In Situ Engineering of Conducting Polymer Nanocomposites at Liquid/Liquid Interfaces: A Perspective on Fundamentals to Technological Significance.

The conducting polymers have continuously been hybridized with their counterparts to overcome the intrinsic functional limitations compared to the metallic or inorganic analogs. Remarkably, the liquid/liquid interface-assisted methods represent an efficient and facile route for developing fully tunable metamaterials for various applications. The spontaneous adsorption of nanostructures at a quasi-two-dimensional interface is energetically favorable due to the reduction in interfacial tension, interfacial area, and interfacial energy (Helmholtz free energy). This Perspective highlights the fundamentals of nanostructure adsorption leading to hierarchical architecture generation at the interface from an experimentalist's point of view. Thereafter, the essential applications of the conducting polymer/nanocomposites synthesized at the interface emphasize the capability of the interface to tune functional materials. This Perspective also summarizes the future challenges and the use of the known fundamental aspects in overcoming the functional limitations of polymer/nanomaterial composites and also provides some future research directions.

Interfacial Tension-Impelled Self-Assembly and Morphology Tuning of Poly(3,4-ethylene dioxythiophene)/Tellurium Nanocomposites at Various Liquid/Liquid Interfaces.

Compared to the enormous number of nanostructures that have been documented, the variety of nanostructures produced by organic polymerization is rather limited. We devised an unconventional route and a sustainable approach to distribute tellurium nanoparticles (Te NPs) in a poly(3,4-ethylene dioxythiophene) (PEDOT) matrix to form semiconducting organic-inorganic nanocomposites for potential applications in electrochemical sensing. The adopted strategy of in situ liquid/liquid interface-assisted polymerization aids in the formation of intimately tethered Te NPs on the PEDOT polymer chains, thereby preventing the aggregation of Te NPs. The untapped versatility inherent to using biphasic systems for interfacial polymerization is explored at three interface systems of immiscible solvents: chloroform/water, dichloromethane/water, and hexane/water, giving rise to PEDOT/Te nanocomposite (PTeNC) of distinct morphology. Chemical nature, crystallinity, and morphology investigations proved the successful formation of PTeNC in different interface systems. Consequently, the temporal evolution of interfacial tension in the preferential adsorption of nanoparticles and final product morphology was monitored by pendant drop tensiometry. Owing to the role of morphology, PTeNC synthesized at the hexane/water interface showcased the best electrocatalytic behavior toward nonenzymatic detection of l-ascorbic acid, an essential nutritional factor, and a neuromodulator with a limit of detection of 0.66 µM and excellent sensitivity, selectivity, and reproducibility. Hence, we envision that interface-assisted polymerization offers a nascent and robust strategy for encapsulating unusual electrode materials in polymeric matrices.

Self-assembly of random networks of zirconium-doped manganese oxide nanoribbons and poly(3,4-ethylenedioxythiophene) flakes at the water/chloroform interface.

Owing to their magnificent chemical and physical properties, transition metal-based heterostructures are potential materials for applications ranging from point-of-care diagnostics to sustainable energy technologies. The cryptomelane-type octahedral molecular sieves (K-OMS-2) are extensively studied porous materials with a hollandite (2 × 2 tunnel of dimensions 4.6 × 4.6 Å2) structure susceptible to the isovalent substitution of metal cations at the framework of MnO6 octahedral chains. Here we report a facile in situ synthesis of framework-level zirconium (Zr)-doped K-OMS-2 nanoribbons in poly(3,4-ethylenedioxythiophene) (PEDOT) nanoflakes at a water/chloroform interface at ambient conditions. An oxidant system of KMnO4 and ZrOCl2·8H2O initiated the polymerisation at temperatures ranging from 5° to 50 °C. The lattice distortions arising from the framework-level substitution of Mn4+ by Zr4+ in the K-OMS-2 structure were evidenced with powder X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, and N2 adsorption-desorption studies. Transmission electron microscopic and mapping images confirmed that PEDOT/Zr-K-OMS-2 comprises a highly crystalline random network of two-dimensional PEDOT flakes and Zr-doped K-OMS-2 nanoribbons. In this regard, the proposed interfacial strategy affirms an in situ method for the morphological tuning of heterostructures on polymer supports at low temperatures.

In situ engineering of Au-Ag alloy embedded PEDOT nanohybrids at a solvent/non-solvent interface for the electrochemical enzyme-free detection of histamine.

