Halloysite-Based Nanorockets with Light-Enhanced Self-Propulsion for Efficient Water Remediation.

Halloysite-based tubular nanorockets with chemical-/light-controlled self-propulsion and on-demand acceleration in velocity are reported. The nanorockets are fabricated by modifying halloysite nanotubes with nanoparticles of silver (Ag) and light-responsive α-Fe2O3 to prepare a composite of Ag-Fe2O3/HNTs. Compared to the traditional fabrication of tubular micro-/nanomotors, this strategy has merits in employing natural clay as substrates of an asymmetric tubular structure, of abundance, and of no complex instruments required. The velocity of self-propelled Ag-Fe2O3/HNTs nanorockets in fuel (3.0% H2O2) was ca. 1.7 times higher under the irradiation of visible light than that in darkness. Such light-enhanced propulsion can be wirelessly modulated by adjusting light intensity and H2O2 concentration. The highly repeatable and controlled "weak/strong" propulsion can be implemented by turning a light on and off. With the synergistic coupling of the photocatalysis of the Ag-Fe2O3 heterostructure and advanced oxidation in H2O2/visible light conditions, the Ag-Fe2O3/HNTs nanorockets achieve an enhanced performance of wastewater remediation. A test was done by the catalytic degradation of tetracycline hydrochloride. The light-enhanced propulsion is demonstrated to accelerate the degradation kinetics dramatically. All of these results illustrated that such motors can achieve efficient water remediation and open a new path for the photodegradation of organic pollutions.

Fabrication of Pd/Mg2 P2 O7 via a Struvite-Template Way from Wastewater and Application as Chemoselective Catalyst in Hydrogenation of Nitroarenes.

A highly efficient heterogeneous catalyst Pd/Mg2 P2 O7 was fabricated by combining palladium nanoparticles (PdNPs) and mesoporous Mg2 P2 O7 fibers/rods. Mg2 P2 O7 fibers with ultra-high specific surface area were prepared from struvite as templates, which were synthesized from waste water containing N- and P-containing pollutants. This strategy provided a novel pathway for developing advanced catalysts from eutrophication-polluted water. The composite Pd/Mg2 P2 O7 showed brilliant performance in selective hydrogenation of nitro aromatics to give anilines. As an example of nitrobenzene hydrogenation, the conversion to aniline and selectivity were found to reach almost 100 % at a temperature of T=90 °C and under a pressure of P H 2 =2.0 MPa. The superior performance was found to originate from PdNPs, which were boosted by electron transfer afforded by the nanofiber Mg2 P2 O7 supports. The favorable adsorption of withdrawing groups (-NO2 ) was realized by synergistic effects between Pd and oxygen vacancies provided by pyrolysis of struvite. The catalyst remained stable after cycles of reuse with little degradation in catalytic performance.

Prolonged-Photoresponse-Lifetime Ni2P Nanocrystalline with Highly Exposed (001) for Efficient Photoelectrocatalytic Hydrogen Evolution.

Seeking highly efficient non-preference electrocatalytic materials that serve photoelectrochemical (PEC) water splitting in acidic systems is expectant in the context of environmentally friendly production. We designed Ni2P electrocatalysts synthesized in oil phases via the hot-bubbling method with superb stability in air and sulfuric acid solution for PEC, which were found with excellent hydrogen evolution performance. A tunable particle size and highly exposed (001) planes of Ni2P nanocrystals were achieved. The designed catalysts achieved a notable promotion in the hydrogen evolution reaction activity compared to that of Ni2P synthesized in the water phase. More specifically, the electrode prepared by self-assembled Ni2P nanoparticles was found to have decent over-potential of η10 = 164 mV in darkness and was further decreased to 129 mV with irradiation of visible light. The cyclic stability tests manifested brilliant durability in 0.5 M H2SO4. Measurement of the transient photocurrent response and PEC water splitting catalytic performance indicated that the Ni2P had high carrier concentration upon irradiation, lower carrier recombination probability, and prolonged photo-response lifetime (3.03-3.14 s).

Novel aluminum vanadate as a cathode material for high-performance aqueous zinc-ion batteries.

