Ions-Silica Percolated Ionic Dielectric Elastomer Actuator for Soft Robots.

Soft robotics systems are currently under development using ionic electroactive polymers (i-EAP) as soft actuators for the human-machine interface. However, this endeavor has been impeded by the dilemma of reconciling the competing demands of force and strain in i-EAP actuators. Here, the authors present a novel design called "ions-silica percolated ionic dielectric elastomer (i-SPIDER)", which exhibits ionic liquid-confined silica microstructures that effectively resolve the chronic issue of conventional i-EAP actuators. The i-SPIDER actuator demonstrates remarkable electromechanical conversion capacity at low voltage, thanks to improved ion accumulation facilitated by interpreting electrode polarization at the electrolyte-electrode interface. This approach concurrently enhances both strain (by approximately 1.52%) and force (by roughly 1.06 mN) even at low Young's modulus (merely 5.9 MPa). Additionally, by demonstrating arachnid-inspired soft robots endowed with user-desired tasks through control of various form factors, the development of soft robots using the i-SPIDER that can concomitantly enhance strain and force holds promise as a compelling avenue for ushering in the next generation of miniaturized, low-powered soft robotics.

Construction of N-Rich Aminal-Linked Porous Organic Polymers for Outstanding Precombustion CO2 Capture and H2 Purification: A Combined Experimental and Theoretical Study.

A large number of scientific investigations are needed for developing a sustainable solid sorbent material for precombustion CO2 capture in the integrated gasification combined cycle (IGCC) that is accountable for the industrial coproduction of hydrogen and electricity. Keeping in mind the industrially relevant conditions (high pressure, high temperature, and humidity) as well as good CO2/H2 selectivity, we explored a series of sorbent materials. An all-rounder player in this game is the porous organic polymers (POPs) that are thermally and chemically stable, easily scalable, and precisely tunable. In the present investigation, we successfully synthesized two nitrogen-rich POPs by extended Schiff-base condensation reactions. Among these two porous polymers, TBAL-POP-2 exhibits high CO2 uptake capacity at 30 bar pressure (57.2, 18.7, and 15.9 mmol g-1 at 273, 298, and 313 K temperatures, respectively). CO2/H2 selectivities of TBAL-POP-1 and 2 at 25 °C are 434.35 and 477.93, respectively. On the other hand, at 313 K the CO2/H2 selectivities of TBAL-POP-1 and 2 are 296.92 and 421.58, respectively. Another important feature to win the race in the search of good sorbents is CO2 capture capacity at room temperature, which is very high for TBAL-POP-2 (15.61 mmol g-1 at 298 K for 30 to 1 bar pressure swing). High BET surface area and good mesopore volume along with a large nitrogen content in the framework make TBAL-POP-2 an excellent sorbent material for precombustion CO2 capture and H2 purification.

A bioinspired hydrogen bond-triggered ultrasensitive ionic mechanoreceptor skin.

Biological cellular structures have inspired many scientific disciplines to design synthetic structures that can mimic their functions. Here, we closely emulate biological cellular structures in a rationally designed synthetic multicellular hybrid ion pump, composed of hydrogen-bonded [EMIM+][TFSI-] ion pairs on the surface of silica microstructures (artificial mechanoreceptor cells) embedded into thermoplastic polyurethane elastomeric matrix (artificial extracellular matrix), to fabricate ionic mechanoreceptor skins. Ionic mechanoreceptors engage in hydrogen bond-triggered reversible pumping of ions under external stimulus. Our ionic mechanoreceptor skin is ultrasensitive (48.1-5.77 kPa-1) over a wide spectrum of pressures (0-135 kPa) at an ultra-low voltage (1 mV) and demonstrates the ability to surpass pressure-sensing capabilities of various natural skin mechanoreceptors (i.e., Merkel cells, Meissner's corpuscles, Pacinian corpuscles). We demonstrate a wearable drone microcontroller by integrating our ionic skin sensor array and flexible printed circuit board, which can control directions and speed simultaneously and selectively in aerial drone flight.

Ultrasensitive, Low-Power Oxide Transistor-Based Mechanotransducer with Microstructured, Deformable Ionic Dielectrics.

The development of a highly sensitive artificial mechanotransducer that mimics the tactile sensing features of human skin has been a big challenge in electronic skin research. Here, we demonstrate an ultrasensitive, low-power oxide transistor-based mechanotransducer modulated by microstructured, deformable ionic dielectrics, which is consistently sensitive to a wide range of pressures from 1 to 50 kPa. To this end, we designed a viscoporoelastic and ionic thermoplastic polyurethane (i-TPU) with micropyramidal feature as a pressure-sensitive gate dielectric for the indium-gallium-zinc-oxide (IGZO) transistor-based mechanotransducer, which leads to an unprecedented sensitivity of 43.6 kPa-1, which is 23 times higher than that of a capacitive mechanotransducer. This is because the pressure-induced ion accumulation at the interface of the i-TPU dielectric and IGZO semiconductor effectively modulates the conducting channel, which contributed to the enhanced current level under pressure. We believe that the ionic transistor-type mechanotransducer suggested by us will be an effective way to perceive external tactile stimuli over a wide pressure range even under low power (<4 V), which might be one of the candidates to directly emulate the tactile sensing capability of human skin.

