The Proton Dissociation of Bio-Protic Ionic Liquids: [AAE]X Amino Acid Ionic Liquids.

[AAE]X composed of amino acid ester cations is a sort of typically "bio-based" protic ionic liquids (PILs). They possess potential Brønsted acidity due to the active hydrogens on their cations. The Brønsted acidity of [AAE]X PILs in green solvents (water and ethanol) at room temperature was systematically studied. Various frameworks of amino acid ester cations and four anions were investigated in this work from the viewpoint of structure-property relationship. Four different ways were used to study the acidity. Acid dissociation constants (pKa) of [AAE]X determined by the OIM (overlapping indicator method) were from 7.10 to 7.73 in water and from 8.54 to 9.05 in ethanol. The pKa values determined by the PTM (potential titration method) were from 7.12 to 7.82 in water. Their Hammett acidity function (H0) values (0.05 mol·L-1) were about 4.6 in water. In addition, the pKa values obtained by the DFT (proton-transfer reactions) were from 7.11 to 7.83 in water and from 8.54 to 9.34 in ethanol, respectively. The data revealed that the cationic structures of [AAE]X had little effect and the anions had no effect on the acidity of [AAE]X. At the same time, the OIM, PTM, Hammett method and DFT method were reliable for determining the acidic strength of [AAE]X in this study.

Passively Q-switched Tm:CaLu0.1Gd0.9AlO4 laser at 2†µm with hematite nanosheets as the saturable absorber.

We report the first passive Q-switching operation at 1.95 µm utilizing the disordered Tm:CaLu0.1Gd0.9AlO4 (Tm:CLGA) crystal and the hematite (α-Fe2O3) nanosheets as the saturable absorber. The nonlinear saturable absorption properties of the hematite nanosheets were investigated by the conventional Z-scan technology. The modulation depth of 14.3% with the low saturation intensity of 205 kW/cm2 was obtained, indicating that the hematite could be a suitable saturable absorber for the mid-infrared pulse generation. Using the disordered Tm:CLGA crystal as the gain medium, the passive Q-switching operation could be realized with the hematite nanosheets as the saturable absorber, producing the shortest pulse duration of 402 ns with a repetition rate of 76 kHz. The experimental results convinced us that the hematite nanosheets could be of great interest in the optical pulse generation in the mid-infrared region.

Ultrafast laser inscribed waveguide lasers in Tm:CALGO with depressed-index cladding.

Depressed-index buried and surface channel waveguides (type III) are produced in a bulk 3.5 at.% Tm3+:CALGO crystal by femtosecond direct-laser-writing at kHz repetition rate. The waveguides are characterized by confocal microscopy and µ-Raman spectroscopy. Under in-band-pumping at 1679 nm (3H6 → 3F4 transition) by a Raman fiber laser, the buried channel waveguide laser with a circular cladding (diameter: 60 µm) generated a continuous-wave output power of 0.81 W at 1866-1947 nm with a slope efficiency of 71.2% (versus the absorbed pump power) and showed a laser threshold of 200 mW. The waveguide propagation losses were as low as 0.3 ± 0.2 dB/cm. The laser performance under in-band pumping was superior compared pumping at ∼800 nm (3H6 → 3H4 transition), i.e., the convetional pump wavelength. Vibronic laser emission from the WG laser above 2 µm is also achieved. The low-loss behavior, the broadband emission properties and good power scaling capabilities indicate the suitability of Tm3+:CALGO waveguides for mode-locked laser operation at ∼2 µm.

An l-cystine/l-cysteine impregnated nanofiltration membrane with the superior performance of an anchoring heavy metal in wastewater.

Considerable efforts are being made to develop new materials and technologies for the efficient and fast removal of toxic ions in drinking water. In this work, we developed a sulfur-complexed strategy to enhance the removal capability of heavy metal ions using the polyamide nanofiltration membrane by the covalent anchoring of l-cystine and l-cysteine. The sulfur-functionalized polyamide nanofiltration membrane exhibits superior complexation of heavy metal ions and can efficiently remove them from high-concentration wastewater. As a result, the sulfur-functionalized nanofiltration membrane not only showed excellent desalination performance but also achieved a record removal rate of heavy metal ions (99.99%), which can effectively reduce Hg(ii) concentration from 10 ppm to an extremely low level of 0.18 ppb, well below the acceptable limits in drinking water (2 ppb). Moreover, the sulfur-functionalized nanofiltration membrane showed an exciting long-term stability and can be easily regenerated without significant loss of Hg(ii) removal efficiency even after six cycles. Such outstanding performances were attributed to the synthetic effect of Hg-S coordinative interaction, electrostatic repulsion, and the sieving action of nanopores. These results highlight the tremendous potential of thiol/disulfide-functionalized NF active layer as an appealing platform for removing heavy metal ions from polluted water with high performance in environmental remediation.

