Catalytic and Light‐Driven ZnO/Pt Janus Nano/Micromotors: Switching of Motion Mechanism via Interface Roughness and Defect Tailoring at the Nanoscale

The first models of mesoporous ZnO/Pt Janus micromotors that show fuel‐free and light‐powered propulsion depending on the interface roughness are shown. Two models of ZnO semiconducting particles with distinct surface morphologies and pore structures are synthesized by self‐aggregation of primary nanoparticles and nanosheets into nanoscale rough and smooth microparticles, respectively. The self‐assembled nanosheet model (smooth) provides a large surface for the formation of a continuous Pt layer with strong adherence, whereas the discontinuous Pt species take place inside the inter‐nanoparticles pores in the self‐assembled nanoparticle model (rough). The effects of the interface, surface porosity, defect, and charge transfer on the light‐powered motion for both well‐designed mesoporous ZnO/Pt Janus micromotors are investigated and compared to find the underlying propulsion mechanisms. The degradation of two model pollutants is demonstrated as a proof‐of‐concept application of these carefully engineered Janus micromotors. In this work, it is shown that by discreet material fabrication together with semiconductor/metal interface charge transport interpretation, it would be possible to develop new light‐driven Janus micromotors based on other photocatalysts containing active surfaces such as TiO₂.     

A Microfluidic Tool for Fine‐Tuning Motion of Soft Micromotors

Microfluidics is an ideal tool for the design of self‐assembled micromotors. It allows for easy change of solutions, catalysts, and flow rates, which affect shape, structure, and motion of the resulting micromotors. A microfluidic tool generating aqueous‐two‐phase‐separating droplets of UV‐polymerizable poly(ethylene glycol)diacrylate (PEGDA) and an inert phase, salt, or polysaccharide, is utilized to fabricate asymmetric microbeads. Different molecular weights and branching of polysaccharides are used to study the effect on shape, surface roughness, and motion of the particles. The molecular weight of the polysaccharide determines the roughness of the motors inner surface. Smooth openings are obtained by low molecular weight dextran, while high surface roughness is obtained with a high molecular weight branched polysaccharide. Since roughness plays an important role in bubble pinning, it influences both speed and trajectory. Increasing speeds are obtained with increasing roughness and trajectories ranging from linear, circular to tumble‐and‐run depending on the nature of bubble pinning. This microfluidic tool allows for fine‐tuning shape, structure, and motion by easy change of solutions, catalysts, and flow rates.     

Magnetically Modulated Pot‐Like MnFe2O4 Micromotors: Nanoparticle Assembly Fabrication and their Capability for Direct Oil Removal

This work demonstrates a simple‐structured, low‐cost magnetically modulated micromotor of MnFe₂O₄ pot‐like hollow microparticles as well as its facile, versatile, and large‐scale growing‐bubble‐templated nanoparticle (NP) assembly fabrication approach. In this approach, the hydrophobic MnFe₂O₄@oleic acid NPs in an oil droplet of chloroform and hexane assembled into a dense NP shell layer due to the hydrophobic interactions between the NP surfaces. With the encapsulated oil continuously vaporizing into high‐pressured gas bubbles, the dense MnFe₂O₄ NP shell layer then bursts, forming an asymmetric pot‐like MnFe₂O₄ micromotor by creating a single hole in it. For the as‐developed simple pot‐like MnFe₂O₄ micromotor, the catalytically generated O₂ molecules nucleate and grow into bubbles preferentially on the inner concave surface rather than on the outer convex surface, resulting in continuous ejection of O₂ bubbles from the open hole to propel it. Dexterously integrating the high catalytic activity for H₂O₂ decomposition to produce O₂ bubbles, excellent magnetic property with the instinctive surface hydrophobicity, the MnFe₂O₄ pot‐like micromotor not only can autonomously move in water media with both velocity and direction modulated by external magnetic field but also can directly serve for environmental oil removal without any further surface modification. The results here may inspire novel practical micromotors.     

Superassembled Biocatalytic Porous Framework Micromotors with Reversible and Sensitive pH‐Speed Regulation at Ultralow Physiological H2O2 Concentration

Synthetic nano/micromotors are a burgeoning class of materials with vast promise for applications ranging from environmental remediation to nanomedicine. The motility of these motors is generally controlled by the concentration of accessible fuel, and therefore, engineering speed‐regulation mechanisms, particularly using biological triggers, remains a continuing challenge. Here, control over the movement of superassembled porous framework micromotors via a reversible, biological‐relevant pH‐responsive regulatory mechanism is demonstrated. Succinylated β‐lactoglobulin and catalase are superassembled in porous framework particles, where the β‐lactoglobulin is permeable at neutral pH. This permeability allows the fuel (H₂O₂) to access catalase, leading to autonomous movement of the micromotors. However, at mild acidic pH, succinylated β‐lactoglobulin undergoes a reversible gelation process, preventing the access of fuel into the micromotors where the catalase resides. To one's knowledge, this study represents the first example of chemically driven motors with rapid, reversible pH‐responsive motility. Furthermore, the porous framework significantly enhances the biocatalytic activity of catalase, allowing ultralow H₂O₂ concentrations to be exploited at physiological conditions. It is envisioned that the simultaneous exploitation of pH and chemical potential of such nanosystems could have potential applications as stimulus‐responsive drug delivery vehicles that benefit from the complex biological environment.     

