(2er) Decarbonization of Fine Chemicals: Development of Alternative Pathways to Close the Carbon Cycle

As sustainable chemical processes and carbon reforming are becoming increasingly critical the development of novel catalytic materials is a pressing concern for the advancement of greener chemical alternatives. The implementation of catalytic processes is responsible for most chemical production. Heterogenous catalysts design has been largely focused on investigating monometallic or bimetallic catalysts supported on an oxide, such as silica, alumina, or ceria. One of the key features driving the high activity of homogeneous catalysts is the use of n/p ligands that serve as electron reservoirs or siphons, however, beyond the use of reducible supports this rich insight is entirely lacking in the heterogenous catalysis community. The work of my group would be focused on developing n/p-doped heterogeneous catalysts that draw upon the findings of homogeneous catalysts, where improvements in process energy far outweigh improvements in catalytic performance to close the carbon cycle.

Herein, my group will bridge the homogeneous/heterogeneous gap via n/p doped catalysts and develop novel means of carbon fixation, where our work will be guided by in situ spectroscopy to obtain a structure/activity relationship for the processes of interest. Ethylene hydroformylation will be used as a model reaction, where inspiration from developments in homogeneous catalysts will guide heterogeneous catalysts design. Furthermore, bifunctional catalysts combining CO₂ hydrogenation and ammonia decomposition will be utilized to develop materials capable of carrying out gas phase amide synthesis.

Research Interests By tuning the electronic properties of supporting materials with either electron withdrawing or electron donating species, we will be able to create catalysts that yield robust active sites, enabling the redox cycles required of classically homogeneously catalyzed reactions. To this end, we will draw inspiration from the semiconductor field, which utilize n/p doping to alter the electronic properties of the support beyond naturally occurring doping found in zeolites. By incorporating n-doped species, such as phosphorus, we can provide preferential adsorption sites for metal precursors during synthesis also providing electron rich ligands to promote metal support interactions. This will facilitate the intricate redox cycles required of homogeneously catalyzed reaction by providing electron reservoirs in the form of phosphorus. In this proposal, the use of rhodium catalysts for ethylene hydroformylation will be explored as a model reaction for the use of phosphorus doped silica and compared against a typical homogeneous catalyst, therefore providing a bridge between heterogeneous and homogeneous catalysts. The work will lay the foundation to addressing one of the key challenges laid out by the Catalysis Science focus area of the Chemical Science, Geoscience, and Biosciences Division of the Department of Energy, which is the convergence of heterogeneous and homogeneous catalysts. The initial work, focusing on simpler model systems such as phosphorus doping into silica over Co/Rh catalysts for light olefin hydroformylation, will then be expanded to more complex systems such as industrially relevant reactions like the enantioselective hydroformylation of styrene to vinyl acetate over several electronically modified supports such as n/p-doped silica, titania, or zirconia.

Research Summary We plan to approach sustainable chemistry and novel carbon reforming from the bottom up to address the global needs for benign and efficient catalysts, beginning with development of well defined electron modified materials and followed by exploring the reaction mechanisms of the processes to gain new insights into the chemistry. To this end, we will develop heterogeneous n/p doped oxide materials and evaluate them over traditionally homogeneous phase catalytic reaction, where the relevant structures will be observed via in situ XAFS and NMR. Furthermore, we propose to advance the field of carbon fixation by pooling inspiration from the CO₂ hydrogenation and ammonia decomposition to develop catalysts capable of gas phase amide synthesis, i.e., C-N chemistry. I believe this work can lead to breakthroughs in feasible carbon utilization, where the shift towards renewable fuel sources will leave a need for alternative carbon sources, such as CO₂, to yield a wide range of commercial and commodity chemicals.

Leveraging existing user facilities, including XPS, XRD, and solid-state NMR; with my existing connection to Brookhaven National Laboratory, the work proposed herein can be readily done. Furthermore, my experience in Brookhaven National Laboratory through my postdoctoral work at the Catalysis: Reactivity and Structure Group strongly positions me to leverage both the capabilities of BNL and NSLS-II, specifically the use of XRD/PDF and in situ XAFS. The instruments I would require purchasing as part of my start up package would initially be an Infrared Spectroscopy bench and a Raman bench, both equipped with in situ cells for powders, in addition to general analytical instrumentation and hardware. Additionally, given the Fu Foundation’s existing expertise in catalysis and material science, I would be more than willing to collaborate with the faculty to develop original research pathways that utilize my materials and insight to trailblaze original and impactful work. Specifically, by contributing my expertise in spectroscopy (XAFS, IR, XPS, XRD and Raman) and novel material synthesis, I can collaborate across of host of different subject matters to maximize my impact in the department. Finally, by bringing with me a strong connection to Brookhaven National Laboratory and its affiliated resources as a Goldhaber Fellow, I can become a strong asset to the department I will join and establish a long-term pipeline between BNL and the University.

Teaching Interest For me, teaching is a passion that underscores the basis that education is a path to greater equality and socio-economic balance in our society, as it was for me personally as a first-generation college graduate and first-generation Dominican American. This can be a transformational process specially for students that originate from minority and under-represented communities. Therefore, I have always taken an interest in teaching as a means of paying forward education that transformed my career path. As early as my sophomore year in undergraduate at the City College of New York holding introductory chemistry workshops, I learned the importance of effectively communicating various topics. My interest in teaching was further expanded during my PhD at the University of South Carolina, where I served as a Teaching Assistant for both undergraduate and graduate courses, often holding both recitations and full classes for the graduate level Mass Transfer course at USC. For the Fall 2022 semester, I also served as an Adjunct Assistant Professor at CUNY City College of New York teaching Reaction Engineering and Kinetics at the senior undergraduate level, where I have been able to give back to my alma mater that helped shape me.

As an adjunct assistant professor, I was responsible for the teaching and preparation of the course, ChE 43200: Reaction Engineering, from course preparation, ABET compliance in course structure, and interfacing with the students. I also directly participated in the ABET accreditation/evaluation process at CCNY, where the process this year was the full 6-year renewal process, which passed with exceptional scores in the Chemical Engineering Department. As teaching is one of the core responsibilities of faculty, gaining this experience has been invaluable in preparing me for the role of a tenure-track assistant professor. While teaching the course, I have developed proficiency in using software that facilitates the dissemination of the work, ranging from Blackboard to open-source teaching materials such as LearnChemE to share interactive teaching material with the students. This experience has allowed me to implement my teaching philosophy into practice, which includes providing students with all the materials they need to succeed to normalize the field. Furthermore, I have made it a goal to not only educate the students on the base material of kinetics, but also to gain an appreciation for the chemical sector at large, including the history of the chemical industry and exploring relevant current issues and processes in rigorous detail as it pertains to reaction engineering, such as the complexities of the Haber-Bosch process for ammonia or hydrogen generation via methane reforming and/or electrolysis. It is essential to show students not only the theory of the course, but also the relevant chemical processes that are underpinned by the theory. This approach to teaching resonated extremely well with my students, where I received exceptional evaluations from my students stating the course was fairly executed and that the class was of high interest to the students.