韩宝斋
,
杨扬
,
许妍妍
,
U. J. Etim
,
乔柯
,
许本静
,
阎子峰
催化学报
doi:10.1016/S1872-2067(15)61097-X
目前，天然气转化为高附加值化工产品的应用越来越受到人们关注.甲烷作为天然气的主要成分，其转化和应用是天然气化工领域的重要研究方向.而甲烷直接氧化制甲醇长久以来一直是研究重点.甲烷直接氧化制甲醇与传统的甲烷二步法间接转化相比，有节能和工艺简化的突出特点.然而，甲醇直接氧化制甲醇过程所面临的主要问题有：(1)甲烷分子的活化能很高，需要苛刻的操作条件才能活化参与反应；(2)反应进行的程度难以控制，生成的甲醇会进一步被氧化生成较多副产物，大大降低甲醇收率.因此，高效活化甲烷分子和抑制甲醇深度氧化是促进该过程工业化的重要研究内容.本文主要论述了非均相、气相均相和液相体系中甲烷直接氧化制甲醇的研究进展.在甲烷非均相氧化过程中，采用过渡金属氧化物作为催化剂在高温条件下催化甲烷部分氧化反应，其中，钼系和铁系催化剂的研究最为广泛.研究表明， MoO3可作为催化剂的主要活性组分，尤以 MoO3/Ga2O3催化剂性能最好，得到甲醇收率最高.在铁系催化剂中， Fe-ZSM-5 ；催化反应的甲醇选择性和收率都相对较高；但是每次反应后催化剂都需要重新活化，这种间歇性操作会增加成本，不利于工业化应用.总之，甲烷的非均相氧化过程存在易形成金属聚集体、催化剂选择性低以及甲醇收率低(5%)等问题，需要深入系统地研究解决.然而，与非均相氧化过程相比，操作较为简单的甲烷气相均相氧化作为目前最有工业前景的过程受到越来越多关注.在此过程中，影响反应的主要因素有反应器、反应条件(反应压力、反应温度和反应时间等)以及添加的介质等.反应器的特殊设计需要考虑的方面有反应产物的分离与转移、反应热的移除以有效提高甲烷的转化率，比如膜反应器对物质的分离作用.反应压力对反应过程的影响较为复杂.基于动力学因素，提高反应压力可以较大幅度地增加甲醇收率，同时最佳反应温度降低，但是，当压力高于8.0 MPa时，设备成本消耗大幅增加.另外，研究表明，进料中加入 NOx作为添加介质可以提高甲烷转化率和甲醇选择性，同时降低初始反应温度.与前两个氧化体系相比，液相均匀氧化过程能够获得较高的甲烷转化率与甲醇选择性.但是液相体系中强腐蚀性介质的使用增加了设备成本，阻碍了该过程工业化的应用进程.因此，促进液相体系工业化的关键就是开发绿色高效的催化剂.
关键词:
甲烷
,
直接氧化
,
甲醇
,
多相氧化
,
气相均相氧化
,
液相催化氧化
Journal of Materials Research
The morphology of the dark and bright regions observed by transmission electron microscopy for the Zr(64.13)Cu(15.75)Ni(10.12)Al(10) bulk metallic glass strongly depends on the ion beam parameters used for ion milling. This indicates that the ion beam could introduce surface fluctuation to metallic glasses during ion milling.
关键词:
room-temperature
陈篪
金属学报
<正> 目前,J_(Ⅰc)的测试引起了国内外的厂泛重视。三点弯曲试样得到了最广泛的应用。我们曾导出 J=(2U/B(W-a) (1)的关系,式中U是试样的应变能。Rice等在[2]中所建议的是另一关系 J=2/(B(W-a)integral from n=0 to △aPd△_a (2)其中 △_a=△-△_0 (3)△_0是同尺寸的无裂纹试样加载到同一载荷P时的位移。(1)和(2)式虽形式相近但内容不同究竟何者更为正确,很有必要加以澄清。 我们的推导是以U=B(W-a)~2f(△)或其等效关系P=B(W-a)~2φ(△)为出发点的,这里不再重复。Rice则假定
关键词:
张军
,
孙学峰
,
赵霞
,
李晓光
低温物理学报
doi:10.3969/j.issn.1000-3258.1999.04.010
本文研究了Hg0.7Cr0.3Sr2Ca2Cu3Oy, HgBa2Ca2Cu2.9Re0.1Oy, HgSr2Ca3Cu3.8}Re0.2Oy的磁性,发现Re的掺入会改变U-J关系.由驰豫测量结果分析得到Hg(Re)-1223,Hg(Re)-1234具有对数钉扎势U=U0H-nln(Jc0/J),其中对Hg(Re)-1223在20K～60K范围里U0和Jc0近似与温度无关; 对Hg(Re)-1234,U0和Jc0与磁场和温度有关.而Hg-1223具有幂次方钉扎势U=U0(Jc0/J)μ.另外,由磁化曲线M(H)的测量得到临界电流密度随磁场的变化关系.结果表明Hg(Re)-1223在20K～90K、Hg(Re)-1234在20K～70K的温度范围内,临界电流密度随磁场的变化关系均可以用由对数钉扎势得出的Jc(H)关系很好地描述.我们认为Re掺入引起的体系的各向异性的减小和岛状钉扎中心,使得材料钉扎能力增强并引起U-J关系的变化.
