Fast and efficient As(III) removal from water by bifunctional nZVI@NBC.

As a notable toxic substance, metalloid arsenic (As) widely exists in water body and drinking As-contaminated water for an extended period of time can result in serious health concerns. Here, the performance of nanoscale zero-valent iron (nZVI) modified N-doped biochar (NBC) composites (nZVI@NBC) activated peroxydisulfate (PDS) for As(III) removal was investigated. The removal efficiencies of As(III) with initial concentration ranging from 50 to 1000 µg/L were above 99% (the residual total arsenic below 10 µg/L, satisfying the contaminant limit for arsenic in drinking water) within 10 min by nZVI@NBC (0.2 g/L)/PDS (100 µM). As(III) removal efficiency influenced by reaction time, PDS dosage, initial concentration, pH, co-existing ions, and natural organic matter in nZVI@NBC/PDS system were investigated. The nZVI@NBC composite is magnetic and could be conveniently collected from aqueous solutions. In practical applications, nZVI@NBC/PDS has more than 99% As(III) removal efficiency in various water bodies (such as deionized water, piped water, river water, and lake water) under optimized operation parameters. Radical quenching and EPR analysis revealed that SO4·- and ·OH play important roles in nZVI@NBC/PDS system, and the possible reaction mechanism was further proposed. These results suggest that nZVI@NBC activated peroxydisulfate may be an efficient and fast approach for the removal of water contaminated with As(III).

Urbanization and residents' health: from the perspective of environmental pollution.

The development of urbanization has important implications for the environment and the human health. However, it is still lacking a comprehensive analysis between urbanization, environmental pollution, and residents' health based on a unified research system. In this study, we assessed the integrated level of urbanization by the entropy method based on the representative indicators. It has been found that there is a significant progress in the urbanization level in the provinces from 2005 to 2020. The impact of urbanization development on environmental pollution was analyzed using the system GMM (Generalized Method of Moments), and the results show an inverted U-shaped relationship between urbanization and environmental pollution. Fixed effect regression model analysis infers that urbanization has a dual impact on population health. Urbanization promotes residents' health by improving medical conditions, but the environmental pollution caused by urbanization is harmful to residents' health. This paper integrated urbanization, environmental pollution, and residents' health into a research system to analyze the impact of urbanization on environmental pollution and residents' health. Some policy recommendations have been proposed based on the research results for promoting high-quality development of urbanization, reducing environmental pollution, and improving residents' health.

Hydrodynamic cavitation-enhanced photocatalytic activity of P-doped TiO2 for degradation of ciprofloxacin: Synergetic effect and mechanism.

Hybrid methods with an enhanced oxidation capacity have been proposed for the removal of organic contaminants based on combining hydrodynamic cavitation (HC) with advanced oxidation processes (AOPs). In this study, we utilize the synergetic effect between photocatalytic processes and HC to strengthen ciprofloxacin (CIP) degradation by P-doped TiO2 catalysts. In comparison to a degradation ratio of 20.37 % in HC and 55.7 % in P-TiO2-based photocatalytic processes alone, the CIP degradation ratio reached as high as 90.63 % in HC-assisted photocatalytic processes with the optimal experimental parameters. The mechanic microjets treatment originated from HC make P-TiO2 nano photocatalysts with significantly increased surface area, smaller particle sizes, cleaner surface and improved dispersion, which were found using SEM, TEM, and BET analysis. Possible degradation mechanisms and reaction pathways of CIP during hybrid HC + photocatalytic processes were explored by coupling free radical capture experiments and liquid chromatography-mass spectrometry . This hybrid HC + photocatalytic technique has a potential application in the treatment of antibiotic sewage at the industrial level.

High Efficiency Adsorption Removal of Arsenilic Acid and Arsenate(V) by Iron-Modified Corncob Biochar.

