Encapsulated Dye in Coordination-Assembled Octahedron for Visible-Light-Driven Proton Reduction and Nitroaromatic Hydrogenation.

To mimic the finely tuned natural photosynthetic systems, a large metal-organic octahedron was synthesized by one-pot self-assembly with modified triphenylamine ligands and redox-active cobalt ions. By encapsulating an organic dye, fluorescein (Fl), within the inner cavity of the octahedron, the host-guest supramolecular system was provided for light-driven hydrogen production. The intimate distance between the redox site and the photosensitizer in the supramolecular metal-organic cage allowed the photoinduced electrons to transfer from the excited state Fl* to the redox cobalt center in a pseudo-intramolecular pathway. The supramolecular system showed good performance in light-driven hydrogen production and the reduction of nitroaromatic compounds. Control experiments based on a mononuclear compound resembling a cobalt corner of the octahedron and inhibitor competition provided evidence of enzyme-like catalytic behavior. The supramolecular reaction pathways within confined spaces contribute to the superior activity of the host-guest system.

Host-Guest Approach to Promoting Photocatalysis Based on Consecutive Photo-Induced Electron-Transfer Processes via Efficient Förster Resonance Energy Transfer.

Supramolecular artificial light-harvesting system with highly efficient host-guest energy transfer pathway provides an ideal platform for optimizing the photochemistry process. The consecutive photo-induced electron transfer (conPET) process overcomes the energy limitation of visible-light photocatalysis, but is often compromised by mismatching between the absorption of ground state dye and its radical, weakening the efficiency of photoredox reaction. By encapsulating a conPET photocatalyst rhodamine 6G into metal-organic cage, the supramolecular approach was undertaken to tackle the intrinsic difficulty of matching the light absorption of photoexcitation between rhodamine 6G and its radical. The highly efficient Förster resonance energy transfer from the photoexcited cage to rhodamine 6G forced by host-guest encapsulation facilitates the conPET process for the single-wavelength light-driven activation of aryl halides by stabilizing and accelerating the production and accumulation of the rhodamine 6G radical intermediate. The tunable and flexible nature of the supramolecular host-guest complex renders the cage-based encapsulation strategy promising for the development of ideal photocatalysts toward the better utilization of solar energy.

Highly efficient Förster resonance energy transfer between an emissive tetraphenylethylene-based metal-organic cage and the encapsulated dye guest.

The host-guest strategy presents an ideal way to achieve efficient Förster resonance energy transfer (FRET) by forcing close proximity between an energy donor and acceptor. Herein, by encapsulating the negatively charged acceptor dyes eosin Y (EY) or sulforhodamine 101 (SR101) in the cationic tetraphenylethene-based emissive cage-like host donor Zn-1, host-guest complexes were formed that exhibit highly efficient FRET. The energy transfer efficiency of Zn-1⊃EY reached 82.4%. To better verify the occurrence of the FRET process and make full use of the harvested energy, Zn-1⊃EY was successfully used as a photochemical catalyst for the dehalogenation of α-bromoacetophenone. Furthermore, the emission color of the host-guest system Zn-1⊃SR101 could be adjusted to exhibit bright white-light emission with the CIE coordinates (0.32, 0.33). This work details a promising approach to enhance the efficiency of the FRET process by the creation of a host-guest system between the cage-like host and dye acceptor, thus serving as a versatile platform for mimicking natural light-harvesting systems.

An artificial light-harvesting system constructed from a water-soluble metal-organic barrel for photocatalytic aerobic reactions in aqueous media.

An artificial light-harvesting system constructed from a water-soluble host-guest complex can be regarded as a high-level conceptual model of its biological counterpart and can convert solar energy into chemical energy in an aqueous environment. Herein, a water-soluble metal-organic barrel Ga-tpe with twelve sulfonic acid units was obtained by subcomponent self-assembly between Ga3+ ions and tetra-topic ligands with tetraphenylethylene (TPE) cores. By taking advantage of host-guest interactions, cationic dye rhodamine B (RB) was constrained in the pocket of Ga-tpe to promote the Förster resonance energy transfer (FRET) process for efficient photocatalytic aerobic oxidation of sulfides and cross-dehydrogenative coupling (CDC) reaction in aqueous media.

