Oil-in-Water Pickering Emulsions Stabilized with Nanostructured Biopolymers: A Venue for Templating Bacterial Cellulose.

Pickering emulsions (PEs) differ from conventional emulsions in the use of solid colloidal particles as stabilizing agents instead of traditional amphiphilic molecules. Nanostructured biopolymers (NBs) emerge as a promising alternative for PE stabilization owing to their remarkable biocompatibility, abundant availability, and low cost. To explore this potential, a study is herein presented, in which cellulose nanocrystals (CNCs), both type I and type II allomorphs, and chitin nanocrystals (ChNCs) were used for stabilizing oil-in-water PEs prepared by the use of ultrasound. Sunflower oil was selected as the oil phase as it offers the advantages of being edible, renewable, and inexpensive. By utilizing ζ-potential, static light diffraction, and visual observations, we determined the optimal oil/water ratio for each type of NB to obtain stable emulsions after 14 days. The optimized PEs were used to form bacterial nanocellulose composites through emulsion templating. To our knowledge, this study represents a pioneering work in exploiting oil-in-water PEs for this approach. Additionally, it entails the first utilization of nonmercerized type II CNCs as stabilizers for PEs, while also establishing a direct comparison among the most relevant NBs. The resulting composites exhibited a unique morphology, composed of larger pores compared to standard bacterial nanocellulose aerogels. These findings highlight the notable potential of NBs as stabilizers for PEs and their ability to generate green nanocomposites with tailored properties.

Effect of nanocellulose polymorphism on electrochemical analytical performance in hybrid nanocomposites with non-oxidized single-walled carbon nanotubes.

Two cellulose nanocrystals/single-walled carbon nanotube (CNC/SW) hybrids, using two cellulose polymorphs, were evaluated as electrochemical transducers: CNC type I (CNC-I/SW) and CNC type II (CNC-II/SW). They were synthesized and fully characterized, and their analytical performance as electrochemical sensors was carefully studied. In comparison with SWCNT-based and screen-printed carbon electrodes, CNC/SW sensors showed superior electroanalytical performance in terms of sensitivity and selectivity, not only in the detection of small metabolites (uric acid, dopamine, and tyrosine) but also in the detection of complex glycoproteins (alpha-1-acid glycoprotein (AGP)). More importantly, CNC-II/SW exhibited 20 times higher sensitivity than CNC-I/SW for AGP determination, yielding a LOD of 7 mg L-1.These results demonstrate the critical role played by nanocellulose polymorphism in the electrochemical performance of CNC/SW hybrid materials, opening new directions in the electrochemical sensing of these complex molecules. In general, these high-active-surface hybrids smartly exploited the preserved non-oxidized SW conductivity with the high aqueous dispersibility of the CNC, avoiding the use of organic solvents or the incorporation of toxic surfactants during their processing, making the CNC/SW hybrids promising nanomaterials for electrochemical detection following greener approaches.

Synthesis and Processing of Nanomaterials Mediated by Living Organisms.

Nanomaterials offer exciting properties and functionalities. However, their production and processing frequently involve complex methods, cumbersome equipment, harsh conditions, and hazardous media. The capability of organisms to accomplish this using mild conditions offers a sustainable, biocompatible, and environmentally friendly alternative. Different nanomaterials such as metal nanoparticles, quantum dots, silica nanostructures, and nanocellulose are being synthesized increasingly through living entities. In addition, the bionanofabrication potential enables also the in situ processing of nanomaterials inside biomatrices with unprecedented outcomes. In this Minireview we present a critical state-of-the-art vision of current nanofabrication approaches mediated by living entities (ranging from unicellular to higher organisms), in order to expand this knowledge and scrutinize future prospects. An efficient interfacial interaction at the nanoscale by green means is within reach through this approach.

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.

Unique Properties and Behavior of Nonmercerized Type-II Cellulose Nanocrystals as Carbon Nanotube Biocompatible Dispersants.

