CAREER: SusChEM: Heavy Atom Isotope Effects in Carbon Dioxide Fixation Catalysis: Fundamental Understanding and Catalyst Discovery

在这个由化学系化学结构、动力学和机理B计划资助的职业项目中，康涅狄格大学化学系的Alfredo Angeles-Boza教授正在开发新的方法，以了解二氧化碳如何转化为其他具有有趣性质的分子。二氧化碳是化石燃料燃烧的大量副产品。它转化为其他具有有用性质的分子，不仅有助于长期供应原材料。许多研究小组正在研究将二氧化碳转化为其他有用分子的方法。显然，更好地淡化此类转换是如何进行的，可能会导致实现此类转换的更有效方式。为了实现这一目标，阿尔弗雷多·安吉利亚-博萨教授正在利用相同元素(在这里是碳和氧)的不同形式之间的反应性差异，这些元素含有相同数量的质子，但原子质量不同，用于研究此类转化所使用的材料。该项目位于无机化学、物理化学和材料化学的交界处，非常适合从高中生到博士研究生的不同层次的科学家的教育。该项目为本科生和研究生提供了一个多学科的培训基地。该提案包括全年本科生研究项目，是系级REU计划的一部分。目标是通过努力解决三个关键问题来降低最初对科学感兴趣的学生的流失率：(I)辅导，以减少限制早期化学课程成功的障碍；(Ii)召集一群志趣相投的拉美裔学生，因为人们普遍认为，需要这样一群临界群体，以帮助给学生环境带来熟悉感；以及(Iii)指导学生，以解决缺乏以科学为导向的少数族裔榜样的问题。为了改进催化剂设计，重要的是要了解反应动力学势垒的来源。该项目是一个全面阐明过渡金属催化二氧化碳还原反应的化学机理的项目。该项目将合成、动力学和重原子(13C和18O)同位素效应与密度泛函理论计算相结合，以解决二氧化碳活化过程中的键形成、键断裂和电子转移机制。该项目试图回答以下问题：(1)过渡金属催化的二氧化碳还原反应的13C和18O动力学同位素效应的值是什么？(2)催化剂的驱动力和亲核性是否会影响二氧化碳还原反应中测量的重原子同位素效应？(3)不同的过渡金属-二氧化碳结合模式的13C和18O平衡同位素效应是如何表征的？在他的教育计划中，安吉丽斯-博萨教授正在为在科学领域代表性不足的学生开发一个有效的学习社区。

In this CAREER project funded by the Chemical Structure, Dynamics & Mechanisms B Program of the Chemistry Division, Professor Alfredo Angeles-Boza of the Department of Chemistry at the University of Connecticut is developing new methods to understand how carbon dioxide can be converted to other molecules with interesting properties. Carbon dioxide is an abundant by-product of fossil fuels combustion. Its conversion into other molecules with useful properties not only contributes to the long term supply of raw materials. Many research groups are investigating ways to convert carbon dioxide into other useful molecules. Clearly, better understating of how such conversions are done may lead to more effective ways of achieving such conversions. Toward such a goal, Professor Alfredo Angeles-Boza is exploiting the differences in reactivity between forms of the same element (here, carbon and oxygen) that contain equal numbers of protons but different atomic masses for the study of materials used in such conversions. The project lies at the interface of inorganic, physical and materials chemistry, and is well suited to the education of scientists at different levels, from high school students to Ph.D. graduates. The program offers a multidisciplinary training ground for undergraduate and graduatestudents. The proposal includes year-round undergraduate research projects and is part of the departmental REU program. A goal is to decrease the attrition rate among the students initially interested in sciences by working on three key issues: (i) tutoring to decrease the barriers that limit success in the early chemistry courses; (ii) assembling a group of like-minded Hispanic students as it is generally understood that such a group of a critical mass is needed to help bring a sense of familiarity to the students environment; and (iii) mentoring student to combat the lack of science-oriented minority role models. To improve catalyst design, it is important to understand the origins of the kinetic barriers of the reactions. This project is a comprehensively illuminates the chemical mechanisms of transition metal-catalyzed carbon dioxide reduction reactions. The project combines the use of synthesis, kinetics, and heavy atom (13C and 18O) isotope effects with density functional theory calculations to address bond formation, bond cleavage, and electron transfer mechanisms during carbon dioxide activation. The project seeks to answer the following questions: (1) What values of 13C and 18O kinetic isotope effects characterize transition metal-catalyzed carbon dioxide reduction reactions? (2) Can the driving force and nucleophilicity of a catalyst influence the heavy atom isotope effects measured in carbon dioxide reduction reactions? (3) What 13C and 18O equilibrium isotope effects characterize the various transition metal- carbon dioxide binding modes? For his educational plan, Professor Angeles-Boza is developing an effective learning community for students underrepresented in science.