High-Temperature Phase Transition with Switchable Dielectric Behavior and Significant Photoluminescence Changes in a Zero-Dimensional Hybrid SbBr6 Perovskite.

In the past decade, metal halide materials have been favored by many researchers because of their excellent physical and chemical properties under thermal, electrical, and light stimuli, such as ferroelectricity, dielectric, nonlinearity, fluorescence, and semiconductors, greatly promoting their application in optoelectronic devices. In this study, we successfully constructed an unleaded organic-inorganic hybrid perovskite crystal: [Cl-C6H4-(CH2)2NH3]3SbBr6 (1), which underwent a high-temperature reversible phase transition near Tp = 368 K. The phase transition behavior of 1 was characterized by differential scanning calorimetry, accompanied by a thermal hysteresis of 6 K. In addition, variable-temperature Raman spectroscopy analysis and PXRD further verified the sensitivity of 1 to temperature and the phase transition from low symmetry to high symmetry. Temperature-dependent dielectric testing shows that 1 can be a sensitive switching dielectric constant switching material. Remarkably, 1 exhibits strong photoluminescence emission with a wavelength of 478 nm and a narrow band gap of 2.7 eV in semiconductors. As the temperature increases and decreases, fluorescence undergoes significant changes, especially near Tc, which further confirms the reversible phase transition of 1. All of these findings provide new avenues for designing and assembling new phase change materials with high Tp and photoluminescence properties.

Sustainable conjunctive water management model for alleviating water shortage.

Water shortage poses a great challenge to the health of population and environment and impedes socio-economic development. Therefore, a comprehensive model is necessary to promote the adaptation of the whole socio-economic system to limited water resources. To achieve it, a sustainable conjunctive water management model (SCWM) was developed. In SCWM, direct (physical) and indirect (virtual or embodied) water consumptions of multiple water resources in future scenarios are projected, and the sustainable performances of various water-saving scenarios are quantified from the perspectives of water resources, economy, and ecosystem under water capping policy. A case study of Shaanxi, a typical water shortage province in central-eastern China, is conducted aimed at conquering the irrational use of surface- and ground-water subjected to the constraint of future total water use quota. Key findings contain optimal possibility of adapting water shortage via saving water through increasing industrial water efficiency to 11.12 m3/10,000 CNY and reducing 40% of agricultural final demand (Summation of direct and indirect water savings of the two scenarios are 41.57 × 108 m3 and 20.27 × 108 m3, respectively.) and nonsynergistic effects of simultaneous decreasing final demand of multiple sectors on water consumption intensity (WCI) of total (all kinds of water) water, surface- and ground-water. To devise effective policies for conjunctive management of surface- and ground-water, positive utility, economic structure and water productivity should be heeded, and proposals emphasize trade-offs between surface water saving and groundwater conservation, water metabolic and socio-economic systems sustainability and negative interaction of multiple sectors on economy and WCI should be framed. The innovation of this study is the development of SCWM, which can provide sustainable solution for future multiple-source water saving management measures thoroughly concerning direct and indirect water and sectorial interactions. The model not only brings insights to Shaanxi's water management but also can be used for other similar arid area.

Adsorption separation of carbon dioxide from flue gas by a molecularly imprinted adsorbent.

CO2 separation by molecularly imprinted adsorbent from coal-fired flue gas after desulfurization system has been studied. The adsorbent was synthesized by molecular imprinted technique, using ethanedioic acid, acrylamide, and ethylene glycol dimethacrylate as the template, functional monomer, and cross-linker, respectively. According to the conditions of coal-fired flue gas, the influencing factors, including adsorption temperature, desorption temperature, gas flow rate, and concentrations of CO2, H2O, O2, SO2, and NO, were studied by fixed bed breakthrough experiments. The experimental conditions were optimized to gain the best adsorption performance and reduce unnecessary energy consumption in future practical use. The optimized adsorption temperature, desorption temperature, concentrations of CO2, and gas flow rate are 60 °C, 80 °C, 13%, and 170 mL/min, respectively, which correspond to conditions of practical flue gases to the most extent. The CO2 adsorption performance was nearly unaffected by H2O, O2, and NO in the flue gas, and was promoted by SO2 within the emission limit stipulated in the Chinese emission standards of air pollutants for a thermal power plant. The maximum CO2 adsorption capacity, 0.57 mmol/g, was obtained under the optimized experimental conditions, and the SO2 concentration was 150 mg/m(3). The influence mechanisms of H2O, O2, SO2, and NO on CO2 adsorption capacity were investigated by infrared spectroscopic analysis.

Synthesis and CO2 adsorption properties of molecularly imprinted adsorbents.

A series of molecularly imprinted adsorbents of CO(2) were developed by molecular self-assembly procedures, using ethanedioic acid, acrylamide, and ethylene glycol dimethacrylate as template, functional monomer, and cross-linker, respectively. Textural properties of these adsorbents were characterized by N(2) adsorption experiment, thermo-gravimetric analysis, and Fourier transform infrared spectroscopy. CO(2) adsorption capacities of adsorbents were investigated by thermo-gravimetric balance under 15% CO(2)/85% Ar atmosphere. Adsorption selectivity of CO(2) was studied by fixed-bed adsorption/desorption experiments. All the adsorbents displayed good thermal stability at 200 °C. Among them, MIP1b, with the higher amine content, exhibited the largest CO(2) capacity, which maintained steady after 50 adsorption-desorption cycles. Although MIP3 showed the highest specific surface, the CO(2) capacity was lower than that of MIP1b. CO(2) adsorption mechanism of molecularly imprinted adsorbents was determined to be physical sorption according to the adsorption enthalpies integrated from the DSC heatflow profiles. The calculated separation factors of CO(2) under 15% CO(2)/85% N(2) atmosphere were above 100 for all adsorbents.

