxide with Enhanced Antibacterial Properties and Preserved Strength.

This work describes a multi-step modification process for the covalent transformation of Kevlar fabric en route to the incorporation of graphene oxide (GO) nanosheets. Spectroscopic, thermal and microscopy imaging techniques have been employed to follow step-by-step the modification of Kevlar and the formation of the corresponding Kevlar-GO hybrid fabric. The level of Kevlar's functionalization can be controlled with the nitration time, the first reaction in the multi-sequence organic transformations, for obtaining the hybrid fabric with a content of GO up to 30 %. Most importantly, the covalent post-modification of Kevlar does not occur in the expense of the other excellent mechanical properties of the fabric. Under optimal conditions, the Kevlar-GO hybrid fabric shows a 20 % enhancement of the ultimate strength. Notably, when the Kevlar-GO hybrid fabric was exposed to cyanobacterial Synechococcus the bacteria growth was fully inhibited. Overall, the covalently modified fabric demonstrated significant antibacterial behavior, excellent strength and stability under common processes. Due to its simplicity, the methodology presented in this work not only promises to result in a standard procedure to functionalize the mer units of Kevlar with a variety of chemicals and nanomaterials but it can be also extended for the modification and hybridization of other fabrics.

Covalently Modified MoS2 Bearing a Hamilton-Type Receptor for Recognizing a Redox-Active Ferrocene-Barbiturate Guest via Multiple H-Bonds.

The covalent modification of the metallic phase of MoS2 with a Hamilton-type ligand is presented, transforming MoS2 to a recognition platform which is able to embrace barbiturate moieties via hydrogen bonding. The successful hydrogen bonding formation is easily monitored by simple electrochemical assessments, if a ferrocene-labeled barbiturate analogue is utilized as a proof of concept. Full spectroscopic, thermal, and electron microscopy imaging characterization is provided for the newly formed recognition system, along with valuable insights concerning the electrochemical sensing. The given methodology expands beyond the sensing applications, confidently entering the territory of supramolecular interactions on the surface of 2D transition metal dichalcogenides. The well-designed host-guest chemistry presented herein, constitutes a guide and an inspiration for hosting customized-structured functional building blocks on MoS2 and its relatives via hydrogen bonding, opening up new opportunities regarding potential applications.

Photo/Electrocatalytic Hydrogen Peroxide Production by Manganese and Iron Porphyrin/Molybdenum Disulfide Nanoensembles.

The oxygen reduction reaction (ORR) 2e- pathway provides an alternative and green route for industrial hydrogen peroxide (H2 O2 ) production. Herein, the ORR photo/electrocatalytic activity in the alkaline electrolyte of manganese and iron porphyrin (MnP and FeP, respectively) electrostatically associated with modified 1T/2H MoS2 nanosheets is reported. The best performing catalyst, MnP/MoS2 , exhibits excellent electrocatalytic performance towards selective H2 O2 formation, with a low overpotential of 20 mV for the 2e- ORR pathway (Eons  = 680 mV vs RHE) and an H2 O2 yield up to 99%. Upon visible light irradiation, MnP/MoS2 catalyst shows significant activity enhancement along with good stability. Electrochemical impedance spectroscopy assays suggest a reduced charge transfer resistance value at the interface with the electrolyte, indicating an efficient intra-ensemble transfer process of the photo-excited electrons through the formation of a type II heterojunction or Schottky contact, and therefore justifies the boosted electrochemical activities in the presence of light. Overall, this work is expected to inspire the design of novel advanced photo/electrocatalysts, paving the way for sustainable industrial H2 O2 production.

Interfacing Carbon Dots for Charge-Transfer Processes.

