Insight into the role of excess hydroxide ions in silicate condensation reactions.

The formation of silicate oligomers in the early stages is key to zeolite synthesis. The pH and the presence of hydroxide ions are important in regulating the reaction rate and the dominant species in solutions. This paper describes the formation of silicate species, from dimers to 4-membered rings, using ab initio molecular dynamics simulations in explicit water molecules with an excess hydroxide ion. The thermodynamic integration method was used to calculate the free energy profile of the condensation reactions. The hydroxide group's role is not only to control the pH of the environment, but also to actively participate in the condensation reaction. The results show that the most favorable reactions are linear-tetramer and 4-membered-ring formation, with overall barriers of 71 kJ mol-1 and 73 kJ mol-1, respectively. The formation of trimeric silicate, with the largest free-energy barrier of 102 kJ mol-1, is the rate-limiting step under these conditions. The excess hydroxide ion aids in the stabilization of the 4-membered-ring structure over the 3-membered-ring structure. Due to a relatively high free-energy barrier, the 4-membered ring is the most difficult of the small silicate structures to dissolve in the backward reaction. This study is consistent with the experimental observation that silicate growth in zeolite synthesis is slower in a very-high-pH environment.

A review on disposal and utilization of phytoremediation plants containing heavy metals.

The reasonable disposal of plant biomass containing heavy metals (HMs) is a difficult problem for the phytoremediation technology. This review summarizes current literature that introduces various disposal and utilization methods (heat treatment, extraction treatment, microbial treatment, compression landfill, and synthesis of nanomaterials) for phytoremediation plants with HMs. The operation process and technical parameters of each disposal method are different. HMs can migrate and transform in different disposal processes. Some disposal and utilization methods can get some by-products. The main purpose of this paper is to provide reference for technical parameters and characteristics of various disposal and utilization methods, so as to choose and use the appropriate method for the treatment of plant biomass containing HMs after phytoremediation.

Geometrical flexibility of platinum nanoclusters: impacts on catalytic decomposition of ethylene glycol.

Catalytic decomposition of ethylene glycol on the Pt13 cluster was studied as a model system for hydrogen production from a lignocellulosic material. Ethylene glycol was chosen as a starting material because of two reasons, it is the smallest oxygenate with a 1 : 1 carbon to oxygen ratio and it contains the C-H, O-H, C-C, and C-O bonds also present in biomass. Density functional theory calculations were employed for predictions of reaction pathways for C-H, O-H, C-C and C-O cleavages, and Brønsted-Evans-Polanyi relationships were established between the final state and the transition state for all mechanisms. The results show that Pt13 catalyzes the cleavage reactions of ethylene glycol more favourably than a Pt surface. The flexibility of Pt13 clusters during the reactions is the key factor in reducing the activation barrier. Overall, the results demonstrate that ethylene glycol and thus biomass can be efficiently converted into hydrogen using platinum nanoclusters as catalysts.

The role of a structure directing agent tetramethylammonium template in the initial steps of silicate oligomerization in aqueous solution.

The understanding of the formation of silicate oligomers in the initial stage of zeolite synthesis is of fundamental scientific and technological importance. The use of different organic structure directing agents is known to be a key factor in the formation of different silicate species, and the final zeolite structure. Tetramethylammonium (TMA(+)), for example, is indispensable for the formation of the LTA zeolite type. However, the role of a TMA(+) template has not yet been elucidated at the molecular level. In this study, ab initio molecular dynamic simulations were combined with thermodynamic integration to arrive at an understanding of the role of TMA(+) in the formation of various silicate species, ranging from dimer to 4-ring. Free energy profiles show that trimer and 3-ring silicate are less favourable than other oligomers such as linear tetramer, branched tetramer and 4-ring structures. TMA(+) exhibits an important role in controlling the predominant species in solution via its coordination with silicate structures during the reaction process. This can explain that formation of D4R·8TMA crystals, as observed in experiment, is controlled by the single 4-ring formation step.

