Collaborative Research: Design of High Entropy Alloy Electrocatalysts for Mineralization of Total Organic Carbon in Municipal Wastewater

合作研究：城市废水中总有机碳矿化的高熵合金电催化剂设计

• 批准号: 2230181
• 负责人: Natalia Soares Quinete
• 金额: $ 6.04万
• 依托单位: Florida International University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-08-01 至 2026-07-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2230181&HistoricalAwards=false
• 关键词: Collaborative; Research; Design; Entropy; Alloy

Advanced oxidation processes (AOPs) such as the commercial UV/AOP process are increasingly being utilized as a final treatment barrier to remove organic micropollutants (OMPs) in advanced water reclamation and reuse plants in the United States and worldwide. In a typical UV/AOP process, UV-C light (200-280 nm in wavelength) is combined with an oxidant (e.g., hydrogen peroxide) to generate OH free radicals that can destroy and mineralize OMPs including personal care products, pharmaceuticals, pesticides, herbicides, etc. Current commercial UV/AOPs require significant amounts of energy to operate, have high CapEx and OpEx or generate toxic products such as bromate when treating water containing bromide ions. Electrochemical advanced oxidation processes (EAOPs) have emerged as promising technologies that can destroy OMPs using electricity to generate OH radicals at the surface of catalytic electrodes. Compared to UV/AOPs, EAOPs have several advantages including high efficiency, modular design, and ease of automation and operation using electricity from clean renewable energy sources. However, the stability, lifetime, and high cost of the required catalytic electrodes (electrocatalysts) are major impediments to the implementation of EAOPs in water reclamation and reuse plants. To address these challenges, the Principal Investigators (PIs) of this project propose to leverage the unique properties of high entropy alloys (e.g., high strength and corrosion resistance) to design, synthesize, and optimize a new class of electrocatalysts for EAOPs. The successful completion of this project will benefit society through the generation of fundamental knowledge and development of novel electrocatalysts to improve the efficiency and cost effectiveness of using EAOPs in water reclamation and reuse systems. Additional benefits to society will be achieved through student education and training including the mentoring of two graduate students at the University of Miami and one undergraduate student at Florida International University. High entropy alloying has emerged as a promising process for the preparation of electrodes with catalytic activity and corrosion resistance comparable to those of noble metals (e.g., Pt and Ir) using earth-abundant metals as precursors. Thus, high entropy alloys (HEAs) provide unique opportunities to develop more stable, durable, and cost-effective catalytic electrodes (electrocatalysts) for electrochemical advanced oxidation processes (EAOPs). However, it is challenging to find the right alloy composition that produces the target HEA electrocatalyst given that HEAs are typically formed by mixing/alloying five or more elements. To address this challenge, the Principal Investigators (PIs) of this project propose to combine atomistic modeling and simulations with experimentation to design, synthesize, and optimize new HEA electrocatalysts for EAOPs using earth-abundant metals. The specific aims of the research are to (1) design earth-abundant HEAs for the electrocatalytic generation of hydroxyl (OH) radicals in aqueous solutions and mixtures by screening a large design space via atomistic modeling/simulations and thermodynamic analysis; (2) evaluate and optimize electrocatalyst structure and performance (activity, corrosion resistance, and durability) using fabrication and bench scale electrochemical and wet chemical experiments, and (3) conduct kinetic and mechanistic investigations of the oxidation of selected organic micropollutants (OMPs) by HEA electrocatalysts using radical scavenging/trapping assays and non-targeted high-resolution mass spectrometry. The successful completion of this research has the potential for transformative impact through the generation of composition-structure-performance relationships to guide the design and development of HEA electrocatalysts for water reuse and reclamation using electrochemical oxidation. To implement the education and training goals of the project, the PIs propose to leverage existing programs at the University of Miami and Florida International University to recruit and mentor undergraduate students from underrepresented groups to work on the project. In addition, the PIs plan to develop and deliver STEM immersion programs to inner-city and underrepresented high school students including presentations at K-12 schools and the Frost Museum of Science in Miami.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.

高级氧化工艺（AOP）如商业UV/AOP工艺越来越多地被用作最终处理屏障，以在美国和世界范围内的高级水回收和再利用工厂中去除有机微污染物（OMP）。在典型的UV/AOP工艺中，将UV-C光（波长为200-280 nm）与氧化剂（例如，过氧化氢）以产生OH自由基，OH自由基可破坏和矿化OMP，包括个人护理产品、药物、杀虫剂、除草剂等。当前的商业UV/AOP需要大量的能量来操作，具有高CapEx和OpEx，或者在处理含有溴离子的水时产生有毒产物，例如溴酸盐。电化学高级氧化过程（EAOPs）已经成为一种很有前途的技术，它可以利用电在催化电极表面产生OH自由基来破坏OMP。与UV/AOP相比，EAOP具有几个优点，包括高效率，模块化设计，以及易于使用清洁可再生能源的电力进行自动化和操作。然而，所需的催化电极（电催化剂）的稳定性、寿命和高成本是在水回收和再利用工厂中实施EAOP的主要障碍。为了应对这些挑战，该项目的主要研究者（PI）建议利用高熵合金的独特性质（例如，高强度和耐腐蚀性）来设计、合成和优化用于EAOP的新型电催化剂。该项目的成功完成将通过基础知识的产生和新型电催化剂的开发来造福社会，以提高在水回收和再利用系统中使用EAOP的效率和成本效益。通过学生教育和培训，包括指导迈阿密大学的两名研究生和佛罗里达国际大学的一名本科生，将为社会带来更多好处。高熵合金化已经成为制备具有与贵金属（例如，Pt和Ir）使用地球上丰富的金属作为前体。因此，高熵合金（HEAs）为开发用于电化学高级氧化过程（EAOP）的更稳定、耐用和具有成本效益的催化电极（电催化剂）提供了独特的机会。然而，考虑到HEA通常通过混合/合金化五种或更多种元素形成，找到产生目标HEA电催化剂的正确合金组合物是具有挑战性的。为了应对这一挑战，该项目的主要研究人员（PI）建议将联合收割机原子建模和模拟与实验相结合，以设计，合成和优化新的HEA电催化剂，用于使用地球丰富的金属的EAOP。本研究的具体目标是（1）通过原子模型/模拟和热力学分析筛选大的设计空间，设计用于在水溶液和混合物中电催化产生羟基（OH）自由基的地球丰富的HEAs;（2）评价和优化电催化剂结构和性能（活性、耐腐蚀性和耐久性），和（3）使用自由基清除/捕获测定和非靶向高分辨率质谱法对HEA电催化剂氧化选定有机微污染物（OMP）的动力学和机理进行研究。这项研究的成功完成具有潜在的变革性影响，通过生成组成-结构-性能关系，指导HEA电催化剂的设计和开发，用于使用电化学氧化进行水的再利用和回收。 为了实现该项目的教育和培训目标，PI建议利用迈阿密大学和佛罗里达国际大学的现有项目，从代表性不足的群体中招募和指导本科生从事该项目。此外，PI还计划为市中心和代表性不足的高中学生开发和提供STEM沉浸式课程，包括在K-12学校和迈阿密的弗罗斯特科学博物馆进行演示。该奖项反映了NSF的法定使命，并被认为值得通过使用基金会的智力价值和更广泛的影响审查标准进行评估来支持。