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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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DOE OSTI2023

Covalent organic frameworks in heterogeneous catalysis: recent advances and future perspective

Catalysis is ubiquitous in ~90% of chemical manufacturing processes and contributes up to 35% of global GDP. Hence, the development of advanced catalytic systems is of utmost importance for academia, industry, and government. Covalent organic frameworks (COFs) are a rapidly emerging class of crystalline porous materials that precisely integrate organic monomer units into extended periodic networks, offering a propitious platform for heterogeneous catalysis due to salient structural merits of ultralow density, high crystallinity, permanent porosity, structural tunability, functional diversity, and synthetic versatility. The past decade has witnessed an upsurge of interest in COFs for heterogeneous catalysis and this trend is expected to continue. In this review, we briefly introduce COF chemistry concerning the design principles, growth mechanism, and cutting-edge advances in structural evolution, linkage chemistry, and facile synthesis. Further, we then scrutinize four leading design strategies for COF catalysts, namely pristine COFs with catalytically active backbones, COFs as hosts for the inclusion of catalytic species, COF-based heterostructures, and COF-derived carbons for thermo-, photo-, and electrocatalysis. Next, we overview the most recent advances (mainly from 2020 to 2023) of COFs in heterogeneous catalysis, along with their fundamentals and advantages. Finally, we outline the current challenges and offer our perspectives on the future directions of COFs for heterogeneous catalysis.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Reproducibility, Replicability, and Research Quality in Homogeneous Catalysis

Researchers from all sectors of homogeneous catalysis convened in response to concerns regarding reproducibility in science to analyze the issue and provide recommendations. In addition to an in- person workshop, the group engaged the broader homogeneous catalysis community through a webinar series and virtually during the workshop. Results of the project affirm that homogeneous catalysis is not in a reproducibility crisis, as evidenced by the field’s current and past contributions to society that have led to economic growth and advances in a range of industries from agriculture to consumer goods to human health. However, it is not uncommon for researchers to encounter obstacles related to reproducibility. Ensuring reproducibility remains the responsibility of the community, both in current work and in training future researchers. This report is intended to engage key stakeholders, including disciplinary societies, publishers, employers, research leaders, and researchers, in practices that maximize reproducible homogeneous catalysis and ensure continued innovation and translatable discoveries. Recommendations made herein are also framed to be applicable beyond homogeneous catalysis, empowering the broader chemical if not scientific community.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Unleashing the Power of Knowledge Extraction from Scientific Literature in Catalysis

Valuable knowledge of catalysis is often hidden in a large amount of scientific literature. There is an urgent need to extract useful knowledge to facilitate scientific discovery. Here this work takes the first step toward the goal in the field of catalysis. Specifically, we construct the first information extraction benchmark data set that covers the field of catalysis and also develop a general extraction framework that can accurately extract catalysis-related entities from scientific literature with 90% extraction accuracy. We further demonstrate the feasibility of leveraging the extracted knowledge to help users better access relevant information in catalysis through an entity-aware search engine and a correlation analysis system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

The Relationship Between Catalyst and Solvent in Hydrogenation via Condensed Phase Heterogeneous Catalysis

To understand a system is to understand its components and their sum. Cascading interactions between catalyst, solvent, and reagent create a complex web of influences when heterogeneous catalysis meets the condensed phase. Due to the importance of heterogeneous catalysis in chemical manufacturing, and the present and growing potential of condensed phase chemistries, the understanding of these interactions is of paramount importance. To develop condensed phase heterogeneous catalysis, the field needs to develop understanding of the role of solvent in heterogeneous catalytic hydrogenation. While no small feat, fields such as biofuel and petroleum refining have established certain applicable generalities that can bridge the knowledge gap in emerging technologies such as integrated carbon capture and conversion to materials (IC 3 M). In this review, we thoughtfully probe the current paradigm of condensed phase catalysis by challenging the idea that catalyst and solvent are independent reaction design choices. Challenges such as lack of experimental stability studies and poor resolution on our conceptualization of the condensed phase environment are discussed. Parameters such as viscosity and the dielectric constant, and their role on reaction activity and stability are explored. Knowledge gained from established biomass and petroleum processes is discussed and used to anticipate behavior in novel processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Decoupling of catalysis and transition state analog binding from mutations throughout a phosphatase revealed by high-throughput enzymology