Self‐Powered Flexible TiO2 Fibrous Photodetectors: Heterojunction with P3HT and Boosted Responsivity and Selectivity by Au Nanoparticles

A novel inorganic–organic heterojunction (TiO₂/P3HT (poly(3‐hexylthiophene)) is easily prepared by a combination of anodization and vacuumed dip‐coating methods, and the constructed flexible fibrous photodetector (FPD) exhibits high‐performance self‐powered UV–visible broadband photoresponse with fast speed, high responsivity, and good stability, as well as highly stable performance at bending states, showing great potential for wearable electronic devices. Moreover, Au nanoparticles are deposited to further boost the responsivity and selectivity by regulating the sputtering intervals. The optimal Au/TiO₂/P3HT FPD yields an ≈700% responsivity enhancement at 0 V under 350 nm illumination. The sharp cut‐off edge and high UV–visible rejection ratio (≈17 times higher) indicate a self‐powered flexible UV photodetector. This work provides an effective and versatile route to modulate the photoelectric performance of flexible electronic devices.     

Reversibly Light‐Switchable Wettability of Hybrid Organic/Inorganic Surfaces With Dual Micro‐/Nanoscale Roughness

Here, an approach to realize “smart” solid substrates that can convert their wetting behavior between extreme states under selective light irradiation conditions is described. Hybrid organic/inorganic surfaces are engineered by exploiting photolithographically tailored SU‐8 polymer patterns as templates for accommodating closely packed arrays of colloidal anatase TiO₂ nanorods, which are able to respond to UV light by reversibly changing their surface chemistry. The TiO₂‐covered SU‐8 substrates are characterized by a dual micro‐/nanoscale roughness, arising from the overlapping of surfactant‐capped inorganic nanorods onto micrometer‐sized polymer pillars. Such combined architectural and chemical surface design enables the achievement of UV‐driven reversible transitions from a highly hydrophobic to a highly hydrophilic condition, with excursions in water contact angle values larger than 100°. The influence of the geometric and compositional parameters of the hybrid surfaces on their wettability behavior is examined and discussed within the frame of the available theoretical models.     

Light‐enhanced surface passivation of TiO2‐coated silicon

Titanium dioxide is shown to afford good passivation to non‐diffused silicon surfaces and boron‐diffused surfaces after a low‐temperature anneal. The passivation most likely owes to the significant levels of negative charge instilled in the films, and passivation is enhanced by illumination—advantageous for solar cells—indicating that a titanium dioxide photoreaction is at least partly responsible for the low surface recombination. We demonstrate a surface recombination velocity of less than 30 cm/s, on a 5‐Ω cm n‐type silicon, and an emitter saturation current density of 90 fA/cm² on a 200‐Ω/sq boron diffusion. If these titanium dioxide passivated boron‐diffused surfaces were employed in a crystalline silicon solar cell, an open‐circuit voltage as high as 685 mV could be achieved. Given that TiO₂ has a high refractive index and was deposited with atmospheric pressure chemical vapour deposition, an inexpensive technique, it has the potential as a passivating antireflection coating for industrial boron‐diffused silicon solar cells. Copyright © 2011 John Wiley & Sons, Ltd.     

Multifunctional Silver‐Exchanged Zeolite Micromotors for Catalytic Detoxification of Chemical and Biological Threats

Multifunctional reactive‐zeolite‐based micromotors have been developed and characterized toward effective and rapid elimination of chemical and biological threats. The incorporation of silver ions (Ag⁺) into aluminosilicate zeolite framework imparts several attractive functions, including strong binding to chemical warfare agents (CWA) followed by effective degradation, and enhanced antibacterial activity. The new zeolite‐micromotors protocol thus combines the remarkable adsorption capacity of zeolites and the efficient catalytic properties of the reactive Ag⁺ ions with the autonomous movement of the zeolite micromotors for an accelerated detoxification of CWA. Furthermore, the high antibacterial activity of Ag⁺ along with the rapid micromotor movement enhances the contact between bacteria and reactive Ag⁺, leading to a powerful “on‐the‐fly” bacteria killing capacity. These attractive adsorptive/catalytic features of the self‐propelled zeolite micromotors eliminate secondary environmental contamination compared to adsorptive micromotors. The distinct cubic geometry of the zeolite micromotors leads to enhanced bubble generation and faster movement, in unique movement trajectories, which increases the fluid convection and highly efficient detoxification of CWA and killing of bacteria. The attractive capabilities of these zeolite micromotors will pave the way for their diverse applications in defense, environmental and biomedical applications in more economical and sustainable manner.     

