Integrated optimization of scheduling for unmanned follow-me cars on airport surface.

To promote the application of automated vehicles in large airports, in this study, we present an integrated optimization method for scheduling Unmanned follow-me cars. The scheduling process is divided into three phases: Dispatch, Guidance, and Recycle. For the Dispatch phase, we establish a vehicle assignment model, to allocate the vehicle resource equitably. For the Guidance phase, we offer an quantitative way, to measure the spacing between Unmanned follow-me car and aircraft. To optimize the efficiency of airport operation in the three phases and ensure safety, the collaborative planning model, and the conflict prediction model are established. An improved grey wolf optimization algorithm is adopted to enhance the convergence speed and generalization performance. A case study at Ezhou Huahu Airport in China demonstrates the effectiveness of the methods. The results show that the model of collaborative planning can make the balance of path selection, Unmanned follow-me car's working time, and departure sequence. The convergence speed of the improved algorithm has been increased by 18.75%. The inequity index of vehicle assignment is only 0.015731, and the spatiotemporal distribution of conflicts is influenced by the airport's surface layout.

Tanshinone IIA and hepatocellular carcinoma: A potential therapeutic drug.

Because of its high prevalence and poor long-term clinical treatment effect, liver disease is regarded as a major public health problem around the world. Among them, viral hepatitis, fatty liver, cirrhosis, non-alcoholic fatty liver disease (NAFLD), and autoimmune liver disease are common causes and inducements of liver injury, and play an important role in the occurrence and development of hepatocellular carcinoma (HCC). Tanshinone IIA (TsIIA) is a fat soluble polyphenol of Salvia miltiorrhiza that is extracted from Salvia miltiorrhiza. Because of its strong biological activity (anti-inflammatory, antioxidant), it is widely used in Asia to treat cardiovascular and liver diseases. In addition, TsIIA has shown significant anti-HCC activity in previous studies. It not only has significant anti proliferation and pro apoptotic properties. It can also play an anti-cancer role by mediating a variety of signal pathways, including phosphatidylinositol-3-kinase (PI3K)/protein kinase B (Akt)/rapamycin (mTOR), mitogen-activated protein kinase (MAPK), and nuclear factor kappa-B (NF-κB). This review not only reviews the existing evidence and molecular mechanism of TsIIA's anti-HCC effect but also reviews the liver-protective effect of TsIIA and its impact on liver fibrosis, NAFLD, and other risk factors for liver cancer. In addition, we also conducted network pharmacological analysis on TsIIA and HCC to further screen and explore the possible targets of TsIIA against hepatocellular carcinoma. It is expected to provide a theoretical basis for the development of anti-HCC-related drugs based on TsIIA.

Insights into the Role of Graphitic Carbon Nitride as a Photobase in Proton-Coupled Electron Transfer in (sp3 )C-H Oxygenation of Oxazolidinones.

Graphitic carbon nitride (g-CN) is a transition metal free semiconductor that mediates a variety of photocatalytic reactions. Although photoinduced electron transfer is often postulated in the mechanism, proton-coupled electron transfer (PCET) is a more favorable pathway for substrates possessing X-H bonds. Upon excitation of an (sp2 )N-rich structure of g-CN with visible light, it behaves as a photobase-it undergoes reductive quenching accompanied by abstraction of a proton from a substrate. The results of modeling allowed us to identify active sites for PCET-the 'triangular pockets' on the edge facets of g-CN. We employ excited state PCET from the substrate to g-CN to selectively cleavethe endo-(sp3 )C-H bond in oxazolidine-2-ones followed by trapping the radical with O2 . This reaction affords 1,3-oxazolidine-2,4-diones. Measurement of the apparent pKa value and modeling suggest that g-CN excited state can cleave X-H bonds that are characterized by bond dissociation free energy (BDFE) ≈100 kcal mol-1 .

Violet phosphorus: an effective metal-free elemental photocatalyst for hydrogen evolution.

Violet phosphorus, a non-metallic elemental layered structure, has not been reported as a photocatalyst due to the lack of its resources. An excellent photocatalytic H2 evolution rate of 675 ± 109 µmol h-1 g-1 with high stability has been achieved by the violet phosphorus simply dispersed in deionized water with addition of 1.0 wt% of co-catalyst Pt, which is much higher than that obtained from black phosphorus. The H2 evolution rate was observed to reach values as high as 553 µmol h-1 g-1 with addition of 0.5 wt% co-catalyst Pt.