Steadfast efforts have been made to develop novel materials and incorporate them into functional devices for practical applications, pushing the research on electroactive materials to the forefront of nano electronics. Liquid/liquid interface-assisted polymerization offers a scalable methodology to fabricate hybrid materials with multifunctional applications, in contrast to the conventional and ubiquitous routes. Here, we explored this efficient and versatile approach toward the in situ tailoring of Au-Ag alloy nanostructures with a conducting polymer, poly(3,4-ethylene-dioxythiophene) (PEDOT). With the appropriate choice of organic and inorganic phases for the distribution of monomer and oxidant, the miscibility restraints of the reactants in a single phase were alleviated. Effective nanostructure tuning of highly crystalline and electroactive PEDOT/Au-Ag alloy has been achieved by varying the molar ratio of Au3+/Ag+ in the reaction mixture. The as-synthesized composite is further explored to detect neuromodulator histamine (HA), which displays high sensitivity with a limit of detection (LOD) of 1.5 nM, and selectivity even in the presence of various interfering analogs of 10-fold concentration. Subsequently, density functional theory (DFT) simulations are employed to assess the mode of interaction between HA and the electroactive surfaces. The competency to detect HA in preserved food entails its potential in food spoilage monitoring. Furthermore, the detection of histamine generated by sub-cultured human neuronal cells SH-SY5Y proves its practical viability in health monitoring devices.

Interfacial tension driven adsorption of MnO2 nanoparticles at the liquid/liquid interface to tailor ultra-thin polypyrrole sheets.

An emerging aspect of research is designing and developing fully tunable metamaterials for various applications with fluid interfaces. Liquid/liquid interface-assisted methods represent an efficient and facile route for synthesizing two-dimensional (2-D) thin films of potential materials. The underlying mechanism behind thin film formation at the liquid/liquid interface involves the preferential adsorption of nano-sized particles at the interface to minimize high interfacial tension. Here, a water/chloroform interface-assisted method is employed for the one-pot synthesis of highly crystalline polypyrrole/manganese dioxide (PPy/MnO2) sheets. The temporal evolution in the dynamic interfacial tension (from 32 mN m-1 to 17 mN m-1) observed in pendant drop tensiometry proved the preferential adsorption of MnO2 atttached PPy oligomers at the water/chloroform interface. An ultra-thin sheet-like morphology and uniform distribution of ∼6 nm highly crystalline MnO2 nanoparticles are evidenced by transmission and atomic force microscopy techniques. The predominance of interfacial polymerization in retaining the electrochemical activity of the PPy/MnO2 sheets is elucidated for the electrochemical detection of nicotine. This study opens a new avenue for the realization of ultra-thin sheets of polymer-nanomaterial hybrids, enabling applications ranging from new classes of sensors to optics.

Interface-assisted synthesis: a gateway to effective nanostructure tuning of conducting polymers.

The interface-assisted polymerization technique can be viewed as a powerful emerging tool for the synthesis of conducting polymers (CPs) on a large scale. Contrary to other bulk or single-phase polymerization techniques, interface-assisted synthesis strategies offer effective nanostructure control in a confined two-dimensional (2-D) space. This review focuses on the types of interfaces, mechanism at the interface, advantages and future perspectives of the interfacial polymerization in comparison to conventional polymerization techniques. Hence, the primary focus is on briefing the different types of the chemical methods of polymerization, followed by uniqueness in the reaction dynamics of interface polymerization. The classification of interfaces into four types (liquid/solid, gas/liquid, liquid/liquid, and gas/solid) is based on the versatility and underlying mechanistic pathway of the polymerization of each type. The role of interface in tuning the nanostructure of CPs and the performance evaluation of pristine CPs based on the electrical conductivity are also discussed. Finally, the future outlook of this emerging field is discussed and proposed in detail through some multifunctional applications of synthesized conducting polymers.

n-Butanol/Water Interface-Aided Physicochemical Tuning of Two-Dimensional Transition-Metal Oxides.

Herein, we report a facile regulation of the interface of two immiscible solvents, n-butanol and water, to achieve the physicochemical tuning of the transition-metal oxide nickel cobaltite. The crystal nucleation and the growth of nickel cobaltite into distinct morphology are highly dependent on the orientation and the mass transfer of the reactive species through the reactive interface layer. A distinct two-dimensional flakelike (1 nm thickness) nickel cobaltite is formed at the interface of n-butanol/water in a 1:1 solvent ratio. Rather, one-dimensional needles and irregular interconnected networks are achieved, as aqueous and organic counterparts are, respectively, increased. The impact of the solvent ratio on doping metal ions (Co2+ and Ni2+) at the interstitial sites of fcc spinel structure is evident from the X-ray and electronic absorption investigations. It is presumed that the interface-assisted synthesis may provide a simple and novel way to develop and adopt various transition-metal oxides for wide applications.

