CAREER: Understanding the electrochemical properties of physical hole defects on functionalized B/C 2D materials for the 2e- reduction of O2 to H2O2

在化学系化学催化项目的资助下，加州州立大学富勒顿分校(CSUF)的迈克尔·格罗夫斯博士将利用计算模型研究过氧化氢(H2O2)合成的替代机制。过氧化氢是一种环境友好的氧化剂，用于许多应用，包括水处理、纺织和木浆漂白、电子工业和个人防护设备杀菌。目前，过氧化氢的工业生产主要是通过破坏环境的蒽醌工艺进行的。一种特别令人感兴趣的方法是基于电化学和由碳和硼组成的二维(2D)纳米材料，利用这些结构中的物理空穴缺陷和官能团促进过氧化氢的合成。根据这一奖项，格罗夫斯研究团队将模拟酸性官能团在相邻物理孔缺陷的大小不同时产生过氧化氢的能力。将准备物理系统来验证从计算研究中得出的量子化学预测。这个项目将被整合到格罗夫斯博士的高级化学实验室课程中，作为本学期进行的几个教育实验之一，为学生提供基于课程的研究体验。这些新的教学实践，以及翻转课堂教学方法，将在这个高级实验室环境中进行评估，以确定它们对提高学生成功的影响。此外，本课程是通过CSUF的Kids 2 College计划专门针对中小学生的科学推广计划的一部分，并借用Groves博士的研究项目进行动手演示。加州州立大学富勒顿分校的迈克尔·格罗夫斯博士正在研究过氧化氢的合成过程。一个特别的焦点是计算定量的物理空穴缺陷的电化学性质的官能化的B，C，和B-C 2D材料上氧(O2)的两电子还原为过氧化氢(H_2O_2)。这个项目可能会对2D材料和电化学产生更广泛的影响，因为它测试了这样一种假设，即石墨烯、硼苯和杂化材料中相邻的物理空穴缺陷可以改变官能团(醇、羧酸、磺酸)的酸性，这将影响O2的电化学还原为H2O2。新开发的大正则势动力学框架被用于这个项目，以确保密度泛函理论计算正确地描述电化学条件。首先，采用由凝聚聚类增强的进化算法来确定作为物理空穴缺陷大小的函数的这些碳/硼2D材料的形态，其中每次重新开始将在势能面的唯一区域中搜索。当为每个物理孔大小和材料确定全局最小候选值时，将确定集合中两个官能团(醇、羧酸、磺酸)的所有组合的酸度。然后，将使用每种材料的最酸性、最弱酸性和两个中等酸性的结构来计算O2电化学还原为H2O2的势垒。曼彻斯特大学的实验合作者正在与格罗夫斯团队合作，合成有希望的候选者，以支持结构-活性关系的发展。最后，格罗夫斯博士将把这个项目纳入高级物理化学实验室，作为基于课程的本科生研究体验(CURE)的延伸。这项治疗、翻转课堂教学和服务学习活动，学生在项目过程中向1400名代表不足的6年级学生提供互动实验，是该奖项下开发的三种潜在的高影响力做法，旨在提高学生的成功。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。

With funding from the Chemical Catalysis Program of the Division of Chemistry, Dr. Michael Groves at California State University-Fullerton (CSUF) will be utilizing computational modeling to investigate alternative mechanisms for the synthesis of hydrogen peroxide (H2O2). Hydrogen peroxide is an environmentally friendly oxidant that is used in many applications including water treatment, textile and wood-pulp bleaching, the electronics industry, and personal protective equipment sterilization. Currently, industrial production of hydrogen peroxide is dominated by the environmentally destructive anthraquinone process. One approach of specific interest is based on using electrochemistry and two-dimensional (2D) nanomaterials composed of carbon and boron, whereby physical hole defects and functional groups in these structures promote hydrogen peroxide synthesis. Under this award, the Groves research team will model the ability of acidic functional groups to produce hydrogen peroxide when the size of adjacent physical hole defects is varied. Physical systems will be prepared to validate quantum chemical predictions derived from the computational studies. This project will be integrated into Dr. Groves’ senior chemistry laboratory course as one of several educational experiments performed over the semester, providing students a course-based research experience. These new teaching practices, as well as a flipped classroom instruction approach, will be assessed in this senior lab setting to determine their impact toward improved student success. Additionally, this course is a part of a scientific outreach program particularly directed at elementary/middle school students through CSUF’s Kids 2 College program, with hands-on demonstrations that borrow from Dr. Groves' research project. Dr. Michael Groves of California State University-Fullerton is investigating processes for H2O2 synthesis. A particular focus is the computational quantification of the electrochemical properties of physical hole defects on functionalized boron, carbon, and boron-carbon 2D materials for the two-electron reduction of oxygen (O2) to hydrogen peroxide (H2O2). This project has the potential for a much broader impact on 2D materials and electrochemistry by testing the hypothesis that the acidity of functional groups (alcohol, carboxylic acid, sulfonic acid) can be modified by adjacent physical hole defects in graphene, borophene and hybrid materials, and that this will influence the electrochemical reduction of O2 to H2O2. The newly developed Grand Canonical Potential Kinetics framework is being used for this project to ensure that the density functional theory calculations properly describe electrochemical conditions. First, an evolutionary algorithm, enhanced by agglomerative clustering, whereby each restart will search in a unique region of the potential energy surface, is being employed to determine the morphology of these carbon/boron 2D materials as a function of physical hole defect size. As global minimum candidates are identified for each physical hole size and material, the acidity of all combinations of two functional groups from the set (alcohol, carboxylic acid, sulfonic acid) will be determined. The most acidic, least acidic, and two structures with intermediate acidities for each material will then used to calculate the barriers for the electrochemical reduction of O2 to H2O2. Experimental collaborators at the University of Manchester are working alongside the Groves team to synthesize promising candidates to support the development of structure-activity relationships. Finally, Dr. Groves will be incorporating this project into the senior physical chemistry laboratory as an extended course-based undergraduate research experience (CURE). This CURE, flipped classroom instruction and a service-learning activity where students present interactive experiments to 1400 local underrepresented 6th grade students over the course of the project, are three potentially high-impact practices being developed under this award that are designed to improve student success.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.