Ion-catalyzed synthesis of N/O co-doped carbon nanorods with hierarchical pores for high-rate Na-ion storage.

Appropriate heteroatom doping and pore structure optimization are cost-effective technologies to improve the electronic conductivity and ion diffusion kinetics of hard carbons (HCs). Here, we report an ion-catalyzed synthesis of N/O co-doped carbon nanorods (NOCNRs) with abundant hierarchical pores, achieving high-capacity and high-rate Na-ion storage (336 mA h g-1 at 0.1 A g-1 and 196 mA h g-1 at 20.0 A g-1).

Hierarchical hollow α-Fe2O3/ZnFe2O4/Mn2O3 Janus micromotors as dynamic and efficient microcleaners for enhanced photo-Fenton elimination of organic pollutants.

Micro/nanomotors that can promote mass transport have attracted more and more research concern in the photocatalysis field. Here we first report a newly-designed hierarchical α-Fe2O3/ZnFe2O4/Mn2O3 magnetic micromotor as a heterogeneous photocatalyst for the degradation of cationic dye methylene blue (MB) from wastewater. The resulting three-dimensional (3D) flower-like hollow Janus micromotors are fabricated through a green and scalable strategy, in which each component has different functions. ZnFe2O4 microspheres serve as a magnetic scaffold for the nucleation and growth of α-Fe2O3 nanosheets and for the recycling of the micromachine. α-Fe2O3 nanosheets have shown great potential as an ideal semiconductor material for the photocatalytic decontamination of pollutants. Mn2O3 nanoparticles are mainly utilized as a catalyst to produce O2 bubbles to propel the autonomic movement of the micromotors in the presence of H2O2 fuel and also as a Fenton-like catalyst to decompose H2O2 to generate reactive oxygen species. Furthermore, the resultant micromotors exhibited linear-like motion form with an average speed of 189.1 µm s-1 in 5 wt% H2O2 solution. Moreover, the self-driven micromotors exhibited a superior catalytic degradation property toward MB, which was attributed to the synergistic effect of heterogeneous photocatalyst and the boosted micro-mixing and mass transfer caused by the vigorous motion of the micro-actuator. The possible degradation intermediates and passways of MB by α-Fe2O3/ZnFe2O4/Mn2O3 micromotor were identified with time of flight mass spectroscopy (TOF-MS). The 3D Janus micromotors have the potential to be used as a high-efficiency and active heterogeneous photocatalyst for the degradation of organic pollutants.

3D hierarchical LDHs-based Janus micro-actuator for detection and degradation of catechol.

Micro/nanomotors that combine the miniaturization and autonomous motion have attracted much research interest for environmental monitoring and water remediation. However, it is still challenging to develop a facile route to produce bifunctional micromotors that can simultaneously detect and remove organic pollutants from water. Herein, we developed a novel Janus micromotor with robust peroxide-like activity for simultaneously colorimetric detection and removal of catechol from water. Such laccase (Lac) functionalized Janus micromotor consisted of calcined MgAl-layered double hydroxides (MgAl-CLDHs) nanosheets and Co3O4-C nanoparticles (Lac-MgAl-CLDHs/Co3O4-C), revealing unique 3D hierarchical microstructure with highly exposed active sites. The obtained Janus micromotors exhibited autonomous motion with a maximum velocity of 171.83 ± 4.07 µm/s in the presence of 7 wt% H2O2 via a chemical propulsion mechanism based on the decomposition of H2O2 by Co3O4-C layer on the hemisphere surface of Janus micromotors. Owing to the combination of autonomous motion and high peroxide-like activity, Lac-MgAl-CLDHs/Co3O4-C Janus micromotors could sensitively detect catechol with the limit of detection of 0.24 µM. In addition, such Janus micromotors also could quickly degrade catechol by •OH generated from a Fenton-like reaction. It is a first step towards using autonomous micromotors for highly selective, sensitive, and facile detection and quick removal of catechol from water.

Storage of Lithium-Ion by Phase Engineered MoO3 Homojunctions.

