Kinetics, Mechanism, and Active Site Requirements for Hydrodeoxygenation over Reducible Metal Oxides

可还原金属氧化物加氢脱氧的动力学、机理和活性位点要求

基本信息

批准号：
1916133
负责人：
Praveen Bollini
金额：
$ 36.49万
依托单位：
University of Houston
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
2019
资助国家：
美国
起止时间：
2019-09-01 至 2024-08-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1916133&HistoricalAwards=false
关键词：
Kinetics Mechanism Active Site Requirements

项目摘要

Bio-oils are obtained from the fast pyrolysis of biomass, and their conversion into fuels and chemicals represents a sustainable alternative to coal, natural gas, and petroleum sources. The critical step in upgrading bio-oil is the selective removal of oxygen atoms from the lignin-derived fraction under ambient pressures of hydrogen and in the presence of a catalyst (otherwise known as "hydrodeoxygenation"). The ideal catalyst for hydrodeoxygenation would be abundant, inexpensive and easy to handle, while also being active, selective, hydrogen efficient, stable, and regenerable. The goal of this research project is to develop a molecular-level understanding of the chemical and physical processes occurring during the hydrodeoxygenation of biomass-derived model compounds over a class of catalysts called reducible metal oxides. Primarily, the studies will focus on cerium oxide (ceria), a material widely used commercially as an oxygen storage component in automotive exhaust systems. The research project serves as a training ground for graduate and undergraduate students to perform cutting edge research. The researchers also will participate in outreach activities in the Houston area, including Energy Day and Chevron Girls Engineering the Future Day, and they will host high school students in the laboratory and provide them with hands-on research experience as part of Project ACS SEED.The fact that bulk ceria selectively cleaves carbon-oxygen bonds in biomass-derived model compounds raises interesting fundamental questions regarding the nature and density of oxygen vacancies in reducible metal oxides. The precise mechanism through which carbon-oxygen bond cleavage over ceria occurs will be studied via four experimental steps: (1) demonstration of the potential of bulk ceria as a hydrodeoxygenation catalyst; (2) elucidation of the mechanism of anisole hydrodeoxygenation over bulk ceria; (3) establishing the active site requirements for hydrodeoxygenation over cerium oxide; and (4) understanding the effect of doping on active site identity, density, and efficacy. This research project aims to optimize energy, cost, and atom-efficiency of biomass conversion processes by guiding the design of hydrodeoxygenation catalysts and clarifying the identity of the mechanistic steps involved in Mars-van Krevelen/reverse Mars-van Krevelen redox cycles, ubiquitous in the realm of bulk oxide catalysis.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.

生物油是从生物质快速热解获得的，它们转化为燃料和化学物质代表了煤炭，天然气和石油来源的可持续替代品。升级生物油的关键步骤是，在氢气压力和存在催化剂的存在下，从木质素衍生的分数中选择性去除氧原子（也称为“氢氧合”）。加氢脱氧的理想催化剂将是丰富的，便宜且易于处理的，同时还具有活性，选择性，氢气效率，稳定且可再生。该研究项目的目的是在生物质衍生的模型化合物在一类称为可还原金属氧化物的催化剂上加氢脱氧化合物中发生的化学和物理过程的分子水平理解。主要是，研究将集中在氧化铜（Ceria）上，这是一种商业上广泛用作汽车排气系统中的氧气存储成分的材料。该研究项目是研究生和本科生进行尖端研究的培训理由。 The researchers also will participate in outreach activities in the Houston area, including Energy Day and Chevron Girls Engineering the Future Day, and they will host high school students in the laboratory and provide them with hands-on research experience as part of Project ACS SEED.The fact that bulk ceria selectively cleaves carbon-oxygen bonds in biomass-derived model compounds raises interesting fundamental questions regarding the nature and density of oxygen vacancies in reducible metal oxides. 将通过四个实验步骤研究碳 - 氧键裂解在谷物上的确切机制：（1）证明散装二氧化碳作为氢氧合催化剂的潜力；（2）阐明大量陶瓷上的弧甲氧化的机理；（3）确定在氧化岩岩含有氧化葡萄氧化的积极位点要求；（4）了解掺杂对主动位点身份，密度和功效的影响。 This research project aims to optimize energy, cost, and atom-efficiency of biomass conversion processes by guiding the design of hydrodeoxygenation catalysts and clarifying the identity of the mechanistic steps involved in Mars-van Krevelen/reverse Mars-van Krevelen redox cycles, ubiquitous in the realm of bulk oxide catalysis.This award reflects NSF's statutory mission and has been认为值得通过基金会的智力优点和更广泛影响的评论标准来评估值得支持。