Perovskites have emerged as a promising candidate for low-cost production of solar cells. However, the most critical barrier for commercialization of perovskite solar cells (PSCs) is the inadequate stability of the organic metal halide perovskites (OMHPs). The degradation of OMHPs is induced by light, heat, air, and electrical bias. The known degradation pathways involve the oxidation of I^- and Sn²⁺, dissolution of perovskites by moisture, irreversible reactions with water, ion migration, and ion segregation. To improve the stability of OMHPs various methods are adopted, such as additive engineering, perovskite surface treatment, and composition engineering. Surface ligands are used on top of perovskite thin films to passivate the undercoordinated ions leading to improved charge collection efficiency and stability of PSCs. However, not all surface ligands stay at the surface of the perovskite. Some of them penetrate the perovskite layer forming reduced dimensional phases at the surface. This kind of behavior not only alters the electronic nature at the interface, but also negatively affects the stability of the OMHPs compared to surface ligands that remain only at the surface. On the other hand, additives are commonly used to reduce defects in bulk of the perovskites and thus improve their stability. They improve the stability of OMHPs by controlling the morphology of OMHP thin films, improving the thermodynamic stability of Sn²⁺ and I^-, and lowering the ion migration and ion segregation. The stability of OMHPs is also significantly improved by incorporating bulky organic cations into the perovskite composition. Although these routes for improving the stability are optimistic, it is not clear how the surface chemistry of OMHPs and chemical nature of additives or organic cations affects stability.

Surface chemistry of OMHPs can be tuned to control the extent of ligand penetration by changing the composition and processing conditions of OMHPs. To this end, it is important to find out what affects the extent of ligand penetration. We find that the perovskite compositions used in this study have little or no effect on ligand penetration. However, the perovskite film processing conditions have a greater effect on ligand penetration. Using a family of phenethylammonium iodide (PEAI) with different substituents on the benzene ring, we show that the ligand penetration can be affected by type of substituents as well. Stabilizing the perovskite precursors is also important as degraded precursors lead to defective perovskites with poor stability. Here, we show that additives influence the thermodynamic stability of Sn²⁺ and I^- by changing the acidity of the precursor solutions. Using additives with a range of pKa we find that additives with higher pKa provide a more stabilizing chemical environment for Sn²⁺ and I^-. 

It is known that bulky organic cations improve the stability of OMHPs by shielding the metal-halide octahedra from air. However, how the structure of the organic cations affect the air, oxygen, and moisture stability of the OMHPs is not well understood. Using twelve different organic cations we show that the stronger the attractive interactions between the organic cations in two dimensional (2D) OMHPs the higher is the stability. The stability of 2D-OMHP thin films decreases as the orientation of the 2D sheets deviates from planarity with respect to the substrate plane.

Abstract: Over the years, nanomaterials research has advanced towards discovering versatile and readily accessible materials tailored for a diverse range of applications. A comprehensive understanding of materials’ phases and their transformations are integral to this effect to enable better synthetic control as well as the functionalization of nanomaterial properties. Among advanced characterization techniques, the transmission electron microscope (TEM) is a powerful tool that provides direct access to the nanoscale and, therefore, an indispensable tool in studying fundamental materials problems. This dissertation discusses several nanomaterial systems where TEM tools and techniques are utilized to gain a deep understanding of their chemistry. 

This dissertation focuses on structural and phase transformations of nanomaterials using in situ heating in the TEM, which allows direct observation of these dynamic processes. Reported here are studies of the phase transformation and stabilization of the mackinawite phase of iron(II) sulfide nanoplatelets, the structural transformation of gold-catalyzed tin(IV) oxide nanowires into gold core/tin(IV) oxide shell nanowire heterostructures, and finally the interaction between aluminum oxide and lead (at. 17%) lithium alloy proposed for use as a coolant in nuclear fusion reactors. These studies showcase the significance of knowledge of the mechanistic details of phase transformations, with the eventual goal of being able to determine and control structure-property relationships. 

KEYWORDS: phase transformations, nanomaterials, transmission electron microscopy (TEM), in situ TEM

Abstract: Compared to ubiquitous functional groups such as alcohols, carboxylic acids, amines, and amides, which serve as central “actors” in most organic reactions, sulfamates, phosphoramidates, and di-tert-butyl silanols have historically been viewed as “extras”. Largely considered functional group curiosities rather than launchpoints of vital reactivity, the chemistry of these moieties is underdeveloped. Our research program has uncovered new facets of reactivity of each of these functional groups, and we are optimistic that the chemistry of these fascinating molecules can be developed into truly general transformations, useful for chemists across multiple disciplines. In the ensuing sections, I will describe our efforts to develop new reactions with these “unusual” functional groups, namely sulfamates, phosphoramidates, and di-tert-butyl silanols.

