Unveiling intrinsic functionality of two-dimensional organic-inorganic ferroelectrics for energy storing/converting devices: integrated computational-experimental approach

揭示用于能量存储/转换装置的二维有机-无机铁电体的内在功能：集成计算实验方法

• 批准号: 2029800
• 负责人: Inna Ponomareva
• 金额: $ 45万
• 依托单位: University of South Florida
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-09-15 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2029800&HistoricalAwards=false
• 关键词: Unveiling; intrinsic; functionality; two; dimensional

Nontechnical:Perovskites are an important class of materials that have shown promise in devices such as light-emitting diodes and solar cells. Some inorganic perovskites simultaneously exhibit the exotic properties of ferroelectricity, piezoelectricity and pyroelectricity. These phenomena are of great scientific interest as well as technologies for conversion of mechanical and thermal energy to electrical power. This allows for diverse applications such as sensors, actuators, energy harvesting, data storage, and optoelectronics. Current technologies are based heavily on inorganic perovskites, but these materials have shortcomings. These include high temperature processing, lack of mechanical flexibility, high costs, and the presence of toxic elements in some cases. Very recently, a new class of hybrid perovskites with organic and inorganic components has emerged with intriguing, but often controversial, evidence for ferroelectricity and piezoelectricity. This project aims to achieve a fundamental understanding of hybrid perovskites through an integrated experimental-theoretical approach. The focus will be on ferroelectricity, piezoelectricity, associated phase transitions and emergent device functionalities of bulk and low-dimensional hybrid perovskites. The research could lead to the discovery of novel forms or manifestations of ferroelectricity, piezoelectricity and how these phenomena are affected by phase transitions. These studies have the potential to transform our current understanding of organic materials and reveal if they exhibit properties and device functionality on par with or even exceeding those of inorganic materials. This in turn could create a route to devices with novel functionality and energy converting properties, and push their technological applications to a new level. The project will also contribute strongly to the training of the STEM workforce with a focus on including students from underrepresented groups. The project will involve undergraduate students in research and enrich the Physics and Chemistry curricula. Outreach will be conducted through organized field trips to local elementary and middle schools.Technical:The project aims to address the following specific objectives. Objective 1: to establish the mechanism for ferroelectricity and uncover the nature of the associated phase transitions in hybrid three-dimensional organic-inorganic perovskites through a combination of multiscale first-principles simulations, synthesis and comprehensive structural and electrical characterization of single crystalline samples. Objective 2: to reveal how ferroelectricity and piezoelectricity mechanisms and manifestations in these materials change at the nanoscale through a combination of state-of-the-art computational and experimental approaches. Objective 3: to explore mechanical tunability of ferroelectric and piezoelectric properties of these novel materials and reveal the possibility of their integration in energy storing and converting devices. Objective 4: to engage in a wide range of educational and outreach activities in order to contribute to creating a world-class diverse materials science and engineering workforce that is trained for careers in academia or industry. The expected outcomes of the project include: potential discovery of novel forms of ferroelectricity and piezoelectricity in bulk and two-dimensional hybrid perovskites, establishment of mechanisms for ferroelectricity and piezoelectricity in these materials, their comprehensive structural and electric characterization, elucidation of the nature and origin of associated phase transitions, computational methodology and software for their exploration and design, predicting their functionality in energy storing devices, and prototypes for nanocapacitor and/or force/displacement (nano)sensors.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.

非技术性：钙钛矿是一类重要的材料，在发光二极管和太阳能电池等设备中显示出了希望。某些无机钙钛矿同时具有铁电性、压电性和热电性。这些现象以及将机械能和热能转换为电能的技术具有很大的科学意义。这允许不同的应用，如传感器，执行器，能量收集，数据存储和光电子。 目前的技术主要基于无机钙钛矿，但这些材料有缺点。这些包括高温加工、缺乏机械柔性、高成本以及在某些情况下存在有毒元素。最近，一类新的具有有机和无机成分的混合钙钛矿出现了有趣的，但往往有争议的铁电性和压电性的证据。该项目旨在通过综合实验-理论方法对混合钙钛矿进行基本了解。重点将放在铁电性，压电性，相关的相变和散装和低维混合钙钛矿紧急设备功能。这项研究可能会发现铁电性、压电性的新形式或表现，以及这些现象如何受到相变的影响。这些研究有可能改变我们目前对有机材料的理解，并揭示它们是否表现出与无机材料相当甚至超过无机材料的性能和器件功能。这反过来又可以为具有新功能和能量转换特性的设备开辟一条道路，并将其技术应用推向一个新的水平。该项目还将大力促进STEM劳动力的培训，重点是包括来自代表性不足群体的学生。该项目将使本科生参与研究，丰富物理和化学课程。将通过有组织的实地考察当地小学和中学进行推广。技术：该项目旨在解决以下具体目标。目标一：通过多尺度第一原理模拟、合成以及单晶样品的全面结构和电学表征的组合，建立铁电性机制并揭示混合三维有机-无机钙钛矿中相关相变的性质。目标二：揭示如何铁电性和压电性机制和表现在这些材料的变化，在纳米尺度通过国家的最先进的计算和实验方法相结合。目标3：探索这些新材料的铁电和压电性能的机械可调性，揭示它们在能量存储和转换器件中集成的可能性。目标4：从事广泛的教育和推广活动，以促进创造一个世界级的多元化材料科学和工程的劳动力，在学术界或工业的职业培训。该项目的预期成果包括：在大块和二维混合钙钛矿中发现新形式的铁电性和压电性的可能性，在这些材料中建立铁电性和压电性的机制，它们的综合结构和电学表征，相关相变的性质和起源的阐明，用于它们的探索和设计的计算方法和软件，该奖项反映了NSF的法定使命，并通过使用基金会的智力价值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

Nanospace Engineering of Metal‐Organic Frameworks for Heterogeneous Catalysis

用于多相催化的金属有机框架的纳米空间工程

• DOI: 10.1002/cnma.202100396
• 发表时间: 2022
• 期刊: ChemNanoMat
• 影响因子: 3.8
• 作者: Qi Wang;Guoxiang Yang;Yangjie Fu;Ningyi Li;Derek Hao;Shengqian Ma
• 通讯作者: Shengqian Ma

Negative Longitudinal Piezoelectricity Coexisting with both Negative and Positive Transverse Piezoelectricity in a Hybrid Formate Perovskite

混合甲酸盐钙钛矿中负纵向压电与负和正横向压电共存

• DOI: 10.1021/acsami.2c09828
• 发表时间: 2022
• 期刊: ACS Applied Materials & Interfaces
• 影响因子: 9.5
• 作者: Ghosh, Partha Sarathi;Lisenkov, Sergey;Ponomareva, Inna
• 通讯作者: Ponomareva, Inna

Chiral Frustrated Lewis Pair@Metal‐Organic Framework as a New Platform for Heterogeneous Asymmetric Hydrogenation

手性受阻路易斯对@金属有机框架作为多相不对称氢化的新平台

• DOI: 10.1002/anie.202213399
• 发表时间: 2022
• 期刊: Angewandte Chemie International Edition
• 作者: Zhang, Yin;Chen, Songbo;Al‐Enizi, Abdullah M.;Nafady, Ayman;Tang, Zhiyong;Ma, Shengqian
• 通讯作者: Ma, Shengqian