硼烯：从理论模型到探究应用

1995年,德国科学家布斯塔尼通过理论计算提出了硼团簇的构造法则——“Aufbau原则”,为硼烯的理论模型研究奠定了基础。在新的理论和计算方法不断提出的背景下,硼烯的理论模型得到了进一步的完善,2014年,美国布朗大学的王来生正式提出“硼烯”这一概念,至此二维硼烯的概念得到了广泛的确信。2015年,研究者首次报道在Ag(111)衬底上生成二维硼烯薄膜。随后,科学家们通过实验探究发现硼烯在超导材料、电池电极材料、催化剂、储氢等领域有巨大的应用前景。硼烯的发展史揭示了理论和实验交互验证的新型科学发展模式,促进了二维材料发展观的演进。     

石墨烯导热性能及其测试方法

石墨烯以其独特的结构和优异的性能引起人们广泛的关注。本文通过总结近期国内外石墨烯导热工作研究进展,梳理了石墨烯的导热机理,根据导热机理指出缺陷、基底、石墨烯边缘是影响石墨烯热导率的主要因素。综述了采用分子动力学及非平衡态格林函数方法进行石墨烯热导率模型计算的研究成果,并在模型的基础上,全面阐述了实验方面针对不同层数石墨烯热导率的测试方法及结果。     

氟元素的发现:从假说到客观实在

通过从科学认识论、科学方法论、化学思想等方面对氟元素的发现历程考证分析可知,氟元素的发现不是先发现元素物质,后形成元素概念,而是一个从假说到客观实在的验证过程。科学家以实践为基础,运用逻辑思维和直觉思维预见了氟元素的存在,并不断探索、创新研究方法、自制实验仪器,最终证实了氟元素假说,同时也验证了元素周期律,使卤族元素概念走向成熟,使化学元素观得以演进。     

石墨烯晶圆的制备：从高品质到规模化

石墨烯晶圆是引领未来的战略材料,在集成电路、微机电系统和传感器等领域具有广阔的应用前景。实现石墨烯晶圆广泛应用的前提是高品质材料的规模化制备。可控性高、工艺兼容性强、成本低的化学气相沉积(chemical vapor deposition,CVD)法,是高品质石墨烯晶圆规模化制备的首选方法。本文将综述石墨烯晶圆的CVD制备进展：首先探讨石墨烯晶圆的制备需求,从实用牵引和应用场景出发,提出石墨烯晶圆的制备品质等级;随后重点介绍石墨烯的晶圆级制备方法和石墨烯晶圆材料的规模化制备技术;最后,对石墨烯晶圆可行的制备路线进行总结,并展望未来可能的发展方向。     

石墨烯研究进展

石墨烯是目前发现的唯一存在的二维自由态原子晶体,它是构筑零维富勒烯、一维碳纳米管、三维体相石墨等sp²杂化碳的基本结构单元,具有很多奇异的电子及机械性能。因而吸引了化学、材料等其它他领域科学家的高度关注。本文介绍了近几年石墨烯的研究进展,包括石墨烯的合成、去氧化、化学修饰及应用前景等方面的内容。     

氧化石墨烯和石墨烯在催化领域中的应用研究进展

石墨烯具有独特的二维平面结构,其导电性能好,比表面积大,耐酸碱,耐高温.基于石墨烯的优异特性,本文作者从材料的合成和结构等方面对石墨烯基催化剂的研制及其催化性能进行了评述.介绍了石墨烯催化体系的类型和机理,对石墨烯催化中存在的问题进行了简单分析,并对石墨烯在催化领域的应用前景进行了展望.     

石墨烯和氧化石墨烯的表面功能化改性

石墨烯和氧化石墨烯由于特殊的电子、光学、力学性能已成为当今科学研究的热点.重点综述了近年来石墨烯和氧化石墨烯的表面功能化改性研究进展.首先介绍了石墨烯、氧化石墨烯的基本结构与性质.然后将表面功能化分为非共价键结合改性、共价键结合改性和元素掺杂改性.非共价键结合的功能化改性分为四类：π-π键相互作用、氢键作用、离子键作用以及静电作用.共价键结合的功能化改性分为四类：碳骨架功能化、羟基功能化、羧基功能化和环氧基功能化.元素掺杂改性分为N、B、P等不同元素的掺杂功能化.总结了石墨烯、氧化石墨烯基体与改性分子的相互作用和反应类型,以及改性产物的性能与应用.最后对石墨烯和氧化石墨烯在表面功能化改性方面的发展前景作了展望和预测.     

