MSn_（10）（M=Sc,Ti,V,Cr,Mn,Fe,Co,Ni）团簇的稳定性和磁性研究

采用密度泛函理论（density functional theory,DFT）中的广义梯度近似（generalized gradient approximation,GGA）对Sn11团簇的4种同分异构体（对称性分别为D5h,D5d,D4h,D4d）的几何结构、电子结构计算研究,得出对称性为D5d的团簇最稳定.将Sn11团簇的中心原子替换成过渡金属原子成为MSn10（M=Sc,Ti,V,Cr,Mn,Fe,Co,Ni）团簇,对其稳定性和磁性进行了分析.在Sn11团簇中将中心原子替换成过渡金属原子后,束缚能都变小了,说明过渡金属原子的替换提高了原锡团簇的稳定性,其中NiSn10团簇的束缚能最小,稳定性最强.过渡金属原子都具有一定的磁性,当把这些原子掺入锡团簇后,过渡金属原子的磁性都有所减弱,其中MSn10（M=Sc,Ti,V,Ni）团簇的磁性完全消失,其原因在于掺杂后,团簇中各原子的电荷分布发生了变化.     

钙钛矿型LaMO3(M= Co,Mn,Fe)对己烷和甲烷催化氧化的活性研究

柠檬酸络合法制备钙钛矿LaMO3（M=Co,Mn,Fe）.对于己烷的完全氧化反应和甲烷完全氧化反应过程的活性进行测试,催化剂的催化活性顺序如下：LaCoO3〉LaMnO3〉LaFeO3,得出了相同的规律性：在氧化过程中,温度在250℃～300℃左右存在游离态的氧;温度高于300℃时,游离态的氧消失.     

MgPn(n=1～10)团簇的最低能量结构与稳定性的密度泛函研究

利用杂化密度泛函B3LYP方法在6-311G基组水平上对MgPn(n=1～10)团簇进行了几何构型优化和频率分析,得到了各个尺寸团簇的最低能量结构,并对体系的最邻近键长、平均结合能、裂化能、二阶能量差分进行了计算和分析. 结果表明: MgPn(n=1～10)团簇中Mg原子没有嵌入P团簇中,在n≥4时,MgPn(n=1～10)团簇最低能量结构的几何构型可以看作一个Mg原子直接替代纯磷团簇的P原子获得. 在优化得到的最低能量结构的基础上,发现可以用平均结合能和Mg-P间最邻近键长来共同描述MgPn(n=1～10)团簇稳定性的变化,MgPn(n=1～10)团簇在n=2,4具有较高的稳定性. 与纯磷团簇相比,MgPn(n=1～10)团簇的对称性与稳定性都有所降低.     

硅基过渡金属掺杂MSi12-(M=V,Cr,Mn)团簇的结构和性质

基于密度泛函理论结合粒子群优化算法程序卡利普索,对硅基过渡金属掺杂团簇MSi₁₂^-（M=V, Cr, Mn）的几何结构、电子和光谱特性、热力学性质进行系统研究.结果表明,MSi₁₂^-（M=V, Cr, Mn）团簇的基态结构为M位于中心的鼓状高对称性(D_3d,D_3d和C_2h点群对称)结构.基于该基态结构,讨论了体系的分子轨道、电荷转移和极化率等电子特性.此外,拟合出了体系的光电子能谱、红外和拉曼光谱,对主要特征峰进行了归属分析.最后,分析了体系的热力学性质.以期该研究能为过渡金属掺杂硅基纳米材料的实验制备和表征提供重要理论参考.     

过渡金属硫化物阳离子(MSn+,M=Sc,Ti,n=1,2,3)的理论研究

用密度泛函理论研究了气相中过渡金属硫化物阳离子(MSn ,M=Sc,Ti,n=1,2,3).获得了各种离子的几何结构、电子结构、光谱性质及热力学数据,确定了其基态结构,并和已有实验数据作了对比.根据我们的理论计算,ScS ,TiS 的基态分别为1∑ ,2△.其主要电子组态分别为1σ22σ21π4,1σ22σ21π41δ.MS2 的各种离子基态结构是三元环型结构,ScS2 ,TiS2 的基态分别为1A′,2A′.MS3 的可能结构有直线型结构、三角锥型结构和以 '为中心的平面结构.经过反复计算,优化各种结构并对每一结构做振动频率分析,得到ScS3 ,TiS3 基态分别为:3A″,2A″.     

