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Photoactivation of Stable Bonds for Energy Conversion and Photoredox Catalysis

用于能量转换和光氧化还原催化的稳定键的光活化

基本信息

批准号：
1855531
负责人：
Daniel Nocera
金额：
$ 90万
依托单位：
Harvard University
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 2023-08-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1855531&HistoricalAwards=false
关键词：
Photoactivation Stable Bonds Energy Conversion

项目摘要

Professor Daniel Nocera's research goal is to convert the U.S. energy sector's focus from fossil fuels to renewables, with a long-term goal of creating a solar fuels industry. The ample supply of solar energy can meet growing energy demands, but it is intermittent due to the daily rising and setting of the sun. A strategy to compensate for this solar cycling is to convert solar energy to carbon-containing fuels in a sustainable and scalable manner. Thus, solar energy would be harnessed in the form of chemical bonds. The basic science needed to drive such a restructuring of the U.S. energy industry begins with an understanding of how light is absorbed by molecules and then transformed into a chemical reaction - a process known as photochemistry. In this project, Dr. Nocera's group at Harvard University is developing an understanding of how to capture light energy by molecules and then productively direct the energy to drive useful chemical reactions. Dr. Nocera is actively engaged in outreach activities that introduce talented students to forefront problems in chemistry and science. He and his research team provide these students with a broad technical skill set so that they can address critical problems in their independent professional careers. Professor Nocera engages with the public to relate how chemistry can address challenges in energy and photochemistry through outreach activities in a variety of forums including national news, TV, radio programs, movies, and other public venues.With funding from the Chemical Catalysis Program of the Chemistry Division, Dr. Nocera of Harvard University is developing a better understanding of the generation of highly energetic species that are critical to storing energy in the form of fuels. Through the interplay of spectroscopy and synthesis, new reagents, reactions and processes are created for the generation of high energy species from stable M-X (M = metal, X = halogen atom) and M-O (O = oxygen) chemical bonds. Photoactivation of M-X bonds is driven from charge transfer excited states. Ligands are crafted that have favorable secondary coordination spheres so as to allow the halogen atom to be escorted from the primary coordination sphere upon photoactivation of the M-X bond. Mechanistic studies focus of stereoelectronic factors of the ligand design that deliver the halogen atom in high yields. The photointermediates are channeled to productive and selective C-H activation and functionalization. The research also focuses on photodriven production of M-O bonds and their subsequent activation at bimetallic centers residing in novel macrocyclic ligands. A new approach for generating reactive M-O bonds by light excitation exploits pre-coordinating oxoanions to the bimetallic center. The ability of light to drive the production of an energetic metal-oxo-metal bond opens an avenue to photo-oxidize C-H bonds. Dr. Nocera is actively engaged in outreach programs with the public to convey how chemistry can address important societal challenges. His outreach activities also focus on the recruitment of female students and students from underrepresented groups. In further support of the broader impacts of the project, Dr. Nocera has developed a new undergraduate curriculum in the subject of inorganic chemistry and photochemistry.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.

丹尼尔·诺塞拉教授的研究目标是将美国能源部门的重点从化石燃料转向可再生能源，长期目标是建立太阳能燃料产业。充足的太阳能供应可以满足日益增长的能源需求，但由于太阳每天升起和落下，它是间歇性的。补偿这种太阳能循环的策略是以可持续和可扩展的方式将太阳能转化为含碳燃料。因此，太阳能将以化学键的形式被利用。推动美国能源行业这种重组所需的基础科学首先要了解光是如何被分子吸收，然后转化为化学反应的，这一过程被称为光化学。在这个项目中，Nocera博士在哈佛大学的团队正在研究如何通过分子捕获光能，然后有效地引导能量来驱动有用的化学反应。Nocera博士积极参与外展活动，向有才华的学生介绍化学和科学的前沿问题。他和他的研究团队为这些学生提供了广泛的技术技能，使他们能够解决他们独立职业生涯中的关键问题。Nocera教授与公众互动，通过各种论坛，包括国家新闻，电视，广播节目，电影和其他公共场所的外联活动，讲述化学如何应对能源和光化学的挑战。在化学部化学催化计划的资助下，哈佛大学的Nocera博士正在更好地理解高能物种的产生，这些物种对以燃料形式储存能量至关重要。通过光谱学和合成的相互作用，创造了新的试剂、反应和工艺，用于从稳定的M-X（M =金属，X =卤素原子）和M-O（O =氧）化学键产生高能物质。M-X键的光活化由电荷转移激发态驱动。配体被制作成具有有利的次级配位球，以允许卤素原子在M-X键的光活化时从初级配位球被护送。机理研究的重点是立体电子因素的配体设计，提供高产量的卤素原子。光中间体被引导到生产性和选择性的C-H活化和官能化。该研究还侧重于光驱动的M-O键的产生及其随后在新的大环配体中的双中心的活化。一种通过光激发产生反应性M-O键的新方法利用了预配位的含氧阴离子。光驱动高能金属-氧代-金属键产生的能力打开了光氧化C-H键的途径。Nocera博士积极参与与公众的外联计划，以传达化学如何应对重要的社会挑战。他的外联活动还侧重于招收女生和来自代表性不足群体的学生。为了进一步支持该项目的更广泛的影响，Nocera博士开发了一个新的无机化学和光化学学科的本科课程。该奖项反映了NSF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（16）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Photohalogen elimination chemistry in low-valent binuclear nickel complexes

低价双核镍配合物中的光卤素消除化学

DOI：
10.1016/j.poly.2021.115228
发表时间：
2021
期刊：
Polyhedron
影响因子：
2.6
作者：
Jun Hwang, Seung;Hadt, Ryan G.;Ruccolo, Serge;Gygi, David;Zheng, Shao-Liang;Chen, Yu-Sheng;Nocera, Daniel G.
通讯作者：
Nocera, Daniel G.

Multielectron C–H photoactivation with an Sb( v ) oxo corrole

Sb(v) 氧咔咯的多电子 C–H 光活化

DOI：
10.1039/c9cc09892e
发表时间：
2020
期刊：
Chemical Communications
影响因子：
4.9
作者：
Lemon, Christopher M.;Maher, Andrew G.;Mazzotti, Anthony R.;Powers, David C.;Gonzalez, Miguel I.;Nocera, Daniel G.
通讯作者：
Nocera, Daniel G.

Ion-pair effects in photoredox chemistry

光氧化还原化学中的离子对效应

DOI：
10.1016/j.chempr.2022.06.010
发表时间：
2022
期刊：
Chem
影响因子：
23.5
作者：
Zhu, Qilei;Nocera, Daniel G.
通讯作者：
Nocera, Daniel G.

Solvent-Induced Spin-State Change in Copper Corroles

DOI：
10.1021/acs.inorgchem.2c02678
发表时间：
2022-12-02
期刊：
INORGANIC CHEMISTRY
影响因子：
4.6
作者：
Lemon，Christopher M.;Maher，Andrew G.;Nocera，Daniel G.
通讯作者：
Nocera，Daniel G.

Ag(III)···Ag(III) Argentophilic Interaction in a Cofacial Corrole Dyad

Ag(III)····Ag(III) 面科罗勒二元体中的亲银相互作用

DOI：
10.1021/acs.inorgchem.2c02285
发表时间：
2023
期刊：
Inorganic Chemistry
影响因子：
4.6
作者：
Lemon, Christopher M.;Powers, David C.;Huynh, Michael;Maher, Andrew G.;Phillips, Austin A.;Tripet, Brian P.;Nocera, Daniel G.
通讯作者：
Nocera, Daniel G.