Image by Jeffery London | Pacific Northwest National Laboratory
San Francisco
Key sessions organized by PNNL
Energy Storage in Chemical Bonds: Challenges and Opportunities from Theory to Applications for Hydrogen Technology
Sunday – Monday, August 13 – 14
Organized by: Sam Johnson
Helping Chemists Manage their Data
Sunday – Monday, August 13 – 14
Co-organized by: Nancy Washton
Selected PNNL presentations
Biofuel-Related Research in a National Laboratory Setting
SUNday, August 13
Presented by: Mariefel Olarte
Summary: Aviation, together with marine, rail and heavy-duty vehicles, are some of the hard to decarbonize sectors of transportation. According to the US Environmental Protection Agency, transportation contributes to about 27% of US greenhouse gas emissions in 2020. Thus, to meet NetZero targets by 2050, it is important to develop sustainable liquid transportation fuels (biofuels) to the afore-mentioned hard to decarbonize transportation sectors, of which, aviation is expected to have increased demand until 2050. This presentation aims to provide vignettes of some research done by the author, with various research teams, related to the production of biofuels and bioproducts at the Pacific Northwest National Laboratory. This research includes catalyst and process development and modeling. READ MORE.
Micro-to-nanoscale Characterization of Anthropogenic Carbonates Recovered from the Wallula Basalt Pilot Project
Monday, August 14
Presented by: Nabajit Lahiri
Summary: Combatting the impending climate crisis will require enhanced mitigation tools beyond the currently employed net-zero approaches. Geologic CO2 sequestration in continental flood basalts offers a promising carbon-negative strategy towards the safe and permanent storage of CO2 as stable carbonates. To this end, the Wallula Basalt Carbon Storage Pilot Project is the world’s first and only field demonstration of carbon sequestration using supercritical CO2 injected into deep layered basalt flows within the Columbia River Basalt Group (CRBG). This presentation will focus on an in-depth micro-to-atomic scale analysis of anthropogenic carbon mineralization products formed within the basalt pores and vesicles. Recovered post-injection side-wall core cross-sections containing carbonate nodules were polished and analyzed using m-XRF chemical mapping techniques that revealed unique compositional zonation within the nodules. Specifically, the core of the nodule was found to be Ca- and Mn-rich while the outer rim was enriched in Fe. These compositional variations point to differences in crystallization mechanisms at various stages of spherulitic growth. To better understand this at an atomic level, TEM lamellae were prepared from the core and the rim on a carbonate nodule using focused-ion beam (FIB) milling techniques. Significant textural differences could be readily observed between these regions along with compositional variations observed using STEM-EDS. Additionally, atomic-scale imaging in combination with selected area diffraction analysis showed that the compositional variations directly correlated with changes in crystallographic structure at different stages of carbonate growth. Collectively, these results highlight the composition of anthropogenic carbon mineralization outcomes in basalts with unprecedented detail and provides critical insights into carbonate growth mechanisms. As such, the findings will help parameterize predictive models for future CO2 sequestration efforts in continental flood basalts. READ MORE.
Innovative Heat Recovery Process for Hydrothermal Liquefaction: Towards Sustainable Transportation Fuel Production
Monday, August 14
Presented by: Mike Thorson
Summary: As the need for sustainable energy sources intensifies, hydrothermal liquefaction (HTL) has emerged as a promising technique for converting wet waste materials into renewable bio-oil or "biocrude." However, challenges such as fouling and high equipment costs have hindered its commercial viability. In this presentation, we propose an innovative heat recovery process that adapts the low-fouling thermal hydrolysis approach to HTL, enhancing its potential for sustainable transportation fuel production. Our novel heat recovery process involves using flash steam generated through the sudden, adiabatic pressure reduction of the reactor product, eliminating the need for heat exchangers. By employing a staged pressure letdown process, higher steam temperatures can be achieved, maximizing the recovery of lower-temperature heat while reducing equipment wear and maintenance requirements. We will present the technical details of hydrothermal liquefaction, thermal hydrolysis, and our innovative heat recovery process. Additionally, we will discuss simulations assessing the use of steam as a means for energy recovery in HTL processes, comparing its performance with and without heat exchangers to evaluate the impact on operational temperature. READ MORE.
