(6bv) Unifying Principles in Thermally and Electrochemically Driven Catalytic Reactions

Overview of past and current Research:

At the atomic level, catalytic reactions involve the making and breaking of chemical bonds between reacting molecules and active sites. This has led to an understanding of heterogeneous catalysis in terms of active site-adsorbate interactions. However, as our ability to characterize the complex nature of active sites advances, it has become apparent that the reaction environment can also have important influences. This includes influencing reactivity through environment-induced restructuring of the catalyst surface, as well as direct participation of the solvating medium in the reaction. Appreciation of this added complexity is necessary for a complete description of catalytic reactions, and once understood, can yield additional tools for designing more efficient catalysts. Optimizing the structure of both the binding site and the non-reactive components in its vicinity can give us exquisite control over chemical reactions, as elegantly demonstrated by nature’s catalysts, enzymes. Throughout my Ph.D. and postdoc, I have sought to understand the impact of these secondary effects on both electrochemical and thermally activated catalytic reactions.

Ph.D. Research- Electrolyte effects on electrochemical CO₂ reduction

(University of California, Berkeley; Advisor: Alexis Bell)

The composition of the electrolyte in which electrocatalysts are tested has been observed to influence reactivity; however, detailed understanding of these effects is still lacking. Through a combination of experimental and theoretical studies, we elucidated the effects of electrolyte cation and anion identity on the activity and selectivity of metal catalysts for this reaction. We showed that cations in solution act as a built-in promoter with a function analogous to alkali metal promoters for gas phase reactions, interacting electrostatically with adsorbates to influence reaction energetics. Anions can also affect CO₂ reduction rates, acting both as a buffer and a proton source, increasing rates of hydrogenation reactions.

Postdoc Research- Developing atomic-scale structure property relations for isolated metal catalysts

(University of California, Santa Barbara; Advisor: Phil Christopher)

Atomically dispersed metals on oxide supports have recently gained significant interest as catalytic materials, but relationships between their structure and properties remain unknown. Through a combination of atomic level and sample averaged in-situ characterization, we demonstrated that the local coordination of the metal to the support determines the ability of the surface site to form additional bonds with adsorbates. We have demonstrated the consequences of these coordination effects for reactions important for producing sustainable fuels.

Future research:

Significant environmental issues associated with the use of fossil fuels, along with advances in technologies to generate renewable electricity have made it likely that future energetic inputs to drive chemical transformations will be electrical in addition to thermal. However, the use of electrocatalytic processes for sustainable fuel and chemical production requires scientific breakthroughs in the design of catalysts and reaction systems to drive these reactions. Understanding the fundamental concepts that govern reactivity in these systems can enable their rational design and facilitate these breakthroughs. In my research, I plan to establish parallels between well studied thermal catalytic reactions and new electrocatalytic processes to provide design rules for catalyst design and highlight what unique opportunities the electrochemical system provides. I plan to understand the diversity of chemical transformations possible by electrochemical processes, beyond the conversion of small molecules such as water and carbon dioxide. To design catalysts for these transformations, I plan to optimize the dynamic structure of both the binding site and the non-reactive components in its vicinity to maximize selectivity and activity.

Teaching Interests:

Teaching, both in the classroom and laboratory, is a major driver in my decision to pursue an academic career. My goal in teaching is to develop a student’s deep understanding of a few core Chemical Engineering concepts and use them as a guide to approach any problem they are faced with. Both as an undergraduate and graduate student, I served as a student instructor for core chemical engineering courses. I was awarded the departmental Outstanding GSI award for the graduate Kinetics Course at Berkeley. Based on these enjoyable and instructive experiences, as a graduate student I independently developed and taught an elective course Fundamentals of Electrocatalysis. As a faculty member, I am excited to teach any of the core courses of Chemical Engineering, particularly courses in Kinetics and Reaction Engineering. Given the opportunity, I am also eager to develop new courses such as Electrochemical Engineering, or an introductory course on current and emerging energy transformations. These courses would aim to expose students to interesting applications of the foundational principles of thermodynamics, kinetics, and transport phenomena. In the laboratory, I have served as a mentor to undergraduate and junior graduate students. Serving as a mentor and aiding in the development of students in research will be an important focus throughout my career as a faculty member.

Selected references:

1. J. Resasco, N.P. Dasgupta, J.R. Rosell, J. Guo, P. Yang, J. Am. Chem. Soc. 136, 10521-10526, (2014).
2. J. Resasco, H. Zhang, N. Kornienko, N. Becknell, H. Lee, J. Guo, A. L. Briseno, P. Yang. ACS Cent. Sci. 2, 80-88, (2016). Cover Article
3. J. Resasco, L. Chan, E. Clark, C. Tsai, C. J. Hahn, K. Chan, T. F. Jaramillo, A. T. Bell, J. Am. Chem. Soc. 32, 11277–11287, (2017).
4. J. Resasco, Y. Lum, E. L. Clark, J. Z. Zeledon, A. T. Bell. ChemElectroChem 5, 1064-1072, (2018).
5. E. L. Clark*, J. Resasco*, A. Landers, J. Lin, L. Chung, A. Walton, C. Hahn. T. F. Jaramillo, A. T. Bell. ACS Catal. 8, 6560-6570, (2018).
6. J. Resasco, S. Dai, G. Graham, X. Pan, P. Christopher. J. Phys. Chem. C 122, 25143-25157 (2018). Cover Article
7. L. DeRita*, J. Resasco*, S. Dai*, A. Boubnov, H. V. Thang, A. S. Hoffman, I. Ro, G. W. Graham, S. R. Bare, G. Pacchioni, X. Pan, P. Christopher. Nat. Mater. 18, 746–751 (2019).

*Denotes equal contribution