The adsorption of uranyl on hydroxylated α-SiO_2(001) in the presence of a series of anionic ligands, i.e. OH^-, CO_32-, NO_3^-, H_2PO_4^-, HPO_42-,CH_3COO^-(Ac^-), C_6H_5COO^-(PhCO_2^-), C_6H_5O^-(PhO^-), was ...The adsorption of uranyl on hydroxylated α-SiO_2(001) in the presence of a series of anionic ligands, i.e. OH^-, CO_32-, NO_3^-, H_2PO_4^-, HPO_42-,CH_3COO^-(Ac^-), C_6H_5COO^-(PhCO_2^-), C_6H_5O^-(PhO^-), was studied by the periodic density functional theory(DFT) implemented in the Vienna ab initio simulation package(VASP). For the ligands other than OH^-and PhO^-, only the bidentate coordination modes to the uranyl were considered. The excess charge effect of a charged system was first evaluated by constructing models with net charge as is or neutralized by creating defect at the bottom of silica, and the results show that a neutralized model, even with defects, is more realistic than the charged ones.All uranyl species prefer to bind with the deprotonated site(—O^-) rather than the protonated one(—O_H), which suggests that the increase of pH,which leads to the deprotonation of the surface, may enhance the uranyl adsorption. On the other hand, the anionic ligands, which are formed at higher pH, have negative effects. The weaker acidic ligands, such as H_2CO_3, H_3PO_4 and H_2O, whose speciation in solutions is sensitive to the fluctuation of pH, have more complex effect on the uranyl adsorption than strong acids or bases. Humic substances may coordinate with uranyl through carboxyl and phenolic groups, with the carboxyl group bound stronger. The ternary complexes with one bidentate(or monodentate)anion and one(or two) H20 as ligands, which leads to the uranyl penta-coordinated in its equatorial plane, are more favorable than other configurations when bound to the same anionic ligand. Both the charged nature and the coordination behavior of an anionic ligand are relevant to its ability to influence the adsorption of uranyl on the mineral surface. In addition, the uranyl species adsorbed at the surface functionalized by anionic ligands were also addressed, and the functionalized surfaces have weaker interaction with hydrated uranyl dication.展开更多
First-principles methods based on the density functional theory(DFT) are used in order to calculate the structural and optical properties of α-SiO2 cluster with the non-bridging oxygen hole centers(NBOHC) and NBOHCE&...First-principles methods based on the density functional theory(DFT) are used in order to calculate the structural and optical properties of α-SiO2 cluster with the non-bridging oxygen hole centers(NBOHC) and NBOHCE' defects. We clarify the stable structure of the NBOHC-E' point defects for the first time using the functional B3 LYP, which is also tested to investigate the influence of electronic properties. The calculation is carried out for cluster configurations extracted from supercell. The results of optical absorption peak for Si2O7H6 and Si5O16H12with NBOHC-E' defects are found at 2.66 e V, which is higher than the often observed OA peak at 2.0 e V for the NBOHC defect in α-SiO2. The overall absorption spectra are in qualitative agreement with the experiment.展开更多
制备了一种含有胺基官能团的α-二亚胺镍配合物,并将该配合物负载在AlEt_3改性的SiO_2-MgCl_2复合载体上制备负载催化剂,不用昂贵的MAO(甲基铝氧烷)而用AlEt_2Cl作助催化剂,研究了其对乙烯的聚合性能。并采用高温13CNMR、高温GPC、...制备了一种含有胺基官能团的α-二亚胺镍配合物,并将该配合物负载在AlEt_3改性的SiO_2-MgCl_2复合载体上制备负载催化剂,不用昂贵的MAO(甲基铝氧烷)而用AlEt_2Cl作助催化剂,研究了其对乙烯的聚合性能。并采用高温13CNMR、高温GPC、差示扫描量热法(DSC)等对得到的聚合物进行了研究。结果发现,该催化剂具有很高的催化活性(1.89×10~6g of PE/mol of Ni h),得到的聚乙烯产品含有各种短支链(甲基、乙基、丙基、丁基)和长支链,分子量在2.15×10~5~9.27×10~5之间,分子量分布为3.12~4.23。展开更多
The mixtures of a-quartz and graphite powder with different mass ratios were, respectively, high-energetically mechanically milled and then treated under high pressure and high temperature. The influences of carbon co...The mixtures of a-quartz and graphite powder with different mass ratios were, respectively, high-energetically mechanically milled and then treated under high pressure and high temperature. The influences of carbon content on the synthesis conditions of coesite were investigated. The experimental products were characterized by XRD, TEM, and Raman spectrometry. The results show that the existence of carbon can obviously inhibit the formation of coesite, and the higher the carbon content of the initial material, the higher the pressure for forming coesite.展开更多