Efficient Blue Perovskite Light‐Emitting Diodes Boosted by 2D/3D Energy Cascade Channels

Lead halide perovskite, as an emerging semiconductor, provides a fire‐new opportunity for high‐definition display and solid‐state lighting. Earthshaking improvements are implemented in green, red, and near‐infrared perovskite light‐emitting diodes (PeLEDs). However, blue PeLEDs are still far behind in performance, which restricts the development of PeLEDs in practical applications. Herein, a facile energy cascade channel strategy via one‐step self‐organized and controllable 2D/3D perovskite preparation by introducing guanidine hydrobromide (GABr) is developed that greatly improves the efficiency of blue PeLEDs. The 2D/3D perovskite structure boosts the energy cascade to induce energy transfer from the wide into the narrow bandgap domains and inhibit free charge diffusion, which increases the density of electrons and holes, and enhances the radiative recombination. Profiting from this energy cascade channels, the external quantum efficiency of blue PeLEDs, emitting at 492 nm, is considerably enhanced from 1.5% of initial blue device to 8.2%. In addition, device operating stability under ambient conditions is also improved by 2.6‐fold. The one‐step self‐organized 2D/3D hybrid perovskites induced by GABr pave a new and simple route toward high‐performance blue emission PeLEDs.     

Cocatalyst‐Free Photocatalysts for Efficient Visible‐Light‐Induced H2 Production: Porous Assemblies of CdS Quantum Dots and Layered Titanate Nanosheets

Highly efficient, visible‐light‐induced H₂ generation can be achieved without the help of a Pt cocatalyst by new hybrid photocatalysts, in which CdS quantum dots (QDs) (particle size ≈2.5 nm) are incorporated in the porous assembly of sub‐nanometer‐thick layered titanate nanosheets. Due to the very‐limited crystal dimension of component semiconductors, the electronic structure of CdS QDs is strongly coupled with that of the layered titanate nanosheets, leading to an efficient electron transfer between them and the enhancement of the CdS photostability. As a consequence of the promoted electron transfer, the photoluminescence of CdS QDs is nearly quenched after hybridization, indicating the almost‐suppression of electron‐hole recombination. These Pt‐cocatalyst‐free, CdS‐layered titanate nanohybrids show much‐higher photocatalytic activity for H₂ production than the precursor CdS QDs and layered titanate, which is due to the increased lifetime of the electrons and holes, the decrease of the bandgap energy, and the expansion of the surface area upon hybridization. The observed photocatalytic efficiency of these Pt‐free hybrids (≈1.0 mmol g^?1 h^?1) is much greater than reported values of other Pt‐free CdS‐TiO₂ systems. This finding highlights the validity of 2D semiconductor nanosheets as effective building blocks for exploring efficient visible‐light‐active photocatalysts for H₂ production.     

Self‐Assembling TiO2 Nanorods on Large Graphene Oxide Sheets at a Two‐Phase Interface and Their Anti‐Recombination in Photocatalytic Applications

TiO₂ nanorods are self‐assembled on the graphene oxide (GO) sheets at the water/toluene interface. The self‐assembled GO–TiO₂ nanorod composites (GO–TiO₂ NRCs) can be dispersed in water. The effective anchoring of TiO₂ nanorods on the whole GO sheets is confirmed by transmission electron microscopy (TEM), X‐ray diffraction (XRD), Fourier transform IR spectroscopy (FTIR), and thermogravimetric analysis (TGA). The significant increase of photocatalytic activity is confirmed by the degradation of methylene blue (MB) under UV light irridiation. The large enhancement of photocatalytic activity is caused by the effective charge anti‐recombination and the effective absorption of MB on GO. The effective charge transfer from TiO₂ to GO sheets is confirmed by the significant photoluminescence quenching of TiO₂ nanorods, which can effectively prevent the charge recombination during photocatalytic process. The effective absorption of MB on GO is confirmed by the UV‐vis spectra. The degradation rate of MB in the second cycle is faster than that in the first cycle because of the reduction of GO under UV light irradiation.     

