CAREER: Iron Complexes for Hydrogen Generation and Oxygen Reduction

职业：用于制氢和氧还原的铁配合物

• 批准号: 1749800
• 负责人: William McNamara
• 金额: $ 40.22万
• 依托单位: College of William and Mary
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-06-01 至 2024-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1749800&HistoricalAwards=false
• 关键词: CAREER; Iron; Complexes; Hydrogen; Generation

SusChEM: CAREER: Iron Complexes for Hydrogen Generation and Oxygen ReductionThe development of clean and sustainable energy is one of the most pressing issues facing modern society. Solar energy is the most abundant form of renewable energy on earth, but is limited by a discontinuous supply. It is therefore critical to develop a way to harness and store solar energy as an energy dense chemical fuel that is compatible with our current infrastructure. Through a process called artificial photosynthesis (AP), sunlight is harnessed and used to split water into oxygen and hydrogen gas. Hydrogen gas is used directly as a fuel, or is combined with oxygen in a hydrogen fuel cell to generate electricity. Owing to expensive materials and inefficient catalysts, hydrogen generation through AP is significantly more expensive than hydrogen generated from fossil fuels. The use of hydrogen fuel cells to convert solar fuels into electricity is also limited by the use of expensive materials (platinum). In this project, Dr. William R. McNamara devises a photocatalytic system for hydrogen generation using cost-effective iron catalysts. The use of inexpensive iron catalysts for the efficient reduction of oxygen gas in hydrogen fuel cells is also investigated. Within this project, several outreach activities promote the development of future generations of scientists. Dr. McNamara is conducting an after-school program at a local public high school with a high concentration of underrepresented groups in science, technology, engineering, and mathematics (STEM). Through this program students actively conduct research in a meaningful and accessible way. These activities advance public scientific literacy while encouraging underrepresented groups to pursue careers in STEM disciplines.Funding from the Chemical Catalysis Program of the National Science Foundation supports the effort of Dr. William R. McNamara at the College of William and Mary towards the development of inexpensive materials for both photocatalytic hydrogen generation and the oxygen reduction reaction of hydrogen fuel cells. The immobilization of robust iron polypyridyl hydrogen generation catalysts on charge-separating supports (carbon nanotubes, TiO2 and SrTiO3) is characterized using attenuated total reflection infrared spectroscopy (ATR-IR) and diffuse reflectance UV-Vis spectroscopy. Hydrogen generation is promoted using an LED photolysis system and analyzed with gas chromatography. In order to decrease cost and improve the widespread applicability of photocatalytic hydrogen generation, the use of naturally occurring humic substances to replace traditional sacrificial donors is also investigated. Additionally, iron polypyridyl sulfinate catalysts are examined for the oxygen reduction reaction in hydrogen fuel cells. Rotating ring disk voltammetry (RRDV) and cyclic voltammetry (CV) are used to evaluate catalytic performance. Rigorous treatment of the data using foot-of-the-wave analysis (FOWA) is also employed to better understand mechanism. Funding from the NSF provides for the training of 15 different students (primarily undergraduates) in this multi-disciplinary research effort. Additionally, Dr. McNamara conducts an after-school research program at a local public high school with a high concentration of underrepresented groups in science. Consistent with the broader impacts of this project, these activities promote the engagement of underrepresented groups in STEM disciplines and increase public engagement in the sciences.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.

发展清洁可持续的能源是现代社会面临的最紧迫的问题之一。太阳能是地球上最丰富的可再生能源，但受到不连续供应的限制。因此，至关重要的是要找到一种方法，将太阳能作为一种能源密集型化学燃料加以利用和储存，并与我们目前的基础设施相适应。通过一种名为人工光合作用(AP)的过程，阳光被利用，并用来将水分解为氧气和氢气。氢气直接用作燃料，或在氢燃料电池中与氧气结合发电。由于昂贵的材料和低效的催化剂，通过AP产生的氢气比用化石燃料产生的氢气要昂贵得多。氢燃料电池将太阳能燃料转化为电能的使用也受到昂贵材料(铂)使用的限制。在这个项目中，威廉·R·麦克纳马拉博士设计了一种使用经济实惠的铁催化剂的光催化制氢系统。还研究了使用廉价的铁催化剂高效还原氢燃料电池中的氧气气体。在该项目范围内，开展了若干外联活动，以促进未来几代科学家的发展。麦克纳马拉博士正在当地一所公立高中开展一项课后计划，那里的科学、技术、工程和数学(STEM)领域的代表人数较少。通过这个项目，学生们以一种有意义和可接触的方式积极开展研究。这些活动提高了公众的科学素养，同时鼓励代表不足的群体从事STEM学科的职业。国家科学基金会化学催化计划的资助支持威廉与玛丽学院的William R.McNamara博士努力开发用于氢燃料电池的光催化制氢和氧气还原反应的廉价材料。用衰减全反射红外光谱(ATR-IR)和漫反射紫外-可见光谱(UV-Vis)表征了负载在电荷分离载体(碳纳米管、二氧化钛和钛酸锶)上的铁系聚吡啶制氢催化剂。利用LED光解系统促进氢气的产生，并用气相色谱进行分析。为了降低成本和提高光催化制氢的广泛适用性，还研究了用自然生成的腐殖质取代传统的牺牲供体。此外，还考察了铁多吡磺酸盐催化剂在氢燃料电池中的氧还原反应。采用旋转环盘伏安法(RRDV)和循环伏安法(CV)对催化剂的性能进行了评价。为了更好地理解机理，还使用了波脚分析(FOWA)对数据进行了严格的处理。来自国家科学基金会的资金为15名不同的学生(主要是本科生)提供了这一多学科研究努力的培训。此外，麦克纳马拉博士还在当地一所公立高中开展了一项课后研究项目，那里的科学界代表不足的群体非常集中。与该项目更广泛的影响相一致，这些活动促进了STEM学科中代表性不足的群体的参与，并增加了公众对科学的参与。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势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

Tridentate bis(2-pyridylmethyl)amine iron catalyst for electrocatalytic proton reduction

用于电催化质子还原的三齿双(2-吡啶甲基)胺铁催化剂

• DOI: 10.1016/j.ica.2019.119394
• 发表时间: 2020
• 期刊: Inorganica Chimica Acta
• 影响因子: 2.8
• 作者: Schiffman, Zachary R.;Margonis, Caroline M.;Moyer, Allison;Ott, Michelle;McNamara, William R.
• 通讯作者: McNamara, William R.

Iron polypyridyl catalysts assembled on metal oxide semiconductors for photocatalytic hydrogen generation

金属氧化物半导体上组装的铁聚吡啶催化剂用于光催化制氢

• DOI: 10.1039/c8cc00453f
• 发表时间: 2018
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Race, N. A.;Zhang, W.;Screen, M. E.;Barden, B. A.;McNamara, W. R.
• 通讯作者: McNamara, W. R.