Soft-template-assisted synthesis: a promising approach for the fabrication of transition metal oxides.

The past few decades have witnessed transition metal oxides (TMOs) as promising candidates for a plethora of applications in numerous fields. The exceptional properties retained by these materials have rendered them of paramount emphasis as functional materials. Thus, the controlled and scalable synthesis of transition metal oxides with desired properties has received enormous attention. Out of different top-down and bottom-up approaches, template-assisted synthesis predominates as an adept approach for the facile synthesis of transition metal oxides, owing to its phenomenal ability for morphological and physicochemical tuning. This review presents a comprehensive examination of the recent advances in the soft-template-assisted synthesis of TMOs, focusing on the morphological and physicochemical tuning aided by different soft-templates. The promising applications of TMOs are explained in detail, emphasizing those with excellent performances.

Water-Chloroform Interface Assisted Microstructure Tuning of Polypyrrole-Silver Sheets.

The liquid-liquid interface of two immiscible solvents remarkably controls the morphology of polymeric nanostructures as compared to the polymerization in single solvent systems. The polymerization of pyrrole in the water-chloroform medium using silver nitrate (AgNO3) as oxidant yields polypyrrole/silver (PPy/Ag) sheets. The water-chloroform interface acts as a template for the growth of PPy/Ag hybrids into sheets by preventing the secondary growth of silver associated pyrrole oligomers in a three-dimensional (3-D) manner. On the contrary, the 3-D growth of pyrrole oligomers into spherical shapes at the water-chloroform interface is observed when ammonium persulfate (APS) is used as the oxidant. Transmission electron microscopic and scanning electron microscopic images reveal the sheetlike morphology of PPy/Ag with a relatively uniform distribution of Ag NPs (∼100 nm) on PPy sheets. The ratio of aqueous-organic bisolvent and the concentration/type of oxidant have a distinct effect on morphology, crystallinity, and electrical properties of PPy/Ag sheets. The dispersed PPy/Ag sheets are stable in moderately polar solvents up to 2 weeks. The electrochemical behavior of PPy/Ag sheets is confirmed by H2O2 sensing capability through cyclic voltammetry experiments. The antibacterial activity toward E. coli and S. aureus is quantitatively assessed using the minimum bactericidal concentration (MBC) determination.

Reduced haze of transparent conductive films by smaller diameter silver nanowires.

Silver nanowires (Ag NWs) have received considerable attention for flexible transparent conductive films (TCFs) since they provide a relatively low sheet resistance at a high transmittance. However, the diffuse light scattering, haze, has been regarded as a hurdle to achieve clarity of films. Here we revisit the Mie scattering theory to calculate the extinction and scattering coefficients of Ag NWs which were employed to estimate haze of TCFs. The theory predicted a decrease in haze with a decrease in Ag NW diameter which was supported by experimental investigations carried out using Ag NWs with 5 different diameters (17.6, 19.9, 22.5, 24.3, and 29.6 nm). Overall, excellent properties of TCFs (haze = 0.21%-1.8%, transmittance = 95.33%-98.45%, sheet resistance = 20.87-81.76 Ω sq-1) were obtained. Ag NWs with a diameter of 17.6 nm provided minimum haze values at equivalent sheet resistances (e.g., haze = 0.21%, transmittance = 98.45%, sheet resistance = 77.36 Ω sq-1) compared with ones with lager diameters and the controls in literatures. This work investigated the interdependence between haze and NW diameter and might provide a design guide for flexible Ag NW TCFs.

Extraordinarily high conductivity of flexible adhesive films by hybrids of silver nanoparticle-nanowires.

Highly conductive flexible adhesive (CFA) film was developed using micro-sized silver flakes (primary fillers), hybrids of silver nanoparticle-nanowires (secondary fillers) and nitrile butadiene rubber. The hybrids of silver nanoparticle-nanowires were synthesized by decorating silver nanowires with silver nanoparticle clusters using bifunctional cysteamine as a linker. The dispersion in ethanol was excellent for several months. Silver nanowires constructed electrical networks between the micro-scale silver flakes. The low-temperature surface sintering of silver nanoparticles enabled effective joining of silver nanowires to silver flakes. The hybrids of silver nanoparticle-nanowires provided a greater maximum conductivity (54 390 S cm(-1)) than pure silver nanowires, pure multiwalled carbon nanotubes, and multiwalled carbon nanotubes decorated with silver nanoparticles in nitrile butadiene rubber matrix. The resistance change was smallest upon bending when the hybrids of silver nanoparticle-nanowires were employed. The adhesion of the film on polyethylene terephthalate substrate was excellent. Light emitting diodes were successfully wired to the CFA circuit patterned by the screen printing method for application demonstration.