基金financially supported by the National Natural Science Foundation of China to Z.Chai(91026000) to D.Wang(91226105)by the CAS Hundred Talents Program to D.Wang(Y2291810S3)
摘要The adsorption of uranyl on hydroxylated α-SiO_2(001) in the presence of a series of anionic ligands, i.e. OH^-, CO_32-, NO_3^-, H_2PO_4^-, HPO_42-,CH_3COO^-(Ac^-), C_6H_5COO^-(PhCO_2^-), C_6H_5O^-(PhO^-), was studied by the periodic density functional theory(DFT) implemented in the Vienna ab initio simulation package(VASP). For the ligands other than OH^-and PhO^-, only the bidentate coordination modes to the uranyl were considered. The excess charge effect of a charged system was first evaluated by constructing models with net charge as is or neutralized by creating defect at the bottom of silica, and the results show that a neutralized model, even with defects, is more realistic than the charged ones.All uranyl species prefer to bind with the deprotonated site(—O^-) rather than the protonated one(—O_H), which suggests that the increase of pH,which leads to the deprotonation of the surface, may enhance the uranyl adsorption. On the other hand, the anionic ligands, which are formed at higher pH, have negative effects. The weaker acidic ligands, such as H_2CO_3, H_3PO_4 and H_2O, whose speciation in solutions is sensitive to the fluctuation of pH, have more complex effect on the uranyl adsorption than strong acids or bases. Humic substances may coordinate with uranyl through carboxyl and phenolic groups, with the carboxyl group bound stronger. The ternary complexes with one bidentate(or monodentate)anion and one(or two) H20 as ligands, which leads to the uranyl penta-coordinated in its equatorial plane, are more favorable than other configurations when bound to the same anionic ligand. Both the charged nature and the coordination behavior of an anionic ligand are relevant to its ability to influence the adsorption of uranyl on the mineral surface. In addition, the uranyl species adsorbed at the surface functionalized by anionic ligands were also addressed, and the functionalized surfaces have weaker interaction with hydrated uranyl dication.
基金Supported by the National Basic Research Program of China(973 Program)under Grant No.2014CB643900the Open Fund of IPOC(BUPT)+1 种基金the Open Program of State Key Laboratory of Functional Materials for Informaticsthe National Natural Science Foundation of China under Grant No.61440061
摘要First-principles methods based on the density functional theory(DFT) are used in order to calculate the structural and optical properties of α-SiO2 cluster with the non-bridging oxygen hole centers(NBOHC) and NBOHCE' defects. We clarify the stable structure of the NBOHC-E' point defects for the first time using the functional B3 LYP, which is also tested to investigate the influence of electronic properties. The calculation is carried out for cluster configurations extracted from supercell. The results of optical absorption peak for Si2O7H6 and Si5O16H12with NBOHC-E' defects are found at 2.66 e V, which is higher than the often observed OA peak at 2.0 e V for the NBOHC defect in α-SiO2. The overall absorption spectra are in qualitative agreement with the experiment.
摘要制备了一种含有胺基官能团的α-二亚胺镍配合物,并将该配合物负载在AlEt_3改性的SiO_2-MgCl_2复合载体上制备负载催化剂,不用昂贵的MAO(甲基铝氧烷)而用AlEt_2Cl作助催化剂,研究了其对乙烯的聚合性能。并采用高温13CNMR、高温GPC、差示扫描量热法(DSC)等对得到的聚合物进行了研究。结果发现,该催化剂具有很高的催化活性(1.89×10~6g of PE/mol of Ni h),得到的聚乙烯产品含有各种短支链(甲基、乙基、丙基、丁基)和长支链,分子量在2.15×10~5~9.27×10~5之间,分子量分布为3.12~4.23。
基金Supported by the National Natural Science Foundation of China(Nos.50872041 and 10674034)the National Foundation for Fostering Talent in Basic Science of China(No.J0730311)the Foundation of State Key Laboratory of Superhand Materials (No.200908)
摘要The mixtures of a-quartz and graphite powder with different mass ratios were, respectively, high-energetically mechanically milled and then treated under high pressure and high temperature. The influences of carbon content on the synthesis conditions of coesite were investigated. The experimental products were characterized by XRD, TEM, and Raman spectrometry. The results show that the existence of carbon can obviously inhibit the formation of coesite, and the higher the carbon content of the initial material, the higher the pressure for forming coesite.