(3hq) Advancing Nanocatalyst Driven Electrochemistry Via Multimodal Metrology

At the heart of green chemical engineering is a dream for implementation of highly energetically efficient, renewably driven, and sustainably sourced chemical transformations in industry. On the verge of harnessing CO₂ as a building block for carbon-based fuels, electrochemistry stands uniquely poised to satisfy this dream if we had better understanding and control over the chemical events occurring within catalyst microenvironments. To accomplish this we can apply the manifold increase in new electrocatalyst information (from high entropy alloys, single atom catalysts, atomic clusters, etc.) to both commercially relevant fabrication and electrolyzer systems. Additionally, emerging measurement platforms are needed to observe the chemical conditions and intermediates at the electrocatalyst’s surface which govern chemical reactivity, efficiency, and selectivity, thus revealing mechanisms for control and providing stringent tests of fundamental theories. Unfortunately, instances of efforts seeking to synergistically accomplish these tasks are limited. To fill this critical knowledge and measurement gap, I will use my expertise in nanomaterial synthesis, catalysis, electrolyzer modeling and in-situ spectroscopy to create a research program enabling unprecedented understanding of electrochemical reactions at catalytic interfaces. Ultimately the goal is to mitigate industry’s continued reliance on unsustainable processes by providing technologies built on sustainable sources whether it is for commercial products, grid scale-energy storage or transportation.

To be succinct, my research program will be built upon the following four efficiencies.

1. Synthesis and evaluation of atomically precise nanomaterials for electrosynthesis, energy conversion and sensing.^{2, 4-6, 12-15}
   1. Develop materials fabrication platforms that enable atomic-scale control of structures and rapid catalyst optimization.
      1. Utilization of novel wet atomic layer deposition techniques
   1. Explore the role of novel nanocatalysts in emerging applications (e.g. electrosynthesis strategies) for sustainability.
      1. Use real-time evaluation techniques (online mass spectroscopy) to analyze temporal evolution of products in commercial reactor configurations.
      2. Evaluate the efficacy of these materials against descriptors that determine commercial viability.
   2. Collaborate with density functional theory experts to draw fundamental trends due to catalyst structure
      1. Determine structural influence over catalytic function (e.g. ensemble, strain effects)
2. Electromagnetically assisted and driven reaction chemistry³
1. Apply cutting-edge synthetic techniques (High-entropy alloy synthesis) to create novel plasmon-active catalyst structures.
2. Apply plasmonic-semiconductor hybrid catalysts in novel reactor configurations that induces optimal reaction environments capable of utilizing electromagnetic energy.
3. Exploring meso-scale architecture on applied function of nanoscale assemblies^7,8,10,11
   
   1. Develop finite simulation modeling methods of nanoscale assemblies
      1. Model transport phenomena that capture mass transport kinetics, local pH effects, ionic effects.
   2. Validate and improve models with novel localized measurements (e.g. scanning probe microscopies).
      1. Use measurements to optimize conditions at electrode-electrolyte interfaces.
4. Measuring surface specific phenomena for characterization of nanoscale assemblies.^1,9
   
   1. Use operando techniques and localized probes (e.g. shell-isolated nanoparticle enhanced Raman spectroscopy, sum-frequency generation) to determine long-lived intermediates and catalytic active sites of reactions.