Identification of the Structure of Triethanolamine Oxygenation Products in Carbon Nitride Photocatalysis.

Triethanolamine (TEOA) is one of the most commonly used sacrificial agents in photocatalysis. Due to its more complex structure compared to, for example, ethanol, and its sacrificial role in photocatalysis, it gives a mixture of products. The structures of these molecules are not usually analyzed. Herein, we obtain and isolate the products of TEOA and N-tert-butyl diethanolamine oxygenation under photocatalytic conditions with ≈15 % yield, and followingly characterized them by NMR and mass spectroscopy. The reaction is mediated by potassium poly(heptazine imide) (K-PHI) in the presence of O2 and affords formyl esters of ß-hydroxyethylene formamides from the corresponding ethanolamines.

Red edge effect and chromoselective photocatalysis with amorphous covalent triazine-based frameworks.

Chromoselective photocatalysis offers an intriguing opportunity to enable a specific reaction pathway out of a potentially possible multiplicity for a given substrate by using a sensitizer that converts the energy of incident photon into the redox potential of the corresponding magnitude. Several sensitizers possessing different discrete redox potentials (high/low) upon excitation with photons of specific wavelength (short/long) have been reported. Herein, we report design of molecular structures of two-dimensional amorphous covalent triazine-based frameworks (CTFs) possessing intraband states close to the valence band with strong red edge effect (REE). REE enables generation of a continuum of excited sites characterized by their own redox potentials, with the magnitude proportional to the wavelength of incident photons. Separation of charge carriers in such materials depends strongly on the wavelength of incident light and is the primary parameter that defines efficacy of the materials in photocatalytic bromination of electron rich aromatic compounds. In dual Ni-photocatalysis, excitation of electrons from the intraband states to the conduction band of the CTF with 625 nm photons enables selective formation of C‒N cross-coupling products from arylhalides and pyrrolidine, while an undesirable dehalogenation process is completely suppressed.

Laser-driven growth of structurally defined transition metal oxide nanocrystals on carbon nitride photoelectrodes in milliseconds.

Fabrication of hybrid photoelectrodes on a subsecond timescale with low energy consumption and possessing high photocurrent densities remains a centerpiece for successful implementation of photoelectrocatalytic synthesis of fuels and value-added chemicals. Here, we introduce a laser-driven technology to print sensitizers with desired morphologies and layer thickness onto different substrates, such as glass, carbon, or carbon nitride (CN). The specially designed process uses a thin polymer reactor impregnated with transition metal salts, confining the growth of transition metal oxide (TMO) nanostructures on the interface in milliseconds, while their morphology can be tuned by the laser. Multiple nano-p-n junctions at the interface increase the electron/hole lifetime by efficient charge trapping. A hybrid copper oxide/CN photoanode with optimal architecture reaches 10 times higher photocurrents than the pristine CN photoanode. This technology provides a modular approach to build a library of TMO-based composite films, enabling the creation of materials for diverse applications.

Ligand-Metal Charge Transfer Induced via Adjustment of Textural Properties Controls the Performance of Single-Atom Catalysts during Photocatalytic Degradation.

Because of their peculiar nitrogen-rich structure, carbon nitrides are convenient polydentate ligands for designing single atom-dispersed photocatalysts. However, the relation between catalysts' textural properties and their photophysical-photocatalytic properties is rarely elaborated. Herein, we report the preparation and characterization of a series of single-atom heterogeneous catalysts featuring highly dispersed Ag and Cu species on mesoporous graphitic C3N4. We show that adjustment of materials textural properties and therefore metal single-atom coordination mode enables ligand-to-metal charge transfer (LMCT) or ligand-to-metal-to-ligand charge transfer (LMLCT), properties that were long speculated in single-atom catalysis but never observed. We employ the developed materials in the degradation of organic pollutants under irradiation with visible light. Kinetic investigations under flow conditions show that single atoms of Ag and Cu decrease the number of toxic organic fragmentation products while leading to a higher selectivity toward full degradation. The results correlate with the selected mode of charge transfer in the designed photocatalysts and provide a new understanding of how the local environment of a single-atom catalyst affects the surface structure and reactivity. The concepts can be exploited further to rationally design and optimize other single-atom materials.

