Ambient plasma treatment of pectin in aqueous solution to produce a polymer used in packaging.

Water resistance, mechanical behavior and coloration of pectin needs to be tuned for packing utilization. Plasma was used for the treatment of natural products, but there is no research on its effect on the biomass in the presence of ammonia. Though the reaction of pectin (PE) and ammonia was known to impart the ammonolysis and de-esterification, the plasma treatment on PE solution containing ammonia was explored to exemplify the amination and polymerization of the carbohydrate at the ambient condition. The plasma treatment increased the coloration of the solution due to the deprotonation of PE for the production of more sp2 carbon. The film from the amination of PE showed higher hydrophobicity and water stability than the bare PE. The plasma treatment alone decreased the Young's modulus (4.3 MPa versus 22 MPa), while the nitrogen addition enhanced the Young's modulus to 160 MPa and increased the tensile strength (28.7 MPa versus 25.8 MPa of PE). The hydrogen bonds from the amine group induced a glass-to-rubber transition at 77.9 °C by the increasing the crosslinking. This work provided a facile way of aminating and conjugating the biomass in solution to produce polymer with improved mechanical properties using plasma and ammonia incorporation.

In Situ Generation of Pseudorutile Oxide as the Cathode for Direct Electrolysis of CO2.

The conversion of CO2 into CO in high-temperature solid oxide electrolysis cells (SOECs) is an attractive route for the CO2 utilization using the intermittent renewables. The low-cost and highly catalytic cathode is important for the direct electrolysis of pure CO2. In this study, non-perovskite Fe0.5Mg0.25+0.5xTi0.25-0.5xNb1-xMoxO4 oxides (denoted as Mo-x when x is equal to 0, 0.1, and 0.2) are evaluated as the cathode of an SOEC for the direct electrolysis of CO2. Mo6+ doping converted the wolframite Mo-0 into an α-PbO2-type with cation disordering, while further doping to Mo-0.2 showed a wolframite with cation ordering again. The SOEC with Mo-0.2 as the cathode exhibits the best electrochemical performance for the direct electrolysis of CO2 as a large portion of the oxide converted into oxygen-deficient pseudorutile-type oxide with a nominal formula of M5O9 (M = cation). The pseudorutile, a crystallographic shear phase of rutile, can be obtained after 60 h of direct electrolysis in CO2 at a 1.3 V bias rather than a reduction under 5% H2. The SOEC with Mo-0.2 as the cathode imparted a stable current density of 0.45 A cm-2, which could be related to the production of pseudorutile decorated with nanoparticles of MoO2. These results show that molybdenum doping is an effective strategy for developing oxygen-deficient rutile (pseudorutile) for the electrolysis of CO2.

Output characteristics and driving factors of non-point source nitrogen (N) and phosphorus (P) in the Three Gorges reservoir area (TGRA) based on migration process: 1995-2020.

Although physical models at present have made important achievements in the assessment of non-point source pollution (NPSP), the requirement for large volumes of data and their accuracy limit their application. Therefore, constructing a scientific evaluation model of NPS nitrogen (N) and phosphorus (P) output is of great significance for the identification of N and P sources as well as pollution prevention and control in the basin. We considered runoff, leaching and landscape interception conditions, and constructed an input-migration-output (IMO) model based on the classic export coefficient model (ECM), and identified the main driving factors of NPSP using geographical detector (GD) in Three Gorges Reservoir area (TGRA). The results showed that, compared with the traditional export coefficient model, the prediction accuracy of the improved model for total nitrogen (TN) and total phosphorus (TP) increased by 15.46 % and 20.17 % respectively, and the error rates with the measured data were 9.43 % and 10.62 %. It was found that the total input volume of TN in the TGRA had declined from 58.16 × 104 t to 48.37 × 104 t, while the TP input volume increased from 2.76 × 104 t to 4.11 × 104 t, and then decreased to 4.01 × 104 t. In addition Pengxi River, Huangjin River and the northern part of Qi River were high value areas of NPSP input and output, but the range of high value areas of migration factors has narrowed. Pig breeding, rural population and dry land area were the main driving factors of N and P export. The IMO model can effectively improve prediction accuracy, and has significant implications for the prevention and control of NPSP.

Br vacancy engineering in Cs3Bi2Br9 for photocatalytic NO oxidation under visible light.

