Biogenic Transition Metal Oxides as Water-Oxidation Electrocatalysts

生物过渡金属氧化物作为水氧化电催化剂

• 批准号: 1665455
• 负责人: Ralph Britt
• 金额: $ 38.77万
• 依托单位: University of California-Davis
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-07-15 至 2021-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1665455&HistoricalAwards=false
• 关键词: Biogenic; Transition; Metal; Oxides; Water

Biogenic Transition Metal Oxides as Water-Oxidation Electrocatalysts.With this award from the Chemical Catalysis Program of the Chemistry Division, Professor R. David Britt of the University of California at Davis is studying a novel type of biological catalyst which will contribute to clean and renewable energy technology. Certain bacteria use an enzyme to generate a manganese oxide material which Britt and coworkers have shown can split water, a key step in making inexpensive solar fuels, using energy from sunlight. The Britt lab is producing this material under different conditions, and exploring the activity of mutants of this enzyme, to optimize the water splitting activity of the manganese oxide material. The goal is to make an inexpensive bio-material using earth abundant manganese to replace existing catalysts based on expensive rare metals. Outreach activities coupled to this research program include summer research opportunities at both the high school and college level, motivating students by introducing them to this interesting interface of chemistry and biology that is relevant to renewable energy and environmental issues.A discrete manganese oxide (MnOx) unit was selected by Nature as the catalyst for O2 evolution - the Mn4O5Ca oxygen-evolving-complex (OEC) found in all oxygenic photosynthetic organisms. Inspired by the OEC, many manganese complexes and nanoparticles have been synthesized and investigated as catalysts for water-oxidation reaction. In this project in the laboratory of Professor R. David Britt of the University of California at Davis, a multicopper oxidase (MCO) enzyme, Mnx, which oxidizes aqueous Mn(II) driven by the oxidation potential of atmospheric O2, is offering a convenient means to generate a MnOx material in a fully biological fashion. The biological reactivity of the Mnx enzyme is allowing the Britt lab to systematically vary the structure and composition of the resulting MnOx and test what factors give rise to the highest activities. Specifically, this project is focusing on the following three aspects. 1) To explore the molecular mechanism of Mnx-catalyzed Mn(II) oxidation. 2) To characterize the resultant biogenic MnOx forms by multiple techniques (high-field EPR, XAS, SEM, etc) and employ the varied forms as water-oxidation electrocatalysts, in order to establish a structure-activity relationship. 3) Biogenic metal/mixed-metal oxides as catalysts: the reduction potential of type 1 Cu in Mnx enzyme can be tuned through site-directed mutagenesis of the axial ligand. Therefore, the type of substrates may be broadened (e.g. Fe(II), Co(II) or Ni(II)) and metal/mixed-metal oxides may be generated and tested as water-oxidation electrocatalysts. The project has broad impacts in training graduate and undergraduate and even visiting high school students in transition metal coordination chemistry, biochemistry, electrochemistry, and spectroscopy, and is being integrated into energy focused chemistry lectures that Professor Britt teaches each year.

生物过渡金属氧化物作为水氧化电催化剂。在化学部的化学催化计划中，加利福尼亚大学戴维斯分校的R. David Britt教授正在研究一种新型的生物催化剂，该催化剂将有助于清洁和可再生能源技术。 某些细菌使用酶来产生Britt和同事所显示的锰氧化物材料，可以将水分开，这是制造廉价太阳能燃料的关键步骤，使用阳光中的能量。 Britt Lab在不同条件下生产这种材料，并探索该酶突变体的活性，以优化锰氧化物材料的水分分裂活性。目的是使用地球丰富的锰制作廉价的生物材料，以基于昂贵的稀有金属来代替现有的催化剂。结合该研究计划的外展活动包括在高中和大学一级的夏季研究机会，通过向学生介绍与可再生能源和环境问题相关的有趣的化学和生物学界面，从而激发了学生。光合生物。受OEC的启发，许多锰配合物和纳米颗粒已合成并研究为水氧化反应的催化剂。在加利福尼亚大学戴维斯分校的R. David Britt教授的实验室中，MNX的多型氧化酶（MCO）酶，该酶氧化了大气O2氧化潜力驱动的水溶液（II），它提供了一种便利的手段，可以在一种完全的生物学方式中产生MNOX材料。 MNX酶的生物反应性使Britt Lab可以系统地改变所得MNOX的结构和组成，并测试哪些因素会导致最高活性。具体而言，该项目重点是以下三个方面。 1）探索MNX催化的Mn（II）氧化的分子机制。 2）通过多种技术（高场EPR，XAS，SEM等）表征所得的生物MNOX形式，并用各种形式作为水氧化电催化剂，以建立结构活性关系。 3）生物金属/混合金属氧化物作为催化剂：MNX酶中1型CU的还原潜力可以通过轴向配体的位置定向诱变来调节。因此，可以扩大底物的类型（例如Fe（II），CO（II）或Ni（ii）），可以生成并将金属/混合金属氧化物作为水氧化电催化剂进行测试。该项目在培训毕业生和本科生中产生了广泛的影响，甚至访问了过渡金属协调化学，生物化学，电化学和光谱学的高中生，并且正在整合到以能源为中心的化学讲座中，布里特教授每年都会教授。

项目成果

Insertion of a Transient Tin Nitride into Carbon–Carbon and Boron–Carbon Bonds

将瞬态氮化锡插入碳-碳和硼-碳键中

• DOI: 10.1021/acs.inorgchem.7b02413
• 发表时间: 2017
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Wang, Shuai;Tao, Lizhi;Stich, Troy A.;Olmstead, Marilyn M.;Britt, R. David;Power, Philip P.
• 通讯作者: Power, Philip P.

Two-Coordinate, Late First-Row Transition Metal Amido Derivatives of the Bulky Ligand -N(SiPr i 3 )Dipp (Dipp = 2,6-diisopropylphenyl): Effects of the Ligand on the Stability of Two-Coordinate Copper(II) Complexes

大配体-N(SiPr i 3 )Dipp (Dipp = 2,6-二异丙基苯基)的双配位后第一行过渡金属氨基衍生物：配体对双配位铜(II)配合物稳定性的影响

• DOI: 10.1021/acs.inorgchem.9b01159
• 发表时间: 2019
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Wagner, Clifton L.;Tao, Lizhi;Fettinger, James C.;Britt, R. David;Power, Philip P.
• 通讯作者: Power, Philip P.

Mn(III) species formed by the multi-copper oxidase MnxG investigated by electron paramagnetic resonance spectroscopy

通过电子顺磁共振波谱研究多铜氧化酶 MnxG 形成的 Mn(III) 物质

• DOI: 10.1007/s00775-018-1587-z
• 发表时间: 2018
• 期刊: JBIC. Journal of biological inorganic chemistry
• 作者: Tao, Lizhi;Stich, Troy A.;Soldatova, Alexandra V.;Tebo, Bradley M.;Spiro, Thomas G.;Casey, William H.;Britt, R. David
• 通讯作者: Britt, R. David

Metallo-inhibition of Mnx, a bacterial manganese multicopper oxidase complex

Mnx（一种细菌锰多铜氧化酶复合物）的金属抑制

• DOI: 10.1016/j.jinorgbio.2021.111547
• 发表时间: 2021
• 期刊: Journal of Inorganic Biochemistry
• 影响因子: 3.9
• 作者: Soldatova, Alexandra V.;Fu, Wen;Romano, Christine A.;Tao, Lizhi;Casey, William H.;Britt, R. David;Tebo, Bradley M.;Spiro, Thomas G.
• 通讯作者: Spiro, Thomas G.