EAGER: Photocatalytic extension of short-chain molecules for biomass conversion

EAGER：用于生物质转化的短链分子的光催化延伸

• 批准号: 2037844
• 负责人: Dunwei Wang
• 金额: $ 25万
• 依托单位: Boston College
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-08-01 至 2022-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2037844&HistoricalAwards=false
• 关键词: EAGER; Photocatalytic; extension; short; chain

The project investigates a sustainable process that uses catalytic reactions driven by solar energy to convert biomass to hydrocarbon chemicals. The process uses a new catalytic material that generates small reactive molecules that combine to form larger molecules with 10-20 carbon atoms, like those found in diesel and jet fuels. By using biorenewable feedstocks in combination with solar-driven chemical processing, the project could lay the groundwork for a near-zero greenhouse gas technology for producing fuels and high-value chemicals from biomass. The project includes a novel outreach program that educates high-school students in current science issues and provides opportunities for them to be spokespersons for conveying those issues to the broader public.Photocatalysis has recently been reported to enable room-temperature dehydrogenative C-C coupling of 2,5-dimethyl furan (2-5 DMF) and 2-methy furan (2-MF) while producing hydrogen simultaneously. However, the process suffers from low conversion and poor selectivity, as well as sensitivity to oxygen. The underpinning mechanism (i.e. the radical species generated from C-H activation of the methyl group would resonate to furan rings and lead to a variety of isomer products) is understood as a key reason for this important deficiency. Recently, one of the investigators has discovered that under photoelectrochemical conditions, Ta3N5 can enable an alternative radical-based pathway that is not only highly efficient but also insensitive to impurities such as H2O or O2 in ambient air. The project will extend those studies to photocatalytic biomass conversion. To that end, detailed understanding of the reaction mechanism is needed. The mechanistic studies will include light-dark experiments, detailed product characterization, and experimentation with various radical generator and acceptor species. Moreover, comparisons will be made between the Ta3N5 utilized as a photoelectrode and as a heterogeneous photocatalyst, with co-catalysts such as platinum included in some cases.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.

该项目研究了一种可持续过程，该过程使用了由太阳能驱动的催化反应将生物量转化为碳氢化合物化学物质。 该过程使用了一种新的催化材料，该催化材料产生了小的反应性分子，该分子结合在一起，形成较大的分子与10-20个碳原子，例如在柴油和喷气燃料中发现的碳原子。 通过将可生物生物的原料与太阳能驱动的化学处理结合使用，该项目可以为接近零温室气体技术奠定基础，用于生产生物质的燃料和高价值化学品。 该项目包括一个新颖的外展计划，该计划在当前的科学问题上教育高中生，并为他们提供了将这些问题传达给更广泛公共的发言人。最近据报道，近代分析可以使室温脱氢C-C偶联到2,5-二甲基呋喃（2-5 dmf）（2-5 dmf）和2-methy furan（2-methy furan）（2-methy furan（2-mf）furan（2-mf）furan（2-mf）furan（2-mf）。 但是，该过程遭受低转化率和差的选择性以及对氧气的敏感性。基础机制（即，甲基C-H激活产生的自由基物种将与Furan环共鸣，并导致各种异构体产物）被认为是这种重要缺陷的关键原因。最近，其中一名研究人员发现，在光电化学条件下，TA3N5可以实现一种基于自由基的途径，该途径不仅高效，而且对环境空气中的H2O或O2等杂质不敏感。 该项目将将这些研究扩展到光催化生物量转化率。为此，需要对反应机制的详细理解。 机械研究将包括浅黑色实验，详细的产品表征以及对各种自由基发电机和受体物种的实验。 此外，将与TA3N5作为光电子的TA3N5进行比较，并作为一种异质的光催化剂，以及某些情况下包含的铂金等共催化剂。该奖项反映了NSF的法定任务，并通过该基金会的知识分子优点和广泛的影响来评估NSF的法定任务，并被认为是值得的支持。

项目成果

Electrochemically Triggered Chain Reactions for the Conversion of Furan Derivatives

电化学引发的呋喃衍生物转化链式反应

• DOI: 10.1002/anie.202016601
• 发表时间: 2021
• 期刊: Angewandte Chemie International Edition
• 作者: Chen, Rong;Yang, Cangjie;Zhou, Zefeng;Haeffner, Fredrik;Dersjant, Alinda;Dulock, Nicholas;Dong, Qi;He, Da;Jin, Jing;Zhao, Yanyan
• 通讯作者: Zhao, Yanyan