GaAs Q-switched Nd:CNGG lasers: operating at 4F3/2 → 2I11/2 and 4F3/2 → 2I13/2 transitions.

The nonlinear absorption properties of GaAs were measured at 1.06 and 1.34 µm by the open aperture Z-scan technique in this paper. Based on a neodymium doped calcium niobium gallium garnet (Nd:CNGG) disordered crystal grown by the Czochralski method, passively Q-switched lasers with the conventional GaAs wafer as the saturable absorber were demonstrated, operating on the transitions of 4F3/2 → 2I11/2 and 4F3/2 → 2I13/2. For the 4F3/2 → 2I11/2 transition, the laser operated at 1063 nm with a pulse duration of 546 ns and a repetition rate of 98.5 kHz. While for the 4F3/2 → 2I13/2 transition operating at 1340 nm, the minimum pulse width was 499.6 ns with the pulse repetition rate of 110.7 kHz.

"Mixed" Tm:Ca(Gd,Lu)AlO4 - a novel crystal for tunable and mode-locked 2 µm lasers.

We report on the crystal growth, spectroscopy characterization and first laser operation of a new tetragonal disordered "mixed" calcium aluminate crystal, Tm:Ca(Gd,Lu)AlO4. The introduction of Lu3+ leads to an additional inhomogeneous broadening of Tm3+ absorption and emission spectra compared to the well-known Tm:CaGdAlO4. The maximum stimulated-emission cross-section for the 3F4 → 3H6 Tm3+ transition is 0.91 × 10-20 cm2 at 1813 nm for σ-polarization, and the emission bandwidth is more than 200 nm. A continuous-wave diode-pumped Tm:Ca(Gd,Lu)AlO4 laser generates 1.82 W at 1945 nm with a slope efficiency of 29%. Under Ti:Sapphire laser pumping, a continuous tuning of the laser wavelength from 1836 to 2083 nm (tuning range: 247 nm) is demonstrated. The Tm:Ca(Gd,Lu)AlO4 crystal is promising for tunable/femtosecond lasers at ~2 µm.

67-fs pulse generation from a mode-locked Tm,Ho:CLNGG laser at 2083 nm.

We report on a mode-locked Tm,Ho:CLNGG laser emitting in the 2 µm spectral range using single-walled carbon nanotubes (SWCNTs) as a saturable absorber (SA). Pulses with duration of 98 fs are generated at 99.28 MHz repetition rate with an average output power of 123 mW, yielding a pulse energy of 1.24 nJ. Using a 0.5% output coupling, pulses as short as 67 fs, i.e., 10 optical cycles, are produced after extracavity compression with a 3-mm-thick ZnS plate.

Sub-80 fs mode-locked Tm,Ho-codoped disordered garnet crystal oscillator operating at 2081 nm.

We demonstrate a mode-locked (ML) femtosecond laser based on the disordered garnet crystal Tm,Ho:CNGG. Employing a single-walled carbon nanotube saturable absorber, pulses as short as 83 and 76 fs at 2081 nm are achieved without and with external compression, respectively. The latter represents, to the best of our knowledge, the shortest pulse duration obtained from any Ho-doped or Tm,Ho-codoped laser. The average power amounts to 67 mW at a repetition rate of 102 MHz. By analyzing the soliton ML regime, the nonlinear refractive index of Tm,Ho:CNGG is estimated to be ∼1.1×10-19 m2/W.

Generation of sub-50fs soliton pulses from a mode-locked Yb,Na:CNGG disordered crystal laser.