Carbon dots (CDs) are a booming material and the most recent incomer in the big family of carbon nanostructures. Specifically, CDs are nanosized fluorescent core-shell nanoparticles with tunable absorption and emission spectra, with high solubility in aqueous media and common organic solvents. Herein, the origins and the development of these unique nanoscale structures are discussed, key synthetic routes are briefly described, and the utilization of CDs in light-induced charge-transfer schemes is mainly focused upon. Beyond the impact of the CD's surface on the photoluminescence properties, functionalization, by covalent or supramolecular means, permits controllable incorporation of new functionalities with novel photophysical properties. Furthermore, the dual nature of CDs as electron donating or electron accepting species, unveiled upon interfacing them with organic chromophores, highlights their potentiality in managing diverse charge-transfer processes. Novel mechanisms, such as symmetry-breaking photoinduced charge-transfer can be activated upon covalent functionalization of CDs with organic dyes. Without a doubt, participation of CDs in energy conversion schemes opens up a wide avenue that may lead to the development of novel prototype devices suitable for technological applications and related to photonics and optoelectronics.

First Synthesis of the Inherently Chiral Trans-4' Bisadduct of C59 N Azafullerene by Using Cyclo-[2]-dodecylmalonate as a Tether.

The multiaddition chemistry of azafullerene C59 N has been scarcely explored, and the isolation of pure bisadducts is in its infancy. Encouraged by the recent regioselective synthesis of the inherently chiral equatorialface bisadduct of C59 N, we focused on the isolation of the first trans-4 bisadduct in a simple two-step approach. The first regioselective synthesis of the trans-4 bisadduct of C59 N by using cyclo-[2]-dodecylmalonate as a tether is now reported. The newly synthesized bisadduct has C1 symmetry, as evidenced by 13 C NMR, while X-ray crystallography validated the trans-4' addition pattern. Furthermore, the inherently chiral trans-4' C59 N bisadduct was enantiomerically resolved, and the mirror-image relation of the two enantiomers was probed by circular dichroism spectroscopy. Finally, UV-Vis and redox assays suggested that the addition pattern has a reflection in the light-harvesting and redox properties of the bisadduct.

Unveiling the Photoinduced Electron-Donating Character of MoS2 in Covalently Linked Hybrids Featuring Perylenediimide.

The covalent functionalization of MoS2 with a perylenediimide (PDI) is reported and the study is accompanied by detailed characterization of the newly prepared MoS2 -PDI hybrid material. Covalently functionalized MoS2 interfacing organic photoactive species has shown electron and/or energy accepting, energy reflecting or bi-directional electron accepting features. Herein, a rationally designed PDI, unsubstituted at the perylene core to act as electron acceptor, forces MoS2 to fully demonstrate for the first time its electron donor capabilities. The photophysical response of MoS2 -PDI is visualized in an energy-level diagram, while femtosecond transient absorption studies disclose the formation of MoS2 .+ -PDI.- charge separated state. The tunable electronic properties of MoS2 , as a result of covalently linking photoactive organic species with precise characteristics, unlock their potentiality and enable their application in light-harvesting and optoelectronic devices.

Noble-Metal-Free Doped Carbon Nanomaterial Electrocatalysts.

Electrocatalytic processes, such as oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER) and carbon dioxide reduction reaction (CO2 RR), play key roles in various sustainable energy storage and production devices and their optimization in an ecological manner is of paramount importance for mankind. In this inclusive Review, we aspire to set the scene on doped carbon-based nanomaterials and their hybrids as precious-metal alternative electrocatalysts for these critical reactions in order for the research community not only to stay up-to-date, but also to get inspired and keep pushing forward towards their practical application in energy conversion.

Chemical Functionalization of 2D Materials.

This Special Issue of Chemistry-A European Journal is dedicated to the Chemical Functionalization of 2D Materials, and features some great contributions from experts in the field of 2D materials. This issue was originally assembled to support the Symposium G "Chemical Functionalization of 2D Materials" at the European Materials Research Society (E-MRS) 2020 Spring Meeting, which was originally scheduled to be held in Strasbourg, France, from May 25th to 29th, 2020. Although the E-MRS 2020 Spring Meeting has been cancelled due to the COVID-19 outbreak, the publication of this Special Issue has proceeded and has become even more important as the contributors discuss diverse and timely research themes related to 2D materials. In this Editorial, a brief overview of the different types of 2D materials is given, together with the chemical functionalization schemes that can be applied to them to achieve new properties as well as enable improved performance in applications. Some of the articles featured in this Special Issue are also highlighted, with the hope that they will inspire readers and further advance the field.