It is crucial that a highly effective adsorbent can be used to simultaneously remove the composite pollution including both inorganic and organic arsenic from wastewater. In this work, the iron modified corncob biochar (MCCB), prepared via the co-precipitation of ferric chloride hexahydrate (FeCl3⋅6H2O) with sodium hydroxide (NaOH) on corncob biochar, was studied for the high efficiency removal of arsenilic acid (ASA) and arsenate [As(V)] in wastewater. X-ray diffraction, scanning electron microscopy, and fourier transform infrared spectroscopy were carried out to characterize the MCCB. At pH of 4.0-5.0, initial concentration of 10 mg/L ASA and 1 mg/L As(V), adsorbent dose of 0.4 g/L, the maximum adsorption capacities of ASA and As(V) were 49.20 and 4.89 mg/g, respectively. The adsorption performance of MCCB for ASA and As(V) was fitted well to the pseudo-second-order kinetic model. Results from this study indicate the promise of MCCB as an efficient, low-cost and environmentally friendly adsorbent for composite arsenic pollution.

Evaluating responses of nitrification and denitrification to the co-selective pressure of divalent zinc and tetracycline based on resistance genes changes.

The responses of nitrification and denitrification to the divalent zinc (Zn(II)) and tetracycline (TC) co-selective pressure were evaluated in a sequencing batch reactor (SBR). The removal rates of organics and nitrogen, nitrifying and denitrifying enzymatic activity, and microbial diversity and richness at the Zn(II) and TC co-selective pressure were higher than those at the alone Zn(II) selective pressure, while were lower than those at the individual TC selective pressure. The Zn(II) and TC co-selective pressure induced the TC resistance genes abundance increase and the Zn(II) resistance genes levels decrease, and enhanced bacterial enzymatic modification resistance to TC and bacterial outer membrane resistance to Zn(II). The network analysis showed that the genera Nitrospira and Nitrosomonas of nitrifiers and the genera Ferruginibacter, Dechloromonas, Acidovorax, Rhodobacter, Thauera, Cloacibacterium, Zoogloea and Flavobacterium of denitrifiers were the potential hosts of antibiotics resistance genes (ARGs) and/or heavy metals resistance genes (HMRGs).

The synergy effect of rare earth cations on local structure and PL emission in a Ce3+:REPO4 (RE = La, Gd, Lu, Y) system.

REPO4 (RE = La, Gd, Lu, Y) serves as an excellent host lattice due to its stable physicochemical properties and optical inertia. Doping Gd3+(La3+) into LuPO4 can form mixed crystals, increasing the Gd3+(La3+) concentration will induce the phase transition from tetragonal to hexagonal lattices, and the variation of the local structure around the Ce3+ activator will influence its 5d-level position and consequently 5d → 4f radiation transition. This can be attributed to the synergy effect of rare earth ions in REPO4, however, the essential mechanism of such a synergy effect on the local structure and optical property is still poorly understood. Here, we study the synergy effect of rare earth ions on the phase transition and PL emission in a Ce3+:REPO4 system on the basis of the relationship between the composition-dependent local structure around Ce3+ and its PL emission properties from a molecular view. The competition between Lu3+ and Gd3+(La3+) in REPO4 not only influences the relative atomic position but also varies the symmetry of anion groups. Infrared absorption bands indicate that the activation of P-O bonding promotes phase transition and enhances PL emission intensity. The PL emission intensity of Ce3+ is higher in a REPO4 host with a lower site symmetry PO43- group (C2) than that with a higher site symmetry PO43- group (D2d). An increased disorder degree in Ce:GdxLu1-xPO4 mixed crystals leads to the shift of the 5d-level of Ce3+ towards a higher position, resulting in the blue shift of the PL emission wavelength. Moreover, the 5d → 4f emission of Ce3+ may also be modulated towards a larger wavelength via substituting the cation site with larger-radius cations under a particular crystallographic structure in REPO4. Our results highlight the importance of disordered local structures as well as activated anion groups in the enhanced PL emission of Ce3+ activators in a host lattice.

