New Catalysts for Hydrocarbon Partial Oxidation

化学工业的原料是从化石资源（主要是天然气和石油）中提取的碳氢化合物，必须将其化学转化为更高价值的材料。化学工业在这些过程中的能源消耗是巨大的，约占全球能源消耗总量的10%，占全球二氧化碳排放量的5%以上。因此，虽然有机会大幅提高大规模化学过程的能源效率，但实现这一目标也存在重大的科学挑战。在这个项目中，弗吉尼亚大学的T. Brent Gunnoe正在研究如何进行选择性和节能的化学转化，这对于以更环保的方式使用天然气和其他化石资源的目标至关重要。该项目是Gunnoe教授与主要本科院校（PUIs）合作开发一个项目的基础，以提高来自不同背景的学生对科学家和工程师职业的兴趣，特别是在能源领域。在这个项目中，研究生访问pui，根据他们的研究提供短期课程，本科生在Gunnoe教授的实验室参加暑期研究实习。该项目在可持续创新和劳动力发展方面对化工行业产生了影响。Gunnoe教授正在开发基于铑（Rh）、铱（Ir）和铜（Cu）的新型催化剂，用于碳氢化合物碳氢键的功能化。一个主要的焦点是如何将过渡金属介导的C-H活化和金属-羟基配体的还原功能化结合到催化循环中。这两种转化都必须在氧化条件下进行，这就需要设计配体来控制金属基氧化还原化学的热力学。这些努力的结果是获得使用空气可回收氧化剂的新催化剂，从而实现碳氢化合物净有氧氧化的新催化过程。提出的化学建立在三个主要发展的基础上，结合实验和计算研究。研究了在酸性溶剂中优化Rh和Ir介导的C-H活化的配体设计的发展，以及优化RhIII-Me和IrIII-Me键的还原功能化以在酸性溶剂（HX）中形成Rh(I)、Ir(I)和MeX的配体基序的发展。研究人员还通过非自由基途径研究了Cu（II）介导的芳烃功能化的使用。该项目是Gunnoe教授与主要本科院校（PUIs）合作开发一个项目的基础，以提高来自不同背景的学生对科学家和工程师职业的兴趣，特别是在能源领域。在这个项目中，研究生访问pui，根据他们的研究提供短期课程，本科生在Gunnoe教授的实验室参加暑期研究实习。该奖项反映了美国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。

The starting materials for the chemical industry are hydrocarbons derived from fossil sources (primarily natural gas and petroleum), which must be chemically converted into higher value materials. The chemical industry's energy consumption for these process is substantial and accounts for approximately 10% of total global energy use and greater than 5% of global carbon dioxide (CO2) emissions. Thus, while there are opportunities to dramatically increase the energy efficiency of large-scale chemical processes, there are also substantial scientific challenges to realizing this goal. In this project, T. Brent Gunnoe of the University of Virginia is developing a better understanding of how to perform selective and energy efficient chemical conversions that are essential to the goal of using natural gas and other fossil resources in a more environmentally benign manner. The project is a foundation for Professor Gunnoe to work with primarily undergraduate institutions (PUIs) to develop a program to increase interest among students from diverse backgrounds in careers as scientists and engineers, especially in the energy arena. In this program, graduate students visit PUIs to deliver short courses based on their research, and undergraduate students participate in summer research internships in Professor Gunnoe's laboratory. This project impacts the chemical industry both in terms of sustainable innovation and workforce development. Professor Gunnoe is developing new catalysts based on rhodium (Rh), iridium (Ir) and copper (Cu) for the functionalization of carbon-hydrogen (C-H) bonds of hydrocarbons. A primary focus is how to combine transition metal mediated C-H activation and reductive functionalization of metal-hydrocarbyl ligands into catalytic cycles. Both transformations must be accessed under oxidizing conditions, which requires design of ligands to control the thermodynamics of metal-based redox chemistry. The outcome of these efforts is to access new catalysts that use air recyclable oxidants, thus enabling new catalytic processes for net aerobic oxidation of hydrocarbons. The proposed chemistry builds on three primary developments, based on combined experimental and computational studies. The development of ligand designs that optimize Rh- and Ir-mediated C-H activation in acidic solvents is investigated along with the development of ligand motifs that optimize reductive functionalization of RhIII-Me and IrIII-Me bonds to form Rh(I) and Ir(I) and MeX in acidic solvents (HX). The investigators also examine the use of Cu(II) mediated arene functionalization by a non-free radical pathway. The project is a foundation for Professor Gunnoe to work with primarily undergraduate institutions (PUIs) to develop a program to increase interest among students from diverse backgrounds in careers as scientists and engineers, especially in the energy arena. In this program, graduate students visit PUIs to deliver short courses based on their research, and undergraduate students participate in summer research internships in Professor Gunnoe's laboratory.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.