By means of the in-situ Fourier transformation infrared spectroscopy（FTIR）, the properties of BBr3/ benzene solution, which is usually used as the reactant and solution to synthesize BN by benzene-thermal method, ha...By means of the in-situ Fourier transformation infrared spectroscopy（FTIR）, the properties of BBr3/ benzene solution, which is usually used as the reactant and solution to synthesize BN by benzene-thermal method, have been investigated. The results show that there are some side reactions between BBr3 and benzene： （1） BBr3 as an electron-deficient molecule reacts with benzene at room temperature; （2） below 100℃, substitution of Br atom for H atom of benzene（ring-H） dominates in BBr3/benzene solution; （3） cracking of benzene ring occurs at a temperature above 100℃; （4） decomposition of benzene molecules and formation of long-chain aliphatic compounds feature the spectra of BBr3/benzene solution collected at above 160℃, They are unfavor for BN to form when BBr3 is excessive in the synthesis of BN by benzene-thermal route. On the basis of the experimental results, a coordination reaction mechanism via a η^2-C6H6 binding mode in BBr3/benzene solution is suggested.展开更多
Swelling clays are found extensively in various parts of the world, and sodium-montmorillonite(NaMMT) is the main constituent of an expansive clay mineral. In this work, the swelling behavior of NaMMT clay with a wide...Swelling clays are found extensively in various parts of the world, and sodium-montmorillonite(NaMMT) is the main constituent of an expansive clay mineral. In this work, the swelling behavior of NaMMT clay with a wide range of organic fluids, high polar through low polar fluids, is studied using a combination of Fourier transform infrared(FTIR) technique and molecular dynamics(MD) simulations.The construction of the representative clayefluid models is carried out, and the nature of nonbonded interactions between clay and fluids is studied using MD. Our FTIR and MD simulations results suggest the significant nonbonded interactions between Na-MMT clay and polar fluids, such as formamide and water. The nonbonded interactions of Na-MMT with methanol and acetone are significantly less than those in Na-MMT with polar fluids. The interactions of the fluids with various entities of the clay such as Sie O, Fee OH, Mge OH, and Ale OH captured via the spectroscopy experiments and modeling provide a finer understanding of the interactions and their contributions to swelling. The MD simulations are able to capture the band shifts observed in the spectra obtained in the spectroscopy experiments. This work also captures the conformations of interlayer sodium ions with formamide, water, methanol, and acetone during swelling. These nonbonded interactions provide insight into the molecular mechanism that the polarity of fluids plays an important role in the initiation of interlayer swelling, alteration in the orientations, and evolution of microstructure of swelling clays at the molecular scale.展开更多
基金Supported by the National Natural Science Foundation of China(No.50672048)the Program of Shandong Science & Technology Council,China(No.2006GG2202039)
文摘By means of the in-situ Fourier transformation infrared spectroscopy（FTIR）, the properties of BBr3/ benzene solution, which is usually used as the reactant and solution to synthesize BN by benzene-thermal method, have been investigated. The results show that there are some side reactions between BBr3 and benzene： （1） BBr3 as an electron-deficient molecule reacts with benzene at room temperature; （2） below 100℃, substitution of Br atom for H atom of benzene（ring-H） dominates in BBr3/benzene solution; （3） cracking of benzene ring occurs at a temperature above 100℃; （4） decomposition of benzene molecules and formation of long-chain aliphatic compounds feature the spectra of BBr3/benzene solution collected at above 160℃, They are unfavor for BN to form when BBr3 is excessive in the synthesis of BN by benzene-thermal route. On the basis of the experimental results, a coordination reaction mechanism via a η^2-C6H6 binding mode in BBr3/benzene solution is suggested.
基金the support of USDoT,Mountain Plains Consortium,UGPTI under grant No.#69A3551747108
文摘Swelling clays are found extensively in various parts of the world, and sodium-montmorillonite(NaMMT) is the main constituent of an expansive clay mineral. In this work, the swelling behavior of NaMMT clay with a wide range of organic fluids, high polar through low polar fluids, is studied using a combination of Fourier transform infrared(FTIR) technique and molecular dynamics(MD) simulations.The construction of the representative clayefluid models is carried out, and the nature of nonbonded interactions between clay and fluids is studied using MD. Our FTIR and MD simulations results suggest the significant nonbonded interactions between Na-MMT clay and polar fluids, such as formamide and water. The nonbonded interactions of Na-MMT with methanol and acetone are significantly less than those in Na-MMT with polar fluids. The interactions of the fluids with various entities of the clay such as Sie O, Fee OH, Mge OH, and Ale OH captured via the spectroscopy experiments and modeling provide a finer understanding of the interactions and their contributions to swelling. The MD simulations are able to capture the band shifts observed in the spectra obtained in the spectroscopy experiments. This work also captures the conformations of interlayer sodium ions with formamide, water, methanol, and acetone during swelling. These nonbonded interactions provide insight into the molecular mechanism that the polarity of fluids plays an important role in the initiation of interlayer swelling, alteration in the orientations, and evolution of microstructure of swelling clays at the molecular scale.