关键词:
谢兰清
,
王彩霞
兵器材料科学与工程
基于重整化平均场理论,在二维空穴掺杂t-t′-J-U模型的框架下,用Gutzwiller平均场近似理论研究高温超导体的基态相图,分析了次近邻跃迁电子(t′)对电子平均双重占据数(d)的影响.发现在掺杂浓度δ≠0的掺杂Gossamer超导态,次近邻跃迁的引入使d的数值在欠掺杂浓度区增大,在过掺杂浓度区显著减少.
关键词:
高温超导体
,
相图
,
电子态
,
电子次近邻跃迁
,
双重占据
Journal of Physics-Condensed Matter
The temperature dependences of the magnetization, internal energy and specific heat in a three-sublattice ferrimagnet or ferromagnet with /J(ab)/ = /J(bc)/ not equal /J(ca)/ are calculated within the framework of the linear spin-wave approximation, by employing retarded Green's functions. For both the ferromagnet and the ferrimagnet, the internal energy and the specific heat decrease with increasing J ' /J and/or the value of the spins. For fixed values of S,, Sb, S, and J ' /J, the internal energy and the specific heat increase, whereas the sublattice magnetization decreases with increasing temperature theta. The three-sublattice ferrimagnet has some particular characteristics which are not shown by the systems with two sublattices. For ferrimagnets, the antiferromagnetism of the system becomes weaker with increasing J ' /J. The sublattice magnetization at low temperatures (also the magnetization M(0) at 0 K) of a ferrimagnet increases with increasing J ' /J for fixed values of S(a), S(b) and S(c). The effects of the spins S(a) (S,) and Sb On the magnetizations of other sublattices differ. The characteristics of the a-sublattice are the same as those of the c-sublattice, due to their similarity as well as the symmetry of the system. The behaviours of the b-sublattice are different from those of the a- and c-sublattices, due to the asymmetry of the three-sublattice system. The spin-value dependences of the spin deviation Deltam per spin land also the energy for the zero-point quantum fluctuation) of the system are different for different sublattices. These differences are ascribed to the asymmetry of the three-sublattice systems, which leads to the new intrinsic properties of the systems.
关键词:
layered heisenberg ferrimagnets;spin-wave theory;elementary;excitations;superlattices;systems;magnetoresistance;antiferromagnet;interfaces
金属学报
J积分的临界值J_(Ic)(张开型)目前被广泛用作中低强度钢的断裂准则.根据线弹性断裂力学理论和弹塑性断裂力学的实验规律,现提出一个新的J积分和应变能间的关系式:J=2/B(W-α)[U—U_o+(M~2ψ)/(BE′W~2)],其中ψ与跨距S/W和裂纹深度α/W有关·此式对于跨距和裂纹深度没有限制,因而作为弯曲试样的J积分计算公式,具有较为广泛的适用范围·当α/W=0时,J=0,从物理意义上看也比较合理,为了便利计算,并列出ψ值表,可以查找。
关键词:
Physical Review B
The Hamiltonian for a four-sublattice Heisenberg ferrimagnet or ferromagnet with different exchange constants (J(ab) = J(cd) not equal J(bc) = J(da)) was established. An extended Bogoliubov transformation was developed by solving an equation group, consisting of 20 equations and 20 unknowns. The procedure for solving the equation group was carried out by introducing a simple way of reducing the numbers of the equations and the unknowns. The spin-wave spectra in the present system have been determined by performing the standard Holstein-Primakoff transformation and the Bogoliubov one. It has been found that the spin-wave spectra of the present system depend on the exchange constants and that the degeneracy of the spin-wave spectra remains. The results for a special case (J(ab) = J(bc)) i.e., an antiferromagnet are discussed briefly. The spin-wave spectra of the four-sublattice Heisenberg antiferromagnet are found to be degenerative also and they are linear in k for small k.
关键词:
model
Computer Physics Communications
Based on a detailed check of the LDA + U and GGA + U corrected methods, we found that the transition energy levels depend almost linearly on the effective U parameter. GGA + U seems to be better than LDA + U, with effective U parameter of about 5.0 eV. However, though the results between LDA and GGA are very different before correction, the corrected transition energy levels spread less than 0.3 eV. These more or less consistent results indicate the necessity and validity of LDA + U and GGA + U correction. (C) 2012 Elsevier B.V. All rights reserved.
关键词:
Band-gap problems;LDA plus U and GGA plus U;ZnO;First-principles;augmented-wave method
