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Flame retardancy in various materials is becoming an increasingly important performance feature. In the textile industries, fire‐related problems have become an important concern over the decade. Herein, the polyvinyl alcohol (PVA) and graphene‐supported material were functionalized with trimethyl phosphate (TMP) for the synthesis of flame retardant (FR) composite material [graphene polymer functionalized trimethyl phosphate (GPTMP)] in the aqueous medium, which improves the stability of cotton fabric against flame. Graphene and PVA fabricated with phosphorus functional groups make the fabric more comfortable against fire and help to avoid further spreading of fire. The composite‐coated fabric sustains for a long time on continuous flame with maintaining its initial shape and size. The GPTMP‐coated fabric shows flame retardancy for up to 540 s on constant flame exposure, whereas control samples such as PVA‐, graphene oxide‐, and TMP‐coated fabrics resist for up to 15, 20, and 14 s, respectively. The limiting oxygen index (LOI) and vertical flammability test (VFT) for synthesized composites were performed to confirm and support the flame retardancy property of GPTMP. The GPTMP shows the 35% LOI value and forms the char length of 2.6 cm during VFT. This work provides a simple and eco‐friendly method to obtain novel GPTMP, which has a high potential as a FR for different fabrics, including cotton. [ABSTRACT FROM AUTHOR]

Organophosphorus compounds (OPCs) are known to be combustion inhibitors (CI), fire suppressants, or flame retardant molecules (FRMs) for polymers and as surrogates (simulants) for the disposal or thermal degradation of chemical war agents (CWAs). Despite a significant number of studies on the mechanism of their action, OPCs’ combustion chemistry is still insufficiently understood. There is a need for further understanding of their auto-ignition and oxidation characteristics at relevant conditions (high pressures and low temperatures). This study reports on new data on the autoignition delays of Trimethyl Phosphate (TMP)-in-air mixtures obtained from experiments performed on a high-pressure shock tube (HPST) at pressures of 5 and 10 bar in the initial temperature range from 1200 to 2200 K. An updated TMP kinetic model deduced from the Glaude et al. model for the thermal degradation of OPCs is also proposed for the estimation of the autoignition delays of the studied mixtures by incorporating new reaction pathways and corresponding rate constants estimation of some reactions involving TMP and some intermediate products of its degradation. The results indicate that the proposed model is in satisfactory agreement with all the investigated mixtures.

The successful implementation of supercapacitors in large‐scale applications necessitates careful consideration of safety aspects, along with factors such as energy density, power density, working voltage, and cycling performance. One effective method for ensuring safety is the utilization of nonflammable trimethyl phosphate (TMP) electrolyte in supercapacitors. However, this approach suffers from the drawback of low power density due to its low ionic conductivity. To overcome this limitation, we propose the addition of co‐solvents, namely propylene carbonate, acetonitrile, and propionitrile (PN), to enhance limited electrochemical properties of TMP‐based electrolytes. We systematically investigate the impact of incorporating TMP into various organic solvents on physical and electrochemical properties. Binary electrolytes show improved ionic conductivity, capacitance, power density, energy density, and working voltage compared to the single TMP‐based electrolyte. Notably, our result highlights that the carbon‐based supercapacitors using TMP‐PN with 70 : 30 volume ratio electrolyte provide the best compromise between ionic conductivity (13.5 mS cm−1), capacitance (24.0 F g−1), energy density (13.2 Wh kg−1), power density (2.3 kW kg−1), working voltage (3.5 V), and safety. By combining the nonflammable properties of TMP with co‐solvents, we can overcome the trade‐off between safety and electrochemical performances, presenting advancement in the development of supercapacitors for energy storage applications. [ABSTRACT FROM AUTHOR]