MnFe2 O4 Nanocrystals Wrapped in a Porous Organic Polymer: A Designed Architecture for Water-Splitting Photocatalysis.

A novel MnFe2 O4 -porous organic polymer (POP) nanocomposite was synthesized by a facile hydrothermal method and using the highly cross-linked N-rich benzene-benzylamine POP. The nanocomposite presented highly efficient photocatalytic performance in the hydrogen evolution reaction (HER) from pure water without addition of any sacrificial agent under one AM 1.5 G sunlight illumination. A photocatalytic activity of 6.12 mmol h-1 g-1 was achieved in the absence of any noble metal cocatalyst, which is the highest H2 production rate reported for nonprecious metal catalysts. The photocatalytic performance of MnFe2 O4 -POP could be attributed to the intrinsic synergistic effects of manganese ferrite (MnFe2 O4 ) nanoclusters interacting with the nitrogen dopant POP with a unique mesoporous nanoarchitecture and spatially confined growth of MnFe2 O4 in the interconnected POP network, leading to high visible-light absorption with fast electron transport.

Tailored Synthesis of Porous TiO2 Nanocubes and Nanoparallelepipeds with Exposed {111} Facets and Mesoscopic Void Space: A Superior Candidate for Efficient Dye-Sensitized Solar Cells.

Anatase TiO2 nanocubes and nanoparallelepipeds, with highly reactive {111} facets exposed, were developed for the first time through a modified one pot hydrothermal method, through the hydrolysis of tetrabutyltitanate in the presence of oleylamine as the morphology-controlling capping-agent and using ammonia/hydrofluoric acid for stabilizing the {111} faceted surfaces. These nanocubes/nanoparallelepipeds were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM) and high angle annular dark-field scanning TEM (HAADF-STEM). Accordingly, a possible growth mechanism for the nanostructures is elucidated. The morphology, surface area and the pore size distribution of the TiO2 nanostructures can be tuned simply by altering the HF and ammonia dosage in the precursor solution. More importantly, optimization of the reaction system leads to the assembly of highly crystalline, high surface area, {111} faceted anatase TiO2 nanocubes/nanoparallelepipeds to form uniform mesoscopic void space. We report the development of a novel double layered photoanode for dye sensitized solar cells (DSSCs) made of highly crystalline, self-assembled faceted TiO2 nanocrystals as upper layer and commercial titania nanoparticles paste as under layer. The bilayered DSSC made from TiO2 nanostructures with exposed {111} facets as upper layer shows a much higher power conversion efficiency (9.60%), than DSSCs fabricated with commercial (P25) titania powder (4.67%) or with anatase TiO2 nanostructures having exposed {101} facets (7.59%) as the upper layer. The improved performance in bilayered DSSC made from TiO2 nanostructures with exposed {111} facets as the upper layer is attributed to high dye adsorption and fast electron transport dynamics owing to the unique structural features of the {111} facets in TiO2. Electrochemical impedance spectroscopy (EIS) measurements conducted on the cells supported these conclusions, which showed that the bilayered DSSC made from TiO2 nanostructures with exposed {111} facets as the upper layer possessed lower charge transfer resistance, higher electron recombination resistance, longer electron lifetime and higher collector efficiency characteristics, compared to DSSCs fabricated with commercial (P25) titania powder or with anatase TiO2 nanostructures having exposed {101} facets as the upper layer.

Synthesis of Multiwalled TiO2 Nanotubes Under Weak Alkaline Conditions for Dye-Sensitized Solar Cells.

Mesoporous Tubular TiO2 nanostructures were synthesised under hydrothermal condition in weak alkaline medium using high surface area mesoporous anatase TiO2 nanoparticles as seeds. These anatase TiO2 nanoparticles react with weak NaOH under hydrothermal conditions to form sheet like structures. By treating these sheets with dilute HCl multilayered nanotubes were obtained. X-ray diffraction, Scanning Electron Microscopy, Transmission Electron Microscopy, N2 sorption analysis were used for the physical characterization of the material. These nanotubes were applied as anode material for Dye-sensitized solar cell and an increase of 7.86% in current density is observed as compared to the commercial paste (Solaronix Ti-Nanoxide T/SC).