We experimentally demonstrated a diode-pumped sub-50 fs Yb,Na:CNGG disordered crystal laser. Pumped by a 980 nm distributed Bragg-reflector tapered diode laser and passively mode-locked with a semiconductor saturable absorber mirror (SESAM), soliton pulses as short as 62 fs and 45 fs were obtained without and with external compression, respectively. The ultrashort pulses had a repetition rate of ~104 MHz at the central wavelength of 1061 nm. To the best of our knowledge, this is the first demonstration of sub-50 fs pulses from the Yb3+-doped CNGG type disordered crystal lasers.

Sub-80 femtosecond pulses generation from a diode-pumped mode-locked Nd:Ca3La2(BO3)4 disordered crystal laser.

We experimentally demonstrated a diode-pumped sub-80 fs Nd:Ca3La2(BO3)4 disordered crystal laser. Pumping by an 808 nm fiber coupled laser diode, stable continuous-wave mode-locked pulses as short as 79 fs were achieved with a semiconductor saturable absorber mirror (SESAM). The ultrashort pulses had a repetition rate of ∼98.9 MHz at the central wavelength of about 1068 nm. To the best of our knowledge, this is the first demonstration of sub-100 fs pulses and the shortest mode-locked pulses generated from the Nd3+-doped crystal lasers.

Hierarchical porous carbon aerogel derived from bagasse for high performance supercapacitor electrode.

Renewable, cost-effective and eco-friendly electrode materials have attracted much attention in the energy conversion and storage fields. Bagasse, the waste product from sugarcane that mainly contains cellulose derivatives, can be a promising candidate to manufacture supercapacitor electrode materials. This study demonstrates the fabrication and characterization of highly porous carbon aerogels by using bagasse as a raw material. Macro and mesoporous carbon was first prepared by carbonizing the freeze-dried bagasse aerogel; consequently, microporous structure was created on the walls of the mesoporous carbon by chemical activation. Interestingly, it was observed that the specific surface area, the pore size and distribution of the hierarchical porous carbon were affected by the activation temperature. In order to evaluate the ability of the hierarchical porous carbon towards the supercapacitor electrode performance, solid state symmetric supercapacitors were assembled, and a comparable high specific capacitance of 142.1 F g(-1) at a discharge current density of 0.5 A g(-1) was demonstrated. The fabricated solid state supercapacitor displayed excellent capacitance retention of 93.9% over 5000 cycles. The high energy storage ability of the hierarchical porous carbon was attributed to the specially designed pore structures, i.e., co-existence of the micropores and mesopores. This research has demonstrated that utilization of sustainable biopolymers as the raw materials for high performance supercapacitor electrode materials is an effective way to fabricate low-cost energy storage devices.

Enhanced photocatalytic performances of CeO2/TiO2 nanobelt heterostructures.

CeO2 /TiO2 nanobelt heterostructures are synthesized via a cost-effective hydrothermal method. The as-prepared nanocomposites consist of CeO2 nanoparticles assembled on the rough surface of TiO2 nanobelts. In comparison with P25 TiO2 colloids, surface-coarsened TiO2 nanobelts, and CeO2 nanoparticles, the CeO2 /TiO2 nanobelt heterostructures exhibit a markedly enhanced photocatalytic activity in the degradation of organic pollutants such as methyl orange (MO) under either UV or visible light irradiation. The enhanced photocatalytic performance is attributed to a novel capture-photodegradation-release mechanism. During the photocatalytic process, MO molecules are captured by CeO2 nanoparticles, degraded by photogenerated free radicals, and then released to the solution. With its high degradation efficiency, broad active light wavelength, and good stability, the CeO2 /TiO2 nanobelt heterostructures represent a new effective photocatalyst that is low-cost, recyclable, and will have wide application in photodegradation of various organic pollutants. The new capture-photodegradation-release mechanism for improved photocatalysis properties is of importance in the rational design and synthesis of new photocatalysts.

Growth, thermal properties and laser operation of Nd:Ca3La2(BO3)4: a new disordered laser crystal.