Rechargeable Zn‐ion batteries (ZIBs), prospective candidates for broad‐scale energy storage, still encounter many challenges such as hydrogen evolution corrosion, Zn dendrite growth, and capacity fading. Therefore, one specific strategy for tuning the internal structure of solid polymer electrolytes (SPEs) via organic additives is proposed to address these urgent bottlenecks simultaneously. With trimethyl phosphate (TMP) addition, the coordination environment of Zn2+ in SPEs is altered and exists as Zn2+(TMP)x(OTf−)y coordinated molecules. Meanwhile, the strong interaction between TMP and Zn enables the preferential growth of Zn(002) planes during electrodeposition, which is proved based on first‐principles calculations, finite element simulations, and multiple in situ characterizations. Such excellent interfacial engineering in situ forms the solid electrolyte interface rich in Zn3(PO4)2 fast ion conductor and guarantees one ultra‐long cycle life for more than 6000 h in a Zn|Zn symmetric cell at 0.1 mA cm−2. Moreover, the universality of TMP‐modified SPEs shows 1000 times stable cycling of VO2(B)|Zn full cells at 1 A g−1 under 0 °C with 95.24% capacity retention, which satisfies potential applications of wide‐ranging energy storage based on solid‐state ZIBs. [ABSTRACT FROM AUTHOR]

High‐concentration "water‐in‐salt" (WIS) electrolytes with the wider electrochemical stability window (ESW) can give rise to safe, non‐flammable, and high‐energy aqueous potassium‐ion energy storage devices, thus highlighting the prospect for applications in grid‐scale energy storage. However, WIS electrolytes usually depend on highly concentrated salts, leading to serious concerns about cost and sustainability. Here, an aqueous low‐concentration‐based potassium‐ion hybrid electrolyte is demonstrated with the regulated core‐shell‐solvation structure by using an aprotic solvent, i.e., trimethyl phosphate, to limit the water activity. This aqueous hybrid electrolyte has a low salt concentration (1.6 mol L−1) of potassium trifluoromethanesulfonate but with an expanded ESW up to 3.4 V and the nonflammable property. Based on this dilute aqueous hybrid electrolyte, electrochemical double‐layer capacitors are capable of working within a large voltage range (0–2.4 V) at a wide range of temperatures from −20 to 60 °C. An aqueous potassium‐ion battery consisting of an organic 3,4,9,10‐perylenetetracarboxylic diimide anode, Prussian blue K1.5Mn0.61Fe0.39[Fe(CN)6]0.77·H2O cathode and this dilute aqueous hybrid electrolyte can operate well at rates between 0.2 and 4.0 C and deliver a high energy density of 66.5 Wh kg−1 as well as a durable cycling stability with a capacity retention of 84.5% after 600 cycles at 0.8 C. [ABSTRACT FROM AUTHOR]

With the increased demands of energy density boosting the electrochemical performance of the rechargeable alkali metal ion batteries, the safe operation of second batteries is attracting much attention and needs to be especially considered during their further development, which is essential in view of the well‐known fire incidents of the lithium‐ion batteries. These dangerous events in the lithium‐ion batteries are as a consequence of the exothermic chemical reactions between the flammable carbonate‐based solutions and the electrode active material under the terrible working conditions. Under this circumstance, some series of flame‐retardant organic liquid‐based solutions have demonstrated the potential towards safer rechargeable batteries with the minimal injurious or the advantageous effect on the batteries' performance. This article reviews the flame‐retardant organic liquid‐based solutions for the rechargeable batteries, providing the reader with an overview of the safe solutions with flame‐retardant additive/co‐solvent involving trimethyl phosphate and its derivative, P‐containing amide/phosphazene, all fluorinated solvent, and ionic liquids, in which the method of adapting concentrated and locally concentrated electrolyte solution are merged in the text content. Moreover, the functionality and purpose of the constituents in some flame‐retardant mixtures are discussed and many flame‐retardant electrolyte solutions are displayed to offer improved cycling and rate performance of different electrodes compared to traditional electrolyte solutions. [ABSTRACT FROM AUTHOR]