Characterization of Steel Slag Filler and Its Effect on Aging Resistance of Asphalt Mastic with Various Aging Methods.

Steel slag is the by-product of the steelmaking industry, the negative influences of which prompt more investigation into the recycling methods of steel slag. The purpose of this study is to characterize steel slag filler and study its feasibility of replacing limestone filler in asphalt concrete by evaluating the resistance of asphalt mastic under various aging methods. Firstly, steel slag filler, limestone filler, virgin asphalt, steel slag filler asphalt mastic and limestone filler asphalt mastic were prepared. Subsequently, particle size distribution, surface characterization and pore characterization of the fillers were evaluated. Finally, rheological property, self-healing property and chemical functional groups of the asphalt mastics with various aging methods were tested via dynamic shear rheometer and Fourier transform infrared spectrometer. The results show that there are similar particle size distributions, however, different surface characterization and pore characterization in the fillers. The analysis to asphalt mastics demonstrates how the addition of steel slag filler contributes to the resistance of asphalt mastic under the environment of acid and alkaline but is harmful under UV radiation especially. In addition, the pore structure in steel slag filler should be a potential explanation for the changing resistance of the asphalt mastics. In conclusion, steel slag filler is suggested to replace limestone filler under the environment of acid and alkaline, and environmental factor should be taken into consideration when steel slag filler is applied to replace natural fillers in asphalt mastic.

Study on Recycling of Steel Slags Used as Coarse and Fine Aggregates in Induction Healing Asphalt Concretes.

Steel slag, a by-product of steelmaking, imposes lots of negative impacts on the environment. For alleviating negative impacts, more and more experiments have been carried out to explore the application possibility of steel slag. The purpose of this study is to explore the feasibility of steel slag being applied in induction healing asphalt concretes to replace coarse and fine aggregate. Surface texture and pore sizes of steel slag were firstly tested, and then steel slag and basalt asphalt mixtures modified with steel fibers were prepared. Moisture susceptibility, dynamic stability, mechanical property, thermal property, induction heating speed, natural cooling speed and healing property of the asphalt mixtures were evaluated. Results showed that steel slags had more obvious holes in the surface while the surface area is much larger than that of basalt. Furthermore, steel fibers and steel slag both have dynamic stability, and steel fibers contribute to increased moisture resistance while steel slag is not. Steel slag asphalt concrete showed better mechanical property and better capacity to store heating. Steel slag asphalt mixtures had a similar heating speed to basalt asphalt mixtures but a significantly slower cooling rate. Finally, the induction healing test and CT scanning test demonstrated that steel slag asphalt mixtures had a similar healing ability to basalt asphalt mixtures. It can be concluded that steel slags have the potential to replace the natural aggregates to be applied in induction heating self-healing asphalt concretes.

Aging Mechanism and Rejuvenating Possibility of SBS Copolymers in Asphalt Binders.

The styrene-butadiene-styrene (SBS)-modified asphalt pavement has been in growing demand in the road construction field owing to its workable mechanical property and temperature durability. This paper prepared a penetrative rejuvenator (PR) with waste cooking oil (WCO) and emulsified asphalt, then applied PR on SBS copolymers to investigate its aging and rejuvenating effects in an asphalt binder. After a thin film oven test (TFOT) and ultraviolet (UV) aging of SBS copolymers, Fourier transform infrared (FTIR) spectra were used to analyse the aged copolymers' chemical structure. Moreover, both aged and rejuvenated SBS copolymers were added into a fresh asphalt binder to get two kinds of modified asphalt binders, namely, MAAC (modified by aged copolymer) and MARC (modified by rejuvenated copolymer). Aiming to analyse the monomer effect of SBS copolymers in the asphalt binder, the rheological characteristic with dynamic shear rheometer (DSR), chemical structure with FTIR and physical properties with penetration, soft point and ductility tests were investigated using MAAC and MAAC samples. The results showed that rejuvenated SBS copolymer could improve MAAC's viscoelasticity, but from FTIR spectral analysis, PR resulted in no chemical changes to SBS copolymers. A tough coat which made MAAC of higher stiffness was observed on the copolymer surface after thermal treatment. UV caused evidently negative effects on SBS copolymer because of accelerating oxidation by ozone, which brought about high possibility of cracks during servicing periods of asphalt pavement. In addition, MAAC was inferior in both rheological and physical properties, which reflected the significance and necessity in consideration of alleviating SBS copolymer aging in field.