Rechargeable aqueous zinc-ion batteries (AZIBs) have garnered widespread attention as a new large-scale energy storage candidate owing to their low cost and high theoretical capacity. Because of the unique divalent state of Zn2+and the existence of a strong electrostatic repulsion phenomenon, researchers are currently focusing on how to prepare high-performance cathode materials. In this study, we synthesized aluminum vanadate (AlV3O9) as a cathode material for AZIBs using a solvothermal method. Al3+acted as a pillar in the resultant structure and stabilized it. Furthermore, this large interlayer spacing enhanced the ion diffusion coefficient and accelerated the ion transport process. Because of these advantages, the AlV3O9(AVO) cathode exhibited excellent electrochemical performance, including a high capacity of 421.0 mA h g-1at 0.1 A g-1and a stable rate capability of 348.2 mA h g-1at 1 A g-1. Moreover, it exhibited a specific capacity of 202 mA h g-1even at a high current density of 3 A g-1(the capacity retention rate reached 84.38% after 1600 cycles). The prepared ZIBs presented a high power density of 366.6 W kg-1at an energy density of 286 W h kg-1. These extraordinary results indicate the great application potential of AVO as a cathode material for AZIBs.

Mn4+ activated Al2O3 red-emitting ceramic phosphor with excellent thermal conductivity.

An Al2O3:Mn4+, Mg2+ red emitting ceramic phosphor, which can be effectively excited by ultraviolet and blue light, was successfully synthesized via solid-state reaction in an oxygen and air atmosphere. The ceramic sintered in oxygen atmosphere has higher optical transmittance and stronger luminescence intensity than the ceramic sintered in the air, which is more suitable for LED application. Since the structure of α-Al2O3 is very simple, it is convenient to study the factors affecting the Mn4+ luminescence. The crystal-strength parameter Dq, Racah parameters B and C, and the nephelauxetic ratio ß1 were calculated to investigate the influence of crystal field strength and nephelauxetic effect on the emission of Mn4+ in the Al2O3 host. The ratio of Dq to B was 1.74, which was lower than 2.2. This indicated that the Mn4+ ions in the α-Al2O3 host were in a weak crystal field environment. Under the 395 nm and 460 nm excitations, quantum yields (QY) of the sample were measured to be 46% and 28.7%, respectively. The density measured by the Archimedes method was 3.61 g/cm3. The ceramic also showed an excellent thermal conductivity value, which was as high as 26.27 W·m-1·K-1@30 °C.

Mg(Al, Fe, Mn, REE)2O4 Spinel Prepared from Pelagic REE-Rich Clays and Application as Magnesium-Ion-Battery Cathodes.

The oxidation and lattice distortion of spinel oxides used for magnesium-ion battery (MIB) cathodes lead to poor stability and cycling performance. Herein, the highly inverted spinel oxide Mg(Al, Fe, Mn, REE)2O4 of i = 0.62 with incorporated rare-earth elements (REE) and decent specific surface area was prepared by utilizing leachate of the pelagic rare-earth-rich clays via a foamed sol-gel/calcination method. Measurements of specific capacity, cycling performance, and multiplicity performance showed that the foamed spinel exhibited distinguished electrochemical performance of MIB. At the current density of 100 mA h-1, the initial discharge and charge specific capacity were 125.7 mAh g-1 and 139.7 mAh g-1, and the reversible discharge and charge specific capacities were maintained as 96.7 mAh g-1 and 102.4 mAh g-1 after 200 cycles of charging-discharging. The Mg-ion diffusion rate for MAFMRO was 1.08 × 10-5 cm2 s-1, which was significantly improved, compared to traditional magnesium spinel anodes. This work highlights an approach for modification of spinel-type cathode materials and the high-value utilization of pelagic clay resources.

Hydrothermal Synthesis of 1T-MoS2/Pelagic Clay Composite and Its Application in the Catalytic Reduction of 4-Nitrophenol.

Pelagic clay is an emerging marine resource with strong hydrophilicity, fine particles and a large specific surface area. In this work, a 1T-MoS2/pelagic clay composite was fabricated by hydrothermal synthesis. In the composite, 1T-MoS2 nanosheets are evenly dispersed on the surface of the clay minerals, significantly reducing the agglomeration of MoS2. Compared with pure 1T-MoS2, the 1T-MoS2 nanosheets generated on the surface of pelagic clay have significantly smaller lateral dimensions and thicknesses. Moreover, the specific surface area is much larger than that of the pure 1T-MoS2 nanosheets fabricated by the same method, indicating that the active sites of the MoS2 sheets are fully exposed. In addition, the composite exhibited excellent hydrophilicity, leading to a high dispersibility in aqueous solutions. In this work, the composite was used as a catalyst in the reduction of 4-nitrophenol (4-NP), and the conversion of 4-NP reached up to 96.7%. This result shows that the 1T-MoS2/pelagic clay composite is a promising catalyst in a variety of reactions.