Using high-throughput microfluidic enzyme kinetics (HT-MEK), we measured over 9,000 inhibition curves detailing impacts of 1,004 single-site mutations throughout the alkaline phosphatase PafA on binding affinity for two transition state analogs (TSAs), vanadate and tungstate. As predicted by catalytic models invoking transition state complementary, mutations to active site and active-site-contacting residues had highly similar impacts on catalysis and TSA binding. Unexpectedly, most mutations to more distal residues that reduced catalysis had little or no impact on TSA binding and many even increased tungstate affinity. These disparate effects can be accounted for by a model in which distal mutations alter the enzyme’s conformational landscape, increasing the occupancy of microstates that are catalytically less effective but better able to accommodate larger transition state analogs. In support of this ensemble model, glycine substitutions (rather than valine) were more likely to increase tungstate affinity (but not more likely to impact catalysis), presumably due to increased conformational flexibility that allows previously disfavored microstates to increase in occupancy. These results indicate that residues throughout an enzyme provide specificity for the transition state and discriminate against analogs that are larger only by tenths of an Ångström. Thus, engineering enzymes that rival the most powerful natural enzymes will likely require consideration of distal residues that shape the enzyme’s conformational landscape and fine-tune active-site residues. Biologically, the evolution of extensive communication between the active site and remote residues to aid catalysis may have provided the foundation for allostery to make it a highly evolvable trait.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Dynamic Interconversion of Metal Active Site Ensembles in Zeolite Catalysis

Catalysis science is founded on understanding the structure, number, and reactivity of active sites. Kinetic models that consider active sites to be static and noninteracting entities are routinely successful in describing the behavior of heterogeneous catalysts. Yet, active site ensembles often restructure in response to their external environment and even during steady-state catalytic turnover, sometimes requiring non-mean-field kinetic treatments to describe distance-dependent interactions among sites. Such behavior is being recognized more frequently in modern catalysis research, with the advent of experimental methods to quantify turnover rates with increasing precision, an expanding arsenal of operando characterization tools, and computational descriptions of atomic structure and motion at chemical potentials and timescales increasingly relevant to reaction conditions. This review focuses on dynamic changes to metal active site ensembles on zeolite supports, which are silica-based crystalline materials substituted with Al that generate binding sites for isolated and low-nuclearity metal site ensembles. Metal sites can become solvated and mobilized during reaction, facilitating interactions among sites that change their nuclearity and function. Such intersite communication can be regulated by the zeolite support, resulting in non-single-site and potentially non-mean-field kinetic behavior arising from mechanisms of catalytic action that combine elements of those canonically associated with homogeneous and heterogeneous catalysis. Here, we discuss recent literature examples that document dynamic active site behavior in metal-zeolites and outline methodologies to identify and interpret such behavior. We conclude with our outlook on future research directions to develop this evolving branch of catalysis science and harness it for practical applications.

operando characterization↗
DOE OSTI2024

Institute for Catalysis in Energy Processes (ICEP) (Final Report)

The Institute for Catalysis in Energy Processes (ICEP) was a multi-PI program located at the Northwestern University Center for Catalysis and Surface Science from 2006-2024. Over several renewal cycles and several organizing themes, ICEP addressed fundamental questions in catalysis science. In turn, the scientific questions addressed were directly relevant to the efficient use of the nation’s resources to produce fuels and commodity chemicals, harness alternate energy sources for chemical reactions such as light or electricity, reduce emissions and waste, and minimize the impact of our use of plastics. Selective oxidation, (oxidative) dehydrogenation, deNOx, CO 2 reduction, hydrogen release, polymer decomposition / depolymerization, and many other reactions of intense interest to the US Department of Energy were studied in the center. Major ICEP strengths were in catalyst synthesis, in measurements that elucidated catalyst properties, in reaction mechanisms and kinetics, and in predictive theory and modeling. ICEP researchers were often the inventors or developers of materials and methods that were brought to bear on the Institute’s catalytic systems. Key characterization tools advanced through this project included resonance Raman and related techniques, sum frequency generation, and X-ray standing wave spectroscopy. Center members relied extensively on computational tools such as density functional theory and microkinetic modeling to fully investigate catalyst structures and catalytic mechanisms. ICEP researchers were early developers of atomic layer deposition (ALD) for catalyst synthesis and were early pioneers of metal organic frameworks for catalysis. ICEP innovations are found in areas of intense research such as single-atom catalysts, catalytic deconstruction of plastics, and catalytic MOFs, to name a few. Research areas initiated by ICEP indirectly led to DOE EFRCs, startup companies, and other achievements. Over its 18 years of existence, ICEP involved two different PIs (Stair and Notestein) and 24 senior investigators across several academic disciplines at Northwestern University. There were tight collaborations with Argonne National Laboratory, including specialized equipment and experiments permanently located there. The center supported ~400 person-years of effort by graduate students and postdocs, either directly through DOE support or indirectly by leveraging independent support provided to the trainees, e.g. through the NSF GRFP or internal fellowships. The project resulted in 328 manuscripts and numerous conference presentations.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Interpretable Deep Learning for Advancing Field-Enhanced Catalysis