Enhanced Organic Photocatalysis in Confined Flow through a Carbon Nitride Nanotube Membrane with Conversions in the Millisecond Regime.

Bioinspired nanoconfined catalysis has developed to become an important tool for improving the performance of a wide range of chemical reactions. However, photocatalysis in a nanoconfined environment remains largely unexplored. Here, we report the application of a free-standing and flow-through carbon nitride nanotube (CNN) membrane with pore diameters of 40 nm for confined photocatalytic reactions where reactants are in contact with the catalyst for <65 ms, as calculated from the flow. Due to the well-defined tubular structure of the membrane, we are able to assess quantitatively the photocatalytic performance in each of the parallelized single carbon nitride nanotubes, which act as spatially isolated nanoreactors. In oxidation of benzylamine, the confined reaction shows an improved performance when compared to the corresponding bulk reaction, reaching a turnover frequency of (9.63 ± 1.87) × 105 s-1. Such high rates are otherwise only known for special enzymes and are clearly attributed to the confinement of the studied reactions within the one-dimensional nanochannels of the CNN membrane. Namely, a concave surface maintains the internal electric field induced by the polar surface of the carbon nitride inside the nanotube, which is essential for polarization of reagent molecules and extension of the lifetime of the photogenerated charge carriers. The enhanced flow rate upon confinement provides crucial insight on catalysis in such an environment from a physical chemistry perspective. This confinement strategy is envisioned not only to realize highly efficient reactions but also to gain a fundamental understanding of complex chemical processes.

Thio linkage between CdS quantum dots and UiO-66-type MOFs as an effective transfer bridge of charge carriers boosting visible-light-driven photocatalytic hydrogen production.

Metal-organic frameworks (MOFs)/semiconductor hybrids have attracted attention in photocatalysis. Herein, we report a new strategy to use thiol-laced UiO-66 (UiO-66-(SH)2) as a porous and functional support for anchoring CdS quantum dots (QDs) (size: 0.5/3 nm). Cd2+ ions are firstly absorbed into the cavities of UiO-66-(SH)2 MOFs via coordinating to the thiol groups in the presence of a base to produce UiO-66-(S-Cd)2, then thiourea is added to form UiO-66-(S-CdS)2 (abbreviated as UiOS-CdS). It is clearly revealed by ultrafast transient absorption spectroscopy that the thio linkage between UiO-66 and CdS acts as an effective transfer bridge of charge carriers, which greatly promotes the interface transfer process of photogenerated electrons and holes, boosting the photocatalytic hydrogen production performance from water splitting. The optimized UiOS-CdS exhibits a photocatalytic H2 production rate of 153.2 µmol h-1 (10 mg of catalyst) under visible-light irradiation (λ > 420 nm) in the absence of nobel metal co-catalyst, corrsponding to an apparent quantum efficiency of 11.9% at 420 nm. This work may provide an effective strategy to construct QDs-linker-MOFs stylephotocatalysts for efficient energy conversion.

Highly efficient reverse osmosis concentrate remediation by microalgae for biolipid production assisted with electrooxidation.

Phytoremediation of reverse osmosis concentrate (ROC) with microalgae can simultaneously achieve multi-functions of ROC treatment, CO2 mitigation and microalgae biolipid production. But the performances are usually inhibited by high free ammonia nitrogen (FAN) concentration and chromaticity of ROC. To offset these negative effects, an integrated technique including electrooxidation pretreatment and Chlorella vulgaris remediation was proposed, in which the ROC was first pretreated with electrooxidation to decrease FAN and chromaticity, and then the oxidized ROC was remediated with microalgae to reclaim nutrients and produce biolipid. Results showed that FAN was sharply reduced from 53.0 mg N/L to 13.9 mg N/L and chromaticity was decreased from 1600 to 100 Pt-Co via electrooxidation. Possible reaction mechanism of nutrients removal was discussed via electron mass balance. Explanation on chromaticity decrease was revealed by analyzing humic acid conversion path with fluorescence characteristics. During microalgae remediation process, nutrients removal rate, microalgae biomass concentration and lipid yield were effectively enhanced in electrooxidized ROC. Energy balance analysis indicated that microalge lipid energy under current density of 3.25 mA/cm2 basically compensated total input energy despite ROC sterilization. This work provided a promising strategy for large-scale ROC treatment and microalgae biolipid production.

