二氧化钛(TiO_(2))的形貌与其功能化应用密切相关,其是一种电子束辐照敏感材料,但特定形貌的纳米晶在电子束辐照下结构演变动力学机制尚未明晰。本研究通过水热法合成了具有条棒状(边缘陡直)、八面体双锥状(锥尖锐利)及薄片状的锐钛矿相...二氧化钛(TiO_(2))的形貌与其功能化应用密切相关,其是一种电子束辐照敏感材料,但特定形貌的纳米晶在电子束辐照下结构演变动力学机制尚未明晰。本研究通过水热法合成了具有条棒状(边缘陡直)、八面体双锥状(锥尖锐利)及薄片状的锐钛矿相TiO_(2)纳米晶,利用透射电子显微镜(transmission electron microscopy,TEM)原位监测不同形貌样品在电子束辐照下的结构演变过程。结合反傅里叶变换(inverse fast Fourier transform,iFFT)、电子能量损失谱(electron energy loss spectroscopy,EELS)和原位电子束辐照质谱等分析发现:TiO_(2)经过电子束辐照解离出O_(2)离子从而转变为γ-TiO;条棒状与双锥状纳米晶沿[100]方向辐照过程中,锐钛矿向γ-TiO的结构转变优先发生于边缘薄区并逐渐向内部扩展;而片状纳米晶沿[001]方向辐照过程中,相变区域无显著空间分布特征,且薄区易伴随非晶化现象。本研究揭示了由位移损伤和电离损伤协同作用下,TiO_(2)的形貌依赖的电子束辐照损伤机制,为辐照环境下TiO_(2)基材料的稳定性优化及利用电子束进行TiO_(2)/TiO异质结构设计提供了依据。展开更多
采用分子动力学模拟的方法,研究了LiCl-KCl-CeCl_3熔盐中CeCl_3的结构性质和热力学,获得了LiClKCl-CeCl_3熔盐中密度与组成、密度与温度的关系数据;径向分布函数g_(Ce-Cl)(r)的第一个峰位置为0.259nm,Ce^(3+)对应的第一个配位数约为6.9...采用分子动力学模拟的方法,研究了LiCl-KCl-CeCl_3熔盐中CeCl_3的结构性质和热力学,获得了LiClKCl-CeCl_3熔盐中密度与组成、密度与温度的关系数据;径向分布函数g_(Ce-Cl)(r)的第一个峰位置为0.259nm,Ce^(3+)对应的第一个配位数约为6.9;混合熔盐中计算数据与纯熔盐中数据的差异可以解释为混合熔盐中Ce^(3+)和Cl^-的相互作用比纯的CeCl_3更强;LiCl-KCl熔盐中Ce^(3+)的自扩散活化能为22.5 k J?mol^(-1),从活化能的本质来说,Ce^(3+)自扩散所需要克服的能垒要略低于U^(3+)(25.8 k J?mol^(-1))。当Ce^(3+)的摩尔分数从0.005增加到0.05时,其指前因子从31.9×10^(-5)cm^2?s^(-1)减少到21.8×10^(-5)cm^2?s^(-1);随着Ce^(3+)摩尔分数从0.005增长到0.05,单位体积内(忽略总体积的变化)Ce^(3+)的增加意味着其扩散阻力增加,而自扩散的能力降低,导致了指前因子的减小。展开更多
The mechanism of decomposition of calcium inosilicate(CaSiO_3) synthesized through chemical deposition method using analytical reagent NaSiO_3·9H_2O and CaCl_2 during the alkali fusion process using NaOH was inve...The mechanism of decomposition of calcium inosilicate(CaSiO_3) synthesized through chemical deposition method using analytical reagent NaSiO_3·9H_2O and CaCl_2 during the alkali fusion process using NaOH was investigated by Raman spectroscopy in situ,X-ray diffraction and Fourier transform infrared spectrometer(FTIR).The results show that the tetrahedral silica chains within CaSiO_3 are gradually disrupted and transformed into nesosilicate with the isolated SiO_4 tetrahedra at the beginning of the alkali fusion process.The three intermediates including Ca_2SiO_4,Na_2CaSiO_4 and Na_2SiO_3 appear simultaneously in the decomposition of CaSiO_3,while the final products are Ca(OH)_2 and Na_4SiO_4.It can be concluded that there exist two reaction pathways in the alkali fusion process of CaSiO_3:one is ion exchange,the other is in the main form of the framework structure change of silicate.The reaction pathway is led by silicate structure transformation in the alkali fusion process.展开更多
文摘二氧化钛(TiO_(2))的形貌与其功能化应用密切相关,其是一种电子束辐照敏感材料,但特定形貌的纳米晶在电子束辐照下结构演变动力学机制尚未明晰。本研究通过水热法合成了具有条棒状(边缘陡直)、八面体双锥状(锥尖锐利)及薄片状的锐钛矿相TiO_(2)纳米晶,利用透射电子显微镜(transmission electron microscopy,TEM)原位监测不同形貌样品在电子束辐照下的结构演变过程。结合反傅里叶变换(inverse fast Fourier transform,iFFT)、电子能量损失谱(electron energy loss spectroscopy,EELS)和原位电子束辐照质谱等分析发现:TiO_(2)经过电子束辐照解离出O_(2)离子从而转变为γ-TiO;条棒状与双锥状纳米晶沿[100]方向辐照过程中,锐钛矿向γ-TiO的结构转变优先发生于边缘薄区并逐渐向内部扩展;而片状纳米晶沿[001]方向辐照过程中,相变区域无显著空间分布特征,且薄区易伴随非晶化现象。本研究揭示了由位移损伤和电离损伤协同作用下,TiO_(2)的形貌依赖的电子束辐照损伤机制,为辐照环境下TiO_(2)基材料的稳定性优化及利用电子束进行TiO_(2)/TiO异质结构设计提供了依据。
基金supported by the National Natural Science Foundation of the People’s Republic of China“Data-driven high-throughput screening of cathode materials for Zn-ion batteries”(22065032)Undergraduate Education and Teaching Research and Reform Project of Universities in Xinjiang Uygur Autonomous Region“Innovative research on ideological and political education in courses and virtual simulation technology in structural chemistry”(XJGXPTJG-202205).