Low‐temperature flexible Ti/TiO2 photoanode for dye‐sensitized solar cells with binder‐free TiO2 paste

An energy‐economical dye‐sensitized solar cell (DSSC) with highly flexible Ti/TiO₂ photoanode was developed through a low‐temperature process, using a binder‐free TiO₂ paste. Ti foils, coated with the binder‐free TiO₂ films were annealed at various temperature. Scanning electron microscopic (SEM) images of the films show uniform, mesoporous and crack‐free surface morphologies as well as interpenetrated TiO₂ network. DSSCs with binder‐free TiO₂ films annealed at 450, 350, 250 and 120°C show solar‐to‐electricity conversion efficiencies (η) of 4.33, 4.34, 3.72 and 3.40%, respectively, which are comparable to the efficiency of 4.56% obtained by using a paste with binder and annealing it at 450°C; this observation demonstrates the benefits of a binder‐free TiO₂ paste for the fabrication of energy‐fugal DSSCs. On the other hand, when organic binder was used in the TiO₂ paste for film preparation, a drastic deterioration in the cell performance with decreasing annealing temperature is noticed. Laser‐induced photo‐voltage transient technique is used to estimate the electron lifetime in various Ti/TiO₂ films. Electrochemical impedance spectroscopic (EIS) analysis shows that the lower the annealing temperature of the TiO₂ coated Ti foil, the larger the charge transfer resistance at the TiO₂/dye/electrolyte interface (R_ct2). Copyright © 2011 John Wiley & Sons, Ltd.     

Tailoring the Surface Chemical Reactivity of Transition‐Metal Dichalcogenide PtTe2 Crystals

PtTe₂ is a novel transition‐metal dichalcogenide hosting type‐II Dirac fermions that displays application capabilities in optoelectronics and hydrogen evolution reaction. Here it is shown, by combining surface science experiments and density functional theory, that the pristine surface of PtTe₂ is chemically inert toward the most common ambient gases (oxygen and water) and even in air. It is demonstrated that the creation of Te vacancies leads to the appearance of tellurium‐oxide phases upon exposing defected PtTe₂ surfaces to oxygen or ambient atmosphere, which is detrimental for the ambient stability of uncapped PtTe₂‐based devices. On the contrary, in PtTe₂ surfaces modified by the joint presence of Te vacancies and substitutional carbon atoms, the stable adsorption of hydroxyl groups is observed, an essential step for water splitting and the water–gas shift reaction. These results thus pave the way toward the exploitation of this class of Dirac materials in catalysis.     

Controllably Engineering Mesoporous Surface and Dimensionality of SnO2 toward High‐Performance CO2 Electroreduction

Currently, the precise control of the architecture and surface of functional materials for high‐performance still remains a great challenge. Here, a feasible approach is presented to synchronously manipulate mesoporous surface and dimensionality of SnO₂ catalysts into hierarchically mesoporous nanosheets and nanospheres within one simple reaction system. By adjustment of the hydrophobic chain length of different fluorinated surfactants, 0D SnO₂ nanospheres with average size of 165 nm, and 2D SnO₂ ulthrathin nanosheets with thickness of 22.5 nm with the distinct dimensionalities are separately obtained (one stone, two birds), both of which are well decorated with ordered mesopore arrays on their surfaces (pore size of 16 nm). The following calcination gave rise to the formation of hierarchically mesopores (5 and 16 nm, respectively) with high crystallization and improved surface area (96.8 m² g^?1). The resultant mesoporous SnO₂ nanosheets as catalyst for CO₂ electroreduction reaction (CO₂ RR) exhibit excellent selectivity, with a high Faraday efficiency (FE) of HCOOH reaching up to 90.0% at ?1.3 V and C₁ FE of 97.4% at ?1.2 V versus reversible hydrogen electrode, as well as long‐term stability, which is among the best performance compared to reported SnO₂ materials, thanks to the collective contributions of the unique architecture and mesoporous structure.     

The Influence of UV Irradiation on Ketonic Defect Emission in Fluorene‐Based Copolymers

The influence of UV irradiation in inert atmosphere on the emission spectrum of fluorenone containing poly[9,9‐bis(2‐ethyl)hexylfluorene] (PF2/6) has been investigated by means of optical absorption, photoluminescence (PL) and Fourier transform infrared (FTIR) spectroscopy. It is shown that a substantial reduction of green emission arising from ketonic defect sites can be achieved by irradiation of thin films with UV light. This is found to be accompanied by partial cross‐linking of the films. FTIR measurements show no reduction of the C=O stretching mode upon irradiation, and, moreover, the degree of cross‐linking does not scale with the relative fluorenone content (0.1, 0.5, and 5%). Therefore, the reduced emission intensity in the green spectral region is rather associated with the occurrence of interruptions in the polymer backbone, which reduce the effective conjugation length and subsequently inhibit the energy transfer onto the ketonic defect sites. The found results enabled us to build organic light emitting devices (OLEDs) that can be structured by selective illumination of the emitting layer with an intense UV light source. This method allows for the fabrication of rather efficient (2000 cd m⁻² at 7 V) two‐color OLEDs.