Abstract With the increased demands of energy density boosting the electrochemical performance of the rechargeable alkali metal ion batteries, the safe operation of second batteries is attracting much attention and needs to be especially considered during their further development, which is essential in view of the well‐known fire incidents of the lithium‐ion batteries. These dangerous events in the lithium‐ion batteries are as a consequence of the exothermic chemical reactions between the flammable carbonate‐based solutions and the electrode active material under the terrible working conditions. Under this circumstance, some series of flame‐retardant organic liquid‐based solutions have demonstrated the potential towards safer rechargeable batteries with the minimal injurious or the advantageous effect on the batteries’ performance. This article reviews the flame‐retardant organic liquid‐based solutions for the rechargeable batteries, providing the reader with an overview of the safe solutions with flame‐retardant additive/co‐solvent involving trimethyl phosphate and its derivative, P‐containing amide/phosphazene, all fluorinated solvent, and ionic liquids, in which the method of adapting concentrated and locally concentrated electrolyte solution are merged in the text content. Moreover, the functionality and purpose of the constituents in some flame‐retardant mixtures are discussed and many flame‐retardant electrolyte solutions are displayed to offer improved cycling and rate performance of different electrodes compared to traditional electrolyte solutions.

[Display omitted] • Low-cost, safe and eco-friendly acetate-based electrolyte was prepared. • Investigating synergistic effect of salt anion and cosolvent in solvation structure. • Effectively inhibiting Zn corrosion in medium-concentration acetate electrolytes. • Achieving compact dendrite-free Zn deposition. Aqueous zinc metal batteries (ZMBs) have attracted increasing attention in the past decades owing to their potentially low cost and non-flammability. However, the poor Coulombic efficiency (CE) and short lifespan caused by side reactions (e.g., H 2 evolution) and dendrite growth limit the practical applications of ZMBs. Given that H 2 evolution is primarily originated from solvated water, here, a low-cost acetate-based electrolyte constituted by 1 m ZnAc 2 and 5 m KAc in an 80:20 water:trimethyl phosphate (TMP) (v/v) mixture is proposed to minimize solvated water and boost the electrochemical performance of aqueous ZMBs without compromising intrinsic advantages of the aqueous electrolyte. The relatively high abundance of Ac− enables preferential coordination with Zn2+, meanwhile, the addition of TMP not only further replaces water molecules in the inner solvation shell, but also significantly interrupts the H-bond network of water. Improved electrochemical performance are demonstrated in Zn||Zn and Zn||Cu half-cells and Zn||I 2 full cells. [ABSTRACT FROM AUTHOR]

In contrast to organic electrolyte systems, rechargeable aqueous magnesium-ion batteries (RAMIBs) offer unparalleled advantages, particularly in environmental sustainability, safety, cost-effectiveness, and their potential for large-scale energy storage. However, the practical implementation of RAMIBs has been hindered by the limited electrochemical stability of aqueous electrolytes. Although polyethylene glycol (PEG)-based aqueous electrolytes provide a wide electrochemical window, the poor ionic conductivity has restricted their widespread adoption. In this study, we address this challenge by employing trimethyl phosphate (TMP) and PEG400 as the co-solvent of aqueous magnesium-ion electrolytes. This combination significantly enhances the ionic conductivity to 4.44 mS cm−1 and increases the electrochemical stability window of the aqueous electrolyte by mitigating the activity of H 2 O. In addition, we underscore the role of TMP as a potent co-solvent in modulating the solvation structures of Mg2+ ions and modifying the electrochemical behavior of the electrolytes. Leveraging this advancement, in conjunction with a V 2 O 5 cathode and a 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) anode, the resulting RAMIBs demonstrate a remarkable discharge capacity of 227.6 mAh g−1, a large energy density of 157 Wh kg−1 and a high power density of 70 W kg−1. Our findings represent a significant stride toward exploiting the full potential of RAMIBs for future energy storage applications. [Display omitted] • A co-solvent of TMP and PEG400 for aqueous magnesium-ion electrolytes is proposed. • Comprehensive characterizations and DFT explore the mechanisms of the co-solvent. • Different H 2 O contents in the electrolytes affect the performance of V 2 O 5 cathode. • V 2 O 5 ||PTCDI full cells exhibit a large capacity and high energy and power density. [ABSTRACT FROM AUTHOR]

