CAREER:Two-Dimensional Materials with Addressable Surfaces

职业：具有可寻址表面的二维材料

• 批准号: 1751949
• 负责人: Xavier Roy
• 金额: $ 61.35万
• 依托单位: Columbia University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-09-01 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1751949&HistoricalAwards=false
• 关键词: CAREER; Two; Dimensional; Materials; Addressable

Non-Technical Summary:Two-dimensional (2D) materials are crystalline materials which are only a single layer or a few layers of atoms thick. Such materials have recently received widespread attention for the development of novel technologies in nano(opto)electronics, catalysis, sensing, and energy production. This NSF CAREER project, supported by the Solid State and Materials Chemistry program in the Division of Materials Research, integrates research and educational activities centered on the design and synthesis of a new family of 2D materials, and advances the understanding of the relation between their surface functionalization and physical properties. Realizing the great transformative promises of 2D materials hinges on the development of effective methods to control the surface chemistry and thereby change the intrinsic physical properties and materials chemistry of the thin layers. This remains a major challenge for most known 2D materials. They are chemically non-reactive. To overcome this hurdle, the project develops a series of cluster-based metal chalcogenide 2D materials. The surfaces of the individual clusters can be modified more easily while leaving the internal structure of the inorganic layer intact. The overall goal is to develop chemical strategies to change the outside of these 2D materials by attaching different molecules, and then study how these modifications alter the optical and electronic properties of the layers. This project advances the scientific understanding and potential technological applications of 2D materials by providing a path towards creating multifunctional 2D materials with tunable physical, chemical and surface properties. Such 2D materials have never been synthesized and their novel cluster-based structures produces unique physical properties. The research effort is integrated with educational and outreach activities aimed at increasing the participation of historically underrepresented groups in STEM, and strengthening the scientific workforce. A coordinated effort spans high school and middle school outreach, interdisciplinary research training for undergraduate and graduate scientists, and curriculum development.Technical Summary:This NSF CAREER project, supported by the Solid State and Materials Chemistry program in the Division of Materials Research, integrates research and educational activities centered on the design and synthesis of a new family of 2D materials, and furthers the understanding of the relation between their surface functionalization and physical properties. The proposed materials are composed of covalently-linked metal chalcogenide clusters capped by substitutionally labile halogen atoms. These 2D materials are exfoliated from bulk layered van der Waals cluster solids, Re6Se8Cl2 and Mo6S3Br6. The research tests the hypothesis that the optical and electronic properties of these 2D materials are strongly influenced by the nature of the ligands on the surface. The PI and his students develop substitution reactions to functionalize the surface of the 2D materials with a series of ligands with programmed characteristics (charge, ligand field strength, dipole), and measure the resulting optical properties and surface electronic states, before and after functionalization. The materials are integrated into model electrical devices to probe the effect of ligand substitution on the electronic properties. A critical factor for the development of the field of 2D materials is the ability to control their properties. In this context, the development of surface functionalization strategies is of great scientific and technological interest as a path towards creating multifunctional 2D materials with tunable physical, chemical and surface properties. Current methods are severely limited because they yield very low surface coverage, they generate a vast number of defects and/or they rely on weak non-covalent interactions. This research overcomes these hurdles and enable the covalent functionalization of 2D materials with high coverage rates while preserving the internal structure of the inorganic framework.The educational component of this NSF CAREER project aims to inspire students (middle school, high school, undergraduate, and graduate) to pursue careers in STEM, as well as broaden the participation of historically underrepresented groups in STEM and enhance the undergraduate chemistry curriculum. The focus on recruiting students form historically underrepresented groups prevails in four approaches: (1) Outreach activities to middle-school and high-school students from Central Harlem and the Bronx in New York City; (2) Recruit undergraduate students to work in the PI's laboratory for early research experiences; (3) Recruit and mentor graduate students in multidisciplinary research combining chemistry and materials science; (4) Integrate the research into the Chemistry undergraduate curriculum.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

