密度泛函理论研究多巴胺在纯的,Fe和Ca掺杂的石墨烯材料表面的吸附机理

本论文用密度泛函理论方法研究了多巴胺在纯的,Fe和Ca掺杂的石墨烯上的吸附机理.通过它们之间的相互作用能,态密度,布局电荷,差分电荷密度分析发现多巴胺平行躺在纯的石墨烯表面主要是π…π,-CH…π相互作用,而垂直放在纯的石墨烯表面主要是-OH…π相互作用,这些都表现为典型的物理吸附.而Fe和Ca掺杂的石墨烯大大增强了多巴胺的吸附,主要体现为典型的化学吸附,因为掺杂金属原子与多巴胺的邻苯二酚羟基主要形成"bridge bidenate"or"monodenate"共价相互作用.而且我们发现"monodenate"共价作用不一定小于"bridge bidenate"共价作用,主要取决于相互作用原子之间最短距离的大小.研究结果有望为多巴胺-石墨烯基体系在生物组织工程,传感器方面的应用上提供有价值的理论指导.     

密度泛函理论研究草甘膦在纯的, 金属原子掺杂石墨烯表面的吸附机理

本研究采用密度泛函理论方法详细讨论了纯的石墨烯及Ti, Fe, Al, Ca原子掺杂石墨烯吸附草甘膦的机理.通过它们之间的吸附能,差分电荷密度,布居电荷,态密度分析发现草甘膦可以被纯的石墨烯及金属原子掺杂石墨烯不同程度地吸附.纯的石墨烯对草甘膦的吸附作用远不及掺杂石墨烯,其中,草甘膦在Ca掺杂石墨烯表面有最强相互作用.这是因为草甘膦与纯的石墨烯之间主要形成了-P=O…π,-COOH…π和-OH…π非共价的相互作用,而与掺杂石墨烯之间主要形成了Metal-O“单齿”和O-Metal-O“双齿”共价相互作用.本研究结果希冀为石墨烯在环境保护方面的应用提供有价值的理论指导.     

本征及掺杂石墨烯对2,3,7,8-四氯二苯并呋喃吸附机理的计算模拟研究

二噁英对人类和环境具有较高的毒性,因此,研制出有效的二噁英有机污染物的去除和检测方法尤为重要.本研究采用密度泛函理论模拟方法详细探讨了本征及Ti,Fe及Pt掺杂石墨烯对2,3,7,8-四氯二苯并呋喃(2,3,7,8-tetrachlorodibenzofuran,TCDF)二噁英污染物的吸附机理.研究结果表明,本征石墨烯及掺杂石墨烯表面对TCDF均有一定程度的吸附,而Ti和Fe掺杂石墨烯对TCDF的吸附远大于本征石墨烯对TCDF的吸附.主要原因是TCDF与本征石墨烯之间主要形成了π…π,C-H…π和C-Cl…π非共价的相互作用,而与掺杂石墨烯之间主要形成了metal-O共价相互作用.研究结果有望为石墨烯材料在二噁英污染物TCDF吸附方面的应用提供有价值的理论指导.     

DFT研究掺杂和电场条件下2,6-二氯苯并-2,4-二氯苯胺在石墨烯表面的吸附

本工作采用密度泛函理论详细探讨了2,6-二氯苯并-2,4-二氯苯胺（2,6-DBDA）氯代有机二噁英与纯的, Fe和Ti掺杂石墨烯之间的吸附机理, 并考虑了外加电场对吸附的影响. 结果表明掺杂 Fe和Ti原子增强了2,6-DBDA 在石墨烯表面的吸附, 这是因为Fe和Ti掺杂石墨烯与2,6-DBDA间形成了metal-N和metal-Cl共价相互作用. 此外, 在外加电场的作用下, 不同原子掺杂的石墨烯对2,6-DBDA的吸附影响不同. 2,6-DBDA-Ti-G体系, 在添加0.010 au的外电场时有最大相互作用, 而2,6-DBDA-Fe-G体系, 相互作用随着电场的施加反而有所减小. 金属掺杂及电场可以灵活调控2,6-DBDA在石墨烯表面的吸附, 此研究有望为氯代有机二噁英的检测及去除提供有价值的理论指导.     