Preparation, Photophysical and Electrochemical Evaluation of an Azaborondipyrromethene/Zinc Porphyrin/Graphene Supramolecular Nanoensemble.

The preparation of an entirely supramolecular, multichromophoric azaborondipyrromethene (ABDP)/zinc tetraphenylporphyrin (ZnTPP)/exfoliated graphene (GR) nanoensemble was accomplished. The ABDP derivative bears glycol chains for enhancing solubility and a pyridine functionality for allowing coordination with ZnTPP. The ABDP/ZnTPP/GR nanoensemble was characterized in terms of morphology and composition by using complementary microscopy imaging, thermogravimetric analysis, Raman as well as steady-state and time-resolved absorption and emission spectroscopy. The photophysical and electrochemical assessment of ABDP/ZnTPP/GR as well as the binding properties of the ABDP/ZnTPP complex, employed as a reference, are presented. Energy and electron transfer events were observed in ABDP/ZnTPP upon photoexcitation. However, in the case of ABDP/ZnTPP/GR, the graphene-induced aggregation of the chromophores alters their electronic interactions, enhancing the energy/electron transfer process between them.

Bottom-Up Synthesized MoS2 Interfacing Polymer Carbon Nanodots with Electrocatalytic Activity for Hydrogen Evolution.

The preparation of an MoS2 -polymer carbon nanodot (MoS2 -PCND) hybrid material was accomplished by employing an easy and fast bottom-up synthetic approach. Specifically, MoS2 -PCND was realized by the thermal decomposition of ammonium tetrathiomolybdate and the in situ complexation of Mo with carboxylic acid units present on the surface of PCNDs. The newly prepared hybrid material was comprehensively characterized by spectroscopy, thermal means, and electron microscopy. The electrocatalytic activity of MoS2 -PCND was examined in the hydrogen evolution reaction (HER) and compared with that of the corresponding hybrid material prepared by a top-down approach, namely MoS2 -PCND(exf-fun), in which MoS2 was firstly exfoliated and then covalently functionalized with PCNDs. The MoS2 -PCND hybrid material showed superior electrocatalytic activity toward the HER with low Tafel slope, excellent electrocatalytic stability, and an onset potential of -0.16 V versus RHE. The superior catalytic performance of MoS2 -PCND was rationalized by considering the catalytically active sites of MoS2 , the effective charge/energy-transfer phenomena from PCNDs to MoS2 , and the synergetic effect between MoS2 and PCNDs in the hybrid material.

Ping-Pong Energy Transfer in Covalently Linked Porphyrin-MoS2 Architectures.

Molybdenum disulfide nanosheets covalently modified with porphyrin were prepared and fully characterized. Neither the porphyrin absorption nor its fluorescence was notably affected by covalent linkage to MoS2 . The use of transient absorption spectroscopy showed that a complex ping-pong energy-transfer mechanism, namely from the porphyrin to MoS2 and back to the porphyrin, operated. This study reveals the potential of transition-metal dichalcogenides in photosensitization processes.

Tether-Directed Regioselective Synthesis of an Equatorialface Bisadduct of Azafullerene Using Cyclo-[2]-octylmalonate.

Bisazafullerene (C59 N)2 has been functionalized under aerobic conditions with cyclo-[2]-octylmalonate through a Mannich-type reaction, furnishing the corresponding monoadduct. A regioselective tether-directed Bingel cyclopropanation reaction was then carried out on the azafullerene core to yield a single bisadduct. Spectroscopic analysis of the formed bisadduct showed it to have a C1 symmetrical structure, making it inherently chiral. Single-crystal X-ray analysis revealed the addition pattern of the azafullerene bisadduct to be equatorialface . Examination of the optical properties showed the evolution of new absorption bands, which can be used as signatures for the characterization of equatorialface bisadducts of C59 N. Finally, redox assays showed that the LUMO level of the equatorialface bisadduct was increased compared to that of the parent (C59 N)2 .