Effect of polybrominated diphenyl ethers on the formation of disinfection byproducts in the water system.

Disinfection byproducts (DBPs) can be formed from many different kinds of carbon- and nitrogen-based organic materials. This study investigated DBP formation in the presence of two types of polybrominated diphenyl ethers (PBDEs), 2,2',4,4'-tetrabromodiphenyl ether (BDE 47) and 2,2',3,3',4,4',5,5',6,6'-decabromodiphenyl ether (BDE 209). The effects of PBDEs on the formation of DBPs upon the chlorination (or chloramination) of Suwannee River humic acid (SRHA) were also evaluated. Results indicated that the chlorination of BDE 47 and BDE 209 resulted in the formation of DBPs, with 1,1,1-trichloro-2-propanone (1,1,1-TCP) being the major DBP type formed. When PBDEs were present in the SRHA solution, a lower amount of CHCl3 was formed, and more 1,1,1-TCP was produced. However, the effects of PBDEs on the formation of DBPs in the real surface water were insignificant because of the complicated water chemistry.

Disinfection byproduct formation and toxicity of graphene oxide in water treatment system.

Graphene oxide (GO) is a structural analog of graphene and contains numerous O-containing functional groups. As rapidly increasing production and usage of GO, it is inevitable to flow into the water and wastewater treatment system and finally oxidized by disinfectants to form DBPs. Meanwhile, as GO is a nano sized carbon material, it may also break the human digestion system when it was absorbed by human body. This study explored the DBP formation when only GO was present. Effects of Br- were also considered during the DBP formation. Both trihalomethanes (THMs) and haloacetic acids (HAAs) were formed during the chlorination and chloramination procedure, but the total concentration of THMs was at least three times higher than that of HAAs. Irradiation can significantly enhance the DBP formation via the formation of radicals. The wrinkled appearance and decomposition of aromatic ring may both be effective on the DBP formation via chlorination or bromination. The findings of this study advance knowledge on the DBP formation of GO in water treatment systems and provide insight on the toxic effects of the transformation products of GO.

Photoreactivity of graphene oxide in aqueous system: Reactive oxygen species formation and bisphenol A degradation.

The phototransformation and environmental implications of graphene oxide (GO) have been widely studied in order to understand its implications upon release into the environment. However, very little is known about the formation of reactive oxygen species (ROS) by GO under solar irradiation. Currently there are no studies on the mechanism of ROS formation by GO or the amount of ROS catalyzed by the nanomaterials in the environment. In this study, we carefully investigated the different types and formation mechanisms of ROS generated by GO in the presence of simulated solar irradiation. The effect of GO's photoactivity on bisphenol A (BPA), a representative organic co-pollutant, was also studied. The conduction band electron (eaq-) of GO led to the formation of different ROS including OH, O2-, and 1O2. Among the three types of ROS investigated, O2- was the most abundant species generated during simulated solar irradiation of GO. BPA was degraded, mainly due to the oxidative potential of the valence band holes produced during solar irradiation of GO. This study advances understanding of the photoactivity of GO and its potential impact on other possible environmental co-pollutants.

Removal of graphene oxide nanomaterials from aqueous media via coagulation: Effects of water chemistry and natural organic matter.

With the increasing use of graphene oxide (GO) nanomaterials, its possible environmental release and human effects have received much attention. As GO may enter drinking or wastewater treatment systems like other carbonaceous nanomaterials, and have potential impact on human and/or environmental health, its removal efficiency during water treatment is important and requires investigation. In this study, the removal efficiency of GO during water treatment procedure via coagulation was evaluated, and the effects of solution chemistry and natural organic matter on the coagulation-based removal of GO nanomaterials were investigated. The results indicate that the removal efficiency of GO with alum coagulation can reach 80% with 20 mg/L alum dosage at neutral pH, and will not change significantly with higher concentration of alum. The coagulation mechanism and efficiency were strongly affected by the Al species in aqueous phase, which are controlled by pH. Co-existing cations (e.g. Na) may have minimal effect on GO removal efficiency, and the presence of humic acid (HA) suppresses coagulation remarkably at alum concentrations below 40 mg/L. The results from this study provide critical information for predicting the removal efficiency of GO nanomaterials during alum coagulation phase of water treatment procedure.

Effect of water chemistry on disinfection by-product formation in the complex surface water system.

The relationship between the disinfection by-products (DBPs) formed with chlorination and chloramination techniques and the water chemistry of Haihe River was compared. Samples were collected at 28 different points within the mainstream and tributaries of the river. The DBPs investigated include trihalomethanes (THMs), haloacetic acids (HAAs), haloacetonitriles (HANs), haloketones (HKs), and trichloronitromethane. THMs formed when the samples were chlorinated mostly exceeded 100 and 600 µg/L in the mainstream and tributaries and in the estuary, respectively. A similar trend was obtained for HAAs whose concentrations exceeded 150 µg/L in almost all samples. The amounts of DBPs formed when the samples were chloraminated were much lower than when chlorination was used. The concentrations and species of THMs and HAAs in samples collected from sites near the estuary were different from those in samples collected from the mainstream, which may be due to high concentrations of Cl- and Br-. Although natural organic matter is the major cause of DBP formation during water disinfection, this study shows that other water chemistry factors such as salt composition and concentrations may also considerably affect the formation of DBPs in natural aquatic systems.