非技术综述：二维(2D)材料是只有一层或几层原子厚度的晶体材料。这种材料在纳米(光电)电子学、催化、传感和能源生产等领域的新技术开发中受到了广泛的关注。这个NSF职业项目由材料研究部的固态和材料化学计划支持，整合了以设计和合成新的2D材料家族为中心的研究和教育活动，并促进了对其表面功能化和物理性能之间关系的理解。实现2D材料的巨大变革前景取决于开发有效的方法来控制表面化学，从而改变薄层的内在物理性质和材料化学。对于大多数已知的2D材质来说，这仍然是一个重大挑战。它们在化学上是非反应性的。为了克服这一障碍，该项目开发了一系列基于团簇的金属硫化物2D材料。在保持无机层内部结构不变的情况下，单个团簇的表面可以更容易地进行修饰。总体目标是开发化学策略，通过附着不同的分子来改变这些2D材料的外部，然后研究这些修饰如何改变这些层的光学和电子性质。该项目通过提供一条创造具有可调物理、化学和表面属性的多功能2D材料的途径，促进了对2D材料的科学理解和潜在的技术应用。这种2D材料从未被合成过，其新颖的基于团簇的结构产生了独特的物理性质。研究工作与教育和外联活动相结合，旨在增加历史上代表性不足的群体在STEM中的参与，并加强科学工作者。技术总结：这个NSF职业项目由材料研究部的固态和材料化学项目支持，整合了以设计和合成新的2D材料家族为中心的研究和教育活动，并加深了对其表面功能化和物理性质之间关系的理解。所提出的材料是由共价连接的金属硫化物簇合物组成的，其顶端是取代基不稳定的卤素原子。这些2D材料是从块状层状van der Waals团簇固体Re6Se8Cl2和Mo6S3Br6剥离而来的。这项研究验证了这样一种假设，即这些2D材料的光学和电子性质强烈地受到表面配体的性质的影响。PI和他的学生开发了取代反应，用一系列具有编程特征(电荷、配位体场强、偶极)的配体对2D材料的表面进行功能化，并测量功能化前后产生的光学性质和表面电子态。将这些材料集成到模型电器件中，以探索配体取代对电子性质的影响。2D材料领域发展的一个关键因素是控制其性能的能力。在这种背景下，表面功能化策略的发展具有重大的科学和技术意义，因为它是创造具有可调物理、化学和表面性质的多功能2D材料的途径。目前的方法受到严重的限制，因为它们产生非常低的表面覆盖率，它们产生大量的缺陷和/或它们依赖于弱的非共价相互作用。这项研究克服了这些障碍，实现了2D材料的共价功能化，覆盖率高，同时保留了无机框架的内部结构。这个NSF职业项目的教育部分旨在激励学生(初中、高中、本科生和研究生)在STEM追求职业生涯，以及扩大历史上代表性不足的群体在STEM的参与，并加强本科化学课程。从历史上代表性不足的群体中招收学生的重点在四个方面盛行：(1)向纽约市哈莱姆区和布朗克斯区的初中生和高中生开展外联活动；(2)招募本科生到PI的实验室工作，以获得早期研究经验；(3)招募和指导结合化学和材料科学的多学科研究的研究生；(4)将研究纳入化学本科课程。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Cyclopropenylidenes as Strong Carbene Anchoring Groups on Au Surfaces

• DOI: 10.1021/jacs.0c10743
• 发表时间: 2020-11-25
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Doud, Evan A.;Starr, Rachel L.;Roy, Xavier
• 通讯作者: Roy, Xavier

Hierarchical Coherent Phonons in a Superatomic Semiconductor

• DOI: 10.1002/adma.201903209
• 发表时间: 2019-07
• 期刊: Advanced Materials
• 影响因子: 29.4
• 作者: Kihong Lee;S. Maehrlein;Xinjue Zhong;D. Meggiolaro;Jake C. Russell;Douglas A Reed;Bonnie Choi;F. De Angelis;Xavier Roy;Xiaoyang Zhu

Room-temperature wavelike exciton transport in a van der Waals superatomic semiconductor

• DOI: 10.1126/science.adf2698
• 发表时间: 2023-06
• 期刊: Science
• 影响因子: 56.9
• 作者: Jakhangirkhodja A. Tulyagankhodjaev;Petra Shih;Jessica Yu;Jake C. Russell;Daniel G. Chica;Michelle E. Reynoso;Haowen Su;Athena C. Stenor;Xavier Roy;Timothy C. Berkelbach;Milan Delor

Site-Selective Surface Modification of 2D Superatomic Re 6 Se 8

二维超原子 Re 6 Se 8 的位点选择性表面修饰

• DOI: 10.1021/jacs.1c10833
• 发表时间: 2022
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: He, Shoushou;Evans, Austin M.;Meirzadeh, Elena;Han, Sae Young;Russell, Jake C.;Wiscons, Ren A.;Bartholomew, Amymarie K.;Reed, Douglas A.;Zangiabadi, Amirali;Steigerwald, Michael L.
• 通讯作者: Steigerwald, Michael L.

A few-layer covalent network of fullerenes

• DOI: 10.1038/s41586-022-05401-w
• 发表时间: 2023-01-05
• 期刊: NATURE
• 影响因子: 64.8
• 作者: Meirzadeh, Elena;Evans, Austin M.;Roy, Xavier
• 通讯作者: Roy, Xavier