With high theoretical specific capacity, the low-cost MoO3 is known to be a promising anode for lithium-ion batteries. However, low electronic conductivity and sluggish reaction kinetics have limited its ability for lithium ion storage. To improve this, the phase engineering approach is used to fabricate orthorhombic/monoclinic MoO3 (α/h-MoO3) homojunctions. The α/h-MoO3 is found to have excessive hetero-phase interface. This not only creates more active sites in the MoO3 for Li+ storage, it regulates local coordination environment and electronic structure, thus inducing a built-in electric field for boosting electron/ion transport. In using α/h-MoO3, higher capacity (1094 mAh g-1 at 0.1 A g-1) and rate performance (406 mAh g-1 at 5.0 A g-1) are obtained than when using only the single phase h-MoO3 or α-MoO3. This work provides an option to use α/h-MoO3 hetero-phase homojunction in LIBs.

Regulating Oxygen Configuration in Hierarchically Porous Carbon Nanosheets for High-Rate and Durable Na+ Storage.

Surface oxygen functionalities (particularly C-O configuration) in carbon materials have negative influence on their electrical conductivity and Na+ storage performance. Herein, we propose a concept from surface chemistry to regulate the oxygen configuration in hierarchically porous carbon nanosheets (HPCNS). It is demonstrated that the C-O/C=O ratio in HPCNS reduces from 1.49 to 0.43 and its graphitization degree increases by increasing the carbonization temperature under a reduction atmosphere. Remarkably, such high graphitization degree and low C-O content of the HPCNS-800 are favorable for promoting its electron/ion transfer kinetics, thus endowing it with high-rate (323.6 mAh g-1 at 0.05 A g-1 and 138.5 mAh g-1 at 20.0 A g-1 ) and durable (96 % capacity retention over 5700 cycles at 10.0 A g-1 ) Na+ storage performance. This work permits the optimization of heteroatom configurations in carbon for superior Na+ storage.

Kinetic Analysis of Bio-oil Derived Hierarchically Porous Carbon for Superior Li+/Na+ Storage.

Herein, an efficient biomass utilization is proposed to prepare bio-oil-derived carbon (BODPC) with hierarchical pores and certain H/O/N functionalities for superior Li+/Na+ storage. Kinetic analyses reveal that BODPC has similar behavior in the electrochemical Li+ and Na+ storage processes, in terms of physical adsorption (Stage I), chemical redox reactions with surface functionalities (Stage II), and insertion into the graphitic interlayer (Stage III). Promisingly, BODPC exhibits a high reversible specific capacity (1881.7 mAh g-1 for Li+ and 461.0 mAh g-1 for Na+ at 0.1 A g-1), superior rate capability (674.1 mAh g-1 for Li+ and 125.7 mAh g-1 for Na+ at 5.0 A g-1), and long-term cyclability. More notably, the BODPC with highly capacitive-dominant behavior would hold great promise for the applications of high-power, durable, and safe rechargeable batteries/capacitors.

Operando mechanistic and dynamic studies of N/P co-doped hard carbon nanofibers for efficient sodium storage.

In situ Raman and electrochemical results reveal that Na+ adsorbs on the surface/defective sites of N/P-HCNF and inserts randomly into its turbostratic nanodomains in the dilute state without a staged formation, which can facilitate fast Na+ diffusion kinetics for efficient sodium storage.

Oxygen vacancies boosted the electrochemical kinetics of Nb2O5-x for superior lithium storage.

The introduction of oxygen vacancies (OVs) into Nb2O5 can not only provide more active sites for lithium storage but also change the electronic structure of Nb2O5 to boost electron/ion transport kinetics. Consequently, the defective Nb2O5-x exhibits high lithium storage capacity, superior rate capability, and cycling stability.

A sand composite with surface gel coating containing alkylamine toward the removal and immobilization of complex metal ions from electroplating wastewater.

SiO2 gel was formed on the grain surface of silica sand by hydrolysis and condensation of tetraethyl orthosilicate in water with the addition of 1-butylamine. The resultant product was a composite consisting of sand grains with mesoporous silica coating containing alkylamine inside. This composite exhibited basicity in the wastewater from copper electroplating due to its release of amine. As a result, the strongly acidic wastewater was neutralized and the co-precipitation of complex metal ions occurred. It was shown that up to 12 major metal ions in the wastewater could be simultaneously removed under static condition at room temperature by using the sand composite. The Fe and Cu in the wastewater could be removed completely, while the concentrations of Al, Cd, Ti, V, and Zn in the wastewater were reduced by two to three orders of magnitude. After the removal of multiple metal ions from the electroplating wastewater, the used sand was further applied as a raw material for making a silicate glass. The glass was chemically stable and thus the heavy metal ions from the wastewater were immobilized.