Photocatalysis using the visible light of the sun is an environmentally friendly method of eliminating the NOx pollutant from the ambient air. Although Cs3Bi2Br9, a semiconductor with a band gap of 2.54 eV, may be a strong absorber of visible light, its photocatalysis towards the abatement of NOx is unknown. In this study, Cs3Bi2-xPbxBr9-x (0 ≤ x ≤ 0.0789) are used for the photocatalytic oxidation of NOx. A significant NO oxidation efficiency (80%) is observed over Cs3Bi2-xPbxBr9-x (x = 0.0443) under visible light, which is attributable to the Br vacancy (VBr) brought about by Pb2+ doping. The presence of VBr increased the ionic selectivity of in the oxidized NO. At higher Pb doping level, two HONOs adsorbed on the VBr, linked, and then reduced by hot electrons to produce N2O22-. The di-azo coupling could passivate the activation of NO on the VBr. This work advances the defect engineering of halide for the photo-driving solid-gas reaction in air.

Pr-Doped SrTi0.5Mn0.5O3-δ as an Electrode Material for a Quasi-Symmetrical Solid Oxide Fuel Cell Using Methane and Propane Fuel.

The use of identical electrodes for both the cathode and the anode in a symmetrical solid oxide fuel cell (SSOFC) can simplify the preparation process and increase the durability of the cell, but it is also demanding on the properties of the electrode including stability, electric conductivity, and electrocatalysis. The doping of variable-valence Mn4+/3+2+ on the B site of stable SrTiO3 is explored in this study as both the cathode and the anode for an SSOFC. Though the limit of Mn doping in SrTiO3 is generally low, the additional Pr3+/4+ donor on the Sr site of SrTi0.5Mn0.5O3 was found to enhance the structure stability, electric conductivity, and electrocatalysis. The cell with Pr0.5Sr0.5Ti0.5Mn0.5O3 electrodes excels under H2, propane, or CH4/H2 fuel, providing the cocatalyst was infiltrated on the anode side. The polarization resistance value of Pr0.5Sr0.5Ti0.5Mn0.5O3 was 0.27 Ω·cm2 as the cathode and 0.33 Ω·cm2 for the SSOFC using H2 fuel. The performance under CH4/H2 fuel can be boosted to above 0.9 W cm-2 if Ni/ceria was loaded onto the anode to enhance the methane reforming. This work contributes to a perovskite anode with high Mn doping in SrTiO3 for application in SSOFC for natural gas with renewable H2 injection.

Spatiotemporal characteristics of air pollution in Chengdu-Chongqing urban agglomeration (CCUA) in Southwest, China: 2015-2021.

Studying the spatiotemporal characteristics of air pollutants in urban agglomerations and their response factors will help to improve the quality of urban living. In combining air quality monitoring data and wavelet analysis from the Chengdu-Chongqing urban agglomeration (CCUA), this study assessed the spatiotemporal distribution characteristics and influential factors of air pollutants on daily, monthly and annual scales. The results showed that the concentration of air pollutants in the CCUA has decreased year by year, and air quality has improved. Except for O3, pollutants in autumn and winter were higher than those in summer. The spatial distribution of air pollutants was obvious distributed in Chengdu, Chongqing, Zigong and Dazhou. Pollution incidents were mainly concentrated in winter. The 6 air pollutants and air quality index (AQI) have dominant periods on multiple time scales. AQI showed positive coherence with PM2.5 and PM10 on multiple time scales, and obvious positive coherence with SO2, CO, NO2 and O3 in the short term scale. AQI was not strongly correlated with the fire point, but exhibited obvious negative coherence in the long term scale. In addition, AQI showed an obvious positive correlation with temperature and sunshine hours in short term, and a clear negative correlation with humidity and rainfall. The research results of this paper will provide a reference for pollution prevention and control in the CCUA.

Crops' response to the emergent air pollutants.

MAIN CONCLUSION: Consequences of air pollutants on physiology, biology, yield and quality in the crops are evident. Crop and soil management can play significant roles in attenuating the impacts of air pollutants. With rapid urbanization and industrialization, air pollution has emerged as a serious threat to quality crop production. Assessing the effect of the elevated level of pollutants on the performance of the crops is crucial. Compared to the soil and water pollutants, the air pollutants spread more rapidly to the extensive area. This paper has reviewed and highlighted the major findings of the previous research works on the morphological, physiological and biochemical changes in some important crops and fruits exposed to the increasing levels of air pollutants. The crop, soil and environmental factors governing the effect of air pollutants have been discussed. The majority of the observations suggest that the air pollutants alter the physiology and biochemical in the plants, i.e., while some pollutants are beneficial to the growth and yields and modify physiological and morphological processes, most of them appeared to be detrimental to the crop yields and their quality. A better understanding of the mechanisms of the uptake of air pollutants and crop responses is quite important for devising the measures ‒ at both policy and program levels ‒ to minimize their possible negative impacts on crops. Further research directions in this field have also been presented.