A novel disordered laser crystal Nd:Ca(3)La(2)(BO(3))(4) is characterized including its crystal growth, structure, thermal properties, inhomogeneously broadened spectra, and laser performance, which result that this crystal should be a promising gain material for the high-power ultrashort pulsed neodymium laser. The complete set of anisotropic thermal properties were systematically studied for the first time. It has been found that thermal contraction happens in the c direction and all the thermal conductivities increase with temperature, indicating a glass-like behavior. Polarized absorption and fluorescence spectra of Nd:Ca(3)La(2)(BO(3))(4) crystal were measured at 298.15 K and 77.3 K, respectively. The results show that both the absorption and the emission spectra of Nd(3+) have been inhomogeneously broadened, and thus it is very promising to be used in laser systems to produce femtosecond pulses. CW laser operations at 1.06 µm along the three crystallographic directions has been demonstrated for the first time. A maximum power of 1.08 W with an optical conversion efficiency of 10.6% and slope efficiency of 12.4% was achieved in the a-cut sample.

Host-guest energetic nanocomposites based on self-assembly of multi-nitro organic molecules in nanochannels of mesoporous materials.

Host-guest energetic nanocomposites have been synthesized by self-assembly of the high energy density compound HNIW in nanometer-scale channels of an ordered mesoporous material SBA-15. The complete impregnation of HNIW can be achieved in acetone solvent at ambient temperature, and the maximum amount was around 70 wt%. Structural characterizations were systematically provided by XRD, TEM, N(2) adsorption, TG, (13)C solid-state NMR and FT-IR. The tendency of multi-nitro organic molecules to self-assemble when the solvent evaporated has been described. Hydrogen bond interactions were considered as the main driving force, so the choices of matched host matrix and guest organic compounds were pivotal for implementing this process. The thermal properties of nanocomposites were measured by DSC analysis. Compared with pure HNIW and a physical mixture, the decomposition peak temperature of the confined crystals decreased about 11 °C, while the total amount of heat released slightly increased. This strategy can also be expanded to other similar host-guest systems.

One-step hydrothermal synthesis of ordered mesostructured carbonaceous monoliths with hierarchical porosities.

Hierarchical carbonaceous monoliths with ordered 2-D hexagonal mesostructures have been successfully synthesized by using phenolic resols as precursors and mixed triblock copolymers as templates via a one-step hydrothermal approach.

Highly ordered mesoporous carbonaceous frameworks from a template of a mixed amphiphilic triblock-copolymer system of PEO-PPO-PEO and reverse PPO-PEO-PPO.

A series of highly ordered mesoporous carbonaceous frameworks with diverse symmetries have been successfully synthesized by using phenolic resols as a carbon precursor and mixed amphiphilic surfactants of poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO) and reverse PPO-PEO-PPO as templates by the strategy of evaporation-induced organic-organic self-assembly (EISA). The transformation of the ordered mesostructures from face-centered (Fd3m) to body-centered cubic (Im3m), then 2D hexagonal (P6mm), and eventually to cubic bicontinuous (Ia3d) symmetry has been achieved by simply adjusting the ratio of triblock copolymers to resol precursor and the relative content of PEO-PPO-PEO copolymer F127, as confirmed by small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and nitrogen-sorption measurements. The blends of block copolymers can interact with resol precursors and tend to self-assemble into cross-linking micellar structures during the solvent-evaporation process, which provides a suitable template for the construction of mesostructures. The assembly force comes from the hydrogen-bonding interactions between organic mixed micelles and the resol-precursor matrix. The BET surface area for the mesoporous carbonaceous samples calcined at 600 degrees C under nitrogen atmosphere is around 600 m2 g(-1), and the pore size can be adjusted from 2.8 to 5.4 nm. An understanding of the organic-organic self-assembly behavior in the mixed amphiphilic surfactant system would pave the way for the synthesis of mesoporous materials with controllable structures.

Study on reactions of 2-(dinitromethylene)-4,5-imidazolidinedione.

Some new reactions of 2-(dinitromethylene)-4,5-imidazolidinedione (1) with water, alcohols, carboxylic acids, and alkalis were discovered. By reaction of 1 with carboxylic acids, large particle size 1,1-diamino-2,2-dinitroethylene (2) was prepared. By reaction of 1 with methanol, the methanol adduct (4) was synthesized and characterized. By reaction of 1 with water, the synthetic pathway of 2-methylimidazole to 2 could be achieved in a continuous process. By reaction of 1 with KOH, 2 and potassium dinitromethane (6) could be formed at different temperature, respectively. Compounds 1 and 4 decomposed into parabanic acid (5), losing nitrogen oxides and carbon oxides. Some explosive properties of 1 were studied. The mechanisms of synthesis of 1, 2, and 5 are discussed.