A GO/CoMo3S13 chalcogel heterostructure with rich catalytic Mo-S-Co bridge sites for the hydrogen evolution reaction.

Molybdenum disulfide (MoS2)-based materials are extensively studied as promising hydrogen evolution reaction (HER) catalysts. In order to bring out the full potential of chalcogenide chemistry, precise control over the active sulfur sites and enhancement of electronic conductivity need to be achieved. This study develops a highly active HER catalyst with an optimized active site-controlled cobalt molybdenum sulfide (CoMo3S13) chalcogel/graphene oxide aerogel heterostructure. The highly active CoMo3S13 chalcogel catalyst was achieved by the synergetic catalytic sites of [Mo3S13]2- and the Mo-S-Co bridge. The optimized GO/CoMo3S13 chalcogel heterostructure catalyst exhibited high catalytic HER performance with an overvoltage of 130 mV, a current density of 10 mA cm-2, a small Tafel slope of 40.1 mV dec-1, and remarkable stability after 12 h of testing. This study presents a successful example of a synergistic heterostructure exploiting both the appealing electrical functionality of GO and catalytically active [Mo3S13]2- sites.

Physisorption and chemisorption of CO2 on Fe-MIL-88B derivatives: Impact of the functional groups on the electronic properties and adsorption tendency - A theoretical investigation.

The carbon dioxide adsorption process on Fe-MIL-88B-X (X = -H, -OH, -CH3, -CN, -F, -NH2) derivatives was investigated using a combination of the density functional theory approach, taking into account van der Waals (vdW) interactions (DFT-D2) method, conformer search algorithm (CREST) combined with the partially polarizable generic force-field (GFN-FF) and the Climbing Images - Nudge Elastic Band (CI-NEB) method. The results demonstrate that CO2 may be adsorbed on different active sites via chemisorption or physisorption. The contribution of the vdW interactions to chemisorption and physisorption nodes has been determined. The presence of functional groups has been shown to have a substantial effect on the electronic characteristics of the Fe-MIL-88B, such as ionization energy (IP), electron affinity (EA), and the global electrophilic index (GEI), and therefore on CO2 selective adsorption in a certain direction. The correlation between adsorption energy and the parameters IP, EA, and GEI was analyzed through a multivariable linear regression method.

New insight into the mechanism of carbon dioxide activation on copper-based catalysts: A theoretical study.

A combination of Artificial Bee Colony algorithm, eXtended Tight Binding and Density functional theory methods were performed to study the activation process of carbon dioxide (CO2) over copper (Cu4 cluster) based catalytic systems. The findings revealed that the activation of the C-O bond resulted from the electron transfer to σ*, π* - MO of CO2. The more the electrons are transferred to CO2, the more the C-O bond is activated and elongated. The suitability of several metal oxide supports (Fe2O3, Al2O3, MgO, ZnO) is estimated using calculated electronic parameters (global electrophilicity index, vertical ionization potential and vertical electron affinity). Aside from demonstrating the appropriateness of Al2O3 and ZnO, a thorough examination of MgO revealed that, due to the formation of stable carbonate products, this oxide is not really appropriate as a support for copper-based catalysts in CO2 conversion. Our studies have also shown that the electron enrichment of copper atoms plays a key role in the activation of C-O bonds. Alkali metal doping (Li, K, Cs) significantly improves the catalytic efficiency of the Cu4 cluster. Based on the results of electron transfer to the CO2 molecule, the effect of doping alkali metal atoms may be organized in the following order: Cs > K > Li. A new core/shell catalytic system with potassium atoms in the core and copper atoms in the shell has been proposed and has proven to be a promising, efficient catalytic system in the CO2 adsorption and activation.

Whether planar or corrugated graphitic carbon nitride combined with titanium dioxide exhibits better photocatalytic performance?

The density functional theory method was performed to study the electronic structures of planar (pGN), corrugated (cGN) graphitic carbon nitride and their interactions with titanium dioxide cluster (TiO2)7. The transfer of photoinduced electrons was analyzed and electronic excitations were calculated. The obtained results show that cGN is thermodynamically more stable than pGN. cGN chemically interacts with titanium dioxide clusters, while the interaction between pGN and the cluster is assigned to physical nature. The combination of cGN and pGN with (TiO2)7 reduces the energy of the first excited states compared to that of the pure substances. The photocatalytic activities were estimated based on hypotheses on the location of the reduction and oxidation sites, the distance between the photoinduced holes and electrons and the electron density of molecular orbitals involved in the excitation. cGN/TiO2 is predicted to have a higher photocatalytic activity than pGN/TiO2.

Electronic properties of the polypyrrole-dopant anions ClO4- and MoO42-: a density functional theory study.

The conductive properties of polypyrrole chains doped with ClO4- or MoO42- anions and the existence of polarons and bipolarons in these doped polypyrrole chains were investigated by performing computational calculations based on density functional theory (DFT). Doping with these anions was found to decrease the band gap of the polypyrrole. Theoretical calculations revealed that changing the type of oxidative agent applied does not affect the conversion of polypyrrole into a conducting polymer, but the conductivity of the doped polypyrrole does depend on the ratio of oxidant to polypyrrole.