Crystal-facet and microstructure engineering in ZnO for photocatalytic NO oxidation.

Photocatalysis is believed to be an important way of reducing NO pollutant in air and the facet engineering of semiconducting oxides could enhance the efficiency of the photocatalysis. ZnO nanoparticles with different exposed crystalline facets were successfully synthesized using a hydrothermal method and their photocatalytic degradation towards NO was investigated. The crystals from ZnCl2 precursor were hexagonal mesoporous ones with exposed (0002) facet, while those from zinc acetate were in the form of flakes or wheat ears with enhanced exposure of (101(-)1) facet. Calcination in air imparted an enhanced the textural coefficient of the orientated facets as well as the oxygen defects. The nanocrystals with enhanced (0002) facet and lower flat-band energy did better in photoelectrochemical water-oxidation than those with exposed (101(-)1) facet that showed superior photocatalytic activity (approaching 76.7 ± 0.6% under 365 nm photons) for NO oxidation. According to theoretical calculations, (101(-)1) facet with O termination showed much higher affinity to NO molecules than other configurations, and the oxygen vacancy in ZnO played an minor role in the photocatalytic oxidation of NO. A high quantum efficiency approaching 97.5 ± 1.4% under 275 nm photons was obtained for the ZnO crystals from zinc acetate with mixed (0002) and (101(-)1) facets. This research explores the special characteristics of ZnO with different exposed facets and is important for the future design of highly efficient photocatalyst for hazardous material removal.

Enhanced perfluorooctane acid mineralization by electrochemical oxidation using Ti3+ self-doping TiO2 nanotube arrays anode.

Perfluorooctanoic acid (PFOA) is of increasing concern due to its worldwide application and extremely environmental persistence. Herein, we demonstrated the electrochemical degradation of PFOA with high efficiency using the Ti3+ self-doping TiO2 nanotube arrays (Ti3+/TiO2-NTA) anode. The fabricated Ti3+/TiO2-NTA anode exhibited vertically aligned uniform nanotubes structure, and was demonstrated good performance on the electrochemical degradation of PFOA in water. The degradation rate, total organic carbon (TOC) removal rate and defluorination rate of PFOA reached 98.1 %, 93.3 % and 74.8 %, respectively, after electrolysis for 90 min at low current density of 2 mA cm-2. The energy consumption (7.6 Wh L-1) of this electrochemical oxidation system using Ti3+/TiO2-NTA anode for PFOA degradation was about 1 order of magnitude lower than using traditional PbO2 anodes. Cathodic polarization could effectively prolong the electrocatalytic activity of the anode by regenerating Ti3+ sites. PFOA molecular was underwent a rapidly mineralization to CO2 and F-, with only low concentration of short-chain perflfluorocarboxylic acids (PFCAs) intermediates identified. A possible electrochemical degradation mechanism of PFOA was proposed, in which the initial direct electron transfer (DET) on the anode to yield PFOA free radicals (C7F15COO•) and hydroxyl radicals (•OH) oxidation were greatly enhanced. This presented study provides a novel approach for the purification of the recalcitrant PFOA from wastewaters.

Carrier extraction from metallic perovskite oxide nanoparticles.

We observe the extraction of carriers excited between two types of bands in the perovskite oxide, Sr-deficient strontium niobate (Sr0.9NbO3). Sr0.9NbO3 exhibits metallic behaviour and high conductivity, whilst also displaying broad absorption across the ultraviolet, visible, and near-infrared spectral regions, making it an attractive material for solar energy conversion. Furthermore, the optoelectronic properties of strontium niobate can easily be tuned by varying the Sr fraction or through doping. Sr-deficient strontium niobate exhibits a split conduction band, which enables two types of optical transitions: intraband and interband. However, whether such carriers can be extracted from an unusual material as such remains unproven. In this report, we have overcome the immense challenge of photocarrier extraction by fabricating an extremely thin absorber layer of Sr0.9NbO3 nanoparticles. These findings open up great opportunities to harvest a very broad solar spectral absorption range with reduced recombination losses.