Teaching Interests

As a student I was motivated by hands-on experiences. Success in my undergraduate career was unrefutably coupled to an undergraduate research symposium that inspired me and gave me purpose in the classroom. As such, I aim to integrate my curriculum with undergraduate research possibilities and expose undergraduates to research through symposia, like the one that directed me towards my career as faculty. As a PhD I promoted this agenda by mentoring over 13 undergraduate students through the full research pipeline from hypothesis through experimentation, data analysis, and presentation. I also extended research opportunities to high school students, by mentoring 2 high school students in the Woman in Science and Engineering Program. To be more engaging in the classroom, keeping the attention of those like my younger self, I will optimize the use of active-learning techniques and evidence-based teaching methods. As a PhD student I equipped myself to implement such strategies through JHU’s Preparing Future Faculty program where I learned alternative teach methods, how to effectively implement them as faculty and practiced them as a co-instructor for “Introduction to Chemical and Biochemical Process Analysis”. On the topic of courses, my research generally keeps me prepared to teach core classes such as Kinetics, Chemical Process Analysis, Reaction Engineering and Mass Transport/Transport Phenomena. I aim to build an upper level course entitled “Functional Nanomaterials for Tomorrow”. The course would focus on generally strategies behind design and control over nano-scale materials, the underlying physics and chemistry that governs them and successful application of these materials. In class, students will be evaluated on their understanding behind fundamental mechanisms that govern nanomaterial fabrication, characterization, and application. However, the bulk of “gradable” content will be based on term papers designed to be “mini-reviews” such as “Nanomaterial Purification and Characterization Techniques” or “Dispersion, Aggregation and Recovery of Metal Nanoparticles in Various Applications”. The apex of the course will require the students to invent a potential novel technology of nanomaterials, disseminate the fundamental mechanisms that govern the process and finally devise metrics that gauge success. This “invention” will be pitched to other students through in-class presentations. Finally, while in Baltimore during my PhD I witnessed the importance of outreach to the local community. I participated in multiple STEM programs that gave underprivileged students opportunities to learn about science and a safe place to be. It is my responsibility to build-up or contribute to existing educational outreach initiatives of my host department or university. Affording university students the opportunity to teach will also serve as a way for them to reflect on their own education.

Lead Proposal Writing Experience

ECS Toyota Fellowship (2020, under review)

National Research Council Research Associateship Program Postdoctoral Fellowship (NIST, 2018)

ETH-Z Postdoctoral Fellowship (2018)

Johns Hopkins Environment, Energy, Sustainability & Health Institute Fellowship (2013-2014)

Additional Proposal Writing Experience

DOE ARPA-E, DE-FOA-0001953 (2020, under review)

DOE Office of Fossil Energy, DE-FOA-0002188 (2020, under review)

DOE EERE Bioenergy Technologies, DE-FOA-0002203 (2020, under review)

DMREF, Design of Nanoscale Alloy Catalysts from First Principles Award #1437396 (2014)

NSF Graduate Research Fellowship Program Honorable Mention (2013)

Multiple CNMS User Proposals while at JHU (Oak Ridge National Laboratory, 2013-2017)

Awards

25^th North American Catalysis Society Meeting: Richard J. Kokes Travel Award, 2017

ACS CATL Graduate Student Travel Award (Fall 2017)

The Johns Hopkins University: Nicholas Letica and Terri Glubin Letica Fellowship, 2014-2017

The Johns Hopkins University: Croft Fellowship, 2013-2014

University of Delaware: Hypercube Scholar, 2012

University of Delaware: Senior Thesis Winter Scholar Recipient, 2012

University of Delaware: Plastino Undergraduate Research Fellowship, 2010

University of Delaware: W&H Billsborough Ludlum Scholar for Chemistry, 2010

University of Delaware: Evelyn E. Stricklin Scholarship, 2008-2012

University of Delaware: Wilbur E. Postles Scholarship, 2008-2009

Select Publications (*Denotes co-first, chronologically ordered)

