Sonochemical degradation of triclosan in water and wastewater

The sonochemical degradation of 5 μg l⁻¹ triclosan, a priority micro-pollutant, in various environmental samples (seawater, urban runoff and influent domestic wastewater) as well as in model solutions (pure and saline water) was investigated. Experiments were conducted with a horn-type sonicator operating at 80 kHz frequency and a nominal applied power of 135 W, while solid-phase microextraction coupled with gas chromatography–electron capture detector (SPME/GC–ECD) was employed to monitor triclosan degradation. The latter followed pseudo-first order kinetics with the rate constant being (min⁻¹): 0.2284 for seawater > 0.1051 for 3.5% NaCl in deionised water > 0.0597 for centrifuged urban runoff  0.0523 for untreated urban runoff > 0.0272 for deionised water > 0.0063 for wastewater influent. SPME/GC–ECD and SPME coupled with gas chromatography–mass spectrometry (SPME/GC–MS) were also used to check for the formation of chlorinated and other toxic by-products; at the conditions in question, the presence of such compounds was not confirmed.     

Segregation of tetracarbon units in low-energy tetracarbindane structures: Major differences from their aluminum and gallium analogs

The structures and energetics of the tetracarbindanes C₄In_n−4Me_n (n = 6-14) have been determined by density functional theory. In contrast to their aluminum and gallium analogs, the lowest energy tetracarbindanes typically have all four carbon atoms segregated into a single C₄ unit. Thus, linear C₄ units resembling butadiene are found in the lowest energy C₄In_n−4Me_n structures. In addition, some higher energy tetracarbindane structures have a structural feature not found in any of the corresponding tetracarbalanes and tetracarbagallanes, namely closed trapezoidal C₄ units resembling cyclobutene. Such trapezoidal C₄ units bind to the In_n−4 subcluster with the CC edge bonding to a single indium atoms as an olefin-metal or 3-center 2-electron bond. These differences may be attributed to the larger size of indium atoms (1.42 Å covalent radius) relative to gallium atoms (1.22 Å covalent radius).     

Revisiting the structural and electronic properties of neutral,mono- and di-anionic titanium-doped silicon clusters TiSin0/−/2− (n = 6-16)

The systematic structures search for neutral and Zintl anionic Ti-doped silicon clusters TiSi_n^0/−/2− (n = 6-16) have been carried out using the ABCluster global search technique combined with a double-hybrid density functional method. Based on the predicted energies, adiabatic electron affinities, vertical detachment energies and the consistency between simulated and experimental photoelectron spectroscopy, the true global minimum structures are confirmed. The results show that structural growth pattern of neutral TiSi_n clusters is from linked structures (n = 10-12) to encapsulated configurations (n = 13-16). In contrast, the evolution pattern of Zintl anionic TiSi_n^−/2− clusters begins with the pentagonal bipyramid structure (n = 6). As the Si atoms increase, these Si atoms attach to the surface adjacent to Ti atom, and gradually surround Ti atom. Eventually, the encapsulated structure is formed when n = 12. Moreover, two extra electrons not only perfect the structure of TiSi₁₂ but also improve its chemical and thermodynamic stability.     

Catalyst- and organic solvent-free synthesis of thioacids in water

Thioacids and thioamino acids were synthesized in excellent yields from readily available acyl benzotriazoles and sodium hydrosulfide in water at room temperature. The new methodology features mild reaction conditions, high yields, short reaction times, and does not involve the use of organic solvents or bases. The reaction is eco-friendly, and the workup procedure is simple and does not require chromatographic separation.     

A Polypyridyl‐Based Layered Complex as Dual‐Functional Co‐catalyst for Photo‐Driven Organic Dyes Degradation and Water Splitting

With the ever‐increasing concerns on environmental pollution and energy crisis, it is of great urgency to develop high‐performance photocatalyst to eliminate organic pollutants from wastewater and produce hydrogen via water splitting. Herein, a polypyridyl‐based mixed covalent Cu^I/II complex with triangular {Cu₃} and rhombic {Cu₂Cl₄} subunits alternately extended by mixed SCN^– and Cl^– heterobridges [Cu₄(DNP)(SCN)Cl₄]_n ( 1 ) [DNP = 2,6‐bis(1,8‐naphthyridine‐2‐yl)pyridine] was solvothermally synthesized and employed as a dual‐functional co‐photocatalyst. Resulting from a narrowed band‐gap of 1.07 eV with suitable redox potential and unsaturated Cu^I/II sites, the complex together with H₂O₂ can effectively degrade Rhodamine B and methyl orange up to 87.4 and 88.2 %, respectively. Meanwhile, the complex mixed with H₂PtCl₆ can also accelerate the photocatalytic water splitting in the absence of a photosensitizer with the hydrogen production rate of 27.5 μmol · g^–1 · h^–1. These interesting findings may provide informative hints for the design of the multiple responsive photocatalysts.     