The synergy between electronic anchoring effect and internal electric field in CdS quantum dots decorated dandelion-like Fe-CeO2 nanoflowers for improved photocatalytic hydrogen evolution.

A series of dandelion-like Fe-CeO2/CdS (FeCex/Cdy) nanoflowers with different molar ratios of Fe-CeO2 to CdS are synthesized by solvothermal method for the first time. The FeCex/Cdy nanoflowers are assembled by a large number of nanoparticles with the diameter of about 3 nm, and the introduction of Fe ions and the couple of CdS quantum dots (QDs) efficiently enhanced the relative percentage of Ce3+ in CeO2. The as-obtained FeCe1/Cd1 heterostructure exhibits the highest photocatalytic H2 evolution ability of 108.9 µmol/h, which is 20.5, 6.1 and 7.1 times higher than CeO2, Fe-CeO2 and CdS, respectively. This significantly enhanced photocatalytic performance can be mainly attributed to the synergy between the electronic anchoring effect of Fe3+/Fe2+ and Ce4+/Ce3+ redox couples and the internal electric field constructed by the II-type heterojunction between Fe-CeO2 and CdS. This work provides a new idea for the design of efficient photocatalysts by combining the advantages of heterostructure and ion anchoring effect.

Formation mechanism of rectangular-ambulatory-plane TiO2 plates: an insight into the role of hydrofluoric acid.

A novel rectangular-ambulatory-plane TiO2 plate with exposed {001} facets was developed for the first time via a facile microwave-assisted hydrothermal approach in the presence of HF solution. Solid evidence demonstrated that HF plays dual roles in the hydrothermal process, both as a stabilizer for the {001} facet growth and as an etching reagent selectively destroying the {001} facets.

Stable 1T-phase MoS2 as an effective electron mediator promoting photocatalytic hydrogen production.

Coupling two semiconductors together to construct a Z-scheme type photocatalytic system is an efficient strategy to solve the serious recombination challenge of photogenerated electrons and holes. In this work, we develop a novel composite photocatalyst by sandwiching metallic 1T-phase MoS2 nanosheets between MoO3 and g-C3N4 (MoO3/1T-MoS2/g-C3N4) for the first time. The metallic 1T-phase MoS2 acts as an efficient electron mediator between MoO3 and g-C3N4 to construct an all-solid-state Z-scheme photocatalytic system, resulting in a highly-efficient spatial charge separation and transfer process. Benefiting from this, the newly developed MoO3/1T-MoS2/g-C3N4 exhibits a drastically enhanced photocatalytic H2 evolution rate of 513.0 µmol h-1 g-1 under visible light irradiation (>420 nm), which is nearly 12 times higher than that of the pure g-C3N4 (39.5 µmol h-1 g-1), and 3.5 times higher than that of MoO3/g-C3N4 (145.7 µmol h-1 g-1). More importantly, the originally unstable 1T-phase MoS2 becomes very stable in MoO3/1T-MoS2/g-C3N4 because of the sandwich structure where 1T-phase MoS2 is protected by MoO3 and g-C3N4, which endows the photocatalyst with excellent photostability. It is believed that this study will provide new insights into the design of efficient and stable Z-scheme heterostructures for photocatalytic applications.

Multiple carrier-transfer pathways in a flower-like In2S3/CdIn2S4/In2O3 ternary heterostructure for enhanced photocatalytic hydrogen production.