Towards Na-ion Battery Cathodes of High Performance and Material Sustainability
TUESday, August 15
Presented by: Xiaolin Li
Summary: Na-ion batteries with similar rocking chair working mechanism to Li-ion batteries are one of the promising alternative battery technologies for a sustainable and green electrical grid. Over the years, extensive research effort has been made on the development of low-cost and high-performance Na-ion battery electrode materials and understanding of the fading mechanisms. Layered transition metal oxides, polyanion materials, and Prussian-blue analogues have been developed. In my group at Pacific Northwest National Laboratory, we have focused on the development of P2 and O3 type layered metal oxide materials and understanding the fading mechanisms in bulk structures and at interfaces. Our recent generation of cathode materials using earth abundant elements can synergistically have low cost and deliver high specific capacity and long cycling stability. Here, we would like to present our recent progress towards the design of these Na-ion battery cathodes.
Towards Practical Aqueous Zinc Batteries
TUESday, August 15
Presented by: Xiaolin Li
Summary: Aqueous Zinc batteries because of the use of earth abundant materials and its stable supply chain are one of the promising battery technologies for grid-scale energy storage applications. However, the limited cycling stability because of dendrite formation of zinc anodes and poor reversibility of cathodes has greatly hampered its practical application. Recently, extensive research effort has been made on the development of rechargeable alkaline batteries and mild acid zinc ion batteries. Novel structured zinc anodes, nanostructured cathode materials and new electrolytes have been developed to improve the performance. Here, we would like to present our effort towards practical aqueous zinc batteries. Representative examples on zinc alloy anodes, organic cathode materials and novel binder selections will be discussed. READ MORE.
Designing Molecular Catalysts Based on Thermodynamic Parameters
TUESday, August 15
Presented by: Aaron Appel
Summary: The design of catalysts based on fundamental thermodynamic parameters has been demonstrated for the formation and utilization of fuels. By understanding the free energies for the transfer of protons, hydrogen atoms, and hydrides from metal hydride complexes and analogous species, our research group seeks to rationally design molecular catalysts for the interconversion of energy and fuels. The utilization of inexpensive substrates such as CO2 provides an opportunity for large-scale energy storage, and in particular, CO2 can potentially be converted to liquid fuels for use in transportation. For the hydrogenation of CO2, solvation has a substantial impact on the free energy for transfer of a hydride from a metal complex to CO2. Through recent studies, we have demonstrated that new catalyst systems can be designed through variation of solvent composition, rather than relying solely on synthetic modification. The impact of solvent composition on hydride transfer as well as catalytic activity will be presented. READ MORE.
Enabling Sustainable Aviation Fuel Production by Adsorptive Denitrogenation
TUESday, August 15
Presented by: Daniel Miki Santosa
Summary: The presence of nitrogen containing compounds (NCCs) has been associated with fuel instability for use in jet engines, emission of harmful pollutants into the environment during engine combustion and cause catalyst deactivation in hydroprocessing. These are detrimental to enabling sustainable aviation fuel (SAF) production from protein-bearing feedstocks such as algae, food, sludge, manure, which contain high amount of NCCs. Thus, strategies for reduction of high NCC’s containing fuels to below 2 ppm N is critical in meeting the anticipated ASTM D7566 requirement for SAF. Currently, NCCs are removed through the hydrodenitrogenation (HDN) process, which requires severe operating conditions along with significant H2 and energy consumption, resulting in yield lost due to significant cracking. Alternatively, adsorptive denitrogenation (ADN) is being investigated as a more energy efficient process that avoids the cracking and subsequent CO2 emission typical of HDN. To this end, high selectivity towards NCCs is achieved by controlling the surface functionalities such as surface acidity and porosity required to fully remove both basic and non-basic NCCs. Materials investigated included activated carbon, silica gel, zeolite, activated aluminum, and polymeric resins. Key parameters such as adsorption time, temperature, the adsorption isotherm, and the ratio of adsorbent to oil (A/O) on the removal of NCCs will be evaluated in both bench-scale batch and continuous system. In addition, effective adsorbent regeneration mechanisms will be investigated by leveraging current and earlier computational and experimental work. And finally, technoeconomic analysis will be performed to understand the economic impact or benefit of adapting adsorptive method to reduce cost and environmental impact. READ MORE.