Trimethyl phosphate (TMP) and triethyl phosphate (TEP) are extensively used as flame retardants, but their analytical methods are scarce. In this study, a robust method for both TMP and TEP in environmental water and human urine was developed by coupling of solid phase extraction (SPE) with liquid chromatography-tandem mass spectrometry (LC-MS/MS). For both TMP and TEP, the method showed good recoveries (>81%) and precisions (RSD < 5%), as well as a limit of quantification of 3 ng/L for water and 40 ng/L for urine samples, respectively. Through this method, the occurrence of TMP and TEP in municipal wastewater treatment plant (WWTP) were profiled and the anoxic step was found as the key role for their removal. Furthermore, TEP (110-2470 ng/L) was detected in all urine samples with generally higher concentration than TMP (70–2330 ng/L), which agreed with their occurrence profiles in the influent and effluent of the WWTP. [ABSTRACT FROM AUTHOR]

Phosphate-based electrolyte propels the advanced battery system with high safety. Unfortunately, restricted by poor electrochemical stability, it is difficult to be compatible with advanced lithium metal anodes and Ni-rich cathodes. To alleviate these issues, the study has developed a phosphate-based localized high-concentration electrolyte with a nitrate-driven solvation structure, and the nitrate-derived N-rich inorganic interface shows excellent performance in stabilizing the LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) cathode interface and modulating the lithium deposition morphology on the anode. The results show that the Li|| NCM811 cell has exceptional long-cycle stability of >80% capacity retention after 800 cycles at 4.3 V, 1 C. A more prominent capacity retention rate of 93.3% after 200 cycles can be reached with the high voltage of 4.5 V. While being compatible with the phosphate-based electrolyte with good flame retardancy and the good electrochemical stability of Ni-rich lithium metal battery (LMBs) systems, the present work expands the construction of anion-rich solvation structures, which is expected to promote the development of the high-performance LMBs with safety., (© 2024 Wiley‐VCH GmbH.)

A 3D fiber-network-reinforced PEO-based composite polymer electrolyte for high-temperature lithium metal batteries is prepared with a polyimide framework and trimethyl phosphate plasticizer. It works stably in a wide working temperature range from 40 to 140 °C. Remarkably, the LiFePO 4 /Li cell with the composite electrolyte performs stably for over 300 cycles at 120 °C and it can still survive 80 cycles at 140 °C. [Display omitted] Traditional liquid lithium-ion batteries are not applicable for extreme temperatures, due to the shrinkage of separators and volatility of electrolytes. It is necessary to develop advanced electrolytes with desirable characteristics in terms of thermal stability, electrochemical stability and mechanical properties. Solid-state electrolytes, such as polyethylene oxide (PEO), outperform other types and bring the opportunity to realize the high-temperature lithium-ion batteries. However, the softness of PEO at elevated temperatures leads to battery failure. In this work, a three-dimensional fiber-network-reinforced PEO-based composite polymer electrolyte is prepared. The introduced polyimide (PI) framework and trimethyl phosphate (TMP) plasticizer decrease the crystallinity of PEO and increase the ionic conductivity at 30 °C from 8.79 × 10−6 S cm−1 to 4.70 × 10−5 S cm−1. In addition, the PEO bonds tightly with PI fiber network, improving both the mechanical strength and thermal stability of the prepared electrolyte. With the above strategies, the working temperature range of the PEO-based electrolytes is greatly expanded. The LiFePO 4 /Li cell assembled with the PI-PEO-TMP electrolyte stably performs over 300 cycles at 120 °C. Even at 140 °C, the cell still survives 80 cycles. These excellent performances demonstrate the potential application of the PI-PEO-TMP electrolyte in developing safe and high-temperature lithium batteries. [ABSTRACT FROM AUTHOR]