Abstract: Low-dimensional (LD) organic-inorganic hybrids have recently emerged as exciting electrocatalytic nanomaterials in which the 0D-1D, 1D-2D or 2D-2D electrochemical interfaces can be finely tuned to generate unprecedented features that are not perceived in the individual counterparts (Scheme 1). 

Low-dimensional interfaces have shown incredible advantages in regulating electron transfer, charge polarization, bonding energy and the adsorption energy of intermediates, thus markedly boosting crucial electrocatalytic parameters such as current density, onset overpotential and faradaic efficiency in many relevant energy conversion reactions including oxygen reduction (ORR), oxygen evolution (OER), and CO₂ electroreduction (CO₂RR). In this seminar, key learning points about the chemical aspects that govern the interfacial effects of low-dimensional hybrids in crucial electrocatalytic reactions will be provided based on both experimental and theoretical findings. The discussion will also cover an in-depth understanding of the heterointerface-electrocatalytic performance relationships as well as their impact for the fabrication of future energy-related devices.

Bio: Alain R. Puente Santiago received his Ph.D. degree in Physical-Chemistry with distinction (July 2017) from the University of Cordoba, Spain. He has worked as a Research Fellow in Prof. Goodenough’s group (Nobel Prize in Chemistry 2019) at the University of Texas at Austin in the development of nanocluster-based electrocatalytic materials. Currently, he is working as a Postdoctoral Associate in the Department of Chemistry at the Florida International University. He has published 67 articles in very prestigious journals such as Journal of the American Chemical Society (7), ACS Sustainable Chemistry and Engineering (5), Journal of Materials Chemistry A (5), Angewandte Chemie (3), Nanoscale (3), ACS Applied Materials and Interfaces (2), Green Chemistry (2), Chemical Society Reviews (2), Advanced Energy Materials (1) and Journal of Catalysis (1).Dr. Santiago’s articles have reached more than 2500 citations and an H index of 27 in the last 5 years. His research interests tackle the development of low-dimensional heterostructures for electrocatalytic, sensing, and energy storage applications.

Speakers
	Dr. Gary W. Brudvig Department of Chemistry and Energy Sciences Institute, Yale University Honors: Searle Scholar, 1983-86, Camille and Henry Dreyfus Teacher-Scholar, 1985-90, Alfred P. Sloan Research Fellow, 1986-88, Elected Fellow of the AAAS, 1995, Outstanding Achievement Award, University of Minnesota, 2016, Elected Member, Connecticut Academy of Science and Engineering, 2019, Graduate Mentor Award in the Natural Sciences, 2021 Biography: Gary Brudvig is the Benjamin Silliman Professor of Chemistry, Professor of Molecular Biophysics & Biochemistry, and Director of the Yale Energy Sciences Institute at Yale University.  He received his B.S. (1976) from the University of Minnesota, his Ph.D. (1981) from Caltech and was a Miller Postdoctoral Fellow at the University of California, Berkeley from 1980 to 1982.  Professor Brudvig has been on the faculty at Yale since 1982. Brudvig served as Chair of the Chemistry Department from 2003-2009 and 2015-2018.  Since 2012, Brudvig has been the Director of the Energy Sciences Institute located at Yale’s West Campus where he oversees the development of new research programs and facilities related to renewable energy, alternative fuels, and materials science.  His research involves study of the chemistry of solar energy conversion in photosynthesis and work to develop artificial bioinspired systems for solar fuel production.
	Dr. Wolfgang Nitschke Research Director, Bioenergetics and protein engineering laboratory (BIP)/CNRS Prof. Nitschke has been studying bioenergetics all his academic life, beginning with a Ph. D. on photosynthetic electron transfer in plants at the University of Regensburg in Germany and, after drifting towards prokaryotic photosynthesis during 5 years as post-doctoral fellow in Paris, serving as a professor in Freiburg Germany. Upon moving to Marseille, France, he addressed electron transport and the implied energetics in an expanding repertoire of biochemical processes and bacterial species. He led the “Evolution of Bioenergetics" research group from 1995 until his retirement in 2023 and was vice-director of the department “Bioenergetics and Protein Engineering” from 2002 to 2006. Through a career dedicated to biological energy conversion, he was convinced of the fundamental importance of energy to life (and beyond). His professional bio reports that since his retirement he is 'able to finally do research without the crazy administrative workload'.
	Dr. Shelley Minteer Dale and Susan Poulter Endowed Chair of Biological Chemistry and Associate Chair of Chemistry  Director, Kummer Institute Center for Resource Sustainability at Missouri University of Science and Technology Honors & Awards: 2020 Bioelectrochemistry Prize of the International Society of Electrochemistry, 2020 University of Utah Distinguished Research Award, 2020 Charles N. Reilley Award of the Society of Electroanalytical Chemistry, 2019 Fellow of the International Society of Electrochemistry, 2019 Grahame Award of the Electrochemical Society, 2018 Fellow of the American Association for the Advancement of Science, 2018 American Chemical Society Analytical Division Electrochemistry Award, 2015 Luigi Galvani Prize of the Bioelectrochemical Society, 2013 Fellow of The Electrochemical Society, 2010 Tajima Prize of the International Society of Electrochemistry, 2008 American Chemical Society St. Louis Award, 2008 Scientific American Top 50 Award, 2008 Society of Electroanalytical Chemists Young Investigator Award, 2006 U.S. Department of Defense Okaloosa Award, 2006 Missouri Inventor of the Year Award, 2005 Academy of Science of St. Louis Innovation Award