MPO4 (M=Sc, Lu, Y) :Ti3+ 自旋哈密顿参量的理论研究

利用高阶微扰方法和完全对角化方法分别计算了MPO4 (M=Sc, Lu, Y) ：Ti3+的自旋哈密顿参量（g 因子 g// , g和超精细结构常数A//, A),两种方法的计算结果非常接近,并且均和实验值吻合的很好,这表明这两种方法都是研究过渡金属离子自旋哈密顿参量的有效方法。另外,还对所研究的三种不同材料的共价性和芯极化常数性质进行了讨论。     

理论研究不对称团簇(HFBN3)n (n=1-6)的结构和稳定性

采用密度泛函理论方法研究不对称团簇(HFBN3)n (n=1-6)的结构和性质。对于n≥2的团簇,B–Nα键易形成,而B–B和Nα–Nα键不存在。讨论了几何参数随团簇尺寸n的变化规律。通过分析团簇平均结合能和二阶差分值,探讨其相对稳定性,发现团簇(HFBN3)3比其它团簇更稳定。计算IR谱有四个特征区。研究了团簇的热力学性质随温度T以及团簇尺寸n的变化趋势。室温下,由焓变可知单体1形成多聚体（2、3、4、5、6）在热力学上有利。     

[(BCO)5]2M(M=Fe,Co,Ni)金属夹心化合物的结构

基于密度泛函理论B3LYP/6-311++G(d,p)方法,对(BCO)5与3d过渡金属离子Fe2+,Co2+,Ni2+形成的夹层配合物进行了稳定性与结构方面的计算研究.计算结果表明,与Cp-具有等瓣相似性的(BCO)5-可以形成类似于二茂化合物的夹层配合物.[(BCO)5]2M(M=Fe,co,Ni)的结合能小于相应Cp2M的结合能.对[(BCO)5]2Fe的电子结构进行了详细的分析,发现其前线轨道与Cp2Fe有着较大的不同.通过电子结构分析,很好地解释了为什么[(BCO)5]2Co的对称性是C2v,为什么[(BCO)5]2Ni是一个具有理想D5d对称性的三重态结构;三种标题化合物的结合能顺序为[(BCO)5]2Fe＞[(BCO)5]2Co＞[(BCO)5]2Ni.并给出了这一稳定性顺序的原因.     

Sc_nN(n=2～12)团簇的结构与稳定性研究

基于第一性原理,在密度泛函理论框架下,用广义梯度近似(GGA)的方法研究了团簇ScnN(n=2～12)的几何构型和电子结构,计算了它的束缚能、结合能、最高占据轨道与最低占据轨道之间的能隙、离解能等性质.结果表明,对于ScnN(n=2～12)的所有团簇,可以有11种基态构型,但稳定的只有Sc6N和Sc10N这两种构型,其原因在于中心原子参与了轨道的杂化,中心原子是否参与轨道的杂化,对团簇稳定性有重要影响.     

CO在钙钛矿型稀土氧化物LaMO_3(M=Cr,Mn,Fe,Co,Ni)上的氧化反应

本文用柠檬酸络合法制取了比表面为18.3～31.2m~2/g的LaMO_3(M-Cr,Mn,Fe,Co,Ni)系列化合物。X射线衍射(XRD)鉴定均为单一相钙钛矿型氧化物。LaCrO_3与LaFeO_3物属于正交晶型;LaMnO_3,LaCoO_3和LaNiO_3属三方晶型。在反应温度低于300℃时,一氧化碳氧化反应催化活性次序为:LaMnO_3>LaCoO_3>LaNiO_3>LaFeO_3>LaCrO_3,呈现出LaMO_3晶格氧化合能愈低,催化活性愈好的规律。     

Hydrogen storage properties of (Ti0.85Zr0.15)1.05Mn1.2Cr0.6V0.1M0.1 (M=Ni, Fe, Cu) alloys easily activated at room temperature

The(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)M_(0.1)(M=Ni, Fe, Cu) alloys with a single C14-type Laves phase have been fabricated by arc melting. They are able to be easily activated by one hydrogen absorption and desorption cycle under 4 MPa hydrogen pressure and vacuum at room temperature. Partial substitution of M for Mn results in the increase of hydrogenation and dehydrogenation capacities in an order of Ni Fe Cu. M elements increase the absorption and desorption plateau pressure in an order of(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Cu_(0.1)(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Fe_(0.1)(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Ni_(0.1). The(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Cu_(0.1) alloy has reversible hydrogen capacities of 1.81 wt% at 273 K and 1.58 wt% at 318 K with formation enthalpy(ΔH_(ab)) of-20.66 kJ mol~(-1) and decomposition enthalpy(ΔH_(de)) of 27.37 kJ mol~(-1). The differences in the hydrogen storage properties can be attributed to the increase of the interstitial size for hydrogen accommodation caused by the increase of unit cell volumes in the order of(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Ni_(0.1)(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Fe_(0.1)(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Cu_(0.1).     