Aqueous electrolytes are extensively applied in electrochemical nitrogen reduction reaction, while the overwhelming H 2 O always produce much protons, favoring the electron-stealing hydrogen evolution reaction (HER) and thus leaving the current ammonia synthesis much to be desired. Here, we propose an aqueous-aprotic hybrid electrolyte system by introducing trimethyl phosphate (TMP) as a cosolvent to achieve highly selective ammonia synthesis. TMP features higher Gutmann donors than that of H 2 O, preferring to serve as hydrogen bond (HB) acceptor and reshaping the HB network in the electrolyte. Molecular dynamics simulations suggest that, compared with H 2 O-H 2 O HB, the H 2 O-TMP HB exhibits longer lifetime and better stability. The intensified interaction between H 2 O and TMP weakens the interaction between H 2 O and H 2 O, which strengthens the O-H bond of H 2 O and makes it more difficult to be broken, thus greatly inhibiting the dissociation of H 2 O and leading to a suppressed HER activity. Correspondingly, a significantly improved NRR performance with a superior NH 3 yield rate of 82.1 ± 2.7 μg h–1 mg–1 and an optimum Faradaic efficiency of 73.3 ± 2.7% is achieved in the H 2 O-TMP hybrid electrolyte, indicative of order of magnitude enhancement compared with that delivered in the conventional aqueous electrolyte. [Display omitted] • An aqueous-aprotic hybrid electrolyte system is proposed. • TMP featuring higher Gutmann donors serves as hydrogen bond acceptor. • The intensified interaction between H 2 O and TMP inhibits the dissociation of H 2 O. • A significantly improved NRR performance is achieved. [ABSTRACT FROM AUTHOR]

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A mild heteroatom methylation protocol using trimethyl phosphate (TMP)–Ca(OH)2 combination has been developed, which proceeds in DMF, or water, or under neat conditions, at 80 °C or at room temperature. A series of O -, N -, and S -nucleophiles, including phenols, sulfonamides, N -heterocycles, such as 9 H -carbazole, indole derivatives, and 1,8-naphthalimide, and aryl/alkyl thiols, are suitable substrates for this protocol. The high efficiency, operational simplicity, scalability, cost-efficiency, and environmentally friendly nature of this protocol make it an attractive alternative to the conventional base-promoted heteroatom methylation procedures. [ABSTRACT FROM AUTHOR]

A zero-waste, environmentally friendly production process of a plant growth regulator, N,N-di(2-hydroxyethyl)-N,N-dimethylammonium dimethyl phosphate, has been developed which makes it possible to obtain the target product in a yield of up to 99.8%. The developed process has been successfully scaled up from the laboratory scale to pilot and further industrial scales.

Polymer electrolytes hold significant potential in solid-state battery applications due to their high flexibility and scalable manufacturing capabilities. However, it is still necessary to address the safety problems and poor rate performance. Herein, the synergistic effect of trimethyl phosphate (TMP) and lithium difluoro(oxalate)borate (LiDFOB) in the in-situ fabricated poly-butyl acrylate (PBA) quasi-solid electrolyte (QSE) is investigated. The non-flammable additive, TMP, has proven to combine with LiDFOB in the electrolytes as TMP-DFOB− pair. The TMP-DFOB− pair can promote the formation of a B–O, B–F, LiF, and Li 3 P containing solid electrolyte interphase (SEI) on the lithium anode, enabling stable lithium striping-plating processes. Besides, it enhances the formation of a LiF-rich cathode electrolyte interphase (CEI) and promotes intimate contact between the cathode active materials and PBA-QSE, thereby enhancing the rate performance. Therefore, the Li/PBA-LiDFOB-0.1TMP/LiFePO 4 (LFP) cell delivers discharge capacity of 132 mAh g−1 with a remarkable capacity retention of 95.68 % after 500 cycles at 1 C. Even at 4 C, the discharge capacity reaches 92.1 mAh g−1. This non-flammable PBA-LiDFOB-TMP QSE exhibits potential application in high energy density systems. Furthermore, this work provides new insights into strategies for improving rate performance from lithium salts and functional additives aspects. [Display omitted] • PBA-based non-flammable QSE has been fabricated via in-situ polymerization. • TMP and LiDFOB plays synergistic effects in solid state lithium metal batteries. • A B–O, B–F, LiF and Li 3 P containing SEI was fabricated on lithium metal surface. • The PBA-LiDFOB-0.1TMP QSE exhibits a high oxidation potential of 5 V. • The Li/LFP cell delivers the highest discharge capacity of 92.1 mAh g−1 at 4 C. [ABSTRACT FROM AUTHOR]

