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.

AbstractPI：Jesse Q Bondpropopals＃：1454346机构：Syracuse University Thiss Project旨在制定一种从生物量生产琥珀酸和马来酸的策略。传统上，这些商品化学物质是通过氧化原油或天然气的氧化成分来制成的，这是挑战。取而代之的是，可以从糖分子中更有效，更便宜地产生它们，这些分子可以从生物量中提取。这种方法将要求我们了解某些催化剂和前体提供所需产品的原因，而其他产品则没有。我们预计，将生物量和生物量衍生品转换为有价值的产品的技术可以帮助生物量加工行业的商业开发。该项目的一个教育部分将通过服务项目建立锡拉丘兹大学学生与锡拉丘兹市社区之间的联系。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的教育，旨在提高公共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在可持续性中的作用的有效方法。这些讲习班将由锡拉丘兹大学的学生作为本科课程的一部分准备。这些学生还将从事设计项目，将新的，能源和资源有效的技术纳入正在进行的城市发展计划中。这将使他们能够利用培训来改善社区并证明STEM教育的有益社会影响。该奖项支持对双功能链氨酰酸（4-氧化苯甲酸）对氧化钒的双功能脱氟蛋白酸（4-氧化甲酸）的研究研究。二肽形成是通过左脱胶酸中末端C-C键的切割而发生的，葡萄酸酸中的末端C-C键在单官能酮类似物（例如2-戊酮）中通常不观察到。中心假设是，葡萄糖酸的结构和双函数是与vox位点的独特相互作用，从而将选择性转移到末端C-C裂解。该项目旨在确定在酮氧化过程中控制C-C切割选择性的描述符。该项目将通过测量VOX/AL2O3催化剂的氧化酮裂解速率和选择性来考虑VOX规范的影响，在VOX/AL2O3催化剂中，VOX相和聚合程度通过不同的钒载荷控制。通过研究单层VOX/AL2O3催化剂，将检查Brønsted和Lewis酸度的作用，其中使用酸性和碱性修饰剂变化了酸性位点密度和分布。 V-O-X键特性的影响将通过比较可降低性不同的氧化物上的Vox位点来探测。使用18O的同位素跟踪将确定晶格和化学吸附的氧在脱光蛋白酸氧化过程中的作用。酮结构，空间相互作用和次级功能的影响将通过动力学研究和光谱研究的组合进行探测，这些研究与各种单功能和双功能酮类似物的影响与左旋蛋白酸氧化对比。电子结构计算将用于构建和参数化微动力模型，拉曼，UV-VIS，FTIR和温度填充的光谱镜（例如TPD，TPSR）将提供位点结构和化学功能的全面表征。