CAREER: Piezoelectric Mechanocatalytic Destruction of PFAS in Solid Matrices at Ambient Conditions: An Integrated Research and Education Plan

全氟烷基和多氟烷基物质（PFAS）是自20世纪40年代以来在众多消费品和工业应用中制造和使用的合成化学品。PFAS是有史以来最稳定的化学品之一。在过去的二十年中，在各种环境介质中越来越多地检测到PFAS，引起了人们对其持久性，稳定性和不利影响（包括对生物体和人类的毒性）的重大关注。随着消费品和工业产品中全氟辛烷磺酸的逐步淘汰，库存的过期全氟辛烷磺酸化学品正在成为固体废物。此外，越来越多地产生大量的PFAS固体废物，包括废水污泥、受污染的土壤以及用于从受污染的饮用水源中去除PFAS的废颗粒活性炭（GAC）和离子交换（IX）介质。目前，热处理，如焚烧和热解已成为最有效的处理和销毁PFAS负载固体废物在工业和商业规模。然而，PFAS热处理工艺需要高温（150-900 °C），并且通常会产生含有有毒中间体和不完全燃烧产物（PIC）的气流，需要额外处理以减少其向环境中的释放。该CAREER项目的总体目标是为开发和验证一种新型压电材料（PZM）辅助球磨（BM）工艺奠定基础，该工艺能够在室温和环境压力下处理和销毁PFAS固体废物。为了推进这一目标，首席研究员建议探索使用BM反应器激活催化压电材料（PZMs）和PFAS化学品/固体废物的混合物，以产生高电势，将PFAS分解和矿化为良性无机产物。该项目的成功完成将通过产生新的基础知识以及活性PZM的设计和合成来促进更有效和可持续的PFAS固体废物处理和销毁技术的开发，从而造福社会。通过学生教育和培训，包括指导克拉克森大学的一名研究生和一名本科生，将为社会带来额外的好处。PFAS固体废物在环境中无处不在。它们包括废弃的PFAS化学品、制造废物、受污染的土壤、城市固体废物以及用于从受污染的饮用水源中去除PFAS的废颗粒活性（GAC）和离子交换（IX）介质。该CAREER项目的总体目标是推进创新机械化学工艺的开发，该工艺可以在环境温度和压力下处理PFAS固体废物并将其转化为良性产品。提出的研究的核心指导假设是，钢球和催化压电材料（PZMs）在球磨（BM）反应器装载PFAS固体化合物/废物之间的碰撞可以产生瞬态高电位降解和破坏PFAS。本研究的具体目标是：（1）优化PFAS机械化学降解过程所需的BM碰撞能量;（2）通过合理设计晶体结构和异质结来最大化PZM的反应活性和催化活性;（3）使用先进的原位和非原位表征工具来探索和揭示PFAS降解的机制和途径，以及（4）评价PZM辅助BM工艺处理和销毁PFAS固体废物的成本效益。该项目的成功完成有可能通过产生新的基础知识来推动PZM辅助球磨（BM）工艺和反应器的设计和演示，以在室内和环境压力下处理和修复PFAS固体废物。为了实现这个职业项目的教育和培训目标，主要研究者（PI）建议利用克拉克森大学的既定计划，以（i）参与和指导本科生从事项目研究活动，（ii）促进K-12 STEM扫盲，以及（iii）提供PFAS相关的劳动力培训。为了促进K-12学生的STEM素养，PI建议根据项目研究活动开发和提供科学课程和实践实验室练习。此外，PI计划与克拉克森大学认可的PFAS分析中心合作，为环境修复工作人员准备PFAS分析和处理方面的培训材料并举办虚拟研讨会。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

Per-and polyfluoroalkyl substances (PFAS) are synthetic chemicals that have been manufactured and used in numerous consumer products and industrial applications since the 1940s. PFAS are among the most stable chemicals ever produced. During the last two decades, increasing detection of PFAS in various environmental media has raised significant concerns about their persistence, stability, and adverse impact including toxicity to living organisms and humans. With the gradual phase-out of PFAS from consumer and industrial products, stocks of obsolete PFAS chemicals are becoming solid wastes. In addition, large quantities of PFAS solid wastes are increasingly being generated including wastewater sludge, contaminated soils, and spent granular activated carbon (GAC) and ion exchange (IX) media used to remove PFAS from contaminated drinking water sources. Currently, thermal processes such as incineration and pyrolysis have emerged as the most effective for treating and destroying PFAS laden solid wastes at industrial and commercial scales. However, PFAS thermal treatment processes require high temperatures (150-900 °C) and often generate gaseous streams containing toxic intermediates and products of incomplete combustion (PICs) that require additional treatment to mitigate their releases into the environment. The overarching goal of this CAREER project is to lay the foundation for the development and validation of a novel piezoelectric material (PZM)-assisted ball milling (BM) process capable of treating and destroying PFAS solid wastes at room temperature and ambient pressure. To advance this goal, the Principal Investigator proposes to explore the activation of mixtures of catalytic piezoelectric materials (PZMs) and PFAS chemicals/solid wastes using a BM reactor to generate high electric potentials to decompose and mineralize PFAS into benign inorganic products. The successful completion of this project will benefit society through the generation of new fundamental knowledge and the design and synthesis of reactive PZMs to advance the development of more effective and sustainable technologies for the treatment and destruction of PFAS solid wastes. Additional benefits to society will be achieved through student education and training including the mentoring of one graduate student and one undergraduate student at Clarkson University.PFAS solid wastes are pervasive in the environment. They include obsolete PFAS chemicals, manufacturing wastes, contaminated soils, municipal solid wastes, and spent granular activated (GAC) and ion exchange (IX) media used to remove PFAS from contaminated drinking water sources. The overarching goal of this CAREER project is to advance the development of an innovative mechanochemical process that could treat and convert PFAS solid wastes to benign products at ambient temperature and pressure. The core guiding hypothesis of the proposed research is that the collisions between steel balls and catalytic piezoelectric materials (PZMs) in a ball milling (BM) reactor loaded with PFAS solid compounds/wastes can generate transient high electric potentials to degrade and destroy the PFAS. The specific objectives of the research are to (1) optimize the BM collision energy required to carry out the PFAS mechanochemical degradation process, (2) maximize the reactivity and catalytic activity of the PZMs via rationale design of crystal structure and heterojunctions, (3) use advanced in-situ and ex-situ characterization tools to probe and unravel the mechanisms and pathways of PFAS degradation, and (4) evaluate the cost-effectiveness of a PZM assisted BM process in the treatment and destruction of PFAS solid wastes. The successful completion of this project has the potential for transformative impact through the generation of new fundamental knowledge to advance the design and demonstration of a PZM-assisted ball milling (BM) process and reactor for the treatment and remediation of PFAS solid wastes at room and ambient pressure. To implement the educational and training goals of this CAREER project, the Principal Investigator (PI) proposes to leverage established programs at Clarkson University to (i) engage and mentor undergraduate students to work on the project research activities, (ii) promote K-12 STEM literacy, and (iii) provide PFAS related workforce training. To promote STEM literacy for K-12 students, the PI proposes to develop and deliver science courses and hands-on laboratory exercises based on the project research activities. In addition, the PI plans to collaborate with the accredited PFAS analysis center at Clarkson University to prepare training materials and host virtual seminars in PFAS analysis and treatment for the environmental remediation workforce.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.