H2O‐Catalyzed Route to Early Lanthanide Tribromide THF and DME Solvates from Oxides

A convenient one‐pot synthetic protocol towards THF and DME solvates of lanthanum and other early lanthanide tribromides was developed using the water‐catalyzed reaction of lanthanide(III) oxides with highly reactive Me₃SiBr in situ formed from commercially available disilane Si₂Me₆ and Br₂. This practical route allows to obtain the target lanthanum tribromide solvates [LaBr₃(thf)₄] ( 1a ) and [LaBr₃(dme)₂]₂ ( 1b ) as well as analogous early lanthanide molecular tribromide solvates [NdBr₃(thf)₄] ( 2a ), [NdBr₃(dme)₂] ( 2b ), [SmBr₃(thf)₂] ( 3a ), and [SmBr₃(dme)₂] ( 3b ) difficult to prepare by other solution‐based procedures. The molecular structure of 1b· 2CH₂Cl₂ was determined by an XRD study.     

Field‐amplified sample injection combined with capillary electrophoresis for the simultaneous determination of five chlorophenols in water samples

A sensitive method of CZE‐ultraviolet (UV) detection based on the on‐line preconcentration strategy of field‐amplified sample injection (FASI) was developed for the simultaneous determination of five kinds of chlorophenols (CPs) namely 4‐chlorophenol (4‐CP), 2‐chlorophenol (2‐CP), 2,4‐dichlorophenol (2,4‐DCP), 2,4,6‐trichlorophenol (2,4,6‐TCP), and 2,6‐dichlorophenol (2,6‐DCP) in water samples. Several parameters affecting CZE and FASI conditions were systematically investigated. Under the optimal conditions, sensitivity enhancement factors for 4‐CP, 2‐CP, 2,4‐DCP, 2,4,6‐TCP, and 2,6‐DCP were 9, 27, 35, 43, and 43 folds, respectively, compared with the direct CZE, and the baseline separation was achieved within 5 min. Then, the developed FASI‐CZE‐UV method was applied to tap and lake water samples for the five CPs determination. The LODs (S/N = 3) were 0.0018–0.019 µg/mL and 0.0089–0.029 µg/mL in tap water and lake water, respectively. The values of LOQs in tap water (0.006–0.0074 µg/mL) were much lower than the maximum permissible concentrations of 2,4,6‐TCP, 2,4‐DCP, and 2‐CP in drinking water stipulated by World Health Organization (WHO) namely 0.3, 0.04, and 0.01 µg/mL, respectively, and thereby the method was suitable to detect the CPs according to WHO guidelines. Furthermore, the method attained high recoveries in the range of 83.0–119.0% at three spiking levels of five CPs in the two types of water samples, with relative standard deviations of 0.37–8.58%. The developed method was proved to be a simple, sensitive, highly automated, and efficient alternative to CPs determination in real water samples.     

TGMin: An efficient global minimum searching program for free and surface-supported clusters

In this article, we introduce an efficient global-minimum structural search program named Tsinghua Global Minimum 2 (TGMin-2), which is the successor of the original TGMin algorithm that was developed in our group in 2011. We have introduced a number of new features and improvements into TGMin-2, including a symmetric structure generation algorithm that can produce good initial seeds for small- and medium-size clusters, the duplicated structure identification algorithm, and the improved structure adaption algorithm that was implemented in the original TGMin code. To predict the simulated photoelectron spectrum (PE spectrum) automatically, we also implemented a standalone program named AutoPES (Auto Photoelectron Spectroscopy), which can be used to simulate PE spectra and compare them with experimental results automatically. We have demonstrated that TGMin-2 and AutoPES are powerful tools for studying free and surface-supported molecules, clusters, and nanoclusters. © 2018 Wiley Periodicals, Inc.     

Hydrogenation of 3d-metal oxide clusters: Effects on the structure and magnetic properties

The geometrical structures and properties of the M₈O₁₂, M₈O₁₂H₈, and M₈O₁₂H₁₂ clusters are explored using density functional theory with the generalized gradient approximation for all 3d-metals M from Sc to Zn. It is found that the geometries and total spin magnetic moments of the clusters depended strongly on the 3d-atom type and the hydrogenation extent. More than the half of all of the 30 clusters had singlet lowest total energy states, which could be described as either nonmagnetic or antiferromagnetic. Hydrogenation increases the total spin magnetic moments of the M₈O₁₂H₁₂ clusters when MMn Ni, which become larger by four Bohr magneton than those of the corresponding unary clusters M₈. Hydrogenation substantially affects such properties as polarizability, forbidden band gaps, and dipole moments. Collective superexchange where the local total spin magnetic moments of two atom squads are coupled antiparallel was observed in antiferromagnetic singlet states of Fe₈O₁₂H₈ and Co₈O₁₂H₈, whereas the lowest total energy states of their neighbors Mn₈O₁₂H₈ and Ni₈O₁₂H₈ are ferrimagnetic and ferromagnetic, respectively. Hydrogenation leads to a decrease in the average binding energy per atom when moving across the 3d-metal atom series. © 2018 Wiley Periodicals, Inc.