Collaborative Research: New Phase Diagrams for Predictive Solvothermal Synthesis in Non-Aqueous Solvents

合作研究：非水溶剂中预测溶剂热合成的新相图

• 批准号: 2240281
• 负责人: Wenhao Sun
• 金额: $ 41.42万
• 依托单位: Regents of the University of Michigan - Ann Arbor
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-02-15 至 2027-01-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2240281&HistoricalAwards=false
• 关键词: Collaborative; Research; New; Phase; Diagrams

Non-Technical Summary Solvothermal synthesis involves precipitating a solid out of a supersaturated solution and is a common materials synthesis route for functional materials. Many classes of important materials cannot be easily precipitated using water as the solvent; including intermetallics, sulfides, and nitrides; which are more readily synthesized in non-aqueous organic solvents. The number of available organic solvents is large, but there is currently no rigorous understanding of which combination of solvent and starting material is best to synthesize a given target material. With this project, supported by the Solid State and Materials Chemistry Program in NSF’s Division of Materials Research, Professor Wenhao Sun at the University of Michigan and Professor Daniel Shoemaker at the University of Illinois Urbana-Champaign build new predictive theoretical models to better understand which compounds precipitate out of supersaturated non-aqueous solutions. This scientific understanding allows chemists to skip the tedious trial-and-error efforts of solution synthesis optimization and enables the rational design of synthesis recipes for the manufacture and processing of new, more complex, or higher-quality materials that drive technological innovation. The research is carried out by undergraduate and graduate students, who are trained in computational materials science and experimental thermochemistry during this project.Technical SummaryMany classes of materials are synthesized in organic solvents, such as ethanol, ethylene-glycol, ammonia, acetonitrile, hydrazine, DMSO, DMF, THF, etc. Currently, there are no thermodynamic frameworks to guide solvothermal synthesis in non-aqueous media, meaning chemists largely rely on heuristics for precursor solubility and laborious trial-and-error efforts for solution synthesis optimization. This project undertakes a combined computational and experimental research program to develop the first thermodynamic phase diagrams to guide solvothermal synthesis in non-aqueous organic solvents. The project involves measuring and developing predictive models for the chemical potentials of solvated species in non-aqueous solvents, and then combining these ion chemical potentials with high-dimensional thermodynamic frameworks to predict the solubility and chemical equilibria of complex materials under various non-aqueous solvents and conditions. These new solvothermal phase diagrams offer a rigorous foundation to rationally design recipes for the targeted solution-based synthesis of advanced solid-state materials. Broad availability for the tools developed in this project is aided by interfacing with freely-available and widely-used thermochemical databases. Hands-on learning is supported by precisely aligning model precipitation reactions with undergraduate thermodynamics lessons in chemistry and materials science.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.

非技术摘要溶剂热合成涉及从过饱和溶液中沉淀出固体，并且是功能材料的常见材料合成途径。许多重要的材料不能轻易地以水为溶液沉淀。包括金属间，硫化物和氮化物；在非水有机溶液中更容易合成。可用的有机溶液的数量很大，但是目前尚无严格了解溶剂和起始材料的组合最好是合成给定的目标材料。在NSF材料研究部的固态和材料化学计划的支持下，密歇根大学的Wenhao Sun教授和伊利诺伊大学Urbana Urbana-Champaign教授的Daniel Shoemaker教授的支持，建立了新的预测理论模型，以更好地理解哪些珍贵的超级非熟食解决方案是珍贵的。这种科学的理解使化学家可以跳过溶液合成优化的繁琐的试验和错误的努力，并可以合理设计合成食谱，用于制造和处理新的，更复杂或更高质量的材料，以推动技术创新。这项研究是由本科和研究生进行的，他们在此项目期间接受了计算材料科学和实验热化学培训。技术摘要材料类别在有机溶液中合成，例如乙醇，乙二醇，乙二醇，乙二醇，氨，ammonia，Ammonia，Acetrile，Hendrozine，Hydrozine，Hydrozine，Hydrozine，dmso，dmso，dmfor，thf，thf，thf，thf，thf，thf，thf，dmf，dmf，等等。非水培养基中的溶剂热合成，这意味着化学家在很大程度上依赖于启发式方法来实现前体溶解度和实验室和错误的努力来进行溶液合成优化。该项目进行了一项组合的计算和实验研究计划，以开发第一个热力学相图，以指导非水有机溶液中的溶剂热合成。该项目涉及测量和开发预测模型的非水溶液中解决物种的化学电位，然后将这些离子化学电位与高维热力学框架相结合，以预测各种非水溶液和条件下复杂材料的溶解度和化学等效物。这些新的溶剂热相图为基于靶向溶液的高级固态材料的合成提供了严格的基础。通过与自由利用和广泛的热化学数据库接口来帮助该项目开发的工具的广泛可用性。精确地对准模型的精度反应与化学和材料科学的本科热力学课程相结合来支持动手学习。该奖项反映了NSF的法定任务，并通过使用基金会的智力优点和更广泛的影响来评估NSF的法定任务。