Crystal growth: an anisotropic mass transfer process at the interface.

Crystal growth is a dynamic physicochemical process, which depends on the multi-parameter synergetic control and directly determines the crystal features such as geometry and size. In this study, both thermodynamic and kinetic factors that determine inorganic single crystal growth are integrated by focusing on the mass transfer process at an interface. For the specific growth system, the integrated parameter is then classified to extract the critical control factors in anisotropic growth. The driving force of mass transfer essentially depends on the anisotropic chemical bonding architectures, leading to different concentration gradients along various [uvw] directions. Exquisitely controlling the chemical bonding architecture can therefore be used to regulate the mass transfer process of a compound in a straightforward manner, encompassing the origin of anisotropic growth as well as a variety of geometries in the formation of a multicomponent crystal.

Nucleation-dependant chemical bonding paradigm: the effect of rare earth ions on the nucleation of urea in aqueous solution.

Rare earth ions can be used to construct a variety of novel structures and are favorable to chemical bonding regulation and design. In this study, the chemical bonding paradigm between rare earth ions (Ln3+) and urea molecules in an aqueous solution can be tracked by the evolution of C[double bond, length as m-dash]O, NH2, and CN vibration bands during the urea nucleation stage. Rare earth ions such as La3+, Gd3+, and Lu3+ can manipulate the nucleation time of urea via regulating the nucleation-dependant N-C[double bond, length as m-dash]OH-N hydrogen-bonding between urea molecules. Two types of chemical bondings between Ln3+ and urea molecules have been confirmed, which are Ln3+O[double bond, length as m-dash]C-N and Ln3+NH2-C. Compared with Ln3+NH2-C, Ln3+ prefers to coordinate with the O[double bond, length as m-dash]C bond in urea. With a higher concentration of rare earth ions in the solution, some N-C[double bond, length as m-dash]OH-N hydrogen bonds are broken as a consequence of the incorporation of Ln3+ into the lattice, resulting in the decreased symmetry of local urea molecules in the crystalline nuclei and the consequent Ln3+ concentration-dependent nucleation time of urea. Moreover, using the ionic electronegativity scale of Ln3+, the different effects of La3+, Gd3+, and Lu3+ on urea nucleation can be further distinguished. The present study provides basic data for unrevealing the chemical bonding regulation role of rare earth ions in the formation of hydrogen bonded materials, which may give insight into the design and fabrication of novel materials utilizing rare earth ions to adjust the chemical bonding process.

Luminescence Mechanistic Study of BaLaGa3O7:Nd Using Density Functional Theory Calculations.

BaLaGa3O7:Nd (BLGO:Nd) has been investigated as a laser crystal material for about three decades. In the present work, the luminescence mechanism of BLGO:Nd is clarified by density functional theory (DFT) calculations. Structural optimization was first performed on the constructed supercell to obtain the equilibrium geometry. On the basis of the optimized crystal, the electronic structures of the BLGO host (without and with single defects) and the BLGO:Nd phosphor (without and with neighboring defects) were comprehensively investigated. Three important features are revealed by theoretical analyses. First, single defects in BLGO have little effect on the light emission, although the impurity levels appeared within the band gap. Second, luminescence can be realized by the introduction of Nd ions. Calculations of optical properties demonstrated that parity-forbidden transitions among the 4f levels are partially allowed because the mixing of 4f and 5d configurations occurs at higher empty 4f levels. It is thus clear that the electronic transitions between occupied 4f and empty 4f-5d states are electric-dipole-allowed. Therefore, light emission in BLGO:Nd can be achieved in the electronic transition process of Nd 4f electrons → empty 4f-5d levels → empty 5d levels → Nd 4f levels. The neighboring intrinsic defects play only an auxiliary role in prolonging the decay time. Third, co-doping of Tb in BLGO:Nd is considered to be beneficial to luminescence in theory because of its shallow to deep distribution of impurity orbitals in the band gap. Therefore, BLGO:Nd co-doped with other lanthanide ions will offer guidelines in the search for the best luminescent materials.