Symbiotic composite composed of MoS2 and pelagic clay with enhanced disinfection efficiency.

Molybdenum disulfide (MoS2) has attracted increasing attention as a promising photocatalyst. In addition to its application in photocatalytic hydrogen production and pollutant degradation, MoS2 is also used in water disinfection. However, its poor disinfection performance limits its practical utility. Herein, we prepared a symbiotic composite composed of MoS2 and pelagic clay (MoS2/PC) as a photocatalyst for water disinfection. The composite achieved a high disinfection rate of 99.95% to Escherichia coli (E. coli) under visible light illumination, which is significantly higher than that of bulk MoS2 (61.87%). Characterization shows that abundant hydroxyl groups in illite/montmorillonite (I/M) formed during hydrothermal synthesis of MoS2, which contributed to the enhanced disinfection activity. Those hydroxyl groups can attract photogenerated holes through electrostatic attraction, and facilitate the separation of photogenerated charge carriers, thereby enhancing the disinfection activity. Moreover, the good hydrophilicity of pelagic clay improves the dispersity of MoS2 in water, which is beneficial for its utility in aqueous solutions. In addition, the symbiotic structure restricts the growth and aggregation of MoS2 nanosheets and shortens the diffusion distance of charge carriers to the material surface, further reducing the recombination of electrons and holes. This study provides a way to improve the disinfection activity of MoS2 and also sheds light on high value-added utilization of pelagic clay.

Self-Propelled Nanojets for Fenton Catalysts Based on Halloysite with Embedded Pt and Outside-Grafted Fe3O4.

Taking inspirations from nature, we endeavor to develop catalytically self-propelled nanojets from a type of tubular clay minerals, halloysite nanotubes (HNTs), and utilize them as catalysts targeted for catalysis where the traditional means of mechanical agitation cannot be implemented. Nanojets of Fe3O4@HNTs/Pt were prepared by impregnating platinum nanoparticles (Pt NPs) in lumens of HNTs and selective grafting of magnetite (Fe3O4) particles on the external surface. The HNT-based nanojets were validated to be highly suitable both in free bulk solution and in microfluidic flow. An example of Fenton degradation catalyzed by these jets was demonstrated. The powerful movement of Fe3O4@HNTs/Pt (368 ± 50 µm·s-1) fueled by 5.0% wt. H2O2 was found to follow a bubble propulsion mechanism, and the motion exhibits collective behavior as swarms. The clay tubes were for the first time observed to self-assemble into fish-like aggregates during swimming, reflecting natural occurrence of motion-evolution philosophy. Guided motion was realized by employing magnetic manipulation which makes jets feasible for reactors with complex microchannels/reactors.

Highly Stable and Recyclable Sequestration of CO2 Using Supported Melamine on Layered-Chain Clay Mineral.

A type of highly stable and recyclable clay-based composite was developed for sequestration of CO2, which was synthesized by loading melamine (MEL) onto attapulgite (ATT) via a wet impregnation method. The synthesized materials were characterized by N2 adsorption-desorption, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TG), and transmission electron microscopy (TEM). By means of thermal and acidic treatments more active sites of ATT were exposed, and large surface areas were obtained. The MEL molecules were well combined with those exposed sites, which enhanced stability and cyclability for CO2 sequestration. On the basis of CO2 adsorption-desorption measurements, the composite of ATT-MEL was found to have a higher CO2 adsorption capacity (4.91 cm3/g) which was much higher than that of CO2 absorption on bare MEL (1.30 cm3/g) at 30 °C. After ten cycles of reusing, the composite exhibited even higher capacity for CO2 adsorption by an increased percentage of 5.91% (30 °C) and 5.77% (70 °C) compared to the capacity in the first cycle. The reason lies in the strong interaction between melamine and attapulgite matrix which was further confirmed by DFT calculations. The MEL was validated to have advantages over aliphatic amines (TEPA) in modifying ATT to get high stability of CO2-adsorbents.