Nanocellulose is increasingly being investigated as a paradigm of a sustainable nanomaterial because of its extraordinary physical and chemical properties, together with its renewable nature and worldwide abundance. The rich structural diversity of cellulose materials is represented by different crystalline allomorphs, from which types I and II stand out. While type I is naturally and ubiquitously present, type II is man-made and requires harsh and caustic synthesis conditions such as the so-called mercerization process. Here, we provide an optimal scenario to obtain either type-I or II nanocrystalline cellulose (NCC) by a mercerization-free method consisting only of the acid hydrolysis commonly used to produce nanocellulose from microcellulose. The possibility of having nonmercerized type-II NCC acquires a great relevance since this nanostructure shows particularly appealing properties. Moreover, an entangled and wrapped system arises when used as a dispersing agent for single-walled carbon nanotubes (SWCNTs), significantly different from that of type I. The biological testing of each NCC type and their respective SWCNT-NCC dispersions in human intestinal (Caco-2) cells reveals a general innocuous behavior in both cancer and normal stages of differentiation; however, the type-II-based SWCNT-NCC dispersions display cytotoxicity for cancer cells while enhancing mitochondrial metabolism of normal cells.

A tool box to ascertain the nature of doping and photoresponse in single-walled carbon nanotubes.

The effect of doping on the electronic properties in bulk single-walled carbon nanotube (SWCNT) samples is studied for the first time using a new in situ Raman spectroelectrochemical method, and further verified by DFT calculations and photoresponse. We use p-/n-doped SWCNTs prepared by diazonium reactions as a versatile chemical strategy to control the SWCNT behavior. The measured and calculated data testify an acceptor effect of 4-aminobenzenesulfonic acid (p-doping), and a donor effect (n-doping) in the case of benzyl alcohol. In addition, pristine and covalently functionalized SWCNTs were used for the preparation of photoactive film electrodes. The photocathodic current in the photoelectrochemical cell is consistently modulated by the doping group. These results validate the in situ Raman spectroelectrochemistry as a unique tool box for predicting the electronic properties of functionalized SWCNTs in the form of thin films and their operational functionality in thin film devices for future optoelectronic applications.

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.

Electronic Interactions in Illuminated Carbon Dot/MoS2 Ensembles and Electrocatalytic Activity towards Hydrogen Evolution.

The preparation, characterization, and photophysical and electrocatalytic properties of carbon dot (CD)/MoS2 ensembles is reported. Based on electrostatic interactions, ammonium-functionalized MoS2 , which was prepared upon reaction of 1,2-dithiolane tert-butyl carbamate with MoS2 followed by acidic deprotection, was coupled with CDs bearing multiple carboxylates on their periphery, as derived upon microwave-assisted polycondensation of citric acid and ethylenediamine followed by alkaline treatment. Insights into electronic interactions between the two species within CD/MoS2 ensembles emanated from absorption and photoluminescence titration assays. Efficient fluorescence quenching of CDs by MoS2 was observed and attributed to photoinduced electron/energy transfer as the decay mechanism for the transduction of the singlet excited state of CDs. Finally, the electrocatalytic performance of the CD/MoS2 ensemble was assessed towards the hydrogen evolution reaction and found to be superior to that of individual CDs species.

Nanocellulose: The Ultimate Green Aqueous Dispersant for Nanomaterials.

Nanocellulose, a nanoscale derivative from renewable biomass sources, possesses remarkable colloidal properties in water, mechanical strength, and biocompatibility. It emerges as a promising bio-based dispersing agent for various nanomaterials in water. This mini-review explores the interaction between cellulose nanomaterials (nanocrystals or nanofibers) and water, elucidating how this may enable their potential as an eco-friendly dispersing agent. We explore the potential of nanocellulose derived from top-down processes, nanocrystals, and nanofibers for dispersing carbon nanomaterials, semiconducting oxide nanoparticles, and other nanomaterials in water. We also highlight its advantages over traditional methods by not only effectively dispersing those nanomaterials but also potentially eliminating the need for further chemical treatments or supporting stabilizers. This not only preserves the exceptional properties of nanomaterials in aqueous dispersion, but may even lead to the emergence of novel hybrid functionalities. Overall, this mini-review underscores the remarkable versatility of nanocellulose as a green dispersing agent for a variety of nanomaterials, inspiring further research to expand its potential to other nanomaterials and applications.

