PECASE: Zeolitic Imidazolate Framework Membranes. Novel Materials for Carbon Dioxide Capture.

从轻质气体中分离CO2是一个非常重要的环境和能源问题。用于纯化CO2的最先进工艺使用胺吸附，这是一种复杂且昂贵的方法。膜分离技术成本低得多，需要的能源消耗也少得多。虽然聚合物和沸石膜可以从轻质气体中分离CO2，但是用于气体混合物分离的上级性能膜的开发需要具有与聚合物和沸石的那些基本上不同的结构、组成、吸附和传输性质的新型材料。在这方面，作为金属有机骨架的子类的沸石咪唑酯骨架（ZIF）已经作为新型的结晶多孔材料出现，其联合收割机结合了高度期望的性质，例如均匀的微孔、高表面积和优异的热稳定性和化学稳定性，使其成为分子分离的理想候选物。该提案旨在证明ZIF作为从轻质气体中分离CO2的膜的潜力。该职业建议的中心智力推力是建立一个坚实的基础科学计划，导致一个新的膜家族的合理设计，由沸石咪唑骨架组成，提供了展示从轻气体中纯化二氧化碳的高分离性能的可能性，以及其他重要的功能气体分离。本论文的具体研究目标是：1）合理设计新型的咪唑类沸石骨架（ZIF）膜，用于从轻气中净化CO2; 2）发展简单的化学合成策略，合理地修饰ZIF膜的孔结构和功能; 3）阐明和理解前体溶液转化为咪唑类沸石骨架相的基本形成机理;建立了ZIF膜在CO2/CH 4、CO2/N2等相关功能气体分离中的基本结构/分离关系。如果成功的话，这个职业发展计划将建立新的自组装和合成概念的可行性，作为广泛的功能性沸石咪唑骨架膜的一般方法，具有可调的结构，表面化学和孔隙率，用于相关工业气体分离，包括天然气和烟道气中的CO2捕获。这将是一个重要的进展，在合理设计的一个子类的金属有机框架膜，并在其结构/分离关系的基本理解。本提案的一个平行目标是有效地将拟议的研究活动与教育和推广计划相结合，以在本科生，研究生和社区层面提供重要的教育机会。拟议的职业计划的教育推广范围包括功能性纳米多孔材料分子工程的双层次课程，在本科教育中纳入代表性不足的群体，国际合作，招聘少数民族进行研究生学习，以及高中教师的短期课程。该项目的成果将通过期刊出版物，会议演示和技术研讨会传播给科学界，并将在PI教授的课程材料讲座中实施，以使对膜科学，分离过程和先进材料感兴趣的学生团体受益。这些教育活动已经促成了一项得到资助的国际合作，以此作为少数民族学生招募的平台;少数民族本科生参加了PI实验室的研究;招募墨西哥学生参加路易斯维尔大学化学工程系的博士课程，并建立了一个名为HISPAIRE的项目（西班牙裔有兴趣在工程学课程），旨在招募西班牙裔和拉丁美洲学生。

The separation of CO2 from light gases is a very important environmental and energy issue. The state-of-the-art process for the purification of CO2 uses amine adsorption, which is a complex, and costly approach. Membrane separation technology is far less expensive and requires less energy consumption. Although polymeric and zeolite membranes can separate CO2 from light gases, the development of superior performance membranes for gas mixture separations requires novel materials with fundamentally different structural, compositional, adsorption and transport properties than those of polymers and zeolites. In this respect, zeolitic imidazolate frameworks (ZIFs) a subclass of metal organic frameworks, have emerged as a novel type of crystalline porous materials which combine highly desirable properties, such as uniform micropores, high surface areas, and exceptional thermal and chemical stability, making them ideal candidates for molecular separations. This proposal aims at demonstrating the potential of ZIFs as membranes for the separation of CO2 from light gases. The central intellectual thrust of this career proposal is to establish a solid fundamental science program leading to the rational design of a novel family of membranes, composed of zeolitic imidazolate frameworks which offer the possibility of demonstrating high separation performance for carbon dioxide purification from light gases, and other important functional gas separations. The specific research objectives are: 1)Rational design of a novel family of zeolitic imidazolate framework (ZIF) membranes for CO2 purification from light gases; 2)Develop facile chemical synthesis strategies to rationally modify the pore structure and functionality of the ZIF membranes; 3)Elucidate and understand the basic formation mechanisms governing the transformation of precursor solutions into zeolitic imidazolate framework phases; and 4)Establish the fundamental structure/separation relationships of ZIF membranes in relevant functional gas separations such as CO2/CH4 and CO2/N2. If successful, this career development plan will establish the viability of novel self-assembly and synthesis concepts as general approaches for a broad range of functional zeolitic imidazolate framework membranes with tunable architectures, surface chemistry, and porosities for applications in relevant industrial gas separations, including CO2 capture from natural gas and flue gas. It will represent an important advance in the rational design of a subclass of metal organic framework membranes and in fundamental understanding of its structure/separation relationships. A parallel objective of this proposal is to effectively integrate the proposed research activities with education and outreach programs to provide significant educational opportunities at the undergraduate, graduate and community levels. The educational outreach of the proposed career plan spans from a dual level course on molecular engineering of functional nanoporous materials, inclusion of underrepresented groups in undergraduate education, international collaboration, recruitment of minorities for graduate studies, and a short course for high school teachers. The results of this project will be disseminated to the scientific community through journal publications, conference presentations and technical seminars, and will be implemented in course material lectures taught by the PI to benefit the student body interested in membrane science, separation processes and advanced materials. The educational activities have already resulted in a funded international collaboration as a platform for minority student recruitment; undergraduate minority student research participation in the PI laboratory; recruitment of Mexican students for the PhD program in Chemical Engineering Department at University of Louisville and the establishment of a program called HISPAIRE (Hispanics with Interest in the Requisites for Engineering), aimed at recruiting Hispanic and Latino students.