A novel flower-like In2S3/CdIn2S4/In2O3 (ICS) ternary heterostructure (HS) is rationally constructed for the first time by a series of carefully designed procedures. In2O3 nanoflakes are the main constituent units which assemble into a flower-like skeleton structure, and CdIn2S4 nanoparticles are in situ generated on the surface of In2O3 nanoflakes through the transformation of CdS quantum dots (QDs) while In2S3 nanoparticles are in situ produced at the region between CdIn2S4 nanoparticles and In2O3 nanoflakes resulting from a synchronous sulfuration procedure. As expected, the rationally designed ICS ternary HSs display significantly enhanced photocatalytic H2 production, especially ICS5 (sulfurized for 5 h) with the highest H2 evolution rate of 20.04 µmol h-1 (10 mg catalyst is used for photocatalytic reaction), which is 26.7 times and 2.6 times higher than that of pure In2O3 (0.75 µmol h-1) and In2S3/In2O3 binary HS (7.88 µmol h-1), respectively. The enhanced photocatalytic activity can be attributed to the multiple interfaces formed in the ICS HSs, including the CdIn2S4-In2O3 interface, the In2S3-In2O3 interface, and the CdIn2S4-In2O3-In2S3 interface, which construct multiple pathways for the transfer of photogenerated charge carriers, effectively promoting the photocatalytic hydrogen production.

WS2 /Graphitic Carbon Nitride Heterojunction Nanosheets Decorated with CdS Quantum Dots for Photocatalytic Hydrogen Production.

Two-dimensional/two-dimensional (2D/2D) stacking heterostructures are highly desirable in fabricating efficient photocatalysts because face-to-face contact can provide a maximized interfacial region between the two semiconductors; this largely facilitates the migration of charge carriers. Herein, a WS2 /graphitic carbon nitride (CN) 2D/2D nanosheet heterostructure decorated with CdS quantum dots (QDs) has been designed, for the first time. Optimized CdS/WS2 /CN without another cocatalyst exhibits a significantly enhanced photocatalytic H2 evolution rate of 1174.5 µmol h-1 g-1 under visible-light irradiation (λ>420 nm), which is nearly 67 times higher than that of the pure CN nanosheets. The improved photocatalytic activity can be primarily attributed to the highly efficient charge-transfer pathways built among the three components, which effectively accelerate the separation and transfer of photogenerated electrons and holes, and thus, inhibit their recombination. Moreover, the extended light-absorption range also contributes to excellent photocatalytic efficiency. In addition, the CdS/WS2 /CN photocatalyst shows excellent stability and reusability without apparent decay in the photocatalytic H2 evolution within 4 cycles in 20 h. It is believed that this work may shed light on specifically designed 2D/2D nanosheet heterostructures for more efficient visible-light-driven photocatalysts.

Highly Efficient Photocatalyst Based on a CdS Quantum Dots/ZnO Nanosheets 0D/2D Heterojunction for Hydrogen Evolution from Water Splitting.

A novel CdS/ZnO heterojunction constructed of zero-dimensional (0D) CdS quantum dots (QDs) and two-dimensional (2D) ZnO nanosheets (NSs) was rationally designed for the first time. The 2D ZnO NSs were assembled into ZnO microflowers (MFs) via an ultrasonic-assisted hydrothermal procedure (100 °C, 12 h) in the presence of a NaOH solution (0.06 M), and CdS QDs were deposited on both sides of every ZnO NS in situ by using the successive ionic-layer absorption and reaction method. It was found that the ultrasonic treatment played an important role in the generation of ZnO NSs, while NaOH was responsible to the assembly of a flower-like structure. The obtained CdS/ZnO 0D/2D heterostructures exhibited remarkably enhanced photocatalytic activity for hydrogen evolution from water splitting in comparison with other CdS/ZnO heterostructures with different dimensional combinations such as 2D/2D, 0D/three-dimensional (3D), and 3D/0D. Among them, CdS/ZnO-12 (12 deposition cycles of CdS QDs) exhibited the highest hydrogen evolution rate of 22.12 mmol/g/h, which was 13 and 138 times higher than those of single CdS (1.68 mmol/g/h) and ZnO (0.16 mmol/g/h), respectively. The enhanced photocatalytic activity can be attributed to several positive factors, such as the formation of a Z-scheme photocatalytic system, the tiny size effect of 0D CdS QDs and 2D ZnO NSs, and the intimate contact between CdS QDs and ZnO NSs. The formation of a Z-scheme photocatalytic system remarkably promoted the separation and migration of photogenerated electron-hole pairs. The tiny size effect effectively decreased the recombination probability of electrons and holes. The intimate contact between the two semiconductors efficiently reduced the migration resistance of photogenerated carriers. Furthermore, CdS/ZnO-12 also presented excellent stability for photocatalytic hydrogen evolution without any decay within five cycles in 25 h.