CAREER: Cold plasma intensified perovskite membrane technology for CO2 utilization

职业：用于二氧化碳利用的冷等离子体强化钙钛矿膜技术

• 批准号: 2403991
• 负责人: Maria Carreon
• 金额: $ 53.87万
• 依托单位: University of Arkansas
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-10-01 至 2028-09-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2403991&HistoricalAwards=false
• 关键词: CAREER; Cold; plasma; intensified; perovskite

Platform chemicals are the essential building blocks used by the chemical processing industries to produce high-value chemical products. Conversion of greenhouse gases (GHG) such as CO2 and CH4 to platform precursors could significantly reduce atmospheric GHG while producing oxygenated chemical feedstocks and fuels. Current production of oxygenated chemicals from GHG requires large-scale, complex, high-pressure reaction processes, and manufacturing operations with significant carbon footprints. Therefore, there is a critical need to explore more sustainable routes to dry methane reforming (DMR), the reaction between CO2 and CH4 to produce highly reactive hydrogen and carbon monoxide. Non-thermal (low temperature) plasma-catalysis processes have recently emerged as an alternative to current DMR. This electrically driven approach will be investigated for one-step production of oxygenated species from GHG under mild conditions, making use of renewable and decentralized electrical power sources, potentially expanding US employment and regional business opportunities. This research program will study the fundamental chemical and physical mechanisms at work in plasma-enhanced conversion of GHG with the goal of reaching chemical processing conditions that are energy flexible and efficient. Over the next five years the research team will focus on understanding plasma chemistry reaction mechanisms and the systematic design of plasma-catalytic membrane reactor concepts capable of on-demand use of renewable electricity. Education and outreach activities include developing an undergraduate/graduate level plasma catalysis class and continuing a STEM Camp for Girl Scouts.In this project, atmospheric low-temperature plasma catalysis will be investigated as an alternative to conventional thermally activated reaction routes to oxygenated fuels and chemical products based on high pressure Dry Methane Reforming (DMR). The key feature of plasma-catalysis is the synergy between the plasma and the catalyst, where the non-equilibrium plasma creates radicals and charged plasma-phase species which react at the catalyst surface to form the chemical product species; however, little is known in terms of fundamental understanding of plasma/catalyst interactions and surface processes. This research will address this knowledge gap by focusing on perovskite catalysts, selected for their unique dielectric and polarization properties. The interaction between the charged species in the plasma and perovskite catalysts may lead to drastic changes in the perovskite structural and surface electronic properties, potentially leading to unprecedented oxygenated species production rates. The in situ diagnostic capabilities of the research team will make possible the systematic synthesis of plasma-enhanced perovskite catalysts designed to operate at low temperature (200 deg C) and atmospheric pressure, opening the door to decentralized and modular production of oxygenated fuels and chemicals from CO2 and CH4. To further improve process performance, the catalyst will be fabricated as a unique macroporous perovskite membrane with the objective of improving selectivity to methanol. The proposed membrane reactor offers the advantages of significantly reduced pressure drop typically found in packed bed reactors enhancing process throughput. Specific research plans focus on: (1) Designing nanocrystalline perovskite membranes for the synthesis of oxygenated chemicals and fuels; (2) Fine tuning the catalytic active sites of selected perovskites for the synthesis of methanol; (3) Evaluating the catalytic performance of perovskite membranes under low-temperature plasma in the conversion of CO2/CH4 mixtures to methanol; (4) Elucidation and understanding of the synergism in plasma-catalyst systems for the synthesis of oxygenated chemical species.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.

平台化学品是化学加工行业用于生产高价值化学产品的基本组成部分。将二氧化碳和甲烷等温室气体转化为平台前体可以在生产含氧化学原料和燃料的同时显著减少大气中温室气体的排放。目前，从温室气体中生产含氧化学品需要大规模、复杂、高压的反应过程，而且制造过程会产生大量的碳足迹。因此，迫切需要探索更可持续的干甲烷重整（DMR）途径，即CO2和CH4之间的反应产生高活性的氢气和一氧化碳。非热（低温）等离子体催化过程最近成为当前DMR的替代方案。这种电力驱动的方法将在温和条件下一步从温室气体中生产含氧物质，利用可再生和分散的电力来源，潜在地扩大美国的就业和区域商业机会。该研究项目将研究等离子体增强温室气体转化的基本化学和物理机制，目标是达到能源灵活和高效的化学处理条件。在接下来的五年里，研究团队将专注于了解等离子体化学反应机制，以及能够按需使用可再生电力的等离子体催化膜反应器概念的系统设计。教育和推广活动包括开设本科/研究生水平的血浆催化课程，并继续为女童子军举办STEM训练营。在本项目中，将研究大气低温等离子体催化作为基于高压干甲烷重整（DMR）的传统热活化反应途径的替代方案，以生产含氧燃料和化学产品。等离子体催化的关键特征是等离子体和催化剂之间的协同作用，其中非平衡等离子体产生自由基和带电等离子体相，它们在催化剂表面反应形成化学产物；然而，就等离子体/催化剂相互作用和表面过程的基本理解而言，所知甚少。这项研究将通过关注钙钛矿催化剂来解决这一知识差距，钙钛矿催化剂因其独特的介电和极化特性而被选中。等离子体中带电物质与钙钛矿催化剂之间的相互作用可能导致钙钛矿结构和表面电子性质的剧烈变化，可能导致前所未有的氧化物质生成速率。研究小组的现场诊断能力将使系统合成等离子体增强钙钛矿催化剂成为可能，这些催化剂设计用于低温（200摄氏度）和大气压下，为分散和模块化生产含氧燃料和由二氧化碳和甲烷产生的化学品打开了大门。为了进一步提高工艺性能，催化剂将被制成一种独特的大孔钙钛矿膜，目的是提高对甲醇的选择性。所提出的膜反应器具有显著降低压降的优点，通常在填充床反应器中发现，提高了工艺吞吐量。具体研究计划集中在：(1)设计用于含氧化学品和燃料合成的纳米钙钛矿膜；(2)对选定的钙钛矿催化合成甲醇的活性位点进行微调；(3)评价低温等离子体条件下钙钛矿膜催化CO2/CH4混合物转化为甲醇的性能；(4)阐明和理解等离子体-催化剂体系在氧化化学物质合成中的协同作用。该奖项反映了美国国家科学基金会的法定使命，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。