Investigation of the Effect of Induction Heating on Asphalt Binder Aging in Steel Fibers Modified Asphalt Concrete.

Induction heating is a valuable technology to repair asphalt concrete damage inside. However, in the process of induction heating, induced particles will release a large amount of heat to act on asphalt binder in a short time. The purpose of this paper was to study the effect of induction heating on asphalt binder aging in steel fibers modified asphalt concrete. The experiments were divided into two parts: induction heating of Dramix steel fibers coated with asphalt binder (DA) and steel wool fibers modified asphalt concrete. After induction heating, the asphalt binders in the samples were extracted for testing aging indices with Fourier Transform Infrared (FTIR), Dynamic Shear Rheometer (DSR), and Four-Components Analysis (FCA) tests. The aging of asphalt binder was analyzed identifying the change of chemical structure, the diversification of rheological properties, and the difference of component. The experiments showed that the binder inside asphalt concrete began aging during induction heating due to thermal oxygen reaction and volatilization of light components. However, there was no peak value of the carbonyl index after induction heating of ten cycles, and the carbonyl index of DA was equivalent to that of binder in asphalt concrete after three induction heating cycles, which indicated the relatively closed environment inside asphalt concrete can inhibit the occurrence of the aging reaction.

The Effect of UV Irradiation on the Chemical Structure, Mechanical and Self-Healing Properties of Asphalt Mixture.

Although huge numbers of investigations have been conducted for the ultraviolet (UV) aging of asphalt binder, research rarely focuses on the asphalt mixture. In order to evaluate the aging effect of UV radiation on the asphalt mixture, a dense grade of asphalt mixture was designated and aged by UV radiation for 7, 14 and 28 days respectively. After that, the chemical functional groups of asphalt binder were tested by Fourier transform infrared spectrometer (FTIR). The semi-circular bending strength and fatigue resistance of asphalt concrete were tested to characterize the mechanical properties of the asphalt concrete. To evaluate the self-healing effect of the macro-structure continuity of asphalt concrete intuitively, the computed tomography (CT) scanning machine was used to characterize the crack size of asphalt concrete samples both before and after self-healing. The results show that, with the increase of UV irradiation time, the relative ratios of the C=O and S=O bands' areas of recovered asphalt binder increase significantly. UV radiation can significantly weaken the mechanical and self-healing properties of asphalt mixture, making the asphalt mixture to have worse macro-structure continuity, lower failure strength and worse fatigue resistance. Moreover, the longer the UV irradiation time is, the degradation effect of UV radiation on asphalt mixture becomes more obvious.

Heating Characteristics and Induced Healing Efficiencies of Asphalt Mixture via Induction and Microwave Heating.

This paper investigates the heating characteristics and induced healing efficiencies of asphalt mixture containing steel fiber under induction heating and microwave heating. The heating characteristics of an asphalt mixture with different heating methods were studied with an infrared camera. The healing performance of the asphalt mixture specimens in different healing conditions were investigated by observing the crack closure and testing the fracture resistance recovery after healing. The results showed that the heating speed at the surface of asphalt mixture with induction heating was much higher than that with microwave machine heating, under a similar output power and the same method of radiation. While the temperature distribution within the asphalt mixture under induction heating was quite uneven, microwave heating resulted in a more uniform temperature distribution. The effective heating depth of microwave heating is much higher than that of induction heating. Gradient healing occurred within the sample heated with induction healing, while a uniform healing effect can be achieved with microwave heating.