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81.
贵金属物种(Rh或Ir络合物)在均相羰基化和氢甲酰化催化过程得到了广泛的应用,但始终存在分离繁琐等问题,其均相多相化可很大程度上简化分离操作,故一直广受重视.单位点催化剂因其具有可与均相相比拟的较高金属利用率和选择性而成为均相多相化的重要研究方向之一.研究发现,在碘物种存在的情况下用于固载金属物种的配位键容易断裂,进而导致金属物种的流失,而通过离子键固载的[Rh(CO)2I2]–物种更加稳定,比如著名的甲醇羰基化“AceticaTM”工艺中,[Rh(CO)2I2]–负一价阴离子物种是以离子键的方式固定在带有阳离子骨架的甲基化聚乙烯吡啶树脂上.与甲醇羰基化过程类似的乙醇羰基化过程是生产重要化工中间体丙酸的主要途径之一,但该过程的均相多相化始终存在着稳定性差这一关键问题.为了解决这一问题,基于之前将固载于季鏻盐聚合物的[Rh(CO)I3]2–应用于甲醇羰基化的工作,我们将类似的季鏻盐聚合物固载Rh基催化剂Rh-TPISP用于多相乙醇羰基化过程,通过多种表征进一步证明了Rh物种和P物种结构,并提出了“双离子键”模型.P的K边XANES证明了聚合物TPISP的季鏻化阳离子骨架特征.HAADF-STEM测试表明Rh-TPISP中的Rh呈现单位点分散的状态.Rh的XPS和XANES结果证明了Rh-TPISP中Rh物种的价态介于0~+1.通过EXAFS的拟合解析给出了[Rh(CO)I3]2–活性中心结构.由于[Rh(CO)2I2]–为经典的羰基化活性中心,为了进一步证明该结构的正确性,我们将Rh-TPISP的EXAFS和IR谱图与标样[PPh3Et]+[Rh(CO)2I2]–对比发现:在EXAFS谱图中,Rh-TPISP中的Rh-C峰高低于[PPh3Et]+[Rh(CO)2I2]–的Rh-C峰高,而Rh-TPISP中的Rh-I峰高高于[PPh3Et]+[Rh(CO)2I2]–的Rh-I峰高,这就说明Rh-TPISP中Rh物种的Rh-C配位数小于2,而Rh-I配位数大于2;在IR谱图中,标样[PPh3Et]+[Rh(CO)2I2]–中有两个羰基振动峰,与该物种的两个Rh-C配位键相符,而Rh-TPISP中的只有一个羰基振动峰,说明Rh-C配位数为1.因此,Rh-TPISP催化剂的季鏻盐骨架中的每个P物种带有一个正电荷,每个带有两个负电荷的[Rh(CO)I3]2–通过与两个[P]+的静电作用进行固载,形成“双离子键”结构.该催化剂在固定床乙醇羰基化过程中表现出优异的羰基化活性、选择性和稳定性.在3.5 MPa、195 oC反应近1000 h后,Rh-TPISP催化剂TOF保持在约350 h–1,丙酰基选择性为95%以上,高出所有文献报道的均相和多相乙醇羰基化活性.其较高的活性主要是因为[Rh(CO)I3]2–比传统Rh活性相[Rh(CO)2I2]–具有更强的富电子性,而较高的稳定性主要是由于“双离子键”这种强静电作用比“AceticaTM”工艺中“单离子键”更有利于Rh物种的固载.故Rh-TPISP催化剂中的“双离子键”对其优异的催化性能具有极其重要的作用,对后续多相乙醇羰基化的发展具有重要意义. 相似文献
82.
Akpan N. Ikot Gaotsiwe Joel Rampho Precious O. Amadi Uduakobong S. Okorie Makagamathe J. Sithole Mantile L. Lekala 《International journal of quantum chemistry》2020,120(24):e26410
The Shannon entropy (S) and the Fisher Information (I) entropies are investigated for a generalized hyperbolic potential in position and momentum spaces. First, the Schrodinger equation is solved exactly using the Nikiforov-Uvarov-Functional Analysis method to obtain the energy spectra and the corresponding wave function. By Fourier transforming the position space wave function, the corresponding momentum wave function was obtained for the low-lying states corresponding to the ground and first excited states. The positions and momentum of Shannon entropy and Fisher Information entropies were calculated numerically. Finally, the Bialynicki-Birula and Mycielski and the Stam-Cramer-Rao inequalities for the Shannon entropy and Fisher Information entropies, respectively, were tested and were found to be satisfied for all cases considered. 相似文献
83.
84.
Faizuddin Ahmed 《理论物理通讯》2020,72(7):75102
In this paper, we investigate the relativistic quantum dynamics of spin-0 massive charged particles in a Gödel-type space–time with electromagnetic interactions. We derive the radial wave equation of the Klein–Gordon equation with an internal magnetic flux field and Coulomb-type potential in the Som–Raychaudhuri space–time with cosmic string. We solve this equation and analyze the analog effect in relation to the Aharonov–Bohm effect for bound states. 相似文献
85.
《Physics letters. A》2020,384(16):126322
Quantum key distribution (QKD) is a promising application to establish unconditional secure communications by quantum mechanics. However, its widespread application still faces a great challenge, that is, the fundamental linear key-rate constraint called Pirandola-Laurenza-Ottaviani-Banchi (PLOB) bound. Recently, twin-field QKD (TF-QKD) was proposed (Lucamarini et al., 2018 [4]), it overcomes the constraint mentioned above. However, the original TF-QKD is based on the phase-encoding strategy, which requires active alignment. In this paper, we improve the original TF-QKD with the photon orbital angular momentum (OAM), and propose a novel reference frame independent protocol to overcome the reference frame dependence. No more alignment procedure is needed, and the intrinsic misalignment errors are eliminated by utilizing the rotation-invariance of OAM photons. Besides, the security performance is also improved. 相似文献
86.