2024 Naff Symposium Committee

Prof. Anne-Frances Miller - (Chemistry) [Chair]

Prof. Marcelo Guzman - (Chemistry)

Prof. Kenneth Graham - (Chemistry)

Prof. Isabel Escobar - (Chemical & Materials Engineering)

Abstract: The living cell is an intricate and synchronized organization with compartmentalization across diverse length scales. While intracellular compartments such as the lysosome and mitochondria are bound by membranes, cells also contain organelles, not confined by membranes, known as “biomolecular condensates”. Recent studies showed that many biomolecular condensates are viscoelastic materials formed from the phase separation of proteins and nucleic acids. The abrupt changes in composition and material properties of these condensates impair their biological function and are often associated with cancer, ribosomopathies, and aging disorders. Therefore, synthetic systems are required to create model biomolecular condensates in living systems. These systems aim to elucidate the biophysical principles of intracellular organization and diseases. In the first part of my talk, I will discuss our work on using protein oligomerization and sequence interactions in vivo to create multiphasic biomolecular condensates that mimic native condensate assemblies. We show that specific molecular and nanoscopic design principles can be exploited to design optogenetic fusion proteins that exhibit targeted condensation with high spatiotemporal resolution. Later in this talk, I will describe our work on synthetic polymers to form condensates that mimic the function of underwater adhesive proteins secreted by marine organisms such as mussels and sandcastle worms. In summary, the bioinspired design of macromolecules that form model biomolecular condensates represents new frontiers to ask fundamental questions on the behavior of mesoscopic biological assemblies in living cells and to inspire the design of novel functional materials.

Abstract: Fossil fuels have been overwhelmingly used in many industry sectors in past decades, suffering from significant CO₂ and other pollutant emissions, low efficiency, and nonsustainability. Clean and efficient energy storage and conversion via electrochemical reactions associated with hydrogen, oxygen, and water have attracted substantial attention for energy and environmental sustainability. Among compelling energy technologies, hydrogen proton exchange membrane fuel cells (PEMFCs) are a promising zero-emission power source for transportation to mitigate environmental pollution and reduce fossil-fuel dependence. Meanwhile, water electrolyzers have been clearly identified as the sustainable pathway to produce cheap green hydrogen efficiently using renewable electricity. However, current materials, including catalysts, membranes, and ionomers, cannot meet the challenging targets of high-efficiency, low-cost, and long-term durability of hydrogen fuel cells and water electrolyzers. Developing high-performance catalysts from earth-abundant elements to replace current precious metals is crucial for making these hydrogen technologies viable for large-scale clean energy applications. U.S. DOE has been continuously supporting his research group at SUNY-Buffalo in the past decade, aiming to address materials issues by designing and scaling up innovative and highly efficient catalysts and electrodes. This talk discusses recent understanding, progress, achievement, and perspective on developing low-cost and high-performance catalysts based on newly emerging atomically dispersed metal-nitrogen-carbon materials for sustainable and clean hydrogen technologies.