This DOE Early Career project developed a physics-informed, interpretable AI-and-modeling framework to understand and exploit electric-field effects in heterogeneous catalysis, with ammonia cracking and synthesis as a representative pathway. The team built and validated methods to map local electric fields on metal surfaces and nanoparticles, showing that low-coordination features (tips/edges/corners) can concentrate fields by several-fold relative to flat facets. Using DFT-generated datasets, the project created physics-guided machine learning models that rapidly predict local electric fields and field-dependent adsorption energetics with near-DFT accuracy while reducing computational cost by orders of magnitude. These predictions were integrated with microkinetic modeling to quantify how field-dipole interactions reshape reaction energetics and mechanisms, enabling large increases in predicted catalytic rates and substantial reductions in operating temperature under favorable field conditions. To accelerate discovery of earth-abundant catalysts, the project combined interpretable ML screening (with electronic-structure descriptors identified as key drivers) with a generative inverse-design workflow based on diffusion models and physics constraints. The resulting closed-loop approach, linking simulation, mechanistic modeling, and AI, provides reusable tools and datasets for designing catalysts and operating conditions in field-enhanced catalysis, with broad relevance to electrostatic catalysis, plasma catalysis, electrocatalysis, and other energy-related chemical transformations.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2026

Grand Challenges and Opportunities in Stimulated Dynamic and Resonant Catalysis

Traditional heterogeneous catalysis is constrained by kinetic and thermodynamic limits, such as the Sabatier principle and reaction equilibrium. Dynamic and resonant catalysts hold promise to overcome these limitations by actively oscillating a catalyst’s physical or electronic structure at the time scale of the catalytic cycle, allowing programmable control over reaction pathways, and leading to improved rate and selectivity. External stimuli such as temperature swing, mechanical strain, electric charge, and light can perturb catalyst surfaces in different ways, altering adsorbate coverage, binding energies, and transition states beyond what steady-state catalysis allows. This work surveys the current state of dynamic catalysis, introduces the concept of “ stimulando ” characterization for observing transient dynamics, and outlines key modeling, mechanistic, and benchmarking strategies to advance the field toward improved chemical transformation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Integrating the Fields of Catalysis: Active Site Engineering in Metal Cluster, Metal Organic Framework and Metal Single Site

Research evolved using nanoparticles synthesized and characterized under reaction conditions opened the door to study all three fields of catalysis: heterogeneous, homogenous, and enzyme. Fundamental studies of catalytic reactions ranging from hydrogenation to understand Fischer-Tropsch synthesis and isomerization ultimately led to the integration of three fields of catalysis. Our recent work on bridging heterogeneous, homogenous, and enzymatic catalysis was present including functionalization of dendrimer encapsulated metal clusters surface for lactonization, active site engineering in metal organic framework catalysts for methanol production and oligomerization, and single site catalyst for hydrogen production. We envision that the combination of active site engineering and unifying fields of catalysis could be applied to solve practical issues of science-based technology and develop new fields useful in energy research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Ensembles of Metastable States Govern Heterogeneous Catalysis on Dynamic Interfaces