Crystallization-Dependent Luminescence Properties of Ce:LuPO4.

The luminescence properties of Ce:LuPO4 depend on both the Ce(3+) center and the host lattice. In this article, we studied the dependence of the luminescence properties of Ce:LuPO4 on both the doping concentration of Ce(3+) and the size and morphology of the LuPO4 matrix at micro- and nanosize regimes. The crystalline behavior of Ce:LuPO4, including its size and shape, was investigated via precursor transformation crystallization. On the basis of this crystallization approach, Ce:LuPO4 hollow nanospheres, nanorods, and regular tetrahedrons were obtained. For micro- and nanostructured Ce:LuPO4, the surface-induced chemical bonding architecture can be effectively varied by controlling the size of the crystalline material and its geometry. Our experimental observations demonstrate that one-dimensional Ce:LuPO4 nanorods doped with 0.1 mol % Ce(3+) possess the best performance among the as-prepared samples. The significant anisotropy of Ce:LuPO4 nanorods can result in a larger specific surface area and enhanced luminescence properties. Moreover, the improved luminescence property of Ce:LuPO4 nanostructures can also be optimized by increasing the preferential anisotropic chemical bonding architecture to regulate the 5d level of Ce(3+). Our work also shows that the photoluminescence emission intensity of Ce:LuPO4 nanorods is increased as the surface area normal to their axial direction increases. From the standpoint of crystallization, the luminescence properties of Ce(3+) in nano- and microsize matrixes can be well-optimized by controlling the crystalline behavior of the host lattice under proper synthesis conditions.

Morphology engineering of high performance binary oxide electrodes.

Advances in materials have preceded almost every major technological leap since the beginning of civilization. On the nanoscale and microscale, mastery over the morphology, size, and structure of a material enables control of its properties and enhancement of its usefulness for a given application, such as energy storage. In this review paper, our aim is to present a review of morphology engineering of high performance oxide electrode materials for electrochemical energy storage. We begin with the chemical bonding theory of single crystal growth to direct the growth of morphology-controllable materials. We then focus on the growth of various morphologies of binary oxides and their electrochemical performances for lithium ion batteries and supercapacitors. The morphology-performance relationships are elaborated by selecting examples in which there is already reasonable understanding for this relationship. Based on these comprehensive analyses, we proposed colloidal supercapacitor systems beyond morphology control on the basis of system- and ion-level design. We conclude this article with personal perspectives on the directions toward which future research in this field might take.

Size-dependent oxygen storage ability of nano-sized ceria.

We thermodynamically studied the size-dependent oxygen storage ability of nano-sized ceria by tracing the surface Ce/O ratio of octahedral particles with different diameters, from the viewpoint of lattice Ce and O in a CeO2 crystallographic structure. The high surface Ce/O ratio with small scale particle size has more excess surface Ce(4+) ions, which allows ceria to have an increasing oxygen storage ability in a crystalline lattice. For the perfect octahedron growth shape of ceria, the nonstoichiometric surfaces can produce excess Ce(4+) ions, Ce(4+) ions can be stabilized by bonding with lattice oxygen, leading to an enhanced oxygen storage ability of ceria. With the increasing particle size, the surface Ce/O ratio approaches to 0.5 owing to the decreased contributions of atoms located at the edges and corners. When the octahedron diameter D = 0.55 nm, the surface Ce/O ratio can reach 0.75. When D = 7.58 nm, the surface Ce/O ratio decreases down to 0.51. If D≥ 14.61 nm, the surface Ce/O ratios are equal to 0.5. The present study deepens the insight of the size-dependent oxygen storage ability of nano-sized ceria, focusing on the size-dependent excess Ce(4+) on nonstoichiometric surfaces of ceria in thermodynamics.