(2jp) Catalytic Interfaces for Thermal Electrfication of Chemical Manufacturing

Motivation: Abating climate change requires decarbonized chemical synthesis of energy-intense processes like methane reforming, cracking, and oxidations, which release >800 million metric tons of CO2 annually. These steps oxidize carbon directly or use high-temperature (400–900 °C) operations heated by fossil fuels. Thus, electrifying the chemical sector may lessen this footprint. Still, this vision requires new reactors and catalysts to convert emerging feedstocks into valuable chemicals with air, water, and renewable energy.

Research Interests: I aim to build a research program to help decarbonize chemical industries using reactors that utilize electrochemical potential across broad ranges of temperatures and pressures, powered by renewable energy. Such steps would significantly mitigate CO2 emissions and toxic byproducts from chemical manufacturing. Thus, my research group will study the thermal and electrochemical activation of O₂, H₂O, and H₂O₂ during transformations of O–H, C–O, C–H, and C–C bonds needed for this revolution. My lab will combine rigorous fundamentals with practical considerations of rates, selectivity, conversion, stability, and transport-coupled kinetics. Thus, I aim to create principles to advance the following fields:

1. Electrolysis of H2O to produce H2O2 as an environmentally benign oxidant and carbon-free fuel
2. Oxidative dehydrogenation and coupling of alkanes as a low-carbon substitute to steam cracking
3. Reductive activation of O2 and H2O2 to oxidize aromatics and olefins to chemical precursors

These studies are critical for (1) generating H2O2 as a valuable co-product during H2 electrolysis, (2) lowering the energy costs of olefin synthesis, and (3) mitigating the carbon footprint of key oxidation steps.

Doctoral Studies (University of Illinois Urbana-Champaign; Advisor: David Flaherty; NSF-GRFP):

I developed a mechanistic understanding of the reactions of H₂ and O₂ at the solid-liquid interface of metal nanoparticles, providing design principles for catalysts that transform H-H, O-O, and O-H bonds into H₂O₂:

• Understanding how surface-bound redox mediators co-catalyze reactions of H₂ and O₂ over Pd ^1,2
• Unifying concepts of thermal and electrocatalysis to elucidate driving forces of H₂O₂ synthesis ^3,4
• Revealing how metal-support interfaces,^5-7 alloys,^8,9 and poisons^10-12 activate H-H and O-O bonds

I combined reactor engineering, material synthesis, operando spectroscopy, DFT calculations, and kinetic modeling to develop molecularly specific insights into reactions at solid-liquid interfaces.¹³ recognized in fellowships, awards, and over ten publications, including journals such as Science ¹ and JACS_.^3,8

Postdoctoral Studies (California Institute of Technology; Advisor: Karthish Manthiram; Began 6/27/22):

My postdoctoral work focus on the cathodic epoxidation of olefins using O₂ as the oxidant. We hypothesize that O₂ reduces to surface species (e.g., OOH*) that react with olefins. The aims of my work are threefold:

• Build an automated reactor to collect rate data as a function of temperature, pressure, and potential
• Use operando XAS, FTIR, and SERS to elucidate surface species and the structure of the catalyst
• Use aims 1 & 2 to create principles for synthesizing catalysts with improved rates and selectivities

Thus, I aim to meld my knowledge of thermal catalysis with a fundamental understanding of organic chemistry, electrochemical techniques, and material synthesis, serving as the basis of my group’s research.

Teaching Interests: My mentors lit a fire of academic ambition within me and inspired me to grow into a better version of myself. Bill Koros showed me the importance of building warm relationships, being approachable, making science fun, and allowing students to become independent thinkers, even as an undergraduate.^14-16 Dave Flaherty taught me the value of challenging students to achieve their full potential and promoting high standards of scientific rigor, scrutiny, and communication. Finally, Karthish Manthiram amazes me with his Socratic pedagogy, presence, patience, empathy, and ability to build group cohesion. I still grow from these experiences, exciting me to inspire similar feelings in my students as we learn together.

Selected Publications:

(1) Adams, J. S.; Chemburkar, A.; Priyadarshini, P.; Ricciardulli, T.; Lu, Y.; Maliekkal, V.; Sampath, A.; Winikoff, S.; Karim, A.M.; Neurock, M.; Flaherty, D.W. “Solvents Molecules Form Surface Redox Mediators in situ and Cocatalyze O₂ Reduction on Pd” Science., 2021, 371, 626-632

(2) Adams, J. S.; Mayank Tanwar; Vijayarghavan, S.; Chen, H.; Ricciardulli, T; Neurock, M.; Flaherty, D.W. “Ligands Block Sites and Mediate Reactions of H₂ and O₂ on Pd to Selectively Form H₂O₂”, Target: Journal of the American Chemical Society, To be submitted December 2022 (manuscript available on request)

(3) Adams, J. S.;^‡ Kromer, M.;^‡ Rodríguez-López, J.; Flaherty, D.W. “Unifying Concepts in Electro- and Thermal Catalysis towards Hydrogen Peroxide Production”, J. Am. Chem. Soc., 2021, 143, 7940-7957.

