New Catalysts for Hydrocarbon Partial Oxidation

化学工业的起始原料是从化石来源(主要是天然气和石油)中提取的碳氢化合物，这些碳氢化合物必须通过化学方法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，约占全球总能源使用量的10%，占全球二氧化碳(CO2)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效，但实现这一目标也面临着重大的科学挑战。在这个项目中，弗吉尼亚大学的T·布伦特·冈诺正在更好地理解如何进行选择性和节能的化学转化，这些转化对于以更环保的方式利用天然气和其他化石资源的目标至关重要。该项目是Gunnoe教授与主要是本科院校(PUI)合作开发一个项目的基础，该项目旨在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PUIS，根据他们的研究提供短期课程，本科生参加冈诺教授实验室的暑期研究实习。该项目在可持续创新和劳动力发展方面都对化学工业产生了影响。Gunnoe教授正在开发基于Rh、Ir和Cu的新型催化剂，用于碳氢(C-H)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-烃基配体的还原官能化结合到催化循环中。这两种转变都必须在氧化条件下进行，这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了使用空气可循环氧化剂的新催化剂，从而实现了碳氢化合物净有氧氧化的新催化工艺。拟议的化学建立在三个主要发展的基础上，基于实验和计算相结合的研究。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，以及在酸性溶剂(HX)中优化RhIII-Me和IrIII-Me键的还原官能化以形成Rh(I)、Ir(I)和Mex的配体基序的发展。研究人员还研究了铜(II)通过非自由基途径介导的芳烃官能化的使用。该项目是Gunnoe教授与主要是本科院校(PUI)合作开发一个项目的基础，该项目旨在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，提供基于他们研究的短期课程，本科生参加Gunnoe教授实验室的暑期研究实习。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。

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.