Tungsten Disulfide-Interfacing Nickel-Porphyrin For Photo-Enhanced Electrocatalytic Water Oxidation.

Covalent functionalization of tungsten disulfide (WS2 ) with photo- and electro-active nickel-porphyrin (NiP) is reported. Exfoliated WS2 interfacing NiP moieties with 1,2-dithiolane linkages is assayed in the oxygen evolution reaction under both dark and illuminated conditions. The hybrid material presented, WS2 -NiP, is fully characterized with complementary spectroscopic, microscopic, and thermal techniques. Standard yet advanced electrochemical techniques, such as linear sweep voltammetry, electrochemical impedance spectroscopy, and calculation of the electrochemically active surface area, are used to delineate the catalytic profile of WS2 -NiP. In-depth study of thin films with transient photocurrent and photovoltage response assays uncovers photo-enhanced electrocatalytic behavior. The observed photo-enhanced electrocatalytic activity of WS2 -NiP is attributed to the presence of Ni centers coordinated and stabilized by the N4 motifs of tetrapyrrole rings at the tethered porphyrin derivative chains, which work as photoreceptors. This pioneering work opens wide routes for water oxidation, further contributing to the development of non-noble metal electrocatalysts.

Preparation of Cellulose Nanocrystals: Controlling the Crystalline Type by One-Pot Acid Hydrolysis.

Cellulose nanocrystals (CNCs) have aroused increasing interest owing to their renewable origin and excellent properties derived from their size and morphology. Based on their chain orientation, CNCs can be prepared as two main allomorphs (I or II). However, achieving pure CNC allomorphs still requires enhanced control on the CNCs synthesis process and improved understanding of the involved reaction parameters. In this work, we study in detail a set of parameters for CNC synthesis using one-pot acid hydrolysis and evaluate their influence on the outcome with respect to yield, purity, and repeatability. We also demonstrate that a fast, nondestructive, and accurate methodology based on dynamic light scattering is an efficient alternative to the usual structural analysis of the synthesis outcome. Finally, we provide an improved protocol to reliably obtain each allomorph with mass yields of 25% for type I and 40% for type II. Emphasis is put on the reduction of the environmental impact and the overall preparation time.

Graphene Oxide: Key to Efficient Charge Extraction and Suppression of Polaronic Transport in Hybrids with Poly (3-hexylthiophene) Nanoparticles.

Nanoparticles (NPs) of conjugated polymers in intimate contact with sheets of graphene oxide (GO) constitute a promising class of water-dispersible nanohybrid materials of increased interest for the design of sustainable and improved optoelectronic thin-film devices, revealing properties exclusively pre-established upon their liquid-phase synthesis. In this context, we report for the first time the preparation of a P3HTNPs-GO nanohybrid employing a miniemulsion synthesis approach, whereby GO sheets dispersed in the aqueous phase serve as a surfactant. We show that this process uniquely favors a quinoid-like conformation of the P3HT chains of the resulting NPs well located onto individual GO sheets. The accompanied change in the electronic behavior of these P3HTNPs, consistently confirmed by the photoluminescence and Raman response of the hybrid in the liquid and solid states, respectively, as well as by the properties of the surface potential of isolated individual P3HTNPs-GO nano-objects, facilitates unprecedented charge transfer interactions between the two constituents. While the electrochemical performance of nanohybrid films is featured by fast charge transfer processes, compared to those taking place in pure P3HTNPs films, the loss of electrochromic effects in P3HTNPs-GO films additionally indicates the unusual suppression of polaronic charge transport processes typically encountered in P3HT. Thus, the established interface interactions in the P3HTNPs-GO hybrid enable a direct and highly efficient charge extraction channel via GO sheets. These findings are of relevance for the sustainable design of novel high-performance optoelectronic device structures based on water-dispersible conjugated polymer nanoparticles.