Heterogeneous catalysis is at the heart of chemical industry. Being able to tune and design efficient catalysts for processes of interest is of an utmost importance, and for this, the molecular-level understanding of heterogeneous catalysts is the first step, and indeed a prime focus of the modern catalysis research. For a long time, a single most thermodynamically stable structure of the catalytic interface attained in reaction conditions had been envisioned as the reactive phase. However, some catalytic interfaces continue to undergo structural dynamics in the steady state, triggered by high temperatures, pressures, and binding and changing reagents. Among particularly dynamic interfaces are such widely-used catalysts as crystalline and amorphous surfaced supporting (sub-)nano metallic clusters. Recently, it became clear that this dynamic fluxionality causes the supported clusters to populate many distinct structural and stoichiometric states in catalytic conditions. Hence, the catalytic interface should be viewed as an evolving statistical ensemble of many (not one) structures. As such, every member in the ensemble contributes to the properties of the catalyst differently, and in proportion to its probability to be populated. This new notion flips the established paradigm and calls for new theory, modeling approaches, operando measurements, and updated design strategies. The statistical ensemble nature of surface-supported sub-nano cluster catalysts can be exemplified by oxide-supported and adsorbate-covered Pt, Pd, Cu, CuPd clusters, catalytic toward oxidative and non-oxidative dehydrogenation. They have access to a variety of 3D and quasi-2D shapes. The compositions of their thermal ensembles are dependent on the cluster size, leading to size-specific catalytic activities and the famous “every atom counts” phenomenon. The support and adsorbates affect catalyst structures, and state of the reacting species causes the ensemble to change in every reaction intermediate. The most stable member of the ensemble dominates the thermodynamic properties of the corresponding intermediate, whereas the kinetics can be determined by more active but less populated metastable catalyst states, and that suggests that many earlier studies might have overlooked the actual active sites. Both effects depend on the relative time-scales of catalyst restructuring and reaction dynamics. The catalyst may routinely operate off-equilibrium. Ensemble phenomena lead to surprising exceptions from established rules of catalysis, such as scaling relations, and Arrhenius behavior. Catalyst deactivation is also an ensemble property, and its extent of mitigation can be predicted through the new paradigm. These findings were enabled by advances in theory, such as global optimization and subsequent utilization of multiple local minima, and pathways sampling, as well as operando catalyst characterization. The fact that the per-site and per-species resolution is needed for the description and predicting of catalyst properties gives theory the central role in catalysis research, as most experiments provide ensemble-average information and cannot detect the crucial minority species that may be responsible for the catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

The 2020 plasma catalysis roadmap

Abstract Plasma catalysis is gaining increasing interest for various gas conversion applications, such as CO 2 conversion into value-added chemicals and fuels, CH 4 activation into hydrogen, higher hydrocarbons or oxygenates, and NH 3 synthesis. Other applications are already more established, such as for air pollution control, e.g. volatile organic compound remediation, particulate matter and NO x removal. In addition, plasma is also very promising for catalyst synthesis and treatment. Plasma catalysis clearly has benefits over ‘conventional’ catalysis, as outlined in the Introduction. However, a better insight into the underlying physical and chemical processes is crucial. This can be obtained by experiments applying diagnostics, studying both the chemical processes at the catalyst surface and the physicochemical mechanisms of plasma-catalyst interactions, as well as by computer modeling. The key challenge is to design cost-effective, highly active and stable catalysts tailored to the plasma environment. Therefore, insight from thermal catalysis as well as electro- and photocatalysis is crucial. All these aspects are covered in this Roadmap paper, written by specialists in their field, presenting the state-of-the-art, the current and future challenges, as well as the advances in science and technology needed to meet these challenges.

Bogaerts, Annemie (ORCID:0000000198756460)↗
DOE OSTI2024

Changes in an enzyme ensemble during catalysis observed by high-resolution XFEL crystallography

Enzymes populate ensembles of structures necessary for catalysis that are difficult to experimentally characterize. We use time-resolved mix-and-inject serial crystallography at an x-ray free electron laser to observe catalysis in a designed mutant isocyanide hydratase (ICH) enzyme that enhances sampling of important minor conformations. The active site exists in a mixture of conformations, and formation of the thioimidate intermediate selects for catalytically competent substates. The influence of cysteine ionization on the ICH ensemble is validated by determining structures of the enzyme at multiple pH values. Large molecular dynamics simulations in crystallo and time-resolved electron density maps show that Asp 17 ionizes during catalysis and causes conformational changes that propagate across the dimer, permitting water to enter the active site for intermediate hydrolysis. ICH exhibits a tight coupling between ionization of active site residues and catalysis-activated protein motions, exemplifying a mechanism of electrostatic control of enzyme dynamics.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Observing one-divalent-metal-ion-dependent and histidine-promoted His-Me family I-PpoI nuclease catalysis in crystallo

Metal-ion-dependent nucleases play crucial roles in cellular defense and biotechnological applications. Time-resolved crystallography has resolved catalytic details of metal-ion-dependent DNA hydrolysis and synthesis, uncovering the essential roles of multiple metal ions during catalysis. The histidine-metal (His-Me) superfamily nucleases are renowned for binding one divalent metal ion and requiring a conserved histidine to promote catalysis. Many His-Me family nucleases, including homing endonucleases and Cas9 nuclease, have been adapted for biotechnological and biomedical applications. However, it remains unclear how the single metal ion in His-Me nucleases, together with the histidine, promotes water deprotonation, nucleophilic attack, and phosphodiester bond breakage. By observing DNA hydrolysis in crystallo with His-Me I-PpoI nuclease as a model system, we proved that only one divalent metal ion is required during its catalysis. Moreover, we uncovered several possible deprotonation pathways for the nucleophilic water. Interestingly, binding of the single metal ion and water deprotonation are concerted during catalysis. Our results reveal catalytic details of His-Me nucleases, which is distinct from multi-metal-ion-dependent DNA polymerases and nucleases.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Can Li: A Career in Catalysis