Preparation of mesoporous silica with pelagic clay and its optical property.

To obtain mesoporous silica with prime properties, we used pelagic clay as the raw material with the precipitation method. According to the specific surface area (SSA) of production, we optimized the technical conditions and characterized it with Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), N2 adsorption, and scanning electron microscopy (SEM). The photoluminescence (PL) and photoluminescence excitation (PLE) of mesoporous silica were tested too. FTIR indicated that the products were pure amorphous silica. XRD showed that the silica was MCM-41. The N2 adsorption test showed that it belongs to the type of Langmuir IV, the aperture is about 2.9 nm, and the distribution is uniform. The SEM test indicated that the silica aggregation is branch-like, and the mesoporous silica is hexagonal with mesh arrangement. PL and PLE spectra proved that the intensities of the PL and PLE of mesoporous silica increase with increasing SSA.

Effective removal of aromatic pollutants via adsorption and photocatalysis of porous organic frameworks.

PAF-45 with a wholly aromatic framework, intrinsic microporosity and π-π conjugation system shows excellent performance in aromatic pollutant removal. It exhibits a high adsorption capacity for the benzene series and moderate photocatalytic performance. As an adsorbent, PAF-45 can adsorb 35 wt% benzene and 68 wt% chlorobenzene in static adsorption experiments at room temperature and pressure. In benzene simulation wastewater, PAF-45 also shows excellent adsorption capacity, without significant reduction after 10 cycles of the adsorption-desorption process. Moreover, PAF-45 exhibits an impressive photocatalytic degradability of aromatic compounds, like aniline and phenol, under visible light illumination.

Swelling suppression of black cotton soil by means of liquid immersion and surface modification.

Although the surface organic modification of smectite has been investigated widely, the swelling behavior of clays has been scarcely studied with consideration of civil engineering applications. In this work a facile strategy of liquid-immersion (dilute H2SO4 aqeuous solution) was proposed, and the 3-aminopropyltrimethoxysilane (APS) was utilized as surface modifier to suppress expansibility of black cotton soil (BCS) which is a type of highly swelling soils in tropical areas. Factors such as the incorporation dosage of APS, surface characters of soil treated by solution of H2SO4 or Na2CO3, and reaction temperatures/time were investigated to get lower swelling ratios. The treatment of BCS by H2SO4 was found more effective in immobilizing APS molecules, and hydronium ions were suppressed after the APS modification. The free swelling index (FSI) of BCS was decreased from 120% to 15% after treatment with H2SO4 and appropriate amount of APS modification. The reaction can be completed within several hours at the room temperature to ~80 °C. The soil samples were characterized by different means including the X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscope, thermogravimetric analysis and Zeta potential measurements. The APS molecules were found to react with -OH groups of the clay, and the hydrophobic groups provide surface hydrophobicity, which prevents hydration of cations within clay minerals. The APS was indicated to re-constructed lamellar structures of smectites after H2SO4 treatment, which suppressed the intra-crystalline and the subsequent osmotic swelling. This research highlights the liquid immersion and surface modification is applicable in diminishing swelling ratios of highly expansive black cotton soil.

Effect of Nd-doping on the optical properties of yttrium aluminum garnet nanopowders.

Nd-doped and Nd/Si-codoped yttrium aluminum garnet powders were synthesized via a solvothermal method using ethanol as the solvent. The photoluminescence spectra of the powders revealed that the intensity of the emission increased with Nd-doping concentration initially and then decreased with further increase in Nd concentration. The powder containing 3.5 atm% Nd exhibited the highest light emission intensity. The fluorescence lifetime of the yttrium aluminum garnet powders was also measured as a function of Nd-doping concentration. The results were fitted with an empirical equation.

Effect of mechanical milling on photoluminescence of gamma-alumina nanoparticles.

The effect of mechanical alloying on the photoluminescence behavior of gamma-Al2O3 nanopowder was studied. Two emission peaks centered at 343 and 378 nm and a broad emission band ranging between 400-600 nm have been observed. It is found that the intensity of the two emission peaks decreases with ball-milling time, while that the broad band remains un-change. These results suggested that the two peaks are resulted from the surface defects that analogs of F+ centers, while the broad band is resulted from impurity.