Hydroxyapatite is intensely studied not only for its bone repair applications but for many other applications, too. In this paper, hydroxyapatite obtained from calcium acetate and dimethyl phosphate was doped with two different metals, one being zirconium and the other one was chosen between M(II) and M(III) metals, under ultrasonication conditions. These types of compounds are not mentioned in the literature. The influence of the doped metals on the thermal behavior of hydroxyapatite precursors was studied using thermal analysis, UATR–FTIR spectrometry, energy dispersive X-ray analysis and ICPOS analysis. [ABSTRACT FROM AUTHOR]

Although trimethyl phosphate (TMP)‐based electrolyte solutions are effective to resist flames in non‐aqueous electrical energy storage devices, they are usually not so compatible with Li‐graphite negative electrodes. Herein, we solve this problem by increasing the concentration of LiPF6 salt in the solution. A benchmark graphite negative electrode (MCMB, mesocarbon microbeads) can deliver a capacity over 325 mAh g−1 and maintain good cyclability in a solution of 3 M LiPF6‐ethyl methyl carbonate (EMC)/TMP (7 : 3 by vol.). Moreover, our previous work has confirmed that the graphite positive electrode also works very well in the above solution. Therefore, this solution can cater to both anion‐graphite and Li‐graphite intercalation electrodes, which enables the construction of dual‐graphite batteries (DGBs). There are some problems arising during the DGB operation, and corresponding strategies are proposed. [ABSTRACT FROM AUTHOR]

To address the safety concern for room‐temperature sodium‐sulfur batteries, such as fires easily triggered by organic electrolytes, an applicable non‐flammable electrolyte formula was developed by introducing trimethyl phosphate (TMP) into 1.0 M NaClO4‐ethylene carbonate/propylene carbonate electrolyte. It is demonstrated that the electrolyte containing 15 wt.% TMP was a optimized formula, exhibiting nonflammability, thermal stability, electrochemical compatibility and lasting cell performance. Using this optimized electrolyte formula, the sulfur cathode exhibited a stable capacity of 788 mAh g−1 at a rate of 0.1 C and excellent rate capability of 441 and 177 mAh g−1 for 200 cycles at rates of 1 C and 5 C, respectively. When the TMP content further increases to 25 wt.%, the specific capacity of batteries declined significantly due to unstable SEI. Our study can shed light on the development of flame‐retardant electrolyte for room‐temperature sodium‐sulfur or other batteries. Try to set the night on fire: a nonflammable electrolyte for room‐temperature sodium‐sulfur (RT Na‐S) batteries is prepared by introducing trimethyl phosphate (TMP) into 1.0 M NaClO4‐ethylene carbonate/ propylene carbonate (EC/PC) electrolyte. With 15 wt.% TMP‐contained electrolyte the C/S electrode shows excellent cycling stability with a reversible capacity of 788 mAh g−1 after 80 cycles as well as a good rate performance. [ABSTRACT FROM AUTHOR]

The conformational switching of trimethyl phosphate (TMP) in Ne, Ar, Kr and Xe matrixes was studied using infrared spectroscopy under isolated conditions at low temperatures. In all the inert matrixes, the vapor phase population of ground state C 3 (G ± G ± G ± ) and the higher energy C 1 (TG ± G ± ) conformers of TMP is preserved during the initial deposition. However, on annealing the inert Ar/Kr/Xe matrixes, the conformational composition of TMP was irreversibly altered. In Ar and Kr matrixes, an interconversion from ground state C 3 (G ± G ± G ± ) to higher energy C 1 (TG ± G ± ) conformer was observed whereas Xe presents an interesting variation. In Xe matrix, the higher energy C 1 (TG ± G ± ) conformer completely depopulated with a concomitant increase in the population of the ground state C 3 (G ± G ± G ± ) conformer. In Ne matrix notably, no conformational interconversion was observed. Computations on the conformers of TMP were performed using B3LYP and M06-2X levels of theory with 6-311++G(d,p) and aug-cc-pVDZ basis sets. The effect of inert matrixes was modeled using Self-Consistent Reaction Field (SCRF) methods. [ABSTRACT FROM AUTHOR]