(4) Zhao, Y.; Adams, J. S.; Baby, A.; Kromer, M. L; Flaherty, D. W.; Rodríguez-López, J. “Electrochemical Screening of Au/Pt Catalysts for the Thermocatalytic Synthesis of Hydrogen Peroxide Based on Their Oxygen Reduction and Hydrogen Oxidation Activity Probed via Voltammetric Scanning Electrochemical Miscropscopy,” ACS Sustain. Chem Eng. In review. (manuscript available on request)

(5) Adams, J. S.; Chen, H.; Ricciardulli, T; Sampath, A; Flaherty, D.W. “Interfacial Sites Determine O₂ and H₂ Activation Pathways on Au Nanoparticles: Effects of Nanoparticle Size and Support Identity on O₂ Reduction.”, Target: Journal of the American Chemical Society, To be submitted November 2022 (manuscript available on request)

(6) Sampath, A; Ricciardulli, T.; Priyadarshini, P.; Ghosh, R.; Adams, J. S.; Flaherty, D.W. “Spectroscopic Evidence for the Involvement of Interfacial Sites in O-O Bond Activation Over Gold Catalysts.”, ACS Catal. 2022, 12, 15, 9549-9558

(7) Ricciardulli, T.; Adams, J. S.; Vijayarghavan, S.; Flaherty, D.W. “Impact of Confined, Supported and Solvated Hydronium Ions on Aqueous H₂O₂ Synthesis Over Pd-Zeolites”, Target: ACS Catalysis, To be submitted Winter 2022 (manuscript available on request)

(8) Ricciardulli, T.; Gorthy, S.; Adams, J. S.; Thompson, C.; Karim, A.M.; Neurock, M.; Flaherty, D.W. “Effect of Pd Coordination and Isolation on the Catalytic Reduction of O₂ to H₂O₂ over PdAu Bimetallic Nanoparticles”, J. Am. Chem. Soc., 2021, 143, 5445-5464

(9) Ricciardulli, T.; Adams, J. S.; DeRiddler, M.; Horton, A.; Bavel, A. P.; Karim, A. M.; Flaherty, D.W. “H₂O-assisted O₂ Reduction by H₂ on Pt and PtAu Bimetallic Nanoparticles: Influence of Coverages on Kinetic Regimes and Selectivities.”, J. Catal, 2021, 404, 661-678

(10) Adams, J. S.;^‡ Vijayarghavan, S.; Chen, H.; Ricciardulli, T; Flaherty, D.W. “Role of Adsorbed sulfur on Stabilizing O-O Bonds during O₂ reduction by H₂ over Pd and Pt Surfaces”, Target: Angewandte Chemie, To be submitted Winter 2023 (manuscript available on request)

(11) Priyadarshini, P.; Ricciardulli, T.; Adams, J. S.; Yun, Y.; Flaherty, D.W. “Effects of Bromide adsorption on the Direct Synthesis of H₂O₂ on Pd Nanoparticles: Formation Rates, Selectivities, and Apparent Barriers at Steady-State”, J. Catal., 2021, 399, 24-40

(12) Priyadarshini, P.; ^‡ Ricciardulli, T.;^‡ Zhang, Z.; Adams, J. S.; Sampath, A.; Flaherty, D.W. “Effect of Surface-Bound Phosphonic Acid-Derived Ligands on the Rates and Selectivities of the Direct Synthesis of Hydrogen Peroxide”, Target: ACS Catalysis, To be submitted Winter 2022 (manuscript available on request)

(13) Potts, D.; Bregante, D.; Adams, J. S.; Torres, C.; Flaherty, D.W. “Influence of Solvent Structure and Hydrogen Bonding on Catalysis at Solid-Liquid Interfaces”, Chem. Soc. Rev., 2021, 50, 12308-12337 ^♣

(14) Adams, J. S.; Bighane N.; Koros, W.J. “Pore Morphology and Temperature Dependence of Gas Transport Properties of Silica Membranes Derived from Oxidative Thermolysis of Polydimethylsiloxane” J. Membr. Sci., 2017, 524, 585-595.

(15) Rungta, M.; ^‡ Wenz, G.B.; ^‡ Zhang, C.; Xu, L.; Qiu, W.; Adams, J. S.; Koros, W.J. “Carbon Molecular Sieve Structure Development and Membrane Performance Relationships” Carbon, 2017, 115, 237-248.

(16) Adams, J. S.; ^‡ Itta, A.K.; ^‡ Zhang, C.; Wenz, G.B.; Sanyal, O.; Koros, W.J. “New Insights into Structural Evolution in Carbon Molecular Sieve Membranes During Pyrolysis” Carbon, 2019, 141, 238-246.