Gang Wu is a professor in the Department of Chemical and Biological Engineering at the University at Buffalo (UB), The State University of New York (SUNY-Buffalo). He completed his Ph.D. studies at the Harbin Institute of Technology in 2004, followed by extensive postdoctoral training at Tsinghua University (2004-2006), the University of South Carolina (2006-2008), and Los Alamos National Laboratory (LANL) (2008-2010). Then, he was promoted to a staff scientist at LANL. He joined SUNY-Buffalo as a tenure-track assistant professor in 2014 and was quickly promoted to a tenured associate professor in 2018 and a full professor in 2020. His research focuses on functional materials and catalysts for electrochemical energy technologies. He has published more than 320 papers in prestigious journals, including Science, Nature Energy, Nature Catalysis, JACS, Angew Chem, and Advanced Materials. His papers have been cited more than > 48,000 times with an H-index of 118 (Google Scholar) by November 2023. He is currently leading and participating in multiple fuel cell, battery, and renewable fuel (e.g., NH₃) related projects with a total research funding of more than $10.0 M. Dr. Wu was continuously acknowledged by Clarivate Analytics as one of the Highly Cited Researchers since 2018. He recently received the SUNY Chancellor’s Award for Excellence in Scholarship & Creative Activities (2021) and UB’s Exceptional Scholar–Sustained Achievement Award (2020). He serves as Associate Editor for a few journals, including the Journal of the Electrochemical Society (JES), the Electrochemical Society’s flagship journal.

Event Info: We will discuss what our program structure, what we do, and how the state program compliments and supports federal CERCLA mandates. We intend on highlighting examples of current site-work and how chemistry is integral to the field of environmental protection, as well as playing a part in protective and sustainable community redevelopment.

Bio: Sheri is a Registered Professional Geologist with over 24 years of experience in the environmental field, specifically in contaminated site characterization & remediation, regulation development, and beneficial reuse. After a brief stint performing geotechnical work in private consulting Sheri started with KDEP in 2000 as a Geologist with the tanks program, becoming a supervisor in the Superfund Branch in 2007.  Between 2007 and 2012, Sheri supervised the State Superfund Section, then the Federal Superfund Section before accepting the branch Environmental Scientist Consultant position.  As an E.S. Consultant, she focuses on scientific research, and regulation & policy development for Kentucky’s Superfund, Brownfields, and other programs.  In addition, Sheri serves as the technical lead for Kentucky's high priority clean-up sites. Outside of her career with the commonwealth of Kentucky, Sheri is on the Board of Advisors to the Kentucky Geological Survey and a long-time active member of the Association of State and Territorial Solid Waste Management Officials. In her free time, she enjoys traveling, hiking, cycling, reading, fiber arts, and creating stained glass. 

ABSTRACT

Ambient ionization mass spectrometry (AIMS) is an evolving soft ionization technique that directly snapshots biomolecular profiles, spatial distributions, and chemical changes from biological tissue or fluids with minimal pretreatment. I will first introduce the methodology development of two representative AIMS techniques, namely air-flow-assisted desorption electrospray ionization mass spectrometry imaging (AFADESI-MSI) and conductive polymer spray ionization (CPSI), along with their applications in preclinical anti-tumor drug research and clinical cancer diagnosis. The topic will be then shifted to using AIMS to create water microdroplets, which exhibit ultrafast kinetic and favorable thermodynamic microenvironment differing from equal volume of bulk solution phase. I will introduce my research on AIMS-based microdroplet chemistry for both bioanalysis and synthesis of basic building blocks of life materials.

Abstract: The vast majority of chemistry and biology occurs in solution, and new label-free analytical techniques that can help resolve solution-phase complexity at the single-molecule level can provide new microscopic perspectives of unprecedented detail. Here, we use the increased light-molecule interactions in high-finesse fiber Fabry-Pérot microcavities to detect individual biomolecules as small as 1.2 kDa (10 amino acids) with signal-to-noise ratios >100, even as the molecules are freely diffusing in solution.  Our method delivers 2D intensity and temporal profiles, enabling the distinction of sub-populations in mixed samples. Strikingly, we observe a linear relationship between passage time and molecular radius, unlocking the potential to gather crucial information about diffusion and solution-phase conformation. Furthermore, mixtures of biomolecule isomers of the same molecular weight can also be resolved. Detection is based on a novel molecular velocity filtering and dynamic thermal priming mechanism leveraging both photo-thermal bistability and Pound-Drever-Hall cavity locking. This technology holds broad potential for applications in life and chemical sciences and represents a major advancement in label-free in vitro single-molecule techniques.