新型石墨烯基LED器件：从生长机理到器件特性

III族氮化物因具有禁带宽度大、击穿电压高、电子饱和漂移速度大、稳定性高等优异特性而广泛应用在发光二极管(LED)、激光器以及高频器件中。目前III族氮化物薄膜通常是异质外延生长在蓝宝石衬底表面,但是由于蓝宝石与III族氮化物之间存在较大的晶格失配与热失配,使得外延生长的III族氮化物内部存在较大的应力与较高的位错密度,严重影响了器件性能;与此同时,蓝宝石衬底热导率差,限制了其在大功率器件方面的应用。近年来研究发现,石墨烯作为外延生长缓冲层,能够有效解决蓝宝石衬底与外延III族氮化物薄膜之间由于晶格失配和热失配导致的高应力与高位错密度等问题,进而获得了高品质薄膜,并提升了器件的性能。本文综述了石墨烯/蓝宝石衬底上III族氮化物生长与LED器件构筑的研究现状,着重介绍了本课题组提出的一种新型外延衬底—石墨烯/蓝宝石衬底的特点,阐明了III族氮化物在该新型衬底上的生长机理,总结了其对III族氮化物质量提升的作用,并对其发展前景进行了展望。     

石墨烯和铂/石墨烯的合成及其表征

以天然鳞状石墨为原料,采用化学氧化法合成氧化石墨,在此基础上采用低温热解膨胀结合微波加热乙二醇还原法合成石墨烯(Gr)以及铂/石墨烯(Pt/Gr)复合材料。SEM和TEM显示所制备的石墨烯为层状结构的半透明薄膜。采用X射线光电子能谱(XPS)和傅立叶转换红外光谱(FTIR)分别确定氧化石墨、膨胀石墨及石墨烯表面含氧官能团的数量和性质。以所制备的碳氧原子比5.94的石墨烯作为载体制备出可用于质子交换膜燃料电池的高负载量的Pt/Gr催化剂,在铂载量高达60%时,表面铂粒子依然具有高分散性,平均粒径为3.8 nm。     

静电纺丝理论模型的研究进展

静电纺丝技术是制备纳米纤维最直接、最有效的方法之一,其生产过程简单经济从而成为世界研究的热点。但是由于静电纺丝过程的复杂性,导致其研究一直处于实验阶段。如何完善数学、力学等理论模型是静电纺丝研究的基础问题,对静电纺丝工艺参数和设备制造有着重要的意义。本文论述了国内外静电纺丝理论模型的研究现状和进展,重点介绍了静电纺丝射流理论模型的研究及需要解决的理论问题,展望了静电纺丝理论模型研究的发展前景。     

Cycloaddition of Nitrile Oxides to Graphene: a Theoretical and Experimental Approach

Density functional theory (DFT) studies of the interaction between graphene sheets and nitrile oxides have proved the feasibility of the reaction through 1,3-dipolar cycloaddition. The viability of the approach has been also confirmed experimentally through the cycloaddition of few-layer exfoliated graphene and nitrile oxides containing functional organic groups with different electronic nature. The cycloaddition reaction has been successfully achieved in one-pot from the corresponding oximes under microwave (MW) irradiation. The successful formation of the isoxazoline ring has been confirmed by Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS).     

实验和理论研究石墨烯氧化物的铁电性

基于独特的结构和性质, 石墨烯在很多领域都表现出了巨大的潜力. 作为制备石墨烯的主要母体材料, 石墨烯氧化物在室温条件下被观测到具有弱的铁电性. 石墨烯氧化物的表面和边界上会存在大量的羟基, 这些羟基有序重复排列而构成了一维的氢键链, 这些有序氢键链可能是石墨烯氧化物呈现铁电性能的主要原因.     

