CAREER: Surface Crystallization of Reactive Oxygen Permeable Hydroxyapatite-based Membranes for Direct Methane Oxidative Conversion

1351384 -Liu AbstractCAREER：用于直接甲烷氧化转化的活性氧可渗透羟基磷灰石膜的表面结晶PI的职业目标是创造创新的催化剂和膜技术，使活性和选择性的化学转化，特别关注C1和生物质原料的催化转化。目的是建立活性氧（O2）渗透的羟基磷灰石（HAP）为基础的膜的甲烷（OCM）氧化偶联C2烃。虽然催化膜反应器领域已经出现了用于OCM的固体氧化物膜，但获得高C2产率（其密切依赖于膜材料的催化和O2可渗透性质之间的协调）仍然是一个挑战。控制膜纳米结构（组成和构造）的表面结晶的独特方法将使薄而致密的膜具有足够的甲烷活化和O2渗透性能的OCM。铅和碳酸盐取代的HAP（Pb-HAP-CO 3）是HAP基膜的研究热点，因为Pb 2+和CO 32-分别赋予单一HAP良好的OCM催化性能和高的O2传输渗透性。本研究的基本原理是系统地操纵Pb-HAP-CO 3膜的组成（Pb 2+和CO 32-浓度）和构成（厚度和晶体取向），以调节其催化和传输性能，从而实现协同CH 4活化和O2渗透OCM用于C2生产。这项研究的引人注目的方面是，它提供了一个具体的战略，以创造新的和潜在的变革性的方式将低成本甲烷转化为增值燃料和化学品。的教育目标是为学生提供学习经验，这将导致教育下一代科学家和工程师的成功，特别是在材料合成，催化和能源领域。该研究将材料科学和化学工程的广泛培训纳入各级学生的研究经验和教育计划。特别是，这包括：（一）一个新的课程开发教育本科生和研究生的基础上PI？在材料，催化，分离和能源的研究兴趣;（ii）在各级学生的研究经验;和（iii）为K-12学生和广大公众观众的推广计划。这些教育活动已经在进行中，并与PI的部门和学院的目标保持一致。知识产权：在膜反应器中从OCM反应获得高C2产率的潜在挑战是具有协调催化和透氧性能的膜材料的稀缺。该项目将侧重于基础研究，以使活性氧渗透膜的出现，有效的OCM过程。研究活动将促进理解（i）通过受控表面结晶方法操纵膜纳米结构，（ii）膜纳米结构对管式反应器中甲烷反应和氧传输动力学的影响，以及（iii）材料合成-结构-功能对OCM性能的预测相关性。从这项工作中获得的基本概念和技术将刺激和开辟新的途径，材料发现和技术开发，可以影响未来的能源和化学品供应的世界。更广泛的影响：甲烷的加工，以获得高附加值的化学品和燃料是科学和社会面临的巨大挑战之一。高效OCM膜反应器的开发将导致新的热化学过程，以满足对高能量密度和甲烷气体中可替代燃料/化学品的需求，以应对这一挑战。该计划将材料科学和化学工程的研究与教育和推广部分相结合，旨在突出这些学科在能源转换领域的重要性。教育将通过开发一个新的课程，在材料，催化，分离和能源的研究兴趣的基础上，通过招募和指导学生从代表性不足的社区在研究活动，并通过推广计划K-12学生和一般公众观众在乔治王子县，MD（UMD所在地）。

1351384 - LiuAbstractCAREER: Surface Crystallization of Reactive Oxygen Permeable Hydroxyapatite-based Membranes for Direct Methane Oxidative ConversionThe PI's career goal is to create innovative catalyst and membrane technologies that enable active and selective chemical conversions with particular focus on the catalytic conversion of C1 and biomass feedstock. The objective is to establish reactive oxygen (O2) permeable hydroxyapatite (HAP)-based membranes for oxidative coupling of methane (OCM) to C2 hydrocarbons. While the field of catalytic membrane reactors has emerged solid oxide membranes for OCM, attaining high C2 yield, which intimately depends on the harmonization between the catalytic and O2 permeable properties of the membrane materials has remained a challenge. The unique approach of surface crystallization in controlling the membrane nanostructures (composition and constitution) will enable thin and dense membranes possessing sufficient methane activation and O2 permeation properties for OCM. Lead and carbonate substituted HAP (Pb-HAP-CO3) is the focus on the HAP-based membranes because Pb2+ and CO32-, respectively, endow a single HAP with good catalytic properties for OCM and high permeance for O2 transport. The rationale of this research is to systematically manipulate the composition (Pb2+ and CO32- concentration) and constitution (thickness and crystal orientation) of the Pb-HAP-CO3 membranes to tune their catalysis and transport properties, and thus, to achieve cooperative CH4 activation and O2 permeation in OCM for C2 production. The compelling aspect of this research is that it offers a specific strategy to create new and potentially transformative ways of converting low cost methane to value-added fuels and chemicals.The PI?s educational goal is to provide learning experiences for students that will lead to success in educating the next generation of scientists and engineers, particularly in the fields of materials synthesis, catalysis, and energy. The research incorporates broad training in materials science and chemical engineering into research experiences and education programs for students at all levels. Particularly, this includes: (i) a new course development for educating undergraduates and graduates based on the PI?s research interests in materials, catalysis, separation, and energy; (ii) research experiences for students at all levels; and (iii) outreach programs for K-12 students and general public audiences. These educational activities are already in progress, and are well aligned with the goals of the PI's department and college.Intellectual Merit: The underlying challenge in attaining high C2 yield from OCM reactions in membrane reactors is the scarcity of membrane materials with harmonized catalytic and oxygen permeable properties. This project will focus on fundamental studies to enable the emergence of reactive-oxygen permeable membranes for efficient OCM processes. The research activities will advance the understanding of (i) manipulation of membrane nanostructures by controlled surface crystallization approach, (ii) effects of membrane nanostructures on methane reaction and oxygen transport kinetics in tubular reactors, and (iii) predictive correlations of materials synthesis-structure- function for OCM performance. The fundamental concepts and technologies obtained from this work will stimulate and open new avenues of material discovery and technique development that can impact future energy and chemical supplies of the world.Broader Impact: The processing of methane to derive highly value-added chemicals and fuels is one of the enormous challenges faced by science and society. The development of efficient OCM membrane reactors will lead to new thermochemical processes to meet the demand for high-energy density and fungible fuels/chemicals from methane gas to address this challenge. The proposed program integrates research on materials science and chemical engineering with an education and outreach component designed to highlight the importance of these disciplines in the area of energy conversion. Education will be enhanced by developing a new course based on the research interests in materials, catalysis, separation, and energy, by recruiting and mentoring students from under-represented communities in research activities, and by outreach programs for K-12 students and general public audience in Prince George's County, MD (where UMD is located).