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:
  • 金额:
    $ 36.49万
  • 依托单位:
  • 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

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.
生物油是从生物质的快速热解中获得的,它们转化为燃料和化学品是煤炭、天然气和石油的可持续替代品。升级生物油的关键步骤是在氢气的环境压力和催化剂的存在下,从木质素衍生的馏分中选择性地去除氧原子(也称为“氢脱氧”)。氢脱氧的理想催化剂应是丰富、廉价、易于操作,同时又具有活性、选择性、氢效率、稳定性和可再生性。该研究项目的目标是在分子水平上了解生物来源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过程中发生的化学和物理过程。首先,研究将集中在氧化铈(ceria)上,这是一种广泛应用于汽车排气系统的储氧材料。该研究项目是研究生和本科生进行前沿研究的训练基地。研究人员还将参加休斯顿地区的推广活动,包括能源日和雪佛龙女孩工程未来日,他们将在实验室接待高中生,并为他们提供实践研究经验,这是ACS SEED项目的一部分。在生物质衍生的模型化合物中,大块铈选择性地切割碳-氧键,这一事实提出了关于可还原金属氧化物中氧空位的性质和密度的有趣的基本问题。本文将通过四个实验步骤来研究氧化铈上碳氧键裂解的确切机理:(1)证明大块氧化铈作为加氢脱氧催化剂的潜力;(2)阐明了苯甲醚在大块氧化铈上加氢脱氧的机理;(3)确定氧化铈加氢脱氧的活性位点要求;(4)了解掺杂对活性位点特性、密度和功效的影响。该研究项目旨在通过指导加氢脱氧催化剂的设计,阐明在体积氧化物催化领域普遍存在的Mars-van Krevelen/逆Mars-van Krevelen氧化还原循环所涉及的机制步骤的特性,优化生物质转化过程的能源、成本和原子效率。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。

项目成果

期刊论文数量(4)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Beyond upper bound estimates of active site densities in heterogeneous catalysis: A note on the critical role of titrant pressure
超越多相催化中活性位点密度的上限估计:关于滴定剂压力的关键作用的说明
  • DOI:
    10.1016/j.jcat.2022.06.006
  • 发表时间:
    2022
  • 期刊:
  • 影响因子:
    7.3
  • 作者:
    Afrin, Sadia;Bollini, Praveen
  • 通讯作者:
    Bollini, Praveen
Cerium Oxide Catalyzes the Selective Vapor-Phase Hydrodeoxygenation of Anisole to Benzene at Ambient Pressures of Hydrogen
On the Utility of Ce 3+ Spin−Orbit Transitions in the Interpretation of Rate Data in Ceria Catalysis: Theory, Validation, and Application
关于 Ce 3 自旋轨道跃迁在解释二氧化铈催化速率数据中的效用:理论、验证和应用
  • DOI:
    10.1021/acs.jpcc.2c06637
  • 发表时间:
    2023
  • 期刊:
  • 影响因子:
    0
  • 作者:
    Afrin, Sadia;Bollini, Praveen
  • 通讯作者:
    Bollini, Praveen
A transient kinetic analysis of the evolution of a reducible metal oxide towards catalyzing nonoxidative alkanol dehydrogenation
  • DOI:
    10.1016/j.jcat.2020.08.023
  • 发表时间:
    2020-08
  • 期刊:
  • 影响因子:
    7.3
  • 作者:
    S. Afrin;Praveen Bollini
  • 通讯作者:
    S. Afrin;Praveen Bollini
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Praveen Bollini其他文献

Scale-up analysis of the oxidative dehydrogenation of ethane over MoVTeNbOsubx/sub catalysts in an autothermal reactor
在自热式反应器中对乙烷在 MoVTeNbOx 催化剂上氧化脱氢的放大分析
  • DOI:
    10.1016/j.ces.2023.118649
  • 发表时间:
    2023-06-05
  • 期刊:
  • 影响因子:
    4.300
  • 作者:
    Jiakang Chen;Zhe Sun;Praveen Bollini;Vemuri Balakotaiah
  • 通讯作者:
    Vemuri Balakotaiah
Exploiting proximity effects to improve ethyl acetate selectivity in the dehydrogenative coupling of ethanol over supported Cu catalysts
利用邻近效应提高乙醇在负载型铜催化剂上脱氢偶联反应中乙酸乙酯的选择性
  • DOI:
    10.1016/j.apcata.2025.120228
  • 发表时间:
    2025-05-05
  • 期刊:
  • 影响因子:
    4.800
  • 作者:
    Varad V. Joshi;Praveen Bollini
  • 通讯作者:
    Praveen Bollini
Technological Options for Direct Air Capture: A Comparative Process Engineering Review.
直接空气捕获的技术选择:比较过程工程评论。
Shallow-bed reactor design for the autothermal oxidative dehydrogenation of ethane over MoVTeNbOsubx/sub catalysts
乙烷在 MoVTeNbOₓ催化剂上自热氧化脱氢的浅床反应器设计
  • DOI:
    10.1016/j.cej.2023.145660
  • 发表时间:
    2023-10-15
  • 期刊:
  • 影响因子:
    13.200
  • 作者:
    Jiakang Chen;Praveen Bollini;Vemuri Balakotaiah
  • 通讯作者:
    Vemuri Balakotaiah
Shallow-bed reactor design for the autothermal oxidative dehydrogenation of ethane over MoVTeNbOx catalysts
MoVTeNbOx 催化剂上乙烷自热氧化脱氢的浅床反应器设计
  • DOI:
    10.1016/j.cej.2023.145660
  • 发表时间:
    2023
  • 期刊:
  • 影响因子:
    15.1
  • 作者:
    Jiakang Chen;Praveen Bollini;V. Balakotaiah
  • 通讯作者:
    V. Balakotaiah

Praveen Bollini的其他文献

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{{ truncateString('Praveen Bollini', 18)}}的其他基金

Understanding and Exploiting the Favorable Role of Non-Stoichiometric Oxygen in Bulk Metal Oxide Catalyzed Partial Oxidation of Light Alkanes
了解和利用非化学计量氧在块体金属氧化物催化轻质烷烃部分氧化中的有利作用
  • 批准号:
    2128846
  • 财政年份:
    2022
  • 资助金额:
    $ 36.49万
  • 项目类别:
    Standard Grant

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