文摘以(NH_(4))_(6)MnMo_(9)O_(32)·9H_(2)O为前体原料,采用水溶液法制备了3种新的Waugh型锰钼杂多酸季铵盐:(NH_(4))_(2)[(C_(4)H_(9))_(4)N]_(4)MnMo_(9)O_(32)(1)、(NH_(4))_(2)[(C_(6)H_(5)CH_(2)(CH_(3))_(3)N]_(4)MnMo_(9)O_(32)(_(2))和(NH_(4))_(2)[C_(6)H_(5)CH_(2)(CH_(2)CH_(2)CH_(2)CH_(3))_(3)N]_(4)MnMo_(9)O_(32)·H_(2)O(_(3)),并利用傅里叶红外光谱、热重分析、元素分析和X线粉末衍射分析对化合物进行了表征.紫外光照下研究了3种化合物对亚甲基蓝模拟染料废水的光催化降解性能和动力学行为,结果表明:3种化合物对亚甲基蓝模拟染料废水均具有高效的光催化活性,降解率为98.28%~99.64%,且化合物3对亚甲基蓝的光催化行为符合一级动力学特征,动力学方程为ln(c_(0)/c_(t))=0.0682t,降解速率常数为0.0682min^(-1),半衰期为10.2 min.
文摘采用分子动力学模拟的方法,研究了LiCl-KCl-CeCl_3熔盐中CeCl_3的结构性质和热力学,获得了LiClKCl-CeCl_3熔盐中密度与组成、密度与温度的关系数据;径向分布函数g_(Ce-Cl)(r)的第一个峰位置为0.259nm,Ce^(3+)对应的第一个配位数约为6.9;混合熔盐中计算数据与纯熔盐中数据的差异可以解释为混合熔盐中Ce^(3+)和Cl^-的相互作用比纯的CeCl_3更强;LiCl-KCl熔盐中Ce^(3+)的自扩散活化能为22.5 k J?mol^(-1),从活化能的本质来说,Ce^(3+)自扩散所需要克服的能垒要略低于U^(3+)(25.8 k J?mol^(-1))。当Ce^(3+)的摩尔分数从0.005增加到0.05时,其指前因子从31.9×10^(-5)cm^2?s^(-1)减少到21.8×10^(-5)cm^2?s^(-1);随着Ce^(3+)摩尔分数从0.005增长到0.05,单位体积内(忽略总体积的变化)Ce^(3+)的增加意味着其扩散阻力增加,而自扩散的能力降低,导致了指前因子的减小。
基金Project(20112120120003)supported by the Science and Technology Projects of Ministry of Education of ChinaProject(L2014120)supported by the Educational Commission of Liaoning Province,China
文摘The mechanism of decomposition of calcium inosilicate(CaSiO_3) synthesized through chemical deposition method using analytical reagent NaSiO_3·9H_2O and CaCl_2 during the alkali fusion process using NaOH was investigated by Raman spectroscopy in situ,X-ray diffraction and Fourier transform infrared spectrometer(FTIR).The results show that the tetrahedral silica chains within CaSiO_3 are gradually disrupted and transformed into nesosilicate with the isolated SiO_4 tetrahedra at the beginning of the alkali fusion process.The three intermediates including Ca_2SiO_4,Na_2CaSiO_4 and Na_2SiO_3 appear simultaneously in the decomposition of CaSiO_3,while the final products are Ca(OH)_2 and Na_4SiO_4.It can be concluded that there exist two reaction pathways in the alkali fusion process of CaSiO_3:one is ion exchange,the other is in the main form of the framework structure change of silicate.The reaction pathway is led by silicate structure transformation in the alkali fusion process.