密度泛函理论研究纯的及不同掺杂原子石墨烯和CaH_2分子相互作用

本研究采用密度泛函理论研究了纯的及V,Fe,Ni,Pd,Si,P,S和Cl掺杂原子的石墨烯和CaH_2分子之间相互作用.研究结果发现CaH_2分子与所有石墨烯表面均具有较大的相互作用,而CaH_2分子与掺杂石墨烯相互作用都大于与纯石墨烯的相互作用,在所有掺杂原子中,其中与Pd掺杂石墨烯具有最大的相互作用,S次之,其它掺杂石墨烯与CaH_2分子相互作用能力相差不大.这些结果表明虽然所有石墨烯均有助于CaH_2中H原子的脱附,但掺杂石墨烯脱附能力仍然大于纯的石墨烯.在掺杂原子中,Pd和S掺杂石墨烯对CaH_2中H原子的脱附效果最好,其它的掺杂原子脱附效果相差不明显.此研究结果将有望为CaH_2分子在石墨烯基材料中吸氢-脱氢行为提供有用的理论参考价值.     

密度泛函理论研究纯的及不同掺杂原子石墨烯和CaH2分子相互作用

本研究采用密度泛函理论研究了纯的及V, Fe, Ni, Pd, Si, P, S和Cl掺杂原子对石墨烯和CaH2分子之间相互作用. 研究结果发现CaH2分子与所有石墨烯表面均具有较大的相互作用, 而CaH2分子与掺杂石墨烯相互作用都大于与纯石墨烯的相互作用, 在所有掺杂原子中, 其中与Pd掺杂石墨烯具有最大的相互作用, S次之, 其它掺杂石墨烯与CaH2分子相互作用能力相差不大. 这些结果表明虽然所有石墨烯均有助于CaH2中H原子的脱附, 但掺杂石墨烯脱附能力仍然大于纯的石墨烯. 在掺杂原子中, Pd和S掺杂石墨烯对CaH2中H原子的脱附效果最好, 其它的掺杂原子脱附效果相差不明显. 此研究结果将有望为CaH2分子在石墨烯基材料中吸氢-脱氢行为提供有用的理论参考价值.     

B、N掺杂对钠在石墨烯上吸附性能的影响

采用基于密度泛函理论的第一性原理方法,研究了本征石墨烯及缺陷石墨烯对Na原子的吸附行为.主要研究了三种石墨烯:本征石墨烯、B掺杂的石墨烯和N掺杂的石墨烯.结果表明,与本征石墨烯相比,B掺杂的石墨烯和N掺杂的石墨烯在吸附能、电荷密度、态密度和储钠量方面表现出很大的差异.B掺杂的石墨烯对Na原子的吸附能是-1.93 e V,约为本征石墨烯对Na原子吸附能的2.7倍;与本征石墨烯相比,N掺杂的石墨烯对Na原子的吸附能明显增大.态密度计算结果表明,Na原子与B掺杂的石墨烯中的B原子发生轨道杂化,而本征石墨烯和N掺杂的石墨烯中不存在轨道杂化现象.B掺杂的石墨烯对Na原子的吸附量是3个,与本征石墨烯相比显著提高.因此,B掺杂的石墨烯有望成为一种新型的储钠材料.     

Na在B掺杂的空位石墨烯上吸附性能的第一性原理研究

采用基于密度泛函理论的第一性原理方法,研究了本征石墨烯和B掺杂的空位石墨烯吸附Na原子的电荷密度、吸附能、态密度、储存量以及电极电压.结果表明,两种石墨烯中,Na原子的最佳吸附位置都是H位.B掺杂的空位石墨烯对Na原子的吸附能是-2.08 eV,比本征石墨烯对Na原子的吸附能(-0.71eV)低很多.B掺杂的空位石墨烯中Na原子与B原子发生轨道杂化,本征石墨烯中没有杂化现象.B掺杂的空位石墨烯能够吸附12个Na原子,较本征石墨烯多.因此,B掺杂的空位石墨烯更适合储钠.     

氮掺杂的石墨烯作为钠离子电池负极材料的第一性原理研究

采用基于密度泛函理论的第一性原理方法,研究了本征石墨烯、氮掺杂的石墨烯和叽咯石墨烯吸附钠原子的电荷密度、吸附能、态密度和储存量.结果表明,三种石墨烯中,钠原子的最佳吸附位置为H位.与本征石墨烯相比,氮掺杂的石墨烯对钠原子的吸附能提高,叽咯石墨烯对钠原子的吸附能是-3.274 eV,约为本征石墨烯对钠原子吸附能的1.7倍.钠原子与叽咯石墨烯中的氮原子发生轨道杂化,而与本征石墨烯和氮掺杂的石墨烯没有发生轨道杂化现象.叽咯石墨烯能够吸附10个钠原子,与本征石墨烯相比显著提高,氮掺杂的石墨烯只能吸附4个钠原子.因此,叽咯石墨烯有望成为一种潜在的储钠材料.     

