Excellence in Research: Transition metal carbides and nitrides supported single-atom catalysts for aqueous-phase methanol reforming

卓越研究：用于水相甲醇重整的过渡金属碳化物和氮化物支持的单原子催化剂

• 批准号: 2200456
• 负责人: Shyam Kattel
• 金额: $ 65.08万
• 依托单位: Florida Agricultural and Mechanical 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: 2022-09-01 至 2025-08-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2200456&HistoricalAwards=false
• 关键词: Excellence; Research; Transition; metal; carbides

Hydrogen, a clean fuel, is primarily produced from fossil resources via the catalytic reforming of hydrocarbons at high temperatures. Alternatively, it can be produced more efficiently at low temperature through the aqueous-phase reforming of simple alcohols such as methanol. The project explores the feasibility of hydrogen generation from methanol (a renewable feedstock) as facilitated by novel catalysts designed to work efficiently at low temperatures in liquid environments. Concomitantly, the project lays the groundwork for a multidisciplinary research program providing research and education opportunities for underrepresented African American students in the area of computational sciences, while more broadly strengthening the research capability of Florida Agricultural and Mechanical University (FAMU), a historically black college and university (HBCU).The study involves a combined computational and experimental study of aqueous-phase reforming of methanol (APRM) on single-atom catalysts (SACs) supported on low-cost transition metal carbides (TMCs) and nitrides (TMNs). SACs are an emerging class of materials that offer near 100% metal utilization and possess the combined advantages of homogeneous and heterogeneous catalysts. Theoretical calculations will be validated with experimental measurements to unravel the stability and structure-activity relationships of Pt, Pd, Rh, and Ni SACs supported on transition metal carbides and nitrides (TMCs and TMNs). The project embraces three objectives: 1) investigation of stability and electronic structure of SACs deposited on various TMCs and TMNs via density functional theory (DFT) calculations, machine learning (ML) methods, and scanning tunneling microscopy/spectroscopy (STM/STS) measurements in ultrahigh vacuum; 2) identification of active sites and reaction mechanisms of APRM on stable SACs through DFT simulations of reaction energetics associated with catalyst structures identified by in-situ and ex-situ STM; and 3) application of Kinetic Monte Carlo (KMC) simulations and results of gas-liquid batch reactor experiments to identify promising SAC candidates for APRM. The atomistic understanding of structure compositions and stability of SACs, as well as the mechanistic insight of APRM obtained from this project, is expected to be transferable to other SAC configurations and other alcohol reforming reactions. Beyond the technical aspects, the project involves educational and outreach activities focused on minorities and underrepresented groups ranging from K-12 through graduate students, and involving student interactions with local high-schools, Tallahassee Community College, and the FAMU affiliated Developmental Research School.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.

氢是一种清洁燃料，主要由化石资源在高温下通过碳氢化合物的催化重整产生。或者，它可以通过简单醇如甲醇的水相重整在低温下更有效地生产。 该项目探索了由甲醇（一种可再生原料）制氢的可行性，该可行性由旨在在液体环境中低温下有效工作的新型催化剂促进。 同时，该项目为多学科研究计划奠定了基础，为计算科学领域代表性不足的非洲裔美国学生提供研究和教育机会，同时更广泛地加强了佛罗里达农业和机械大学（FAMU）的研究能力。一所历史悠久的黑人学院和大学（HBCU）。这项研究涉及甲醇水相重整的计算和实验研究（APRM）在负载于低成本过渡金属碳化物（TMC）和氮化物（TMN）上的单原子催化剂（SAC）上。 SAC是一类新兴的材料，其提供接近100%的金属利用率，并具有均相和非均相催化剂的综合优势。理论计算将与实验测量进行验证，以解开支持过渡金属碳化物和氮化物（TMCs和TMN）的Pt，Pd，Rh和Ni SAC的稳定性和结构-活性关系。本项目包括三个目标：1）通过密度泛函理论（DFT）计算、机器学习（ML）方法和扫描隧道显微镜/光谱（STM/STS）测量，在真空中研究沉积在各种TMC和TMN上的SAC的稳定性和电子结构;（二）通过DFT模拟与催化剂结构相关的反应能量学确定APRM在稳定SAC上的活性中心和反应机理通过原位和非原位STM确定;和3）应用动力学蒙特卡罗（KMC）模拟和气液间歇反应器实验的结果来确定有希望的SAC候选人用于APRM。从原子角度理解SAC的结构组成和稳定性，以及从该项目中获得的APRM的机理见解，有望转移到其他SAC构型和其他醇重整反应。 除了技术方面，该项目还涉及教育和外联活动，重点是从K-12到研究生的少数民族和代表性不足的群体，并涉及学生与当地高中、塔拉哈西社区学院、该奖项反映了NSF的法定使命，并被认为值得通过使用基金会的智力价值进行评估来支持和更广泛的影响审查标准。

项目成果

Density functional theory study of bulk properties of transition metal nitrides

过渡金属氮化物体性能的密度泛函理论研究

• DOI: 10.1039/d2cp06082e
• 发表时间: 2023
• 期刊: Physical Chemistry Chemical Physics
• 影响因子: 3.3
• 作者: Lynn, Michael O.;Ologunagba, Damilola;Dangi, Beni B.;Kattel, Shyam
• 通讯作者: Kattel, Shyam