Green synthesis of Pt-doped TiO2 nanocrystals with exposed (001) facets and mesoscopic void space for photo-splitting of water under solar irradiation.

We report a non-trivial facile chemical approach using ionic liquid ([bmim][Cl]) as a porogen for the synthesis of (001) faceted TiO2 nanocrystals having mesoscopic void space. This faceted TiO2 nanomaterial has been doped with Pt nanoclusters through chemical impregnation. The resulting Pt-doped TiO2 nanomaterials are thoroughly characterized by powder X-ray diffraction (PXRD), Raman spectroscopy, field emission scanning electron microscopy (FE-SEM), ultra high resolution transmission electron microscopy (UHR-TEM), energy dispersive X-ray spectrometry (EDX), UV-vis diffuse reflection spectroscopy (DRS) and N2 sorption studies. These Pt/TiO2 nanocrystals with (001) exposed facets are employed as efficient and benign catalysts for hydrogen production from pure water and methanol-water systems under one AM 1.5G sunlight illumination. The effect of platinum loading and methanol-water ratio on the photocatalytic activity of the faceted TiO2 nanocrystals are investigated and it is found that hydrogen evolution rates have been enhanced significantly upon Pt loading. Under optimized reaction conditions the highest photocatalytic activity of 11.2 mmol h(-1) g(-1) has been achieved over ca. 1.0 wt% Pt loaded Pt/TiO2 nanocrystals with (001) exposed facets, which is one of the highest hydrogen evolution rates over the noble metal/TiO2 system reported to date in the literature.

Faceted titania nanocrystals doped with indium oxide nanoclusters as a superior candidate for sacrificial hydrogen evolution without any noble-metal cocatalyst under solar irradiation.

Development of unique nanoheterostructures consisting of indium oxide nanoclusters like species doped on the TiO2 nanocrystals surfaces with {101} and {001} exposed facets, resulted in unprecedented sacrificial hydrogen production (5.3 mmol h(-1) g(-1)) from water using methanol as a sacrificial agent, under visible light LED source and AM 1.5G solar simulator (10.3 mmol h(-1) g(-1)), which is the highest H2 production rate ever reported for titania based photocatalysts, without using any noble metal cocatalyst. X-ray photoelectron spectroscopy (XPS) analysis of the nanostructures reveals the presence of Ti-O-In and In-O-In like species on the surface of nanostructures. Electron energy-loss spectroscopy (EELS) elemental mapping and EDX spectroscopy techniques combined with transmission electron microscope evidenced the existence of nanoheterostructures. XPS, EELS, EDX, and HAADF-STEM tools collectively suggest the presence of indium oxide nanoclusters like species on the surface of TiO2 nanostructures. These indium oxide nanocluster doped TiO2 (In2O3/T{001}) single crystals with {101} and {001} exposed facets exhibited 1.3 times higher visible light photocatalytic H2 production than indium oxide nanocluster doped TiO2 nanocrystals with only {101}facets (In2O3/T{101}) exposed. The remarkable photocatalytic activity of the obtained nanoheterostructures is attributed to the combined synergetic effect of indium oxide nanoclusters interacting with the titania surface, enhanced visible light response, high crystallinity, and unique structural features.

Structurally stabilized organosilane-templated thermostable mesoporous titania.

Structurally thermostable mesoporous anatase TiO2 (m-TiO2) nanoparticles, uniquely decorated with atomically dispersed SiO2, is reported for the first time. The inorganic Si portion of the novel organosilane template, used as a mesopores-directing agent, is found to be incorporated in the pore walls of the titania aggregates, mainly as isolated sites. This is evident by transmission electron microscopy and high-angle annular dark field scanning transmission electron microscopy, combined with electron dispersive X-ray spectroscopy. This type of unique structure provides exceptional stability to this new material against thermal collapse of the mesoporous structure, which is reflected in its high surface area (the highest known for anatase titania), even after high-temperature (550 °C) calcination. Control of crystallite size, pore diameter, and surface area is achieved by varying the molar ratios of the titanium precursor and the template during synthesis. These mesoporous materials retain their porosity and high surface area after template removal and further NaOH/HCl treatment to remove silica. We investigate their performance for dye-sensitized solar cells (DSSCs) with bilayer TiO2 electrodes, which are prepared by applying a coating of m-TiO2 onto a commercial titania (P25) film. The high surface area of the upper mesoporous layer in the P25-m-TiO2 DSSC significantly increases the dye loading ability of the photoanode. The photocurrent and fill factor for the DSSC with the bilayer TiO2 electrode are greatly improved. The large increase in photocurrent current (ca. 56%) in the P25-m-TiO2 DSSC is believed to play a significant role in achieving a remarkable increase in the photovoltaic efficiency (60%) of the device, compared to DSSCs with a monolayer of P25 as the electrode.