Metal Chalcogenide and Pnictide OER Catalysts: The Impact of the Crystalline Precursor on the Active Amorphous Catalyst

金属硫族化物和磷族化物 OER 催化剂：结晶前驱体对活性非晶催化剂的影响

• 批准号: 1664941
• 负责人: Charles Mullins
• 金额: $ 45万
• 依托单位: University of Texas at Austin
• 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: 2017-07-01 至 2022-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1664941&HistoricalAwards=false
• 关键词: Metal; Chalcogenide; Pnictide; OER; Catalysts

Metal Chalcogenide and Pnictide OER Catalysts: The Impact of the Crystalline Precursor on the Active Amorphous CatalystDeveloping earth-abundant, cheap materials that can chemically transform water into oxygen and hydrogen is an important goal in the quest to build a sustainable energy future. This catalytic process, referred to as water electrolysis or water-splitting, is used to produce hydrogen in an environmentally-friendly manner. Hydrogen is employed in many industries (e.g., petroleum processing) and could also be used as a fuel for transportation as well as other purposes. Currently metal-chalcogenide (e.g., nickel and sulfur) and metal-pnictide (e.g., cobalt and phosphorous) materials show great promise as earth-abundant compounds with good catalytic properties for the water oxidation reaction (which is one of the two reactions involved in water splitting) but their true chemical compositions and structures are not well-understood. In this project, Dr. Buddie Mullins is conducting experiments on metal-chalcogenide and metal-pnictide materials and studying their chemical and structural transformations during the water oxidation reaction. Dr. Mullins is actively involved in scientific public awareness and promotion activities through his research that encourage the participation and intellectual development of students in science, technology, engineering and mathematics (STEM) disciplines. These activities include laboratory internships for high school students and college undergraduates with the aim of encouraging these students (especially women and those historically underrepresented in STEM) to pursue careers in the STEM fields.With funding from the Chemical Catalysis Program of the Chemistry Division, Professor Buddie Mullins is working to verify or disprove the hypothesis that (i) metal-chalcogenide (MC) and metal-pnictide (MP) electrocatalysts are simply precursors to highly active metal-oxide (MO) electrocatalysts and (ii) that the underlying layers of MC or MP don't influence the catalytic performance. It is clear that the outer layers of MCs and MPs transform into MOs under water oxidation conditions. During this transformation an amorphous high surface area film is created that is more catalytically active than its' crystalline oxide analog. Professor Mullins is studying the mechanism by which the amorphous film is created as well as its enhanced activity. He is also synthesizing both nanocolumnar and dense films of MCs and MPs for use as model electrocatalysts by glancing angle physical vapor deposition, which can reproducibly create electrocatalyst films. Mullins is probing the films with many different ex situ characterization techniques, including molecular beams and thermal desorption mass spectrometry for characterization and measurement of the surface area. Dr. Mullins is actively involved in promoting science and science education to students of all ages and especially those historically underrepresented in the sciences. This is accomplished via videos, internships and public demonstrations; these activities support the broader impacts of the research project.

金属硫族化物和磷族元素化物OER催化剂：晶体前体对活性非晶态催化剂的影响开发地球上丰富的廉价材料，可以将水化学转化为氧气和氢气，是寻求建立可持续能源未来的重要目标。 这种催化过程被称为水电解或水分解，用于以环境友好的方式生产氢气。氢气用于许多工业（例如，石油加工），并且还可以用作运输以及其他目的的燃料。 目前金属硫属化物（例如，镍和硫）和金属磷属元素化物（例如，钴和磷）材料显示出作为地球上丰富的化合物的巨大前景，该化合物对于水氧化反应（这是水裂解中涉及的两个反应之一）具有良好的催化性能，但是它们的真实化学组成和结构还没有被很好地理解。 在这个项目中，Buddie Mullins博士正在对金属硫属化物和金属磷属化物材料进行实验，并研究它们在水氧化反应过程中的化学和结构转变。 Mullins博士通过他的研究积极参与科学公众意识和促进活动，鼓励学生参与科学，技术，工程和数学（STEM）学科的智力发展。 这些活动包括高中生和大学生的实验室实习，目的是鼓励这些学生（特别是妇女和那些在STEM历史上代表性不足的人）在STEM领域追求职业生涯。在化学部化学催化计划的资助下，Buddie Mullins教授正致力于验证或反驳以下假设：（i）金属硫族化物（MC）和金属磷族化物（MP）电催化剂仅仅是高活性金属氧化物（MO）电催化剂的前体，以及（ii）MC或MP的下层不影响催化性能。 很明显，在水氧化条件下，MCs和MP的外层转化为MO。 在这种转变过程中，产生了比其结晶氧化物类似物更具催化活性的无定形高表面积膜。 Mullins教授正在研究无定形膜的形成机制及其增强的活性。 他还通过掠射角物理气相沉积法合成了MCs和MPs的纳米柱状和致密薄膜，用作模型电催化剂，这可以重现地创建电催化剂薄膜。Mullins正在用许多不同的非原位表征技术来探测薄膜，包括分子束和热解吸质谱法，用于表征和测量表面积。 穆林斯积极参与促进科学和科学教育的所有年龄段的学生，特别是那些在科学历史上代表性不足。 这是通过视频，实习和公开演示完成的;这些活动支持研究项目的更广泛的影响。

项目成果

Cobalt Metal–Cobalt Carbide Composite Microspheres for Water Reduction Electrocatalysis

• DOI: 10.1021/acsaem.0c00321
• 发表时间: 2020-03
• 期刊: Cancer research
• 影响因子: 11.2
• 作者: Kenta Kawashima;Kihyun Shin;Bryan R. Wygant;Jun-Hyuk Kim;C. Cao;Jie Lin;Yoon Jun Son;Yang Liu;G. Henkelman;C. Mullins

Mass transport-enhanced electrodeposition of Ni–S–P–O films on nickel foam for electrochemical water splitting

• DOI: 10.1039/d0ta12097a
• 发表时间: 2021-03
• 期刊: Journal of Materials Chemistry A
• 影响因子: 11.9
• 作者: R. Márquez-Montes;Kenta Kawashima;Yoon Jun Son;J. Weeks;H. H. Sun-H.;H. Celio;V. Ramos-Sánchez;C. Mullins

Catalyst or Precatalyst? The Effect of Oxidation on Transition Metal Carbide, Pnictide, and Chalcogenide Oxygen Evolution Catalysts

• DOI: 10.1021/acsenergylett.8b01774
• 发表时间: 2018-11
• 期刊: ACS Energy Letters
• 影响因子: 22
• 作者: Bryan R. Wygant;Kenta Kawashima;C. Mullins

Effects of Electrochemical Conditioning on Nickel-Based Oxygen Evolution Electrocatalysts

• DOI: 10.1021/acscatal.2c01001
• 发表时间: 2022-08
• 期刊: ACS Catalysis
• 影响因子: 12.9
• 作者: Yoon Jun Son;Seonwoo Kim;V. Leung;Kenta Kawashima;Jungchul Noh;Kihoon Kim;Raúl A. Márquez;Omar A

An active nanoporous Ni(Fe) OER electrocatalyst via selective dissolution of Cd in alkaline media

• DOI: 10.1016/j.apcatb.2017.11.053
• 发表时间: 2018-06-05
• 期刊: APPLIED CATALYSIS B-ENVIRONMENTAL
• 影响因子: 22.1
• 作者: Kim, Jun-Hyuk;Youn, Duck Hyun;Mullins, C. Buddie
• 通讯作者: Mullins, C. Buddie