Implementing IUPAC FAIRspec Principles in the Natural Products Magnetic Resonance Database (NP-MRD), an Operational Database of Spectroscopic Data
TUESday, August 15
Presented by: John Cort
Summary: The Natural Products Magnetic Resonance Database (NP-MRD, np-mrd.org) was established in 2020 with a goal of becoming the essential database and repository for all natural products and specialized metabolites NMR data. NP-MRD contains raw data (FIDs), derived data (e.g. chemical shift assignments and coupling constants) curated from the scientific literature or accompanying raw data, predicted data (from DFT calculations and machine learning), and simulated spectra. The database also provides structures, synonyms, search and other tools, links to other databases, and data deposition interfaces. Deposition of raw data is now required by some natural products journals as well as some funding agencies, and NP-MRD currently accepts raw data collected in support of novel structure elucidation or characterization of mixtures. Historically, raw (FID) NMR data has not been archived, and much of what has been acquired over the decades is likely irretrievably lost. NP-MRD can accept legacy raw data still residing on mass storage systems in individual laboratories. NP-MRD is committed to being a free, open, searchable, and connected database that complies with FAIR database principles. However, there is no prescribed recipe for FAIR compliance in most specific instances, including NMR spectroscopy, and particularly with regard to metadata, such as what form metadata should take and how much metadata should accompany raw NMR spectroscopic data of natural products in a database. Moreover, there are competing pressures to include as much metadata as possible, on the one hand, but not disincentivize data deposition on the other. This presentation describes a collaboration between NP-MRD and IUPAC which aims to define the minimum necessary and preferred metadata for natural products NMR spectroscopy and propose a standard for IUPAC FAIRSpec compliance that will facilitate straightforward data deposition, archival, and distribution of natural products NMR data and its associated molecular structures. READ MORE.
Syngas Derived Mixed Olefin Oligomerization: A Pathway Towards Sustainable Aviation Fuel
TUESday, August 15
Presented by: Udishnu Sanyal
Summary: Near term decarbonization of aviation sector requires the development of low-risk technologies that are already tied to existing industrial process and feedstock, thereby, enhances the potential for successful commercialization. Utilizing syngas as feedstock is appealing due to the existing infrastructure for its production and utilization in petrochemical industry. Although syngas predominantly obtained from coal, it can be produced via gasification from any ecologically disadvantages feedstocks such as municipal solid waste (MSW) and residual biomass that offers significant reduction in carbon footprint.1, 2 Although, various syngas-based technologies are available to produce jet range products, they are suffered by either lower selectivity to desired products or requirement of significant downstream separation. On the other hand, conversion of syngas to methanol followed by methanol to olefins (MTO) are already commercialized with high process yield (99% and 92% respectively). Thus, developing single step oligomerization process utilizing the olefin feedstock generated by MTO process is critical to develop end-to-end commercial pathway for producing SAF from syngas. Oligomerization of either C2 (ethylene) or C3+ (propylene, butene, pentene) olefins over heterogeneous catalysts are demonstrated in literature. However, there is significant technological gap exists for the co-oligomerization of C2 and C3+ olefins. The primary challenge lies in the difference in activity in reactivity and corresponding oligomerization pathways between C2 and C3+ olefins. Current C2 and C3+ based industrial processes use metal and acid catalyzed pathways respectively to achieve oligomerization. Herein we developed a catalyst system that integrates both these chemistries and efficiently co-oligomerize C2 and different C3+ olefins. Tuning the different process parameters along with the catalyst composition allowed us to obtain >90% conversion of both C2 and C3+ olefins and ~80% selectivity to jet range hydrocarbons. The efficiency of this process has also been demonstrated using olefin feedstock with different composition further suggests the technology developed herein could be adapted to various upstream process that produces olefins. The catalyst developed herein also demonstrated ~150 h stability on time on stream without any deactivation. READ MORE.
Cost Competitive and Long Duration Energy Storage: Na Batteries and Beyond
TUESday, August 15
Presented by: David Reed
Summary: Battery energy storage is essential to a reliable and resilient electrical grid, particularly with the integration of more and more renewable wind and solar energy into the grid. In this talk, we discuss efforts at Pacific Northwest National Laboratory on the development of sodium batteries and various other types of cost competitive battery technologies including redox flow batteries for long and short duration energy storage applications. We will discuss high level progress on the investigation of new battery materials and chemistries. The safe and reliable deployment of energy storage systems for the grid is of utmost importance and is thereby accelerating the development of new materials and chemistries for grid-scale energy storage applications. Battery reliability testing activities, protocols, and capabilities will be reviewed along with discussion of the new Grid Storage Launchpad at PNNL. READ MORE.
