Understanding the bottom-up, scalable synthesis of anatase nanofilament-based two-dimensional titanium carbo-oxide flakes and their optoelectronic properties

了解基于锐钛矿纳米丝的二维碳氧化钛薄片的自下而上、可扩展合成及其光电特性

• 批准号: 2211319
• 负责人: Michel Barsoum
• 金额: $ 44.09万
• 依托单位: Drexel University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-07-15 至 2025-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2211319&HistoricalAwards=false
• 关键词: Understanding; bottom; up; scalable; synthesis

NON-TECHNICAL ABSTRACT: Nanomaterials, which are a thousand times smaller than the diameter of a hair, possess properties that are different and unique compared to those of the same materials when they are larger. Typically, it is quite difficult to prepare one dimensional (1D) and two dimensional (2D) nanomaterials. This often requires toxic chemicals, is expensive and/or it takes a long time to produce a larger amount of them. Recently, researchers at Drexel University in Philadelphia have reported a simple approach to synthesize 1D and 2D ceramic nanomaterials at kilogram-scale at near ambient conditions, meaning room temperature and pressure, from inexpensive, environmentally benign precursors. With this project, supported by the Ceramics program in NSF’s Division of Materials Research, the researchers now want to find out how exactly these nanomaterials form, what chemical reactions are involved, how they can control their chemistry and structure, and answer many other questions. Additionally, they study the optical and electrical properties of these new nanomaterials to understand whether they are suitable for specific technological applications. First experiments indicate that these ceramic nanomaterials could be used as Li battery electrodes that, in principle, could result in batteries that can store much more energy that today’s Li-batteries. Other potential applications could include water remediation and biomedical applications, water splitting using sunlight and catalysis among others. Professors Barsoum and Hu also use this project to provide training and research opportunities for graduate students pursuing PhDs and undergraduate involvement in the research.TECHNICAL ABSTRACT: Recently, researchers at Drexel University discovered a one-pot, near ambient, bottom-up approach, to convert 10+ binary and ternary titanium carbides, nitrides, borides, phosphides and silicides into C-containing, anatase-based 1D nanofilaments, NFs, - ≈ 6x10 Å2 in cross-section, some of which are microns long - by simply immersing their powders in a tetraalkylammonium, TAA, hydroxides (e.g. TMAOH) aqueous solutions in the 25 to 85 °C temperature range under ambient pressures for tens of hours. Filtration of the resulting colloidal suspension self-assembles the 1D NFs into 2D flakes. This project, supported by the Ceramics program in NSF’s Division of Materials Research, enables the researchers to investigate the reaction mechanism(s) leading to the formation of the 1D nanofilaments and their subsequent self-assembly into 2D flakes. They examine the microstructural evolution of the nanofilaments as a function of time and temperature and study what effect these parameters have on the material’s optoelectronic properties. Understanding the reaction mechanism should lead to understanding how to control the Ti:C:O ratios in the nanofilaments. Flakes are characterized using high resolution transmission electron microscopy, X-ray photoelectron spectroscopy, nuclear magnetic resonance, scanning electron microscopy, atomic force microscopy, and ultra-violet and visible light spectroscopy. Solid state NMR of 13C, 1H and 1D are employed to locate carbon in the structure and the sources and locations of hydroxide anions, respectively. Optoelectronic properties – conductivity, band gaps and optical properties are characterized. The experimental work is complemented by DFT calculations. Synthesizing 1D C-containing, anatase-based NFs that self-assemble into 2D flakes, at near ambient conditions, from non-layered, inexpensive, green and abundant precursors (e.g., TiC) is paradigm shifting and predicted to open new and exciting avenues for research and applications in multiple areas.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.