Understanding the adsorptive interactions of arsenate-iron nanoparticles with curved fullerene-like sheets in activated carbon using a quantum mechanics/molecular mechanics computational approach.

The prevalence of global arsenic groundwater contamination has driven widespread research on developing effective treatment systems including adsorption using various sorbents. The uptake of arsenic-based contaminants onto established sorbents such as activated carbon (AC) can be effectively enhanced via immobilization/impregnation of iron-based elements on the porous AC surface. Recent suggestions that AC pores structurally consist of an eclectic mix of curved fullerene-like sheets may affect the arsenic adsorption dynamics within the AC pores and is further complicated by the presence of nano-sized iron-based elements. We have therefore, attempted to shed light on the adsorptive interactions of arsenate-iron nanoparticles with curved fullerene-like sheets by using hybridized quantum mechanics/molecular mechanics (QMMM) calculations and microscopy characterization. It is found that, subsequent to optimization, chemisorption between HAsO42- and the AC carbon sheet (endothermic process) is virtually non-existent - this observation is supported by experimental results. Conversely, the incorporation of iron nanoparticles (FeNPs) into the AC carbon sheet greatly facilitates chemisorption of HAsO42-. Our calculation implies that iron carbide is formed at the junction between the iron and the AC interface and this tightly chemosorbed layer prevents detachment of the FeNPs on the AC surface. Other aspects including electronic structure/properties, carbon arrangement defects and rate of adsorptive interaction, which are determined using the Climbing-Image NEB method, are also discussed.

Theoretical study of carbon dioxide activation by metals (Co, Cu, Ni) supported on activated carbon.

The activation of carbon dioxide (CO2) by catalytic systems comprising a transition metal (Co, Cu,Ni) on an activated carbon (AC) support was investigated using a combination of different theoretical calculation methods: Monte Carlo simulation, DFT and DFT-D, molecular dynamics (MD), and a climbing image nudged elastic band (CI-NEB) method. The results obtained indicate that CO2 is easily adsorbed by AC or MAC (M: Cu, Co, Ni). The results also showed that the process of adsorbing CO2 does not involve a transition state, and that NiAC and CoAC are the most effective of the MAC catalysts at adsorbing CO2. Adsorption on NiAC led to the strongest activation of the C-O bond, while adsorption on CuAC led to the weakest activation. Graphical Abstract Models of CO2 activation on: a)- activated carbon; b)- metal supported activated carbon (M-AC), where M: Co, Cu, Ni.

Trace element concentrations in barramundi (Lates calcarifer) collected along the coast of Vietnam.

We determined concentrations of 23 trace elements (TEs), and stable carbon and nitrogen isotope (δ(13)C and δ(15)N) signatures in barramundi (Lates calcarifer) specimens collected along the coast of Vietnam in the Northern (NCZ), Central (CCZ) and Southern (SCZ) zones in the period 2007-2010. A combination of δ(13)C and δ(15)N signatures provided insight into ontogenetic shifts in barramundi foraging choices. There were clear zone-dependent differences in Mn, As, Sr and Tl concentrations; levels of Tl were highest in the NCZ, As in the CCZ, and Mn and Sr in the SCZ. Lowest concentrations of Rb occurred in the NCZ, Bi was lowest in the CCZ, and Cd and Cs were lowest in the SCZ. δ(15)N values significantly increased with increasing Zn, Se, Sn and Cs. Concentrations of TEs in barramundi from Vietnam were below worldwide guidelines for human consumption.

Theoretical study on the adsorption of phenol on activated carbon using density functional theory.

Density functional theory (DFT) calculations performed at the PBE/DZP level using the DFT-D2 method were utilized to investigate the adsorption of phenol on pristine activated carbon (AC) and on activated carbon functionalized with OH, CHO, or COOH groups. Over the pristine AC, the phenol molecule undergoes weak physical adsorption due to van der Waals interactions between the aromatic part of the phenol and the basal planes of the AC. Among the three functional groups used to functionalize the AC, the carboxylic group was found to interact most strongly with the hydroxyl group of phenol. These results suggest that functionalized AC-COOH has great potential for use in environmental applications as an adsorbent of phenol molecules in aqueous phases.

Study on the role of SBA-15 in the oxidative dehydrogenation of n-butane over vanadia catalyst using density functional theory.

The first step in the mechanism of n-butane oxidative dehydrogenation (ODH) on a V4O10 cluster and V4O10 supported SBA-15 is examined using DFT method. The activation and adsorption energies, oxidation state of V atoms are calculated. Over V4O10 the obtained results indicate that the activation of C-H bond of methylene group can occur at both the terminal and the bridging oxygen atoms with similar barrier (21.5-22.5 kcal mol(-1)). The role of SBA-15 (with and without modification by Al) in n-butane adsorption step has been studied in detail. SBA-15 itself has mild effect on the reaction process, but the substitution of silicon atoms by aluminum atoms results in an active supporter for V2O5 in ODH reaction. In that, the ratio of Si/Al will decide the direction of initial interaction steps between n-butane and catalyst surface and it will result in the selectivity of the reaction products.