Porous α-Fe2O3 nanoparticles encapsulated within reduced graphene oxide as superior anode for lithium-ion battery.

A facile route for the controllable synthesis of porous α-Fe2O3 supported by three-dimensional reduced graphene oxide (rGO) is presented. The synergistic effect between α-Fe2O3 and rGO can increase the electrolyte infiltration and improve lithium ion diffusion as well. Moreover, the combination of rGO nanosheets can increase the available surface area to provide more active sites and prevent α-Fe2O3 nanoparticles from agglomeration during the cycling process to ensure its long-term cycle performance. Consequently, the α-Fe2O3/rGO nanocomposites exhibit higher reversible specific capacity (1418.2 mAh g-1 at 0.1 A g-1), better rate capability (kept 804.5 mAh g-1 at 5.0 A g-1) and cycling stability than the α-Fe2O3 nanoparticles. Owing to the superior electrochemical performance, the α-Fe2O3/rGO nanocomposites might have a great potential as anode for lithium-ion batteries.

A colorimetric strategy for ascorbic acid sensing based on the peroxidase-like activity of core-shell Fe3O4/CoFe-LDH hybrid.

A novel core-shell Fe3O4/CoFe-LDH (layered double hydroxides) hybrid as a peroxidase mimic for the colorimetric detection of ascorbic acid was first fabricated via a facile two-step route. The resulting Fe3O4/CoFe-LDH hybrid exhibited much higher peroxidase-like catalytic activity for the oxidation of 3,3',5,5'- tetramethylbenzidine (TMB) with H2O2 than the pristine Fe3O4 and CoFe-LDH nanosheets owing to the unique hierarchical architecture containing more exposed active sites and the synergistic effect between Fe3O4 and CoFe-LDH. A sensitively and selectively visual sensor for the determination of ascorbic acid (AA) was successfully constructed based on the reduction effect of AA with enediol group on the formed oxidation of TMB, which exhibited a sensitive response to AA in the range of 0.5 ∼ 10 µM with the detection limit of 0.2 µM. Additionally, the Fe3O4/CoFe-LDH magnetic hybrid could be easily recycled by applying a magnetic field. This work provided a feasible means for the fabrication of magnetic nanomaterials with encouraging prospect in biosensing, environmental monitoring and medical diagnostics.

Sonochemical assisted fabrication of 3D hierarchical porous carbon for high-performance symmetric supercapacitor.

A scalable fabrication of 3D hierarchical porous carbon structure (3D-HPC) has been achieved via a simple sonochemical route at different pyrolysis temperatures. It is worth noting that all the 3D-HPC samples possess oxygen-functional groups after activation by KOH and self-doped by nitrogen, which are beneficial to improving their surface wettability as well as increasing the electro-active surface area between the electrode and the surrounding electrolyte, consequently enhancing their electrochemical performance. Remarkably, the resulting carbon sample pyrolyzed at 850 °C (AC-850) possesses a maximum doping level of 2.75 at% and a high surface area of 1376.19 m2 g-1, which exhibits high electrochemical performance with high capacitance up to 269.19 F g-1 at a current density of 2 A g-1. Moreover remarkably, the AC-850-based symmetric supercapacitor delivers a high energy density of 21.4 Wh kg-1 at a power density of 531.2 W kg-1 with excellent rate performance and superior cycling stability (94.7% retention over 5000 cycles). The present approach is very suitable for large scale production of high-quality porous carbon materials at low cost, which can be used in different aspects, such as energy storage, gas storage, environmental remediation, and so on.

Recovery of nickel ions from wastewater by precipitation approach using silica xerogel.

A facile route was developed to recover nickel ions from a synthetic wastewater. It involved the use of silica xerogel containing amine in the nickel sulphate solution resulting in the formation of a greenish precipitate. It was found that this precipitate was mostly amorphous Ni(OH)2 spherical aggregate composed of nanosheets. The pH level of the solution was monitored, and it was maintained in the range of 10-10.5 due to the steady release of amine from the xerogel into the waste solution. The prepared silica xerogel would provide a stable environment for the chemical precipitation of metal ions in wastewater during the whole precipitation process. The silica xerogel was collected and reused for two more cycles of recovery. The nickel removal efficiencies (99.34˜99.65%) kept unchanged and higher than those reported earlier. The collected precipitate that contained nickel hydroxide with some residual silica could be utilized as glass colorant.

