NSF-BSF: Steering Selectivity in Aldol Reactions by Control of Relative Effective Reaction Rates in Porous Catalysts

NSF-BSF：通过控制多孔催化剂中的相对有效反应速率来控制羟醛反应的选择性

• 批准号: 1804041
• 负责人: Friederike Jentoft
• 金额: $ 33万
• 依托单位: University of Massachusetts Amherst
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-09-01 至 2023-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1804041&HistoricalAwards=false
• 关键词: NSF; BSF; Steering; Selectivity; Aldol

This project, funded under the National Science Foundation (NSF) and US-Israel Binational Science Foundation (BSF) collaborative opportunity NSF 17-520, focuses on the study of catalysis to make chemical processes more environmentally friendly by reducing chemical waste. The chemical transformation of interest is the aldol condensation, which results in a new bond between two carbon atoms. Aldol condensation is an essential reaction in many syntheses of bulk, fine, and specialty chemicals. This reaction shows promise for upgrading biomass-derived feedstocks to fuels or chemicals. The objective is to steer this chemical reaction to give the desired product without generating a multitude of side products. The approach is to develop new solid catalysts and, by varying their surface chemical composition and pore morphology, tune their chemical and physical properties for optimal performance. The new knowledge and fundamental understanding emerging from this collaborative work between the University of Massachusetts Amherst and the Technion-Israel Institute of Technology will serve to better direct aldol condensations and other similarly complex and pivotal chemical reactions. In addition, the project will contribute to U.S. competitiveness in chemical manufacturing of biorenewable products and will promote training of a diverse workforce skilled in biomass processing. Aldol reactions consist of two sequential steps, addition and subsequent dehydration. Cross aldol condensations, particularly those involving unsymmetrical ketones, can lead to a multitude of primary and secondary products. The central hypothesis of this project is that selectivity in aldol reactions, which is governed by relative effective reaction rates, can be tuned by tailoring the active surface sites and effectiveness factors. While theory on the influence of transport limitations on the selectivity in parallel and sequential reactions has been outlined long ago, there are few realizations of these concepts in complex liquid phase reactions. This research project rigorously tests the practical viability of these concepts by manipulating surface chemistry and pore structure of the catalysts. The main catalyst platform is layered double hydroxides, because they allow for a wide and independent variation of chemical and physical properties; that is, acid-base and pore characteristics can be tailored. Porous model materials serve to independently investigate transport limitations. Reactant complexity and reaction conditions are varied to ensure broad validity of the findings. The project benefits from complementary expertise and instrumental capability at the U.S. institution and at Technion in Israel. Student training will include visits of the partner laboratory and a subject-relevant graduate course. The participation of women in science is sought to be broadened through appropriate recruiting efforts and outreach activities targeting female high school students.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.

该项目由美国国家科学基金会（NSF）和美国-以色列两国科学基金会（BSF）合作机会NSF 17-520资助，重点研究催化剂，通过减少化学废物使化学过程更加环保。感兴趣的化学转化是羟醛缩合，其导致两个碳原子之间的新键。羟醛缩合反应是许多合成大宗、精细和特种化学品的重要反应。该反应显示出将生物质衍生的原料升级为燃料或化学品的前景。目的是控制这种化学反应，以得到所需的产物，而不产生大量的副产物。该方法是开发新的固体催化剂，并通过改变它们的表面化学组成和孔形态，调整它们的化学和物理性质以获得最佳性能。从马萨诸塞州阿默斯特大学和以色列理工学院的合作工作中产生的新知识和基本理解将有助于更好地指导羟醛缩合和其他类似的复杂和关键的化学反应。 此外，该项目将有助于提高美国在生物可再生产品的化学制造方面的竞争力，并将促进对生物质加工技术熟练的多样化劳动力的培训。 羟醛缩合反应包括两个连续的步骤，加成和随后的脱水。交叉羟醛缩合反应，特别是那些涉及不对称酮的缩合反应，可以产生大量的初级和次级产物。该项目的中心假设是，羟醛缩合反应的选择性，这是由相对有效的反应速率，可以通过定制的活性表面位点和有效性因子进行调整。虽然在平行和顺序反应中，传输限制对选择性的影响的理论很久以前就已经概述，但在复杂的液相反应中，这些概念很少实现。该研究项目通过操纵催化剂的表面化学和孔结构来严格测试这些概念的实际可行性。主要的催化剂平台是层状双氢氧化物，因为它们允许化学和物理性质的广泛和独立的变化;也就是说，可以定制酸碱和孔特征。多孔模型材料用于独立研究运输限制。反应物的复杂性和反应条件是不同的，以确保广泛的有效性的调查结果。该项目得益于美国机构和以色列理工学院的互补专业知识和仪器能力。学生培训将包括参观合作实验室和与主题相关的研究生课程。通过适当的招聘努力和针对女高中生的外联活动，寻求扩大妇女对科学的参与，该奖项反映了国家科学基金会的法定使命，并通过使用基金会的知识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

Elucidating Cooperative Interactions between Grafted Amines and Tin or Titanium Sites on Silica

• DOI: 10.1021/acscatal.2c02276
• 发表时间: 2022-07
• 期刊: ACS Catalysis
• 影响因子: 12.9
• 作者: Christine Khoury;S. Holton;Dina Shpasser;Elior Hallo;A. Kulkarni;F. Jentoft;Oz M. Gazit