CAREER: SusChEM: Development of Governing Mechanistic and Kinetic Models for the Selective Oxidative Cleavage of Levulinic Acid Over Supported Vanadium Oxides

职业：SusChEM：开发在负载的氧化钒上选择性氧化裂解乙酰丙酸的控制机制和动力学模型

• 批准号: 1454346
• 负责人: Jesse Bond
• 金额: $ 50万
• 依托单位: Syracuse University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-01-01 至 2020-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1454346&HistoricalAwards=false
• 关键词: CAREER; SusChEM; Development; Governing; Mechanistic

AbstractPI: Jesse Q BondProposal #: 1454346Institution: Syracuse UniversityThis project aims to develop a strategy for producing succinic acid and maleic acid from biomass. Traditionally, these commodity chemicals are made by oxidizing components of crude oil or natural gas, which is challenging. Instead, it may be possible to produce them more efficiently and inexpensively from sugar molecules, which can be extracted from biomass. This approach would require that we understand the reasons why certain catalysts and precursors deliver the desired products, while others do not. We anticipate that a technology that converts biomass and biomass derivatives to valuable products could help with commercial development of biomass processing industries. An educational component of the project will build a connection between Syracuse University students and communities in the city of Syracuse through service projects. The education program includes public workshops designed to improve public scientific literacy by educating participants on topics in energy and resource sustainability. Workshops will also outline effective methods for reducing society?s dependence on fossil resources and technology?s role in sustainability. The workshops will be facilitated by Syracuse University students as part of their undergraduate curriculum. These students will also work on design projects that incorporate new, energy- and resource-efficient technologies into ongoing urban development initiatives. This will allow them to use their training to improve their community and demonstrate the beneficial societal impacts of a STEM education.This award supports the study of gas-phase, aerobic oxidative cleavage of bifunctional levulinic acid (4-oxopentanoic acid) over supported vanadium oxides to yield C4 diacids. Diacid formation occurs through cleavage of the terminal C-C bond in levulinic acid, which is not generally observed in monofunctional ketone analogs, such as 2-pentanone. The central hypothesis is that the structure and bifunctionality of levulinic acid underlie unique interactions with VOx sites that shift selectivity toward terminal C-C cleavage. The project seeks to identify descriptors that govern C-C cleavage selectivity during ketone oxidation.This project will consider the influence of VOx speciation by measuring rates and selectivities of oxidative ketone cleavage over VOx/Al2O3 catalysts in which VOx phase and degree of polymerization are controlled by varying vanadium loading. The roles of Brønsted and Lewis acidity will be examined by studying oxidative cleavage over monolayer VOx/Al2O3 catalysts in which both acid site density and distribution are varied using acidic and basic modifiers. The influence of V-O-X bond character will be probed by comparing VOx sites on oxides that differ in reducibility. Isotopic tracing using 18O will identify the roles of lattice and chemisorbed oxygen during levulinic acid oxidation. Influences of ketone structure, steric interactions, and secondary functionality will be probed through a combination of kinetic and spectroscopic studies that contrast levulinic acid oxidation with that of various mono- and bifunctional ketone analogs. Electronic structure calculations will be used to build and parameterize a microkinetic model, which will reconcile first-principles expectations with experimental outcomes. Raman, UV-Vis, FTIR, and Temperature-Programmed spectroscopies (e.g., TPD, TPSR) will provide comprehensive characterization of site structure and chemical functionality.

摘要PI：Jesse Q Bond提案编号：1454346机构：雪城大学该项目旨在开发一种从生物质生产琥珀酸和马来酸的策略。传统上，这些商品化学品是通过氧化原油或天然气的成分来制造的，而这具有挑战性。或许可以更有效、更便宜地从糖分子中生产它们，而糖分子可以从生物质中提取。这种方法需要我们了解某些催化剂和前体的原因。我们预计，将生物质和生物质衍生物转化为有价值的产品的技术可以帮助生物质加工行业的商业发展，该项目的教育部分将在雪城大学学生和社区之间建立联系。该教育计划包括旨在通过对参与者进行能源和资源可持续性主题教育来提高公众科学素养的公共研讨会，研讨会还将概述减少社会对化石资源和技术的依赖的有效方法。的角色这些研讨会将由雪城大学的学生主持，作为其本科课程的一部分，这些学生还将致力于将新的能源和资源高效技术融入到正在进行的城市发展计划中。培训以改善他们的社区并展示 STEM 教育的有益社会影响。该奖项支持双功能乙酰丙酸（4-氧代戊酸）在支持的钒氧化物上的气相有氧氧化裂解的研究生成 C4 二酸是通过乙酰丙酸末端 C-C 键的裂解而形成的，这在单官能酮类似物（例如 2-戊酮）中通常观察不到。中心假设是乙酰丙酸的结构和双官能性是独特相互作用的基础。具有将选择性转向末端 C-C 裂解的 VOx 位点 该项目旨在确定控制酮过程中 C-C 裂解选择性的描述符。该项目将通过测量 VOx/Al2O3 催化剂上氧化酮裂解的速率和选择性来考虑 VOx 形态的影响，其中 VOx 相和聚合度通过不同的钒负载量进行控制。将检查布朗斯台德和路易斯酸度的作用。通过研究单层 VOx/Al2O3 催化剂的氧化裂解，其中酸位点密度和分布使用酸性和通过比较还原性不同的氧化物上的 VOx 位点，可以探究 V-O-X 键特性的影响，并使用 18O 进行同位素示踪，以确定在乙酰丙酸氧化过程中晶格和化学吸附氧的作用。将通过动力学和光谱研究的结合来探讨次要功能，将乙酰丙酸氧化与各种不同的氧化进行对比单功能和双功能酮类似物。电子结构计算将用于构建和参数化微动力学模型，该模型将使第一原理预期与实验结果相一致。 TPSR）将提供位点结构和化学功能的全面表征。