Silver nanowires decorated with silver nanoparticles for low-haze flexible transparent conductive films.

Silver nanowires have attracted much attention for use in flexible transparent conductive films (TCFs) due to their low sheet resistance and flexibility. However, the haze was too high for replacing indium-tin-oxide in high-quality display devices. Herein, we report flexible TCFs, which were prepared using a scalable bar-coating method, with a low sheet resistance (24.1 Ω/sq at 96.4% transmittance) and a haze (1.04%) that is comparable to that of indium-tin-oxide TCFs. To decrease the haze and maintain a low sheet resistance, small diameter silver nanowires (~20 nm) were functionalized with low-temperature surface-sintering silver nanoparticles (~5 nm) using bifunctional cysteamine. The silver nanowire-nanoparticle ink stability was excellent. The sheet resistance of the TCFs was decreased by 29.5% (from 34.2 to 24.1 Ω/sq) due to the functionalization at a low curing temperature of 85 °C. The TCFs were highly flexible and maintained their stability for more than 2 months and 10,000 bending cycles after coating with a protective layer.

Hierarchically Structured Hole Transport Layers of Spiro-OMeTAD and Multiwalled Carbon Nanotubes for Perovskite Solar Cells.

The low electrical conductivity of spiro-OMeTAD hole transport layers impedes further enhancements of the power conversion efficiency (PCE) of perovskite solar cells. We embedded multiwalled carbon nanotubes (MWNTs) in spiro-OMeTAD (spiro-OMeTAD/MWNTs) to increase carrier mobility and conductivity. However, direct electrical contact between CH3 NH3 PbI3 and the MWNTs created pathways for undesirable back-electron transfer, owing to the large work function of MWNTs, limiting enhancements of the PCE. A hierarchical structure of pure spiro-OMeTAD and spiro-OMeTAD/MWNTs was designed to block back-electron transfer and fully exploit the enhanced charge transport of spiro-OMeTAD/MWNTs. The enhanced fill factor, short-circuit current density, open-circuit voltage, and PCE (15.1 %) were achieved by using this hierarchical hole transport layer structure (MWNT concentration=2 wt %). The perovskite solar cells were fabricated by a low-temperature solution process, further decreasing their per-Watt cost.

Large work function difference driven electron transfer from electrides to single-walled carbon nanotubes.

A difference in work function plays a key role in charge transfer between two materials. Inorganic electrides provide a unique opportunity for electron transfer since interstitial anionic electrons result in a very low work function of 2.4-2.6 eV. Here we investigated charge transfer between two different types of electrides, [Ca(2)N](+)·e(-) and [Ca(24)Al(28)O(64)](4+)·4e(-), and single-walled carbon nanotubes (SWNTs) with a work function of 4.73-5.05 eV. [Ca(2)N](+) · e(-) with open 2-dimensional electron layers was more effective in donating electrons to SWNTs than closed cage structured [Ca(24)Al(28)O(64)](4+) · 4e(-) due to the higher electron concentration (1.3 × 10(22) cm(-3)) and mobility (∼ 200 cm(2) V(-1) s(-1) at RT). A non-covalent conjugation enhanced near-infrared fluorescence of SWNTs as high as 52%. The field emission current density of electride-SWNT-silver paste dramatically increased by a factor of 46,000 (14.8 mA cm(-2)) at 2 V µm(-1) (3.5 wt% [Ca(2)N](+) · e(-)) with a turn-on voltage of 0.85 V µm(-1).

Transparent stretchable single-walled carbon nanotube-polymer composite films with near-infrared fluorescence.

We report transparent stretchable single-walled carbon nanotube-polymer composite films that emit pronounced Raman and near-infrared fluorescence with a fine spatial resolution. The independent modulation in Raman and fluorescence spectra is demonstrated in response to touch and temperature. The optical signal transduction of transparent stretchable optoelectronic films may enable a paradigm shift in touch-sensing devices eliminating electrical interconnects.