CAREER SusChEM: Recyclable transfer hydrogenation catalysts by tuning non-innocent catalytic supports

SusChEM 事业：通过调整非无害催化载体实现可回收转移氢化催化剂

• 批准号: 1554963
• 负责人: Adelina Voutchkova-Kostal
• 金额: $ 49.45万
• 依托单位: George Washington University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-02-01 至 2022-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1554963&HistoricalAwards=false
• 关键词: CAREER; SusChEM; Recyclable; transfer; hydrogenation

CAREER SusChEM: Recyclable transfer hydrogenation catalysts by tuning of non-innocent catalytic supports The development of sustainable catalytic processes requires minimizing the use of rare, expensive, and toxic metals in catalysis, thus increasing reliance on earth-abundant and benign catalytic materials that are applicable to industrial processes. Concurrently, there is a need for finding new ways of constructively using industrial waste products, such as carbon dioxide generated in combustion processes and glycerol generated in biodiesel production. With funding from the Chemical Catalysis program, Dr. Voutchkova-Kostal is addressing these challenges by developing recyclable catalysts based on earth-abundant metals that are useful for converting carbon dioxide and glycerol into formic acid and dihydroxyacetone, thus turning two waste streams into useful industrial chemicals. She is extending the broader impacts of her work to the University and greater DC communities via an interdisciplinary Green Chemistry, Environmental Health and Science Policy Forum and new research-based organic chemistry laboratory modules that emphasize inquiry-based learning. These activities bridge the fields of green chemistry, policy and public health by engaging graduate and undergraduate students across these disciplines.The development of supported single-site heterogeneous catalysts (SSHCs) that can match the activity and selectivity of homogeneous analogs requires fundamental understanding of the interactions and potential synergies between supports and immobilized metal complexes. With funding from the Chemical Catalysis program, Dr. Voutchkova-Kostal is probing the structure-property-activity relationships that are needed to predictably design active, selective and long-lived SSHCs for challenging transfer hydrogenation reactions. Specifically, iridium and rhodium organometallic complexes are immobilized onto electronically-tunable layered double-hydroxide supports via sulfonate linkers. A complement of surface-sensitive and bulk spectroscopic techniques is used to probe the electronic effects that impact catalytic activity and stability. The insights developed are applied to optimizing the activity, selectivity and stability of a recyclable heterogeneous catalyst for transfer hydrogenation CO2 from glycerol, as well as recyclable catalysts for asymmetric transfer hydrogenation. To translate the broader impacts of this work and other developments in green chemistry to the university and greater DC communities, Dr. Voutchkova-Kostal is co-organizing an interdisciplinary Green Chemistry, Environmental Health and Science Policy Forum that facilitates dialogue on topical scientific issues across scientists and the public. To engage students in research she is also implementing new research-based organic chemistry laboratory modules that emphasize inquiry-based learning.

职业Suschem：可回收转移氢化催化剂通过调整非中性催化性支持可持续的催化过程的发展，需要最大程度地减少在催化中使用稀有，昂贵和有毒的金属的使用，从而增加对地球丰富和良性催化材料的依赖，从而适用于工业过程。同时，需要寻找新的方法来建设性地使用工业废物，例如在燃烧过程中产生的二氧化碳和生物柴油生产中产生的甘油。通过化学催化计划的资助，Voutchkova-Kostal博士通过开发基于地球丰富的金属的可回收催化剂来解决这些挑战，这些金属有助于将二氧化碳和甘油转化为甲酸和二羟基乙酮，从而将两种废物流变成有用的工业化学品。她通过跨学科的绿色化学，环境健康和科学政策论坛以及新的基于研究的有机化学实验室模块，将工作的更广泛影响扩大到大学和更大的DC社区，该模块强调基于询问的学习。这些活动通过在这些学科中吸引研究生和本科生来弥合绿色化学，政策和公共卫生领域。开发支持的单位单位异质催化剂（SSHC）可以匹配同质类似物的活动和选择性，需要对相互作用的基本理解以及支持的基础和潜在的协同体之间的潜在协同，并需要匹配。通过化学催化计划的资助，Voutchkova-Kostal博士正在探测结构性 - 肥胖活动关系，这些关系是可以预见的，可预测设计的有效，选择性和长期寿命的SSHC，以挑战转移氢化反应。具体而言，通过磺酸盐接头将虹膜和铑有机金属络合物固定在可电子脉冲的分层双氧化物支撑物上。表面敏感和大量光谱技术的补充用于探测影响催化活性和稳定性的电子效应。开发的见解应用于优化可回收的异质催化剂的活性，选择性和稳定性，用于从甘油中转移氢化二氧化碳，以及可回收的催化剂以进行非对称转移氢化。为了将这项工作的更广泛影响以及绿色化学中的其他发展转化为大学和更大的DC社区，Voutchkova-Kostal博士正在共同组织一个跨学科的绿色化学，环境健康和科学政策论坛，该论坛促进了科学家和公众关于局部科学问题的对话。为了让学生参与研究，她还正在实施新的基于研究的有机化学实验室模块，该模块强调基于询问的学习。

项目成果

Transfer Hydrogenation from Glycerol: Activity and Recyclability of Iridium and Ruthenium Sulfonate-Functionalized N-Heterocyclic Carbene Catalysts

• DOI: 10.1021/acssuschemeng.6b03156
• 发表时间: 2017-05-01
• 期刊: ACS SUSTAINABLE CHEMISTRY & ENGINEERING
• 影响因子: 8.4
• 作者: Azua, Arturo;Finn, Matthew;Voutchkova-Kostal, Adelina
• 通讯作者: Voutchkova-Kostal, Adelina