Prof. Can Li is distinguished for his seminal achievements in fundamental and applied researches in catalysis, especially in advancing the characterization of catalysts and catalytic reactions related to solar energy conversion and fine chemical synthesis. The scope of his research is wide ranging, and he is leading some of the fields. This account highlights his major scientific achievements in advancing the fundamental sciences of characterizing catalysts and understanding the mechanisms of catalytic reactions by developing in situ spectroscopic techniques (e.g., infrared (IR), ultraviolet (UV), Raman, space- and time-resolved spectroscopies and photoelectric imaging), and applying the obtained knowledge in the rational design and synthesis of catalysts for practical applications in photocatalytic, electrocatalytic and photoelectrocatalytic water splitting and CO 2 reduction, chiral synthesis in nanoreactors and ultradeep desulfurization of fuels, and fine chemical synthesis. In particular, his demonstration of the kiloton scale solar fuel production project will be introduced as a successful model for converting fundamental science into practical and impactful applications to convert CO 2 and water into solar fuels. This account also highlights his services to the catalysis communities and international collaborations for promoting catalysis science worldwide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Evaluating the Origins of Aerobic Oxidation Catalysis with TAM-3, a MOF with Accessible Co(II) Sites and Large Pores

Metal-organic frameworks (MOFs) are attractive platforms that merge concepts of homogeneous and heterogeneous catalysis. Catalyst design and optimization are enabled by an array of synthetic methods that offer independent control over the local chemical structure of lattice-embedded metal ions (i.e., ligand identity and geometry) and the long-range materials properties (i.e., porosity). Establishing the origin of catalytic activity in MOF-promoted reactions remains a significant challenge: The relative rates of catalyst turnover and substrate diffusion dictate the extent to which interstitial sites are accessible and operational in catalysis. To minimize the contributions of surface sites in catalysis, materials with large pore dimensions are often sought, however, the impact of pore expansion on the origins of catalytic activity is similarly challenging to establish. Here, we describe TAM-3, a Co(II) based MOF with accessible metal sites supported by a facially coordinating tris-tetrazole ligand set. TAM-3 features large channel-like pores (17 × 23 Å) and promotes aerobic C−H oxidation and olefin epoxidation. Using a set of simple kinetics experiments, based on the analysis of kinetic isotope effects and olefin oxidation diastereoselectivities, we demonstrate that despite the large pores, interstitial metal ions do not significantly contribute to the observed substrate oxidation. This study highlights the importance of conducting kinetic experiments to assess the origin of apparent catalytic activity with MOFs and the challenge of harnessing reactive oxidants with microporous catalyst materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Impact of Surface Enhanced Raman Spectroscopy in Catalysis

Catalysis stands as an indispensable cornerstone of modern society, underpinning the production of over 80% of manufactured goods and driving over 90% of industrial chemical processes. As the demand for more efficient and sustainable processes grows, better catalysts are needed. Understanding the working principles of catalysts is key, and over the last 50 years, surface-enhanced Raman Spectroscopy (SERS) has become essential. Discovered in 1974, SERS has evolved into a mature and powerful analytical tool, transforming the way in which we detect molecules across disciplines. In catalysis, SERS has enabled insights into dynamic surface phenomena, facilitating the monitoring of the catalyst structure, adsorbate interactions, and reaction kinetics at very high spatial and temporal resolutions. This review explores the achievements as well as the future potential of SERS in the field of catalysis and energy conversion, thereby highlighting its role in advancing these critical areas of research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Data as a Key Resource in Catalysis: A Community Account

The deployment of artificial intelligence (AI) is transforming the scientific fields central to interdisciplinary catalysis research. By enabling more effective use of data, AI (including simpler machine learning and data science tools) holds great promise for accelerating discoveries. However, progress has so far been modest, largely due to the lack of standardized, machine-readable, and openly shared catalysis data. This perspective, accounting for community insights emerging at conferences, analyses the underlying reasons for these challenges and proposes solutions to a future whereFAIR data management becomes an integral part of research in catalysis. In the short-term, we deem that mandatory FAIR data depositing prior to scientific publications along with consensualized top-down guidelines on data sharing powered by ease-to-use tools can make the necessary step change happen to catalyse data as key resource in our community.

36 - MATERIALS SCIENCE↗