High-activity base metal catalysts for strong carbon-heteroatom bond activation

用于强碳-杂原子键活化的高活性贱金属催化剂

• 批准号: RGPIN-2016-04848
• 负责人: Stryker, Jeffrey
• 金额: $ 5.46万
• 依托单位: University of Alberta
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2020
• 资助国家: 加拿大
• 起止时间: 2020-01-01 至 2021-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=708204
• 关键词: activity; base; metal; catalysts; strong

Discovery research in fundamental inorganic and coordination chemistry of the “earth abundant" transition metals manganese, iron, cobalt, nickel, and copper is proposed. This program is new to my Discovery Grant proposal, but it is not new to my research group. In 2008, major funding was obtained to create and develop “new-generation” hydrotreatment catalysts for petroleum upgrading. The objective of this industry-funded research is resolutely applied: introduce into industrial practice “process-ready” catalysts for hydrodesulfurization and hydrodenitrogenation of bitumen and other heavy oils, replacing the energy-intensive, unselective, and environmentally compromising catalysts in ubiquitous use today, worldwide. What we proposed we could do was unprecedented, with a central hypothesis unsupported by “prior art” and attributed to no identifiable school of current catalysis research. But the idea actually works. We would like to know how. And we need to know why. Our industrial funding does not extend to fundamental and exploratory investigations beyond those required to make and optimize our initial discoveries. This proposal is about turning discovery into scholarship. We propose the basic science necessary to understand structure, reveal mechanism, and provide a rational basis for iterative improvements in design. We also target a range of other important catalytic processes that currently require “energy-intensive” conditions (typically, high pressure and temperature) or precious metal catalysts, or both. This proposal is about exploring a new concept in designing high-activity catalysts of the earth-abundant transition metals. It is about fundamental research design, synthesis, structure, bonding, electronic character, reactivity, and mechanism. Over the past fifty years, research in transition metal catalysis has been mostly about ligand design. First-row transition metals are physically small and favour high-spin (paramagnetic) electronic configurations. Ligand lability and structural stability is a serious issue for these elements; most of modern catalysis has adopted polydentate ligands, which stabilize the metal, but limit coordinative unsaturation, inhibiting reactivity and limiting substrate scope. The incorporation of “redox active” ligands also provide key advantages in this area, leading to steady, incremental, improvements in the field. With few exceptions, however, today's first-row catalysts suffer from poor structural integrity, low activity, and limited substrate scope. In this work, a non-traditional approach to catalyst design is taken, nucleating multiple metals into functional, cooperative units using a single anionic ligand, one per metal. Many metals, one ligand a “metallocentric” approach to first-row transition metal catalyst design.

提出了“地球上丰富的”过渡金属锰、铁、钴、镍和铜的基础无机和配位化学的发现研究，这个项目对我的发现资助提案来说是新的，但对我的研究小组来说并不新鲜。 2008年，获得了重大资金来创建和开发用于石油升级的“新一代”加氢处理催化剂，该行业资助的研究目标是坚决应用：将“工艺就绪”催化剂引入工业实践。用于沥青和其他重油的加氢脱硫和加氢脱氮，取代当今世界范围内普遍使用的能源密集型、非选择性且对环境不利的催化剂。我们提出我们可以做的事情是前所未有的，其中心假设不受“现有技术”和但我们想知道为什么我们的工业资助没有扩展到基础和催化研究。我们提出了理解结构、揭示机制并为设计迭代改进提供合理基础所必需的基础科学。目前需要“能源密集型”条件（通常是高压和高温）或贵金属催化剂，或两者兼而有之的其他重要催化过程。该提案旨在探索设计地球资源丰富的高活性催化剂的新概念。过渡它涉及基础研究设计、合成、结构、键合、电子特性、反应性和机理。在过去的五十年里，过渡金属催化的研究主要是关于配体设计。有利于高自旋（顺磁）电子构型配体不稳定性和结构稳定性是这些元素的一个严重问题；大多数现代催化都采用多齿配体，它可以稳定金属，但限制配位不饱和度，抑制反应性和限制底物范围也提供了该领域的关键优势，导致该领域的稳定、渐进的改进，然而，除了少数例外，当今的第一排催化剂都存在结构完整性差的问题。 、低活性和有限的底物范围在这项工作中，采用了一种非传统的催化剂设计方法，使用单个阴离子配体将多种金属成核成功能性协同单元，每种金属一个，一个配体一个。第一行过渡金属催化剂设计的“金属中心”方法。