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NASA NTRS1992

Theoretical study of the design of a catalyst for para to ortho hydrogen conversion

The theory of Petzinger and Scalapino (1973) was thoroughly reviewed, and all of the basic equations for paramagnetic para to ortho hydrogen catalysis re-derived. There are only a few minor phase errors and errors of omission in the description of the theory. Three models (described by Petzinger and Scalapino) for the rate of para to ortho H2 catalysis were worked out, and uniform agreement obtained to within a constant factor of 2 pi. The analytical methods developed in the course of this study were then extended to two new models, which more adequately describe the process of surface catalysis including transfer of hydrogen molecules onto and off of the surface. All five equations for the para to ortho catalytic rate of conversion are described. The two new equations describe the catalytic rate for these models: H2 on the surface is a 2-D gas with lifetime tau; and H2 on the surface is a 2-D liquid undergoing Brownian motion (diffusion) with surface lifetime tau.

Coffman, Robert E.↗

NASA NTRS1993

Thermal coatings for titanium-aluminum alloys

Titanium aluminides and titanium alloys are candidate materials for use in hot structure and heat-shield components of hypersonic vehicles because of their good strength-to-weight characteristics at elevated temperature. However, in order to utilize their maximum temperature capability, they must be coated to resist oxidation and to have a high total remittance. Also, surface catalysis for recombination of dissociated species in the aerodynamic boundary layer must be minimized. Very thin chemical vapor deposition (CVD) coatings are attractive candidates for this application because of durability and very light weight. To demonstrate this concept, coatings of boron-silicon and aluminum-boron-silicon compositions were applied to the titanium-aluminides alpha2 (Ti-14Al-21Nb), super-alpha2 (Ti-14Al-23-Nb-2V), and gamma (Ti-33Al-6Nb-1Ta) and to the titanium alloy beta-21S (Ti-15Mo-3Al-3Nb-0.2Si). Coated specimens of each alloy were subjected to a set of simulated hypersonic vehicle environmental tests to determine their properties of oxidation resistance, surface catalysis, radiative emittance, and thermal shock resistance. Surface catalysis results should be viewed as relative performance only of the several coating-alloy combinations tested under the specific environmental conditions of the LaRC Hypersonic Materials Environmental Test System (HYMETS) arc-plasma-heated hypersonic wind tunnel. Tests were also conducted to evaluate the hydrogen transport properties of the coatings and any effects of the coating processing itself on fatigue life of the base alloys. Results are presented for three types of coatings, which are as follows: (1) a single layer boron silicon coating, (2) a single layer aluminum-boron-silicon coating, and (3) a multilayer coating consisting of an aluminum-boron-silicon sublayer with a boron-silicon outer layer.

Cunnington, George R.↗

DOE OSTI2023

Case Study: Calorimetry

This chapter presents the use of adsorption microcalorimetry to study acid-base catalysis over mixed metal oxides. Understanding the acid-base properties of catalysts is of paramount importance for steering product selectivity in a wide variety of catalytic industrial processes. In particular, catalytic conversion of biomass into biofuels and chemicals demands comprehensive understanding of the acid-base properties of the catalyst to selectively convert functional groups. Herein, the use of probe molecules to measure the strength and density of acid and basic sites on mixed metal oxide surfaces is introduced. Further, the challenges when characterizing mixed metal oxides, presenting surface reconstruction, are explained. An example displays how combining adsorption calorimetry with ab initio calculations explains the activation of a reactant on the surface of a mixed metal oxide. Acid-base catalysis over nanoshapes is studied to unveil that different nanoshapes lead to different extents of surface reconstruction, which ultimately affect acid-base catalysis. The use of steady-state isotopic transient kinetic analysis (SSITKA), in combination with adsorption microcalorimetry, unveils that surface reconstruction of a set of perovskites impacts the density of active sites to a greater extent than the intrinsic reactivity of the active site. At the end of this chapter, fundamental insights into catalyst transient behavior during isomerization of n-butane, and the reaction mechanism for conversion of 4-methylpentan-2-ol, are presented.

Polo Garzon, Felipe↗

DOE OSTI2022

Intraligand Charge Transfer Enables Visible‐Light‐Mediated Nickel‐Catalyzed Cross‐Coupling Reactions**

Abstract We demonstrate that several visible‐light‐mediated carbon−heteroatom cross‐coupling reactions can be carried out using a photoactive Ni II precatalyst that forms in situ from a nickel salt and a bipyridine ligand decorated with two carbazole groups (Ni(Czbpy)Cl 2 ). The activation of this precatalyst towards cross‐coupling reactions follows a hitherto undisclosed mechanism that is different from previously reported light‐responsive nickel complexes that undergo metal‐to‐ligand charge transfer. Theoretical and spectroscopic investigations revealed that irradiation of Ni(Czbpy)Cl 2 with visible light causes an initial intraligand charge transfer event that triggers productive catalysis. Ligand polymerization affords a porous, recyclable organic polymer for heterogeneous nickel catalysis of cross‐coupling reactions. The heterogeneous catalyst shows stable performance in a packed‐bed flow reactor during a week of continuous operation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Nontraditional Catalyst Supports in Surface Organometallic Chemistry