Evaluation of Ca3(Co,M)2O6 (M=Co, Fe, Mn, Ni) as new cathode materials for solid-oxide fuel cells

Series compounds Ca_3(Co_(0.9)M_(0.1))_2O_6(M = Co,Fe,Mn,Ni) with hexagonal crystal structure were prepared by sol-gel route as the cathode materials for solid oxide fuel cells(SOFCs).Effects of the varied atomic compositions on the structure,electrical conductivity,thermal expansion and electrochemical performance were systematically evaluated.Experimental results showed that the lattice parameters of Ca_3(Co_(0.9)Fe_(0.1))_2O_6and Ca_3(Co_(0.9)Mn_(0.1))_2O_6 were both expanded to certain degree.Electron-doping and hole-doping effects were expected in Ca_3(Co_(0.9)Mn_(0.1))_2O_6and Ca_3(Co_(0.9)Ni_(0.1))_2O_6 respectively according to the chemical states of constituent elements and thermal-activated behavior of electrical conductivity.Thermal expansion coefficients(TEC) of Ca_3(Co_(0.9)M_(0.1))_2O_6 were measured to be distributed around 16×10~(-6)K~(-1) and compositional elements of Fe,Mn,and Ni were especially beneficial for alleviation of the thermal expansion problem of cathode materials.By using Ca_3(Co_(0.9)M_(0.1))_2O_6 as the cathodes operated at 800 ℃,the interfacial area-specific resistance varied in the order of M = Co M = Fe M = Ni M = Mn,and the over-potential increased in the order of M = Fe ≈ M = Co M = Mn M = Ni.Among all of these compounds,Ca_3(Co_(0.9)Fe_(0.1))_2O_6 showed the best electrochemical performance and the power density as high as ca.500 mW cm~(-2) at800 ℃ achieved in the single cell with La_(0.8)Sr_(0.2)Ga_(0.83)Mg_(0.17)O_(2.815) as electrolyte and Ni-Ce_(0.8)Sm_(0.2)O_(1.9) as anode.Ca_3(Co_(0.9)M_(0.1))_2O_6(M = Co,Fe,Mn,Ni) can be used as the cost-effective cathode materials for SOFCs.     

An atomistic simulation of site preference and vibrational properties of UMxAl12-x （M = Fe, Co, Ni, Cr and Mn） and UMxAl1z-xHx

A series of lattice inversion pair potentials are used to evaluate the phase stability and site preference for uranium intermetallics UMxAl12-x (M = Fe, Co, Ni, Cr and Mn) and their related hydrides. Calculated results show that Fe, Co, Ni, Cr or Mn atoms preferentially substitute Al at the 8f site. Interstitial H atoms only occupy 2b interstitial sites in UMxAl12-x. Calculated lattice constants are found to agree with a report in the literature. Elastic constants and bulk modulus of UMxAl12-x and UMxAl12-xH were also investigated. In particular, the phonon densities of states (DOS) of these actinide compounds were evaluated for the first time.     

Azo dye degradation behavior of AlFeMnTiM(M = Cr,Co, Ni) high-entropy alloys

Because of the potential carcinogenic effects and difficult degradation of azo dyes, their degradation has been a longstanding problem. The degradation of azo dye Direct Blue 6(DB6) using ball-milled(BM) high-entropy alloy(HEA) powders was characterized in this work. Newly designed AlFeMnTiM(M = Cr, Co, Ni) HEAs synthesized by mechanical alloying(MA) showed excellent performance in the degradation of azo dye DB6. The degradation efficiency of AlFeMnTiCr is approximately 19 times greater than that of the widely used commercial Fe–Si–B amorphous alloy ribbons and more than 100 times greater than that of the widely used commercial zero-valent iron(ZVI) powders. The galvanic-cell effect and the unique crystal structure are responsible for the good degradation performance of the BM HEAs. This study indicates that BM HEAs are attractive, valuable, and promising environmental catalysts for wastewater contaminated by azo dyes.     

Azo dye degradation behavior of AlFeMnTiM (M=Cr,Co, Ni) high-entropy alloys

Because of the potential carcinogenic effects and difficult degradation of azo dyes, their degradation has been a longstanding problem. The degradation of azo dye Direct Blue 6(DB6) using ball-milled(BM) high-entropy alloy(HEA) powders was characterized in this work. Newly designed AlFeMnTiM(M = Cr, Co, Ni) HEAs synthesized by mechanical alloying(MA) showed excellent performance in the degradation of azo dye DB6. The degradation efficiency of AlFeMnTiCr is approximately 19 times greater than that of the widely used commercial Fe–Si–B amorphous alloy ribbons and more than 100 times greater than that of the widely used commercial zero-valent iron(ZVI) powders. The galvanic-cell effect and the unique crystal structure are responsible for the good degradation performance of the BM HEAs. This study indicates that BM HEAs are attractive, valuable, and promising environmental catalysts for wastewater contaminated by azo dyes.     

Microstructure characterization and hydrogen storage properties study of Mg2Ni0.92M0.08 (M = Ti, V, Fe or Si) alloys

In the present study Mg_2Ni-type compounds alloyed independently with Ti,V,Fe and Si were successfully prepared by wet-milling followed by sintering.Although these alloyed Mg_2Ni compounds exhibited a similar hydrogen storage mechanism as that of pure Mg_2Ni,the dissolution of Ti,V or Fe into the Mg_2NiH_4lattice had a considerable catalytic effect on hydrogen desorption from additional MgH_2.The further structure investigations clearly indicated that the substitution of Ti for Ni could suppress the formation of the micro-twined low-temperature phase(LT2)and promote the formation of the high-temperature phase(HT),thus resulting in remarkably improved hydrogen desorption kinetics for the Mg_2Ni_(0.92)Ti_(0.08)–H system.