Blue-light emitting aminated pectin for detecting Cu2+ ion.

This research studied the chemo-sensing of low-cost aminated pectin (PE) obtained by a facile calcination under ammonia gas at temperature no higher than 175 °C without excessive use of alkaline, acid or solvents. The ammonia gas was found to replace the hydroxyl and methoxyl group, enhancing the crystallinity and solubility of the resultant pectin than those calcined in air or in 5% H2. Though the increase of light absorption could be attributed mainly to the dehydration during calcination which caused the formation of CC double bond or aromatic ring, the N incorporation could be important to the photoluminescence (PL) emission. The PL quenching of the blue fluorescent aminated pectin showed a good linearity with the concentration of Cu2+, Fe3+ and the highest sensitivity toward Cu2+ among the investigated metal ions. In order to further increase the PL quenching toward Cu2+ and decrease the interference of Fe3+, a method involving H2O2 and ultraviolet illumination was developed to catalyze the oxidation of fluorophores on the polymer. This work provides new horizon on the modification and application of pectin in chemosensing.

Controlling the Energy-Level Alignment of Silicon Carbide Nanocrystals by Combining Surface Chemistry with Quantum Confinement.

The knowledge of band edges in nanocrystals (NCs) and quantum-confined systems is important for band alignment in technologically significant applications such as water purification, decomposition of organic compounds, water splitting, and solar cells. While the band energy diagram of bulk silicon carbides (SiCs) has been studied extensively for decades, very little is known about its evolution in SiC NCs. Moreover, the interplay between quantum confinement and surface chemistry gives rise to unusual electronic properties and remains barely understood. Here, we report for the first time the complete band energy diagram of SiC NCs synthesized such that they span the regime from strong to intermediate to weak quantum confinement. The absolute positions of the highest occupied (HOMO) and lowest unoccupied (LUMO) molecular orbitals show clear size dependence. While the HOMO level follows the expected behavior for quantum-confined electronic states, the LUMO energy shifts below the bulk conduction band minimum, which cannot be explained by a simple quantum confinement caused by the size effect. We show that this effect is a result of the interplay between quantum confinement and the formation of surface states due to partial and site-selective oxygen passivation.

Nanostructured Perovskite Solar Cells.

Over the past decade, lead halide perovskites have emerged as one of the leading photovoltaic materials due to their long carrier lifetimes, high absorption coefficients, high tolerance to defects, and facile processing methods. With a bandgap of ~1.6 eV, lead halide perovskite solar cells have achieved power conversion efficiencies in excess of 25%. Despite this, poor material stability along with lead contamination remains a significant barrier to commercialization. Recently, low-dimensional perovskites, where at least one of the structural dimensions is measured on the nanoscale, have demonstrated significantly higher stabilities, and although their power conversion efficiencies are slightly lower, these materials also open up the possibility of quantum-confinement effects such as carrier multiplication. Furthermore, both bulk perovskites and low-dimensional perovskites have been demonstrated to form hybrids with silicon nanocrystals, where numerous device architectures can be exploited to improve efficiency. In this review, we provide an overview of perovskite solar cells, and report the current progress in nanoscale perovskites, such as low-dimensional perovskites, perovskite quantum dots, and perovskite-nanocrystal hybrid solar cells.

Carbon dots derived from algae as H2O2 sensors: the importance of nutrients in biomass.

Carbon dots produced hydrothermally from algae were used directly for H2O2 sensing. The mineral nutrients in biomass were found be important for the composition, crystallinity, dispersion and photoluminescence (PL) quenching of the carbon dots under reactive oxygen species, which catalysed the oxidation of passivating ligands.

Performance and stability gain in zero-dimensional perovskite solar cells after >2 years when hybridized with silicon nanocrystals.

We report highly stable zero-dimensional (CH3NH3)3Bi2I9 photovoltaic cells which demonstrate a 33% increase in performance after 2 years when hybridized with silicon nanocrystals (SiNCs). The natural oxidation of SiNCs is expected to consume radical species and improve the SiNC/(CH3NH3)3Bi2I9 interface and electronic coupling whilst also inhibiting defect-induced degradation.

Probing the structure-property-composition relationship in organic-inorganic tri-halide perovskites.

Here, we have synthesised a range of samples, with the formula (CH3NH3)1-2x(H3NC2H4NH3)xPbI3, with different levels of ethylenediammonium substitution to probe non-stoichiometry at the A-site of the perovskite. A single phase region was identified and is accompanied by a change in photophysical properties. The influence of aliovalent substitution with ethylenediammonium results in a decrease in HOMO level from -5.31 eV for x = 0 to -5.88 eV for x = 0.15.