Practical strategies of phosphorus reclamation from sewage sludge after different thermal processing: Insights into phosphorus transformation.

In the context of circular economy and global shortage of phosphorus (P) fertilizer production, it is crucial to effectively recover P during the treatment and disposal of sewage sludge (SS). Although thermal treatment of SS has been widely applied, a targeted P reclamation route is not yet well established. This study has comprehensively investigated and compared the physicochemical properties of SS and solid residues (hydrochar (HC), biochar (BC), sewage sludge ash (SSA), hydrochar ash (HCA), and biochar ash (BCA)) after application of three typical thermal treatment techniques (i.e., hydrothermal carbonization (180‒240 °C), pyrolysis (400‒600 °C) and combustion (850 ℃). P speciation and transformation during thermal processes were extensively explored followed by a rational proposal of effective P reclamation routes. Specifically, thermal processing decomposed organic P and converted non-apatite P to apatite P. Orthophosphate-P was found to be the main species in all samples. Physicochemical properties of the resulting thermal-derived products were significantly affected by the thermal techniques applied, thereby determining their feasibility for different P reclamation purposes. In particular, ash is not recommended for agricultural use due to higher harmful metals content, while acid leaching can be an alternative solution to synthesize non-Fe-containing P products because of the lower co-dissolved Fe content in the leachate. HC and BC offer the option for synthesis of Fe containing products. Eventually, HC and BC demonstrate great potential for agriculture application, however, a comprehensive risk assessment should be conducted before their real-world applications.

Microleakage and characteristics of resin-tooth tissues interface of a self-etch and an etch-and-rinse adhesive systems.

OBJECTIVES: This study was conducted to compare the microleakage and characteristics of the resin-tooth tissue interface between self-etch and etch-and-rinse adhesive systems after 48 hours and 3 months. MATERIALS AND METHODS: 40 extracted premolar teeth were randomly divided into 2 groups: 1-step self-etch adhesive system - Optibond™ All-In-One, and 2-step etch-and-rinse adhesive system - Adper™ Single Bond 2. Both groups were subjected to 500 thermocycles (5°C-55°C) before scanning electron microscope (SEM) analysis or microleakage trial at 48-hour and 3-month time periods. RESULTS: SEM images showed the hybrid layer thickness, diameter, and length of resin tags of the self-etch adhesive (0.42 ± 0.14 µm; 1.49 ± 0.45 µm; 16.35 ± 14.26 µm) were smaller than those of the etch-and-rinse adhesive (4.39 ± 1.52 µm; 3.49 ± 1 µm; 52.81 ± 35.81 µm). In dentin, the microleakage scores of the 2 adhesives were not different in both time periods (48 hours/3 months). However, the microleakage score of etch-and-rinse adhesive increased significantly after 3 months (0.8 ± 0.63 and 1.9 ± 0.88, p < 0.05). CONCLUSIONS: The self-etch adhesive exhibited better long-term sealing ability in dentin when compared to that of the etch-and-rinse adhesive. The greater hybrid layer thickness and dimensions of resin tags did not guarantee reliable, long-lasting sealing in the bonding area.

Elucidating the Role of Tetraethylammonium in the Silicate Condensation Reaction from Ab Initio Molecular Dynamics Simulations.