1. Raciti, D.; Hight-Walker A.; Moffat, T. P. “Operando SHINERS Investigation of Sulfonate Accelerated Cu Superfilling” in prep.
2. Raciti, D.; Braun, T.; Xu, H; Cruz, M; Wiley, B.; Moffat, T. P. “Self-Conducting High Aspect Ratio Nanomaterials for Electrochemical CO­₂ Reduction” in prep.
3. Wang, C.; Yang, W.; Bruma, A.; Raciti, D.; Agrawal, A.; Sharma, R. “Endothermic Reactions enabled by High Energy Plasmons at Room Temperature.” Nature, 2019, In review.
4. Wang, Y.; Shen, H.; Livi, K. J. T.; Raciti, D.; Zong, H.; Gregg, J.; Onadeko, M.; Wan, Y.; Watson, A.; Wang, C. “Copper Nanocubes for CO₂ Reduction in Gas Diffusion Electrodes” Nano Letters, 2019, 19, 8461-8468.
5. Wang, L.; Zeng, Z.; Gao, W.; Maxson, T.; Raciti, D.; Giroux M.; Pan, X.; Wang, C.; Greeley, J. “Tunable Intrinsic Strain in Two-Dimensional Transition Metal Electrocatalysts.” Science, 2019, 363, 870-874.
6. Liu, Y.; Yu, W.; Raciti, D.; Gracias, D. H.; Wang, C. “Electrocatalytic Oxidation of Glycerol on Platinum.” Phys. Chem. C. 2018, 8, 426-432.
7. Raciti, D.; Wang, B; Mao, M.; Park, J. H.; Wang, C. “Three-Dimensional Hierarchical Copper-Based Nanostructures as Advanced CO₂ Electroreduction” ACS Appl. Energy Mater., 2018, 1, 2392-2398. 10.1021/acsaem.8b00356.
8. Raciti, D.; Mao, M.; Park J. H.; Wang, C. “Local pH Effect in the CO₂ Reduction Reaction on High-Surface-Area Copper Electrocatalyst” J Electrochem Soc., 2018, 165, F799-F8044. 10.1149/2.0521810jes.
9. Dewan, S.; Raciti, D.*; Liu, Y.; Gracias, D. H.; Wang, C. “Comparative Studies of Ethanol and Ethylene Glycol Oxidation on Platinum Electrocatalysts.” Top Catal, 2018, 1-8. 1007/s11244-018-0930-5.
10. Raciti, D.; Mao, M.; Park J. H.; Wang, C. “Mass Transfer Effects in CO₂ Reduction on Cu Nanowire Electrocatalysts” Sci. Technol., 2018, 8, 2364-2369. 10.1039/C8CY00372F.
11. Raciti, D.; Mao, M.; Wang, C. “Mass Transport Modeling for the Electroreduction of CO₂ on Cu Nanowires” Nanotechnology, 2018, 29, 044001. 1088/1361-6528/aa9bd7.
12. Raciti, D.; Cao, L.; Li, C.; Rottman, P. F.; Tang, X.; Hicks, Z.; Livi, K.; Bowen, K.; Hemker, K. J.; Mueller, T.; Wang, C. “Low-Overpotential Electroreduction of Carbon Monoxide Using Copper Nanowires” ACS Catal. 2017, 7, 4467-4472. 1021/acscatal.7b01124.
13. Huang, Z.; Raciti, D.; Yu, S.; Zhang, L.; Deng, L.; He, J.; Liu, Y.; Khashab, N. M.; Wang, C. Gong, J. “Synthesis of Platinum Nanotubes and Nanorings via Simultaneous Metal Alloying and Etching.” Am. Chem. Soc. 2016, 138, 6332-6335. 10.1021/jacs.6b01328.
14. Raciti, D.; Kubal, J.; Ma, C.; Barclay, M.; Gonzalez, M.; Chi, M; Greeley, J.; More, K. M.; Wang, C. “Pt₃Re Alloy Nanoparticles as Electrocatalysts for the Oxygen Reduction Reaction.” Nano Energy 2016, 20, 202-211. 1016/j.nanoen.2015.12.014.
15. Raciti, D.; Livi, K.; Wang, C. “Highly Dense Cu Nanowires for Low-Overpotential CO₂” Nano Letters 2015, 15, 6829-6835. 10.1021/acs.nanolett.5b03298.