溶剂化效应对阴离子型天冬氨酸在HA (110)表面吸附行为影响的密度泛函理论研究

本工作用密度泛函理论研究了溶剂化效应对阴离子型天冬氨酸(Aspartic acid, ASP)在羟基磷灰石(110)表面[HA (110)]表面的吸附影响.通过分析相互作用能,态密度,布居电荷,差分电荷密度发现阴离子型天冬氨酸在真空条件下(Vacuum)与HA (110)表面主要形成"monodenate" Ca-O和"bridge bidenate" O-Ca-O相互作用,在隐形溶剂水分子(COSMO Water, CW)中也存在上述两种相互作用;在水环境条件下(Water Environment, WE),主要在天冬氨酸的羧基,水分子和HA表面的PO_4之间形成"water-bridge"氢键;在水层条件下(Water Layer, WL),主要形成"bridge bidenate" O-Ca-O相互作用,"water-bridge"氢键以及天冬氨酸中氨基与水分子形成的氢键.而且,研究发现ASP-HA (110)-Vacuum模型中吸附能最大,其次是ASP-HA (110)-WL模型,然后是ASP-HA (110)-CW模型,吸附能最小的模型是ASP-HA (110)-WE.研究结果表明在隐形溶剂水分子条件下, ASP在HA (110)表面吸附相对于真空条件下有所减小.当ASP中羧基在被水分子包围的水环境条件下,由于水分子阻碍了Ca-O静电相互作用,所以吸附达到最低.在水层条件下, HA (110)表面有一层水分子,但是未完全阻挡ASP中羧基时,羧基仍然可以与HA (110)表面的Ca原子形成Ca-O相互作用,此时吸附相对于水环境大大增大,但对于真空条件仍然有所减小.研究结果有望为氨基酸在不同溶剂中的应用提供有价值的理论指导.     

溶液法制备Graphene

Graphene因其优异的物理性能和潜在的应用前景,引起物理界和化学界的广泛关注,成为继碳纳米管后凝聚态物理和材料科学领域中又一研究热点,文章详细介绍了近几年发展起来的Graphene的溶液制备方法,例如石墨插层法、液相分散法、氧化石墨还原法、溶剂热法、芳香偶联法等,并对各种方法的特点进行了评述.     

Graphene的制备与结构特性

Graphene是一种严格的二维晶体材料,因其具有独特的结构和性能,已迅速成为国际新材料领域的研究前沿和热点,文章详细介绍了近几年发展起来的Graphene的化学制备方法,如SiC高温热解外延法、过渡金属催化外延法、化学修饰分散/还原法等,并对各种方法的特点,研究现状及应用前景进行了评述.     

Graphene的物理性质与器件应用

Graphene因其新奇的物理性质和广泛的应用前景已迅速成为国际新材料领域的研究前沿和热点.文章详细介绍了Graphene奇特的物理性质(多体相互作用、量子霍尔效应、双极场效应、弱局域化效应等),并对其在微纳米器件、分子电子学、自旋电子学等领域的应用进展给出了综述.     

Molecular dynamics simulation study on mechanical responses of nanoindented monolayer-graphene-nanoribbon

We investigated the mechanical responses of the nanoindented graphene-nanoribbon (GNR)-resonator using classical molecular dynamics simulations. The nanoindented force in this work was applied to the GNR's local point and then, GNR-resonator's frequency could be tuned by a nanoindented depth. We found the hardening or the softening of the GNR during its nanoindented-deflections, and such properties were recognized by the shift of the resonance frequency. The linear elastic regime in low applied force is explicitly separated with the non-linear elastic regime in high applied force. In particular, at the threshold point, a very small change of the nanoindented depth can cause great change in the resonance frequency, and this property can enable the GNR to be applied to electromechanical relay switching devices and the quantum-computer in quantum-mechanical coupling as well as mass detectors, pressure sensors, accelerometers, and alarms.     

Facile preparation of graphene nitride by irradiating MHz ultrasound

The present study aimed at developing a simple sonochemical method to prepare graphene nitride from the mixture of graphite and aqueous ammonia solution. Ultrasound of 1.6 MHz was irradiated to the sample in a fabricated sonoreactor at predetermined ultrasonic power and duration. The one-pot method succeeded in the preparation of graphene nitride. The generation was proven by XPS analysis in finding N1S peak in the spectrum. Detail analysis of N1s peak suggested that the major nitrogen species was pyrrolic type. Furthermore, the presence of CO bond proved the oxidation by OH radical. The reaction product had the value of N/C as high as 0.08, which is comparable to reported values for ultrasonic preparation of graphene nitride. The fact indicates that the significance of chemical effects of MHz range ultrasound, and the finding of the simple preparation method will accelerate practical application of graphene nitride.     