The understanding of the formation of silicate oligomers in the initial stage of zeolite synthesis is important. The use of organic structure-directing agents (OSDAs) is known to be a key factor in the formation of different silicate species and the final zeolite structure. For example, tetraethylammonium ion (TEA+) is a commonly used organic template for zeolite synthesis. In this study, ab initio molecular dynamics (AIMD) simulation is used to provide an understanding of the role of TEA+ in the formation of various silicate oligomers, ranging from dimer to 4-ring. Calculated free-energy profiles of the reaction pathways show that the formation of a 4-ring structure has the highest energy barrier (97 kJ/mol). The formation of smaller oligomers such as dimer, trimer, and 3-ring has lower activation barriers. The TEA+ ion plays an important role in regulating the predominant species in solution via its coordination with silicate structures during the condensation process. The kinetics and thermodynamics of the oligomerization reaction indicate a more favorable formation of the 3-ring over the 4-ring structure. The results from AIMD simulations are in line with the experimental observation that TEA+ favors the 3-ring and double 3-ring in solution. The results of this study imply that the role of OSDAs is not only important for the host-guest interaction but also crucial for controlling the reactivity of different silicate oligomers during the initial stage of zeolite formation.

Towards sustainable production of biofuels from microalgae.

Renewable and carbon neutral biofuels are necessary for environmental and economic sustainability. The viability of the first generation biofuels production is however questionable because of the conflict with food supply. Microalgal biofuels are a viable alternative. The oil productivity of many microalgae exceeds the best producing oil crops. This paper aims to analyze and promote integration approaches for sustainable microalgal biofuel production to meet the energy and environmental needs of the society. The emphasis is on hydrothermal liquefaction technology for direct conversion of algal biomass to liquid fuel.

Fast hydrothermal liquefaction for production of chemicals and biofuels from wet biomass - The need to develop a plug-flow reactor.

Hydrothermal liquefaction (HTL) is a promising technology for converting wet plant biomass directly to liquid fuels and chemicals. However, some aspects of the technology are not fully understood and still disputed. The reactor material constraints and difficulties coupled with the formation of unwanted products are the main challenges limiting the applications of the technology. In addition, heat and mass transfer limitations in the reaction system result in a lower conversion efficiency and selectivity, of which the later would make it difficult and expensive for products separation, purification, and/or modification of the products. This paper discusses the challenges and current status of possible solutions to the challenges, focusing on the need of developing a special plug-flow reactor for scaling up of the HTL process.

Development of a biomass torrefaction process integrated with oxy-fuel combustion.

Torrefaction of forest residues was studied under conditions relevant to oxy-fuel combustion flue gases. The results showed that the torrefaction in CO2 had a lower solid mass yield (81.36%) than that (83.06%) in N2. Addition of steam into CO2 (CO2/H2O=1/0.7 mole/mole) resulted in a higher mass yield (83.30%) compared to 81.36% in CO2. The energy yield was consistently increased from 79.17% to 84.12% or 88.32% for the torrefaction in N2, CO2, or the CO2 and steam mixture, respectively. On the other hand, additions of O2 into the mixture of steam and CO2 led to reductions in both mass yield (from 83.30% to 82.57% or 76.44%) and energy yield (from 88.32% to 84.65% or 79.16%, for the torrefaction in steam and CO2 without O2, with 5% v/v, or 10% v/v of O2, respectively).

Pyrolysis of microalgae residues--A kinetic study.

Pyrolysis of residues from the oil extraction process of two types of microalgae, Chlamydomonas (C. sp. JSC4) and Chlorella sorokiniana (C. Sorokiniana CY1) was studied by means of a thermogravimetric analyzer. Five pseudo-components (hemicellulose, cellulose, lignin, lipid and protein) model with n=1 or n#1 was assumed for a kinetic analysis of the collected pyrolysis data. The model with n#1 resulted in a slightly better fit quality and reasonable kinetic parameters. The calculated activation energy of hemicellulose, cellulose, lignin, lipid, protein was 115.12-117.12 kJ/mol, 181.67-198.30 kJ/mol, 61.74-62.75 kJ/mol, 104.93-114.14 kJ/mol and 90.75-99.31 kJ/mol, respectively, for C. sp. JSC4; and 113.12-117.12 kJ/mol, 218.73-28.79 kJ/mol, 64.77-66.39 kJ/mol, 131.97-143.63 kJ/mol and 108.03-118.13 kJ/mol, respectively, for C. Sorokiniana CY1.