CAREER: Rational Design of Nanoporous Catalysts for Carbonylation Reactions

职业：羰基化反应纳米多孔催化剂的合理设计

• 批准号: 2144360
• 负责人: Peng Bai
• 金额: $ 55.1万
• 依托单位: University of Massachusetts Amherst
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-09-01 至 2027-08-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2144360&HistoricalAwards=false
• 关键词: CAREER; Rational; Design; Nanoporous; Catalysts

Annually, millions of tons of alcohols and carboxylic acids (used to create polymers, food additives, solvents, and pharmaceuticals) are produced industrially via catalytic carbonylation. Because this process makes use of expensive rare-metal catalysts and requires corrosive chemical agents to promote the desired reactions, the result is stringent and costly reactor designs, complex catalyst recycling schemes, and environmentally unfriendly waste streams. This project aims to discover effective porous solid-acid catalysts as a technologically and environmentally appealing alternative. Designing an optimal solid acid, however, is a challenging task, as there are hundreds of potential structures to choose from, each with unique, molecular-scale cavities that can stabilize or prevent different reactions. This project will develop computer models that allow us to make accurate predictions of which chemical reactions will take place, enabling a computationally efficient approach to catalyst design. These developments will positively impact manufacturing processes based on carbonylation chemistry, and also many other large-scale industrial processes that create the chemical products for our modern society. The research efforts are closely integrated with educational and outreach activities to serve our overarching goals of improving computational competency in the training of the next-generation workforce and promoting diversity and broadening participation of underrepresented students in STEM fields.Recent experimental work has demonstrated that nanoporous zeolites with 8-membered rings can potentially catalyze the carbonylation reaction with high selectivity, providing a compelling alternative to traditional rare metal-based catalyst systems. Despite the tantalizing potential, fundamentally important questions remain, including: What are the structural motifs that will make possible effective carbonylation of small methoxy groups versus larger carbocations in different zeolite architectures? How can acid-catalyzed side reactions be controlled by selectively suppressing undesired reactions? What are the mechanisms that determine the function of promoters and poisoners in these nanoporous solid acids? This research program will address these questions by developing and applying computational tools that integrate quantum chemical and forcefield-based molecular-scale simulations. The project will generate fundamental insights into confinement effects in nanoporous catalysts and will make possible the rational design of catalysts that target reactions selectively. A successful outcome may not only lead to industrially feasible, environmentally friendly solid acids for the synthesis of ethanol and acetic acid, but also provide general strategies for using solid acids in other organic syntheses and for controlling side reactions in many existing, large-scale solid acid catalytic processes.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.

每年，数以百万计的醇和羧酸(用于制造聚合物、食品添加剂、溶剂和药品)通过催化羰化反应在工业上生产。由于这一过程使用昂贵的稀有金属催化剂，并需要腐蚀性化学试剂来促进所需的反应，结果是严格而昂贵的反应器设计，复杂的催化剂回收方案，以及不环保的废流。该项目旨在发现有效的多孔固体酸催化剂，作为一种具有技术和环境吸引力的替代品。然而，设计一种最佳的固体酸是一项具有挑战性的任务，因为有数百种潜在的结构可供选择，每一种结构都有独特的分子规模的空穴，可以稳定或防止不同的反应。这个项目将开发计算机模型，使我们能够准确预测将发生哪些化学反应，从而实现一种计算高效的催化剂设计方法。这些发展将对以羰化化学为基础的制造过程以及许多其他为现代社会创造化学产品的大型工业过程产生积极影响。研究工作与教育和推广活动紧密结合，以服务于我们的总体目标，即在培训下一代劳动力方面提高计算能力，促进多样性和扩大STEM领域中代表性不足的学生的参与。最近的实验工作表明，具有8元环的纳米孔沸石可以高选择性地催化羰化反应，为传统的稀有金属催化剂体系提供了一种引人注目的替代方案。尽管有诱人的潜力，但根本上重要的问题仍然存在，包括：在不同的沸石结构中，什么结构基序将使小甲氧基与大碳正离子的有效羰化成为可能？如何通过选择性地抑制不受欢迎的反应来控制酸催化的副反应？决定这些纳米多孔固体酸中的促进剂和毒剂功能的机制是什么？这项研究计划将通过开发和应用将量子化学和基于力场的分子尺度模拟相结合的计算工具来解决这些问题。该项目将对纳米孔催化剂中的限制效应产生基本的见解，并将使选择性地针对反应的催化剂的合理设计成为可能。成功的结果不仅可能导致工业上可行的、环境友好的固体酸用于乙醇和醋酸的合成，而且还为在其他有机合成中使用固体酸以及在许多现有的大型固体酸催化过程中控制副反应提供一般策略。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。