Thenoyltrifluoroacetone as an Extractant for Column Chromatography: Radiochemical Separations from Mixed Fission and Activation Product Samples
TUESday, August 15
Presented by: Evan Warzecha
Summary: Radiochemical analysis of short-lived isotopes depends greatly on the ability to separate interferences and the speed at which separations can be performed. New methods and materials are useful in improving separation times, which is particularly important for short-lived isotopes. A new chromatographic resin was created using the extractants 2-thenolyltrifluoroacetone and 1-octanol adhered to an inert support. In high acid concentrations the resin is highly selective for gold, iron, and gallium. This high selectivity allows for the rapid isolation of these analytes from complex matrices. Separations utilizing the new thenolyltrifluoroacetone-based resin have been demonstrated using irradiated uranium with added activation products. READ MORE.
Battery500 Consortium: Addressing Fundamental Challenges in Rechargeable Lithium Metal Batteries
WEDNESday, August 16
Presented by: Jie Xiao
Summary: To significantly boost the energy of the state-of-art lithium ion (Li-ion) batteries, one of the most effective approaches is to replace graphite anode with Li metal which is ultralight but energy concentrated. However, its thermodynamically instable nature in liquid electrolytes causes many well-known problems such as dendrite formation which plagues the implementation of the proposed technology. Although many approaches have been proposed to rescue Li metal anodes, most of the work are performed in small-scale coin cells and tested in the conditions drastically different from the reality. A full knowledge of Li metal activities at the cell level is lacking but extremely critical for the success of developing next-generation rechargeable Li metal batteries. This talk will review progress of Battery500 Program led by PNNL. A Li metal prototype pouch cell with 350 Wh/kg energy with 600 cycles will be demonstrated. The key fundamentals that enable the long-term cycling of Li metal anodes in pouch cells are discussed and the root causes of the poor cycling of realistic Li metal pouch cells have been revisited. A series of fundamentally new insights have been provided to inspire scientific innovations to tackle the real challenges of developing next-generation battery technologies. READ MORE.
Integrated CO2 Capture and Conversion: Role of Heterogeneous Catalysts for Selective Conversion of Captured CO2 to Methanol
WEDNESday, August 16
Presented by: Shazia Satter
Summary: An efficient and selective heterogeneous catalyst has been identified for the condensed-phase hydrogenation of captured CO2 in the presence of an advanced water-lean post-combustion capture solvent, N-(2-ethoxyethyl)-3-morpholinopropan-1-amine (2-EEMPA). This work describes the role of different types of heterogeneous catalysts for the conversion of captured CO2 to methanol. Various combination of metal/support catalysts were initially screened in a batch reactor to study the conversion of captured CO2. Effect of temperature, metal loading and hydrogen pressure were also studied on the conversion of CO2 and yield of the target product. The reaction was then carried out in a continuous flow system where the effect of space velocity along with temperature was evaluated. A range of characterizations were conducted on the fresh and spent catalyst to evaluate intermediates formed during the reaction. READ MORE.
Prediction of the 13C and 1H NMR Chemical Shifts of Ionic Liquids: A Machine Learning-Based Computational Framework
THURSday, August 17
Presented by: Difan Zhang
Summary: Promising applications of ionic liquids in various fields such as catalysis, electrochemical energy storage, chemical separation, and drug delivery have made them a topic of intensive research over the past decades. As an efficient approach to characterize the dynamic structures of ionic liquids, nuclear magnetic resonance (NMR) spectroscopy has been widely used in experiments and to inform theoretical modeling. However, accurate prediction of NMR chemical shifts at affordable computational cost remains a grand scientific challenge. In this work, we established an NMR dataset of ionic liquids by collecting data from previous publications and applied different machine-learning algorithms to predict 13C and 1H NMR chemical shifts. We also employed a transfer learning approach to evaluate the NMR chemical shifts of ionic liquids via learning from the NMR chemical shifts of general organic compounds. Our modeling suggests comparable prediction accuracy to other state-of-art machine learning models with the advantage that our input features and modeling parameters are more concise and chemically interpretable. This work provides an open-source tool to the ionic liquid research community to rapidly compute 13C and 1H NMR shifts relevant to a broad range of applications. READ MORE.
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