Explosive percolation yields highly-conductive polymer nanocomposites.

Explosive percolation is an experimentally-elusive phenomenon where network connectivity coincides with onset of an additional modification of the system; materials with correlated localisation of percolating particles and emergent conductive paths can realise sharp transitions and high conductivities characteristic of the explosively-grown network. Nanocomposites present a structurally- and chemically-varied playground to realise explosive percolation in practically-applicable systems but this is yet to be exploited by design. Herein, we demonstrate composites of graphene oxide and synthetic polymer latex which form segregated networks, leading to low percolation threshold and localisation of conductive pathways. In situ reduction of the graphene oxide at temperatures of <150 °C drives chemical modification of the polymer matrix to produce species with phenolic groups, which are known crosslinking agents. This leads to conductivities exceeding those of dense-packed networks of reduced graphene oxide, illustrating the potential of explosive percolation by design to realise low-loading composites with dramatically-enhanced electrical transport properties.

Nanoscale Charge Density and Dynamics in Graphene Oxide.

Graphene oxide (GO) is widely used as a component in thin film optoelectronic device structures for practical reasons because its electronic and optical properties can be controlled. Progress critically depends on elucidating the nanoscale electronic structure of GO. However, direct experimental access is challenging because of its disordered and nonconductive character. Here, we quantitatively mapped the nanoscopic charge distribution and charge dynamics of an individual GO sheet by using Kelvin probe force microscopy (KPFM). Charge domains are identified, presenting important charge interactions below distances of 20 nm. Charge dynamics with very long relaxation times of at least several hours and a logarithmic decay of the time correlation function are in excellent agreement with Monte Carlo simulations, revealing an universal hopping transport mechanism best described by Efros-Shklovskii's law.

Waterborne Graphene- and Nanocellulose-Based Inks for Functional Conductive Films and 3D Structures.

In the vast field of conductive inks, graphene-based nanomaterials, including chemical derivatives such as graphene oxide as well as carbon nanotubes, offer important advantages as per their excellent physical properties. However, inks filled with carbon nanostructures are usually based on toxic and contaminating organic solvents or surfactants, posing serious health and environmental risks. Water is the most desirable medium for any envisioned application, thus, in this context, nanocellulose, an emerging nanomaterial, enables the dispersion of carbon nanomaterials in aqueous media within a sustainable and environmentally friendly scenario. In this work, we present the development of water-based inks made of a ternary system (graphene oxide, carbon nanotubes and nanocellulose) employing an autoclave method. Upon controlling the experimental variables, low-viscosity inks, high-viscosity pastes or self-standing hydrogels can be obtained in a tailored way. The resulting inks and pastes are further processed by spray- or rod-coating technologies into conductive films, and the hydrogels can be turned into aerogels by freeze-drying. The film properties, with respect to electrical surface resistance, surface morphology and robustness, present favorable opportunities as metal-free conductive layers in liquid-phase processed electronic device structures.

Optical properties and carrier dynamics in Co-doped ZnO nanorods.

The controlled modification of the electronic properties of ZnO nanorods via transition metal doping is reported. A series of ZnO nanorods were synthesized by chemical bath growth with varying Co content from 0 to 20 atomic% in the growth solution. Optoelectronic behavior was probed using cathodoluminescence, time-resolved luminescence, transient absorbance spectroscopy, and the incident photon-to-current conversion efficiency (IPCE). Analysis indicates the crucial role of surface defects in determining the electronic behavior. Significantly, Co-doping extends the light absorption of the nanorods into the visible region, increases the surface defects, and shortens the non-radiative lifetimes, while leaving the radiative lifetime constant. Furthermore, for 1 atomic% Co-doping the IPCE of the ZnO nanorods is enhanced. These results demonstrate that doping can controllably tune the functional electronic properties of ZnO nanorods for applications.