Toshio Nishi Hideyuki Nukaga So Fujinami Ken Nakajima 《高分子科学》2007,(1):35-41
Atomic force microscopy (AFM) has the advantage of obtaining mechanical properties as well as topographic information at the same time. By analyzing force-distance curves measured over two-dimensional area using Hertzian contact mechanics, Young's modulus mapping was obtained with nanometer-scale resolution. Furthermore, the sample deformation by the force exerted was also estimated from the force-distance curve analyses. We could thus reconstruct a real topographic image by incorporating apparent topographic image with deformation image. We applied this method to carbon black reinforced natural rubber to obtain Young's modulus distribution image together with reconstructed real topographic image. Then we were able to recognize three regions; rubber matrix, carbon black (or bound rubber) and intermediate regions. Though the existence of these regions had been investigated by pulsed nuclear magnetic resonance, this paper would be the first to report on the quantitative evaluation of the interfacial region in real space. 相似文献
87.
气相色谱-质谱法检测沉积物中自由态与束缚态多溴联苯醚和四溴双酚-A 总被引:3,自引:1,他引:3
建立了一种同时测定沉积物中不同赋存形态的多溴联苯醚(PBDEs)和四溴双酚A(TBBPA)的分析方法.样品由等体积的丙酮和正己烷混合溶剂抽提得到自由态目标物,再通过碱性水解反应释放束缚态目标化合物.通过调节酸度(pH值)实现PBDEs和TBBPA的分离和提取.PBDEs由复合硅胶柱净化,运用气相色谱-质谱(负离子化学源)-分时段选择离子监测技术测定;TBBPA经重氮甲烷衍生化反应后由酸性硅胶柱预纯化,运用气相色谱-质谱(电子轰击源)-分时段选择离子监测技术测定.8种低溴联苯醚(BDE28,-47,-66,-100,-99,-154,-153,-183),十溴联苯醚(BDE209)和TBBPA的检出限分别为0.6~12.5 pg/g,172 pg/g,4 2 pg/g.方法具有良好的准确度和精确度,回收率均在74%~106%之间,RSD≤10%.对东江沉积物样品的分析表明,本方法能够实现不同形态的PBDEs 和TBBPA的有效检测. 相似文献
88.
The behavior of a terminally anchored freely-jointed bead-rod chain, subjected to solvent shear flow, was investigated via Brownian dynamics simulations. Previous calculations have been improved by computing the segment density and fluid velocity profiles self-consistently. The segment density distributions, components of the radius of gyration, and chain attachment shear and normal stresses were found to be sensitive to low values of shear rate. Additionally, it was found that the thickness of a model polymer layer was a strong function of the shear rate, and that the functional dependence on shear rate changed dramatically as the chain length increased. For the longest chains studied, the thickness of the model polymer layer first increased as the shear rate increased, passed through a maximum, and then decreased at high shear rates, in accordance with experimental results in theta solvents. These results suggest that a dilute or semi-dilute layer model may explain hydrodynamic behavior previously thought to be due to the entanglements that occur in dense surface bound polymer layers.Nomenclature
a
i
acceleration of bead i
-
b
radius of the beads
-
d
length of the rods connecting the chain beads
-
d
i
vector from bead i to bead i + 1
-
F
i
external force applied to bead i
-
F
i
b
external force on bead i due to Brownian motion of surrounding fluid
-
F
i
h
external force on bead i due to viscous drag
-
F
i
s
external force on bead i due to surface interactions
-
f
Stokes drag coefficient
-
Boltzmann's constant
-
L
h
effective hydrodynamic thickness
-
m
i
mass of bead i
-
N
number of beads on a model chain
-
n
number of chains anchored to the surface per unit surface area
-
P
segment density distribution P pressure
-
Q
flow in a tube with no surface bound polymer layer
-
Q
a
flow in a tube with a surface bound polymer layer
-
R
g
vector representation of the radius of gyration
-
R
tube radius
-
r
radial coordinate in the tube geometry
-
S
ij
pair hydrodynamic interaction tensor for beads i and j
-
T
i
internal chain force in rod i connecting beads i and i + 1
-
T
X
component of the surface attachment force in the direction of the fluid flow
-
T
y
component of the surface attachment force perpendicular to the surface
-
T
temperature
-
v
i
velocity of the center of mass of bead i
-
V
if
average fluid velocity at the location of bead i
-
v
if
0
fluid velocity in the absence of a polymer chain
-
v
if
perturbation to the fluid velocity due to hydrodynamic interactions
-
V
b
bead volume = 4 b
3/3
-
scalar fluid speed in the axial direction down the tube
-
x
axial coordinate in the tube geometry
Greek symbols w
apparent shear rate
-
fluid viscosity
-
polymer layer permeability
-
volume fraction of space occupied by chain beads
- (w)a
chain attachment stress perpendicular to the surface
- (w)a
chain attachment stress in the plane of the surface and in the direction of fluid flow 相似文献
89.
根据单个保单理赔额分布函数F(z)的一些特殊性质,研究了开放个别风险模型在保单个数N为Poisson分布下,总理赔额分布函数F_S(x)对任意x(x≥0)的界值问题,得到一些实用的、便于数值计算的界值结果,具有重要的应用价值. 相似文献
90.