Core-Shell Pd@M (M=Ni, Cu, Co) Nanoparticles/Graphene Ensembles with High Mass Electrocatalytic Activity Toward the Oxygen Reduction Reaction.

Herein, it is demonstrated that pyrene butyric acid (PBA)-stabilized metal nanoparticles with core-shell morphology, Pd@MNPs (M=Ni, Cu, Co), non-covalently supported on graphene (G) sheets, are more active towards oxygen electroreduction in alkaline environments than the benchmark Pd/C catalyst, albeit with a 70 % lower precious metal loading. The PBA-stabilized Pd@MNPs (M=Ni, Cu, Co)/G ensembles were prepared by employing a simple modified polyol method and galvanic replacement and thoroughly characterized with advanced microscopy imaging and complementary spectroscopic techniques. Electrochemical studies revealed that Pd@NiNPs /G presents the optimum performance, exhibiting a 30 mV more positive onset potential and 3.2 times greater mass activity over Pd/C. Moreover, chronoamperometric assays showed the minimum activity loss for Pd@NiNPs /G, not only among its core-shell counterparts but importantly when compared with the benchmark catalyst. The excellent performance of Pd@NiNPs /G was attributed to the (a) presence of PBA as stabilizer, (b) uniform Pd@NiNPs dispersion onto the graphene sheets, (c) efficient intra-ensemble interactions between the two species, (d) existence of the core-shell structure for Pd@NiNPs , and (e) stability of the Ni core metal under the reaction conditions. Last, the oxygen reduction on Pd@NiNPs /graphene occurs by the direct four-electron reduction pathway, showing great potential for use in energy related applications.

A Long-Lived Azafullerenyl Radical Stabilized by Supramolecular Shielding with a [10]Cycloparaphenylene.

A major handicap towards the exploitation of radicals is their inherent instability. In the paramagnetic azafullerenyl radical C59 N. , the unpaired electron is strongly localized next to the nitrogen atom, which induces dimerization to diamagnetic bis(azafullerene), (C59 N)2 . Conventional stabilization by introducing steric hindrance around the radical is inapplicable here because of the concave fullerene geometry. Instead, we developed an innovative radical shielding approach based on supramolecular complexation, exploiting the protection offered by a [10]cycloparaphenylene ([10]CPP) nanobelt encircling the C59 N. radical. Photoinduced radical generation is increased by a factor of 300. The EPR signal showing characteristic 14 N hyperfine splitting of C59 N. ⊂ [10]CPP was traced even after several weeks, which corresponds to a lifetime increase of >108 . The proposed approach can be generalized by tuning the diameter of the employed nanobelts, opening new avenues for the design and exploitation of radical fullerenes.

Excited-State Charge Transfer in Covalently Functionalized MoS2 with a Zinc Phthalocyanine Donor-Acceptor Hybrid.

The functionalization of MoS2 is of paramount importance for tailoring its properties towards optoelectronic applications and unlocking its full potential. Zinc phthalocyanine (ZnPc) carrying an 1,2-dithiolane oxide linker was used to functionalize MoS2 at defect sites located at the edges. The structure of ZnPc-MoS2 was fully assessed by complementary spectroscopic, thermal, and microscopy imaging techniques. An energy-level diagram visualizing different photochemical events in ZnPc-MoS2 was established and revealed a bidirectional electron transfer leading to a charge separated state ZnPc.+ -MoS2 .- . Markedly, evidence of the charge transfer in the hybrid material was demonstrated using fluorescence spectroelectrochemistry. Systematic studies performed by femtosecond transient absorption revealed the involvement of excitons generated in MoS2 in promoting the charge transfer, while the transfer was also possible when ZnPc was excited, signifying their potential in light-energy-harvesting devices.