In-Situ Growth and Immobilization of CdS Nanoparticles onto Functionalized MoS2 : Preparation, Characterization and Fabrication of Photoelectrochemical Cells.

A facile strategy for the controllable growth of CdS nanoparticles at the periphery of MoS2 en route the preparation of electron donor-acceptor nanoensembles is developed. Precisely, the carboxylic group of α-lipoic acid, as addend of the modified MoS2 obtained upon 1,2-dithiolane functionalization, was employed as anchor site for the in situ preparation and immobilization of the CdS nanoparticles in an one-pot two-step process. The newly prepared MoS2 /CdS hybrid material was characterized by complementary spectroscopic, thermal and microscopy imaging means. Absorption spectroscopy was employed to register the formation of MoS2 /CdS, by observing a broad shoulder centered at 420 nm due to CdS nanoparticles, while the excitonic bands of MoS2 were also evident. Moreover, based on the efficient quenching of the characteristic fluorescence emission of CdS at 725 nm by the presence of MoS2 , strong electronic interactions at the excited state between the two species within the ensemble were identified. Photoelectrochemical assays of MoS2 /CdS thin-film electrodes revealed a prompt, steady and reproducible anodic photoresponse during repeated on-off cycles of illumination. A significant zero-current photopotential of -540 mV and an anodic photocurrent of 1 µA were observed, underlining improved charge-separation and electron transport from CdS to MoS2 . The superior performance of the charge-transfer processes in MoS2 /CdS is of direct interest for the fabrication of photoelectrochemical and optoelectronic devices.

Carbon Nanotube Film Electrodes with Acrylic Additives: Blocking Electrochemical Charge Transfer Reactions.

Carbon nanotubes (CNTs) processed into conductive films by liquid phase deposition technologies reveal increasing interest as electrode components in electrochemical device platforms for sensing and energy storage applications. In this work we show that the addition of acrylic latex to water-based CNT inks not only favors the fabrication of stable and robust flexible electrodes on plastic substrates but, moreover, sensitively enables the control of their electrical and electrochemical transport properties. Importantly, within a given concentration range, the acrylic additive in the films, being used as working electrodes, effectively blocks undesired faradaic transfer reactions across the electrode-electrolyte interface while maintaining their capacitance response as probed in a three-electrode electrochemical device configuration. Our results suggest a valuable strategy to enhance the chemical stability of CNT film electrodes and to suppress non-specific parasitic electrochemical reactions of relevance to electroanalytical and energy storage applications.

Cobalt-Doped ZnO Nanorods Coated with Nanoscale Metal-Organic Framework Shells for Water-Splitting Photoanodes.

Developing highly efficient and stable photoelectrochemical (PEC) water-splitting electrodes via inexpensive, liquid phase processing is one of the key challenges for the conversion of solar energy into hydrogen for sustainable energy production. ZnO represents one the most suitable semiconductor metal oxide alternatives because of its high electron mobility, abundance, and low cost, although its performance is limited by its lack of absorption in the visible spectrum and reduced charge separation and charge transfer efficiency. Here, we present a solution-processed water-splitting photoanode based on Co-doped ZnO nanorods (NRs) coated with a transparent functionalizing metal-organic framework (MOF). The light absorption of the ZnO NRs is engineered toward the visible region by Co-doping, while the MOF significantly improves the stability and charge separation and transfer properties of the NRs. This synergetic combination of doping and nanoscale surface functionalization boosts the current density and functional lifetime of the photoanodes while achieving an unprecedented incident photon to current efficiency (IPCE) of 75% at 350 nm, which is over 2 times that of pristine ZnO. A theoretical model and band structure for the core-shell nanostructure is provided, highlighting how this nanomaterial combination provides an attractive pathway for the design of robust and highly efficient semiconductor-based photoanodes that can be translated to other semiconducting oxide systems.