从理论模型到探究应用：二维材料锡烯的发展史

2011年,中科院物理研究所的姚裕贵教授从理论上对二维锡进行了研究,首次预测了二维锡是一种拓扑绝缘体。至2013年,二维锡的理论研究已较为成熟,美国斯坦福大学的张首晟教授基于锡的拉丁文stannum和二维烯材料2D-Xene后缀组合正式提出了锡烯(Stanene)的概念。2015年,上海交通大学的贾金锋教授等人利用分子束外延技术在Bi₂Te₃(111)衬底上首次成功地生长出了二维锡烯。随后,锡烯在不同衬底上相继生成,其制备方法取得了一定的进展。人们也在制备探究中逐渐发现,锡烯具有优异的物化性质,在众多领域内有良好的应用前景。锡烯的发展史重新诠释了二维材料的发展机制,为新型二维材料的预测、制备与应用提供了新的视角和思路。     

From Graphene to Carbon Nanotubes: Variation of the Electronic States and Nonlinear Optical Responses

From the same piece of graphene sheet, (3, 3) and (6, 0) carbon nanotube clips were obtained on the basis of the different manners of rolling. The nature of the electronic state varies differently with different manners of rolling and is significantly affected by zigzag edges. The intermediate structures formed during the rolling process were functionalized with fluorine and oxygen atoms to investigate the electronic states and nonlinear optical (NLO) responses. Passivation of the intermediate structures with fluorine neither changes the nature of electronic states and nor improves the NLO responses. In constrast, passivation with oxygen enhances the NLO properties and changes the electronic states of the structures upon passivating at the open zigzag edges.     

Theoretical Study on the Aggregation and Adsorption Behaviors of Anticancer Drug Molecules on Graphene/Graphene Oxide Surface

Graphene and its derivatives are frequently used in cancer therapy, and there has been widespread interest in improving the therapeutic efficiency of targeted drugs. In this paper, the geometrical structure and electronic effects of anastrozole(Anas), camptothecin(CPT), gefitinib (Gefi), and resveratrol (Res) on graphene and graphene oxide(GO) were investigated by density functional theory (DFT) calculations and molecular dynamics (MD) simulation. Meanwhile, we explored and compared the adsorption process between graphene/GO and four drug molecules, as well as the adsorption sites between carriers and payloads. In addition, we calculated the interaction forces between four drug molecules and graphene. We believe that this work will contribute to deepening the understanding of the loading behaviors of anticancer drugs onto nanomaterials and their interaction.     

A New Member of the Graphene Family: Graphene Acid

A new member of the family of graphene derivatives, namely, graphene acid with a composition close to C₁(COOH)₁, was prepared by oxidation of graphene oxide. The synthetic procedure is based on repeated oxidation of graphite with potassium permanganate in an acidic environment. The oxidation process was studied in detail after each step. The multiple oxidations led to oxidative removal of other oxygen functional groups formed in the first oxidation step. Detailed chemical analysis showed only a minor amount of other oxygen‐containing functional groups such as hydroxyl and the dominant presence of carboxyl groups in a concentration of about 30 wt %. Further oxidation led to complete decomposition of graphene acid. The obtained material exhibits unique sorption capacity towards metal ions and carbon dioxide. The highly hydrophilic nature of graphene acid allowed the assembly of ultrathin free‐standing membranes with high transparency.     

From 2D Graphene Nanosheets to 3D Graphene‐based Macrostructures

The combination of exceptional functionalities offered by 3D graphene‐based macrostructures (GBMs) has attracted tremendous interest. 2D graphene nanosheets have a high chemical stability, high surface area and customizable porosity, which was extensively researched for a variety of applications including CO₂ adsorption, water treatment, batteries, sensors, catalysis, etc. Recently, 3D GBMs have been successfully achieved through few approaches, including direct and non‐direct self‐assembly methods. In this review, the possible routes used to prepare both 2D graphene and interconnected 3D GBMs are described and analyzed regarding the involved chemistry of each 2D/3D graphene system. Improvement of the accessible surface of 3D GBMs where the interface exchanges are occurring is of great importance. A better control of the chemical mechanisms involved in the self‐assembly mechanism itself at the nanometer scale is certainly the key for a future research breakthrough regarding 3D GBMs.     

Defect‐Assisted Covalent Binding of Graphene to an Amorphous Silica Surface: A Theoretical Prediction

We propose a mechanism for defect‐assisted covalent binding of graphene to the surface of amorphous silica (a‐SiO₂) based on first‐principles density functional calculations. Our calculations show that a dioxasilirane group (DOSG) on a‐SiO₂ may react with graphene to form two Si? O? C linkages with a moderate activation barrier (≈0.3 eV) and considerable exothermicity (≈1.0 eV). We also examine DOSG formation via the adduction of molecular O₂ to a silylene center, which is an important surface defect in a‐SiO₂, and briefly discuss modifications in the electronic structure of graphene upon the DOSG‐assisted chemical binding onto the a‐SiO₂ surface.