非技术摘要：纳米材料，比头发直径小一千倍，与同一材料较大时相比，它们的潜在特性不同且独特。通常，制备一维（1D）和二维（2D）纳米材料非常困难。这通常需要有毒化学物质，价格昂贵和/或需要很长时间才能产生更多的化学物质。最近，费城德雷克塞尔大学的研究人员报告了一种简单的方法，可以在千克尺度上在近乎环境条件下合成1D和2D陶瓷纳米材料，这意味着室温和压力，来自廉价的，环保的前体。在NSF材料研究部的陶瓷计划的支持下，研究人员现在想了解这些纳米材料形式，涉及哪些化学反应，如何控制其化学和结构并回答许多其他问题。此外，他们还研究了这些新纳米材料的光学和电气性能，以了解它们是否适合特定技术应用。第一个实验表明，这些陶瓷纳米材料可以用作LI电池电子，从原则上讲，可以产生电池，这些电池可以存储更多的能量，这些能量能够与当今的Li-Batteries相比。其他潜在的应用可能包括水补救和生物医学应用，使用阳光和催化剂等水分裂。 Barsoum和Hu教授还使用该项目为研究生提供培训和研究机会，从而追求博士学位和本科参与研究。技术摘要：最近，Drexel University的研究人员发现了一种接近环境，自下而上的方法，可将10多种二元和二核酸盐，氮化物，磷化物，磷化物和硅胶转化为二甲硅烷和三核酸盐，磷酸盐，磷酸盐和硅胶的含量。纳米丝Nfs， - ≈6x10Å2在横截面中，其中一些是微米长的，仅将其粉末浸入四烷基铵，TAA，TAA，氢氧化物（例如TMAOH）水溶液中，在25至85°C的环境压力下，在25到85°C的温度范围内，以供小时的范围用于小时的小时。产生的胶体悬浮液的过滤自组装将1D NFS成2D薄片。该项目得到了NSF材料研究部的陶瓷计划的支持，使研究人员能够研究反应机制，导致形成1D纳米丝及其随后的自组装成2D片。他们检查了纳米丝的微观结构演化，这是时间和温度的函数，并研究了这些参数对材料光电特性的影响。了解反应机制应导致理解如何控制纳米丝中的Ti：C：O比。使用高分辨率透射电子显微镜，X射线光电子光谱，核磁共振，扫描电子显微镜，原子力显微镜以及超紫外线和可见光光谱法对薄片进行表征。使用13C，1H和1D的固态NMR在结构中定位碳，源和位置光电特性 - 电导率，带隙和光学性质。实验工作是通过DFT计算完成的。合成的1D C含1D，基于解剖酶的NFS在几乎环境条件下自我组装成2D片，来自非上层，廉价，绿色和丰富的前体（例如，TIC）的范式转移范式，预计将在多个领域中开放新的和令人兴奋的途径。智力优点和更广泛的影响审查标准。

项目成果

Repairable reinforced composites of 1D TiO2 lepidocrocite mesoparticles and thiol-yne click networks via alkylborane-initiated in situ polymerization

• DOI: 10.1016/j.xcrp.2023.101434
• 发表时间: 2023-06-21
• 期刊: CELL REPORTS PHYSICAL SCIENCE
• 影响因子: 8.9
• 作者: Wilson，Olivia R.;Carey，Michael S.;Magenau，Andrew J. D.
• 通讯作者: Magenau，Andrew J. D.

Electronic Structure of 1D Lepidocrocite TiO 2 as Revealed by Optical Absorption and Photoelectron Spectroscopy

光学吸收和光电子能谱揭示一维纤铁矿TiO 2 的电子结构

• DOI: 10.1021/acs.jpcc.2c06719
• 发表时间: 2023
• 期刊: The Journal of Physical Chemistry C
• 作者: Colin-Ulloa, Erika;Martin, Julia L.;Hanna, Ryan J.;Frasch, Michelle H.;Ramthun, Rebecca R.;Badr, Hussein O.;Uzarski, Joshua R.;Barsoum, Michel W.;Grimm, Ronald L.;Titova, Lyubov V.
• 通讯作者: Titova, Lyubov V.

Scalable, inexpensive, one-pot, facile synthesis of crystalline two-dimensional birnessite flakes

• DOI: 10.1016/j.matt.2022.05.038
• 发表时间: 2022-06
• 期刊: Matter
• 影响因子: 18.9
• 作者: H. Badr;Kiana Montazeri;Tarek Aly Elmeligy;Varun Natu;M. Carey;Ramchandra Gawas;Phu-Cuong Phan;Q. Qian;Christopher Y. Li;U. Wiedwald;M. Farle;Erika Colin-Ulloa;L. Titova;M. Currie;T. Ouisse;M. Barbier;A. Rogalev;F. Wilhelm;M. Hans;J. Schneider;Chris Tandoc;Young-Jie Hu;J. Snyder;M. Barsoum

On the structure of one-dimensional TiO2 lepidocrocite

一维TiO2纤铁矿的结构研究

• DOI: 10.1016/j.matt.2022.10.015
• 发表时间: 2023
• 期刊: Matter
• 影响因子: 18.9
• 作者: Badr, Hussein O.;Lagunas, Francisco;Autrey, Daniel E.;Cope, Jacob;Kono, Takayuki;Torita, Takeshi;Klie, Robert F.;Hu, Yong-Jie;Barsoum, Michel W.
• 通讯作者: Barsoum, Michel W.

Structural and electronic properties of two-dimensional titanium carbo-oxides

• DOI: 10.1088/2053-1583/aca8b7
• 发表时间: 2022-12
• 期刊: 2D Materials
• 影响因子: 5.5
• 作者: Yong-Jie Hu;Chris Tandoc;M. Barsoum;Johanna Rosen;Jonas Björk