Supramolecular-Enhanced Charge Transfer within Entangled Polyamide Chains as the Origin of the Universal Blue Fluorescence of Polymer Carbon Dots.

The emission of a bright blue fluorescence is a unique feature common to the vast variety of polymer carbon dots (CDs) prepared from carboxylic acid and amine precursors. However, the difficulty to assign a precise chemical structure to this class of CDs yet hampers the comprehension of their underlying luminescence principle. In this work, we show that highly blue fluorescent model types of CDs can be prepared from citric acid and ethylenediamine through low temperature synthesis routes. Facilitating controlled polycondensation processes, the CDs reveal sizes of 1-1.5 nm formed by a compact network of short polyamide chains of about 10 monomer units. Density functional theory calculations of these model CDs uncover the existence of a spatially separated highest occupied molecular orbital and a lowest unoccupied molecular orbital located at the amide and carboxylic groups, respectively. Photoinduced charge transfer between these groups thus constitutes the origin of the strong blue fluorescence emission. Hydrogen-bond-mediated supramolecular interactions between the polyamide chains enabling a rigid network structure further contribute to the enhancement of the radiative process. Moreover, the photoinduced charge transfer processes in the polyamide network structure easily explain the performance of CDs in applications as revealed in studies on metal ion sensing. These findings thus are of general importance to the further development of polymer CDs with tailored properties as well as for the design of technological applications.

Interfacing Transition Metal Dichalcogenides with Carbon Nanodots for Managing Photoinduced Energy and Charge-Transfer Processes.

Exfoliated semiconducting MoS2 and WS2 were covalently functionalized with 1,2-dithiolane-modified carbon nanodots (CNDs). The newly synthesized CND-MoS2 and CND-WS2 hybrids were characterized by spectroscopic, thermal, and electron microscopy imaging methods. Based on electronic absorption and fluorescence emission spectroscopy, modulation of the optoelectronic properties of TMDs by interfacing with CNDs was accomplished. Electrochemical studies revealed facile oxidation of MoS2 over WS2 in the examined hybrids, suggesting it to be better electron donor. Excited state events, investigated by femtosecond transient absorption spectroscopic studies, revealed ultrafast energy transfer from photoexcited CNDs to both MoS2 and WS2. Interestingly, upon MoS2 photoexcitation, charge transfer from an exciton dissociation path of MoS2 to CNDs, within CND-MoS2, was observed. However, such a process in CND-WS2 was found to be absent due to energetic reasons. The present study highlights the importance of TMD-derived donor-acceptor hybrids in light energy harvesting and optoelectronic applications. Furthermore, the fundamental information obtained from the current results will benefit design strategies and impact the development of additional TMD-based hybrid materials to efficiently manage and perform in electron-transfer processes.

Molecular Functionalization of Two-Dimensional MoS2 Nanosheets.

Molybdenum disulfide (MoS2 ) nanosheets have attracted great scientific interest for their remarkable electronic and optical properties. During the last few years significant progress on exfoliation methods of such nanosheets allowed the development of surface functionalization in covalent or noncovalent fashion. Markedly, the chemical modification allows tailoring and tuning the optical and electronic characteristics of MoS2 , opening new avenues for the potentiality of MoS2 -based hybrids in diverse technological fields. Physisorption of organic molecules onto MoS2 through the development of numerous van der Waals interactions is the most widely approach employed for the surface noncovalent immobilization of organic species onto MoS2 nanosheets. Conversely, developed strategies for the edge and in-plane covalent functionalization of MoS2 mainly concern chemistry at S vacancies, direct C-S bond formation, and coordination of S edges at metal centers. Herein, we focus into the most representative molecular doping strategies and material designing of MoS2 -based hybrid nanostructures carrying photo- and/or electro-active components. Key points related with the exfoliation routes, the surface functionalization approaches and their impact on the electronic properties of the functionalized nanosheets are comprehensively discussed, offering a toolbox for scientists of different disciplines interested in putting a step forward in the field of transition-metal dichalcogenide-based materials.