Enhancement of nitrogen and phosphorus removal in landscape water using polymeric ferric sulfate as well as the synergistic effect of four kinds of natural rocks as promoter.

Eutrophication in lakes and rivers caused by the nitrogen (N) and phosphorus (P) is urgent since the accumulation of N and P can possibly cause the algal blooms and devastation to the water ecological system. The removal of N and P in the landscape water would be an efficient way to reduce the enrichment of nutrition before they reach the large water system. The N and P removal efficiency of PFS as well as the synergistic effect of natural rocks (four types of purple parent rock (J3p, J2s, T1f, and J3s)) as promoter was examined under laboratory conditions. The results indicated that TN and TP removal efficiency of the composite coagulant was significantly better than that of PFS or purple parent rock alone and J3p + PFS (combination of PFS and J3p purple parent rock) showed the best TN and TP removal efficiency. TN and TP removal efficiency of 53.53 and 86.48%, respectively, were achieved with coagulant dosage of 6 g L-1 J3p and 30 mg L-1 PFS, water temperature of 30 °C, and wastewater initial pH of 9. In addition, Fourier transformed infrared (FTIR) spectrophotometer, X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive analysis (EDX), and the water quality index analysis revealed that the treatment of TN and TP by using J3p + PFS was taking advantage of the flocculation function of PFS and the adsorption function of PFS and J3p. In which, the flocculation mechanism was mainly charge neutralization; adsorption mechanism was mainly physical and chemical adsorption.

Zero-dimensional methylammonium iodo bismuthate solar cells and synergistic interactions with silicon nanocrystals.

Organometal trihalide perovskite solar cells have attracted monumental attention in recent years. Today's best devices, based on a three-dimensional perovskite structure of corner-sharing PbI6 octahedra, are unstable, toxic, and display hysteresis in current-voltage measurements. We present zero-dimensional organic-inorganic hybrid solar cells based on methylammonium iodo bismuthate (CH3NH3)3(Bi2I9) (MABI) comprising a Bi2I9 bioctahedra and observe very low hysteresis for scan rates in the broad range of 150 mV s-1 to 1500 mV s-1 without any interfacial layer engineering. We confirm good stability for devices produced and stored in open air without humidity control. The MABI structure can also accommodate silicon nanocrystals, leading to an enhancement in the short-circuit current. Through the material MABI, we demonstrate a promising alternative to the organometal trihalide perovskite class and present a model material for future composite third-generation photovoltaics.

Charge carrier localised in zero-dimensional (CH3NH3)3Bi2I9 clusters.

A metal-organic hybrid perovskite (CH3NH3PbI3) with three-dimensional framework of metal-halide octahedra has been reported as a low-cost, solution-processable absorber for a thin-film solar cell with a power-conversion efficiency over 20%. Low-dimensional layered perovskites with metal halide slabs separated by the insulating organic layers are reported to show higher stability, but the efficiencies of the solar cells are limited by the confinement of excitons. In order to explore the confinement and transport of excitons in zero-dimensional metal-organic hybrid materials, a highly orientated film of (CH3NH3)3Bi2I9 with nanometre-sized core clusters of Bi2I93- surrounded by insulating CH3NH3+ was prepared via solution processing. The (CH3NH3)3Bi2I9 film shows highly anisotropic photoluminescence emission and excitation due to the large proportion of localised excitons coupled with delocalised excitons from intercluster energy transfer. The abrupt increase in photoluminescence quantum yield at excitation energy above twice band gap could indicate a quantum cutting due to the low dimensionality.Understanding the confinement and transport of excitons in low dimensional systems will aid the development of next generation photovoltaics. Via photophysical studies Ni et al. observe 'quantum cutting' in 0D metal-organic hybrid materials based on methylammonium bismuth halide (CH3NH3)3Bi2I9.

Promoting photocatalytic H2 evolution by tuning cation deficiency in La and Cr co-doped SrTiO3.

Cation defects in La and Cr co-doped SrTiO3 have been specifically studied for elucidating correlations between defect concentration, electronic properties, structural properties and photocatalytic activity for H2 production. A moderate cation deficiency can promote the photocatalytic activity by ca. 3 fold, which can be mainly linked to the enhancement of the charge carrier mobility.