Trimethyl phosphate (TMP) is a typical simulant of the CWA nerve agents and its adsorption on pristine and ozonized ACF has been studied by FT-IR and ESR spectroscopy. The FT-IR analysis is effective in putting in evidence the strong interaction of TMP with the ACF surfaces through the P = O stretching band shift toward lower frequencies after adsorption. Ozonized ACF ensures a stronger interaction with the adsorbate through the hydrogen bond formation between the adsorbed TMP and the oxygenated functional groups present on carbon surface. At room temperature the ozonized ACF is able to adsorb larger amounts of TMP than the pristine ACF and shows also a better retention of the adsorbate at room temperature. The TGA-FTIR analysis of TMP desorption from both ozonized and pristine ACF has shown that TMP undergoes a partial thermal decomposition into methanol and phosphoric acid above 175°C. The maximum methanol production rate was observed at 250°C in the TMP desorption process from ozonized ACF and at 280°C from TMP desorption from pristine ACF. [ABSTRACT FROM AUTHOR]

Abstract: A sensitive, accurate, and cost effective method for the quantification of trimethyl phosphate, which is highly polar and volatile, in environmental water is presented. Trimethyl phosphate was headspace solid‐phase microextracted on a molecularly imprinted polymeric fiber, and then the fiber was thermally desorbed in the gas chromatograph injector, and the compound was determined. The trimethyl phosphate imprinted polymeric fiber was prepared by copolymerization in a fused silica capillary tube and obtained by removal of the wall of fused silica capillary tube. The monolithic fiber displayed good selectivity toward trimethyl phosphate among its structural analogues. It was thermally stable up to 320°C so that it can withstand the high temperature of the gas chromatograph injector for desorption. The factors influencing the performance of its headspace solid‐phase microextraction were studied. Under the optimal conditions, the method for quantification of trimethyl phosphate in environmental water was well developed. It exhibited significant linearity, the lowest limit of quantification to date, and good recoveries. Using this method, trimethyl phosphate was detected in five out of seven environmental water samples at concentration levels from 0.28 to 1.22 μg/L, illustrating the heavy pollution of trimethyl phosphate in environmental water. [ABSTRACT FROM AUTHOR]

Hydroxyapatite (HAP) materials with various morphologies including microrods, nanoparticle-assembled microflowers (NAMs), nanoparticle-assembled dendritic superstructures (NADSs), and microrod-assembled ordered arrays (MAOAs) are prepared by a facile solvothermal synthesis strategy using trimethyl phosphate as an organic phosphorus source. The morphologies of the as-prepared HAP products vary significantly with the change of the solvothermal temperature and amount of NaOH. The present study provides a new platform for the synthesis of HAP materials with various morphologies. Among the as-prepared HAP products, the HAP MAOAs show similar structures to those of apatite in the hard tissues of vertebrates. The as-prepared products show excellent biocompatibility, and thus are potentially useful in biomedical fields. [ABSTRACT FROM AUTHOR]

The presently used electrolytes in Lithium ion batteries, dimethyl carbonate (DMC), and ethylene carbonate are flammable. Trimethyl phosphate (TMP) and dimethyl methyl phosphonate (DMMP) have been shown to be potential nonflammable electrolytes. Density functional theory is used to calculate the structure and stability of the solvation complexes of TMP and DMMP. The calculations indicate that TMP and DMMP can form a solvation complex of the form Li+(X)4 where X is the TMP or DMMP molecule. Calculations of the solvation energy and bond dissociation energies to remove one TMP and DMMP from the solvation complexes are compared with the same calculations on DMC. The results indicate that TMP and DMMP are considerably more stable than DMC. [ABSTRACT FROM AUTHOR]

Protonation of the reactive intermediate produced in the reaction between trimethyl phosphite and dimethyl acetylenedicarboxylate or diethyl acetylenedicarboxylate by resorcinol, 5-methylresorcinol, 2,5-dihydroxyacetophenone, 4-chloro-2-methylphenol, 4-chloro-3,5-dimethy-lphenol, 4-hydroxypyridine, 2-hydroxypyridine, 3-hydroxypyridine, or 8-hydroxyquinoline leads to vinylphosphonium salts, which undergo Michael addition with the conjugate base of the OH-acid to produce highly functionalized 2-oxo-2H-chromene or azacoumarins in good yields.