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的过程，利用太阳能驱动的催化反应将生物质转化为碳氢化合物。 该过程使用一种新的催化材料，可以产生小的反应分子，这些分子结合形成具有 10-20 个碳原子的较大分子，就像柴油和喷气燃料中的分子一样。 通过使用生物可再生原料与太阳能驱动的化学加工相结合，该项目可以为利用生物质生产燃料和高价值化学品的近零温室气体技术奠定基础。 该项目包括一项新颖的外展计划，该计划对高中生进行当前科学问题的教育，并为他们提供成为向更广泛公众传达这些问题的代言人的机会。最近有报道称，光催化可以实现 2,5-二甲基呋喃 (2-5 DMF) 和 2-甲基呋喃 (2-MF) 的室温脱氢 C-C 偶联，同时产生氢气。 然而，该方法存在转化率低、选择性差以及对氧气敏感的问题。基础机制（即甲基的 C-H 活化产生的自由基物质会与呋喃环共振并产生各种异构体产物）被认为是造成这一重要缺陷的关键原因。最近，一位研究人员发现，在光电化学条件下，Ta3N5 可以实现另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。 该项目将把这些研究扩展到光催化生物质转化。为此，需要详细了解反应机制。 机理研究将包括明暗实验、详细的产品表征以及各种自由基产生剂和受体物种的实验。 此外，还将对用作光电极的 Ta3N5 和用作异质光催化剂（在某些情况下还包括铂等助催化剂）进行比较。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力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

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