Surface adhesion properties of graphene and graphene oxide studied by colloid-probe atomic force microscopy

Surface adhesion properties are important to various applications of graphene-based materials. Atomic force microscopy is powerful to study the adhesion properties of samples by measuring the forces on the colloidal sphere tip as it approaches and retracts from the surface. In this paper we have measured the adhesion force between the colloid probe and the surface of graphene (graphene oxide) nanosheet. The results revealed that the adhesion force on graphene and graphene oxide surface were 66.3 and 170.6 nN, respectively. It was found the adhesion force was mainly determined by the water meniscus, which was related to the surface contact angle of samples.     

Energy exchange between vibration modes of a graphene nanoflake oscillator: Molecular dynamics study

We investigated the oscillatory behaviors of a square graphene-nanoflake (GNF) on a rectangular GNF via classical molecular dynamics simulations, and analyzed the energy exchange and the oscillation frequencies for three different modes. The simulation results using a model structure show that the GNF oscillator can be considered as a high frequency oscillator. As its initial velocity increases, its telescoping region increases, then its structural asymmetry along the axis due to own small rotation exerted asymmetric van der Waals (vdW) force on it, and finally, this asymmetric vdW force enhances its rotational motions during its axial translational motions. So the initial kinetic energy of the axial translational motion is changed into the energy of the orthogonal vibrational and the rotational motions. Its resonance frequencies are dependent on the aspect ratio of the bottom rectangular GNF, the difference between the lengths of the GNF oscillator and the bottom rectangular GNF, and the initial velocity.     

Graphene nanoribbon based terahertz antenna on polyimide substrate

Graphene nano ribbon based terahertz patch antenna on polyimide substrate is designed and its radiation characteristics are investigated in the 725–775 GHz band. The terahertz communication system consists of higher data rate transmission, low transmit power with secured wireless communication. The proposed antenna consists of graphene nano ribbon as radiating patch and also the ground plane separated by a 20 μm thin polyimide substrate. The antenna has achieved the broad impedance bandwidth (>5%) in the band of operation. The design has yielded a peak gain of 5.71dB at 750 GHz. The antenna is simulated by using the finite element method based simulator Ansys - HFSS.     

Ultrasound assisted reduction of graphene oxide to graphene in l-ascorbic acid aqueous solutions: Kinetics and effects of various factors on the rate of graphene formation

The reduction of graphene oxide (GO) to graphene (rGO) was achieved by using 20 kHz ultrasound in l-ascorbic acid (l-AA, reducing agent) aqueous solutions under various experimental conditions. The effects of ultrasound power, ultrasound pulse mode, reaction temperature, pH value and l-AA amount on the rates of rGO formation from GO reduction were investigated. The rates of rGO formation were found to be enhanced under the following conditions: high ultrasound power, long pulse mode, high temperature, high pH value and large amount of l-AA. It was also found that the rGO formation under ultrasound treatment was accelerated in comparison with a conventional mechanical mixing treatment. The pseudo rate and pseudo activation energy (E_a) of rGO formation were determined to discuss the reaction kinetics under both treatment. The E_a value of rGO formation under ultrasound treatment was clearly lower than that obtained under mechanical mixing treatment at the same condition. We proposed that physical effects such as shear forces, microjets and shock waves during acoustic cavitation enhanced the mass transfer and reaction of l-AA with GO to form rGO as well as the change in the surface morphology of GO. In addition, the rates of rGO formation were suggested to be affected by local high temperatures of cavitation bubbles.     

Nonvolatile graphene nanoflake shuttle memory

We present the possible schematics of nanoscale graphene-flake shuttle-memory, discuss its basic principles, and investigate the energetic and the dynamic properties via classical molecular dynamics simulations. Graphite flake surface, where the nanoscale graphene-flake’s stage of activity takes place, has a dumbbell shape, and a nanoscale graphene-flake is placed on its surface. The van der Waals interactions between the graphene-flake and the patterned graphite make the bistable potential energy wells in the larger surface area regions of the patterned graphite, and then the graphene-flake keeps its seat on one of the bistable positions, which is the place where the binary data is archived. Since the movable graphene-flake can be also shuttled between the bistable states through the narrow passageway, this proposed nano-graphene-flake shuttle-memory can be utilized from nanoscale switchable nonvolatile memory.