Porous Nb4N5/rGO Nanocomposite for Ultrahigh-Energy-Density Lithium-Ion Hybrid Capacitor.

To meet the increasing demands for high-performance energy storage devices, an advanced lithium-ion hybrid capacitor (LIHC) has been designed and fabricated, which delivers an ultrahigh energy density of 295.1 Wh kg-1 and a power density of 41 250 W kg-1 with superior cycling stability. The high-performance LIHC device is based on the uniform porous Nb4N5/rGO nanocomposite, which has an intimate interface between the firmly contacted Nb4N5 and rGO through the Nb(Nb4N5)-O(rGO)-C(rGO) bonds, significantly improving the electron transport kinetics. Moreover, the introduction of rGO nanosheets can prevent the Nb4N5 nanoparticles from agglomeration, not only resulting in a larger specific surface area to provide more active sites but also accommodating the strain during Li ion insertion/deinsertion. Therefore, the Nb4N5/rGO nanocomposite exhibits a higher reversible specific capacity and better rate and cycling performance than the Nb4N5 nanoparticle. In view of the scalable preparation and superior electrochemical characteristics, the Nb4N5/rGO nanocomposite would have great potential practical applications in the future energy storage devices.

Three-dimensional biogenic C-doped Bi2MoO6/In2O3-ZnO Z-scheme heterojunctions derived from a layered precursor.

Novel 3D biogenic C-doped Bi2MoO6/In2O3-ZnO Z-scheme heterojunctions were synthesized for the first time, using cotton fiber as template. The as-prepared samples showed excellent adsorption and photodegradation performance toward the hazardous antibiotic doxycycline under simulated sunlight irradiation. The morphology, phase composition and in situ carbon doping could be precisely controlled by adjusting processing parameters. The carbon doping in Bi2MoO6/In2O3-ZnO was derived from the cotton template, and the carbon content could be varied in the range 0.9-4.4 wt.% via controlling the heat treatment temperature. The sample with Bi2MoO6/In2O3-ZnO molar ratio of 1:2 and carbon content of 1.1 wt.% exhibited the highest photocatalytic activity toward doxycycline degradation, which was 3.6 and 4.3 times higher than those of pure Bi2MoO6 and ZnInAl-CLDH (calcined layered double hydroxides), respectively. It is believed that the Z-scheme heterojunction with C-doping, the 3D hierarchically micro-meso-macro porous structure, as well as the high adsorption capacity, contributed significantly to the enhanced photocatalytic activity.

Electrostatically Assembled Magnetite Nanoparticles/Graphene Foam as a Binder-Free Anode for Lithium Ion Battery.

Lithium ion batteries (LIBs) are promising candidates for energy storage, with the development of novel anode materials. We report the fabrication of Fe3O4 nanoparticles/graphene foam via electrostatic assembly and directly utilize it as a binder-free anode for LIBs. Owing to the integrated effect of the well-dispersed Fe3O4 nanoparticles and the conductive graphene foam network, such composite exhibited remarkable electrochemical performances. It delivered a large reversible specific capacity reaching to ∼1198 mAh g-1 at a current density of 100 mA g-1, a good rate capacity, and an excellent cyclic stability over 400 cycles. This work demonstrated a facile methodology to design and construct high-performance anode materials for LIBs.

High efficiency photocatalysis for pollutant degradation with MoS2/C3N4 heterostructures.

Porous graphitic carbon nitride was synthesized by controllable thermal polymerization of urea in air. Their textural, electrical, and optical properties were tuned by varying the heating rate. The presence of proper residual oxygen in carbon nitride matrix had enhanced light absorption and inhibited the recombination of charge carriers. Furthermore, the MoS2 nanosheets were coupled into the carbon nitride to form MoS2/C3N4 heterostructures via a facile ultrasonic chemical method. The optimized MoS2/C3N4 heterostructure with 0.05 wt % MoS2 showed a reaction rate constant as high as 0.301 min(-1), which was 3.6 times that of bare carbon nitride. As analyzed by SEM, TEM, UV-vis absorption, PL and photoelectrochemical measurements, intimate contact interface, extended light response range, enhanced separation speed of charge carriers, and high photocurrent density upon MoS2 coupling led to the photocatalytic promotion of the MoS2/C3N4 heterostructures. In this architecture, MoS2 served as electron trapper to extend the lifetime of separated electron-hole pairs. Meanwhile, the accumulated holes on the surface of carbon nitride oxidized the organic dye directly, which was a predominant process in the photodegradation of organic pollutants in water treatment. The promotional mechanisms and principles reported here would have great significance in heterogeneous photocatalysis.