Stable isotope-guided analysis of biomagnification profiles of arsenic species in a tropical mangrove ecosystem.

We performed stable carbon and nitrogen-guided analyses of biomagnification profiles of arsenic (As) species, including total As, lipid-soluble As, eight water-soluble As compounds (arsenobetaine (AB), arsenocholine (AC), tetramethylarsonium ion (TETRA), trimethylarsine oxide (TMAO), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), arsenate (As[V]), and arsenite (As[III])), and non-extracted As in a tropical mangrove ecosystem in the Ba Ria Vung Tau, South Vietnam. Arsenobetaine was the predominant As species (65-96% of water-soluble As). Simple linear regression slopes of log-transformed concentrations of total As, As fractions or individual As compounds on stable nitrogen isotopic ratio (δ15N) values are regarded as indices of biomagnification. In this ecosystem, lipid-soluble As (slope, 0.130) and AB (slope, 0.108) were significantly biomagnified through the food web; total As and other water-soluble As compounds were not. To our knowledge, this is one of the first reports on biomagnification profiles of As compounds from a tropical mangrove ecosystem.

Exposure, metabolism, and health effects of arsenic in residents from arsenic-contaminated groundwater areas of Vietnam and Cambodia: a review.

In this review, we summarize the current knowledge on exposure, metabolism, and health effects of arsenic (As) in residents from As-contaminated groundwater areas of Vietnam and Cambodia based on our findings from 2000 and other studies. The health effects of As in humans include severe gastrointestinal disorders, hepatic and renal failure, cardiovascular disturbances, skin pigmentation, hyperkeratosis, and cancers in the lung, bladder, liver, kidney, and skin. Arsenic contamination in groundwater is widely present at Vietnam and Cambodia and the highest As levels are frequently found in groundwater from Cambodia. Sand filter system can reduce As concentration in raw groundwater. The results of hair and urine analyses indicate that residents from these As-contaminated areas are exposed to As. In general, sex, age, body mass index, and As exposure level are significantly associated with As metabolism. Genetic polymorphisms in arsenic (+III) methyltransferase and glutathione-S-transferase isoforms may be influenced As metabolism and accumulation in a Vietnamese population. It is suggested oxidative DNA damage is caused by exposure to As in groundwater from residents in Cambodia. An epidemiologic study on an association of As exposure with human health effects is required in these areas.

Contamination by trace elements at e-waste recycling sites in Bangalore, India.

The recycling and disposal of electronic waste (e-waste) in developing countries is causing an increasing concern due to its effects on the environment and associated human health risks. To understand the contamination status, we measured trace elements (TEs) in soil, air dust, and human hair collected from e-waste recycling sites (a recycling facility and backyard recycling units) and the reference sites in Bangalore and Chennai in India. Concentrations of Cu, Zn, Ag, Cd, In, Sn, Sb, Hg, Pb, and Bi were higher in soil from e-waste recycling sites compared to reference sites. For Cu, Sb, Hg, and Pb in some soils from e-waste sites, the levels exceeded screening values proposed by US Environmental Protection Agency (EPA). Concentrations of Cr, Mn, Co, Cu, In, Sn, Sb, Tl, Pb and Bi in air from the e-waste recycling facility were relatively higher than the levels in Chennai city. High levels of Cu, Mo, Ag, Cd, In, Sb, Tl, and Pb were observed in hair of male workers from e-waste recycling sites. Our results suggest that e-waste recycling and its disposal may lead to the environmental and human contamination by some TEs. To our knowledge, this is the first study on TE contamination at e-waste recycling sites in Bangalore, India.

Regional variations in trace element concentrations in tissues of black tiger shrimp Penaeus monodon (Decapoda: Penaeidae) from South Vietnam.

The goal of the present study was to examine the specific bioaccumulation of 22 trace elements in muscle, exoskeleton and hepatopancreas of black tiger shrimp Penaeus monodon from the Mekong River Delta (MRD), and the South Key Economic Zone (SKEZ), South Vietnam. The general tendency in most trace element concentrations among different tissues were hepatopancreas>exoskeleton>muscle. Comparisons of trace element levels in tissues between the two regions showed that concentrations of Se in muscle and As in all three tissues were higher in SKEZ; whereas in MRD, the higher concentrations of most elements such as Mn, Cu, Cd, Ba, Hg, were observed in tissues. These geographical variations in trace element levels may reflect the differences in human activities between the two regions of South Vietnam. The target hazard quotient (THQ) values for trace elements (<1) indicate that local residents are not exposed to potential health risks via the consumption of shrimp.