Microwave-assisted fabrication of nanoparticulate TiO(2) microspheres for synergistic photocatalytic removal of Cr(VI) and methyl orange.

High yield production of micro/nanostructured nanoparticulate TiO2 microspheres (NTMs) via a facile microwave-assisted hydrothermal approach was investigated. The rapid and uniform microwave heating could reduce the reaction time to 30 min, an order of magnitude shorter than that of conventional hydrothermal methods. The characterization data confirmed that the resultant NTMs were highly uniform in size, having an average diameter of ∼0.5 µm. The obtained NTMs were found to be constructed by well-crystallized anatase phase nanoparticles ranging from 5 to 10 nm that can be readily controlled by the microwave radiation temperature. Nitrogen sorption isotherm analysis revealed that the obtained NTMs possessed abundant mesoporous structures with a high specific surface area of 124 m(2) g(-1). An in situ self-aggregation formation process under controllable pH in presence of urea was proposed. The results obtained from the application of NTMs for simultaneous photocatalytic decontamination of Cr(VI) and methyl orange (MO) demonstrated a strong synergistic effect that dramatically enhanced both Cr(VI) reduction and MO oxidation removal efficiencies. This work not only enriched the synthesis methods of the micro/nanostructured TiO2, but also provided a new means to improve the photocatalytic efficiency via structural-induced synergistic effect, applicable to the other catalysis systems.

Synthesis of Carbon Materials-TiO2 Hybrid Nanostructures and Their Visible-Light Photo-catalytic Activity.

Activated carbon, graphene, carbon nanotubes and fullerene were incorporated into TiO2 by a solvothermal approach and thermal annealing to produce carbon materials-TiO2 hybrid nanostructures. The carbon materials-TiO2 products were characterised by using SEM, TEM, XRD, Raman spectroscopy, X-ray photo-electron spectroscopy, UV-visible spectroscopy and photo-luminescence. The aim was to study the interactions between the main TiO2 phase and the carbon components, and the relationships between morphology, structure and photo-degradation of the rhodamine B (RhB) dye. An enhanced photo-catalytic degradation of RhB was achieved when using these nanocomposites over that for only using pure TiO2 . The superiority in photo-catalytic activities on the RhB molecules resulted from contributions from the excellent adsorption property, favourable chemical bond formation (TiOC), narrower band gap, smaller particle size and effective charge-carrier separation of the nanocomposites. Compared with the graphene-, carbon nanotube- and fullerene-TiO2 products, activated carbon-TiO2 exhibited weaker interactions between carbon and titania, lower adsorption for RhB and a larger band gap, which led to lower photo-catalytic activity of RhB.

Mesoporous (ZnO)(x)(MgO)(1-x) nanoplates: template-free solvothermal synthesis, optical properties, and their applications in water treatment.

Mesoporous (ZnO)x(MgO)1-x nanoplates were synthesized from a solution containing zinc acetate and magnesium acetate by a template-free solvothermal synthetic method followed by subsequent calcination. After thermal treatment, the plate-like morphology was retained. The formation of pores was due to thermal decomposition of Mg(OH)2 and the release of H2O. The optical properties of the mesoporous (ZnO)x(MgO)1-x nanoplates had been investigated by UV-vis absorption and cathodoluminescence (CL) emission spectroscopy. The UV-vis absorption spectra showed the band gap variation of the as-prepared samples due to the presence of ZnO in the MgO nanostructures. The CL spectra showed strong broad peaks in the visible range from 450 to 700 nm, indicating significant oxygen vacancy defects on the surface of the (ZnO)x(MgO)1-x nanoplates. Moreover, the samples were evaluated as photocatalysts for the UV-induced degradation of methyl orange (MO) in aqueous solution. The (ZnO)x(MgO)1-x nanoplates showed high photocatalytic performance and thus would be promising candidates for polluted water treatment.