The field of Surface Organometallic Chemistry (SOMC) aims to blend the positive attributes of homogeneous and heterogeneous catalysis. Significant insight into heterogeneous systems has been gained over the years through the synthesis, characterization, and application of well-defined surface organometallic catalysts, predominantly supported on silica and alumina. Considerable research efforts have focused on the application of homogeneous methods to the synthesis and characterization of these systems. Homogeneous catalysis has thrived on its ability to electronically and sterically tune ligands to yield desired reactivity and selectivity. Efforts in SOMC, however, have only recently turned to harnessing the stereoelectronic diversity of potential inorganic support materials beyond silica and alumina in order to exert similar control on the reactivity of the organometallic active site. The support material is intrinsically linked to electronic structure and reactivity of heterogeneous organometallic systems in the same way that ligands exert control over homogeneous catalyst systems. The ability to tune the reactivity of heterogeneous catalysts by changing the support is of great value, and it is anticipated that this will represent an area of significant growth in the field. In this Perspective, the use and future of nontraditional catalyst supports, such as sulfated metal oxides, modified silicas, and redox active supports are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Remotely Bonded Bridging Dioxygen Ligands Enhance Hydrogen Transfer in a Silica-Supported Tetrairidium Cluster Catalyst

A longstanding challenge in catalysis by noble metals has been to understand the origin of enhancements of rates of hydrogen transfer that result from bonding of oxygen near metal sites. We investigated structurally well-defined catalysts consisting of supported tetrairidium carbonyl clusters with single-atom (apical iridium) catalytic sites for ethylene hydrogenation. Reaction of the clusters with ethylene and H 2 followed by O 2 led to the onset of catalytic activity as a terminal CO ligand at each apical Ir atom was removed and bridging dioxygen ligands replaced CO ligands at neighboring (basal-plane) sites. The presence of the dioxygen ligands caused a 6-fold increase in the catalytic reaction rate, which is explained by the electron-withdrawing capability induced by the bridging dioxygen ligands, consistent with the inference that reductive elimination is rate determining. Electronic structure calculations demonstrate an additional role of the dioxygen ligands, changing the mechanism of hydrogen transfer from that involving equatorial hydride ligands to that involving bridging hydride ligands. This mechanism is made evident by an inverse kinetic isotope effect observed in ethylene hydrogenation reactions with H 2 and, alternatively, with D 2 on the cluster incorporating the dioxygen ligands, and is a consequence of quasi-equilibrated hydrogen transfer in this catalyst. The same mechanism accounts for rate enhancements induced by the bridging dioxygen ligands for the catalytic reaction of H 2 with D 2 to give HD. Here, we posit that the mechanism involving bridging hydride ligands facilitated by oxygen ligands remote from the catalytic site may have some generality in catalysis by oxide-supported noble metals.

02 PETROLEUM↗

DOE OSTI2024

Mechanism of Ni-Catalyzed Photochemical Halogen Atom-Mediated C(sp 3 )–H Arylation

Within the context of Ni photoredox catalysis, halogen atom photoelimination from Ni has emerged as a fruitful strategy for enabling hydrogen atom transfer (HAT)-mediated C(sp 3 )–H functionalization. Despite the numerous synthetic transformations invoking this paradigm, a unified mechanistic hypothesis that is consistent with experimental findings on the catalytic systems and accounts for halogen radical formation and facile C(sp 2 )–C(sp 3 ) bond formation remains elusive. We employ kinetic analysis, organometallic synthesis, and computational investigations to decipher the mechanism of a prototypical Ni-catalyzed photochemical C(sp 3 )–H arylation reaction. Our findings revise the previous mechanistic proposals, first by examining the relevance of SET and EnT processes from Ni intermediates relevant to the HAT-based arylation reaction. Our investigation highlights the ability for blue light to promote efficient Ni–C(sp 2 ) bond homolysis from cationic Ni III and C(sp 2 )–C(sp 3 ) reductive elimination from bipyridine Ni II complexes. However interesting, the rates and selectivities of these processes do not account for the productive catalytic pathway. Instead, our studies support a mechanism that involves halogen atom evolution from in situ generated Ni II dihalide intermediates, radical capture by a Ni II (aryl)(halide) resting state, and key C–C bond formation from Ni III . Oxidative addition to Ni I , as opposed to Ni 0 , and rapid Ni III /Ni I comproportionation play key roles in this process. Furthermore, the findings presented herein offer fundamental insight into the reactivity of Ni in the broader context of catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Accessing monomers from lignin through carbon–carbon bond cleavage

Lignin, the heterogeneous aromatic macromolecule found in the cell walls of vascular plants, is an abundant feedstock for the production of biochemicals and biofuels. Here, many valorization schemes rely on lignin depolymerization, with decades of research focused on accessing monomers through C–O bond cleavage, given the abundance of β–O–4 bonds in lignin and the large number of available C–O bond cleavage strategies. Monomer yields are, however, invariably lower than desired, owing to the presence of recalcitrant C–C bonds whose selective cleavage remains a major challenge in catalysis. In this Review, we highlight lignin C–C cleavage reactions, including those of linkages arising from biosynthesis (β–1, β–5, β–β and 5–5) and industrial processing (5–CH 2 –5 and α–5). We examine multiple approaches to C–C cleavage, including homogeneous and heterogeneous catalysis, photocatalysis and biocatalysis, to identify promising strategies for further research and provide guidelines for definitive measurements of lignin C–C bond cleavage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

A heterogeneous iridium single-atom-site catalyst for highly regioselective carbenoid O–H bond insertion

Transition-metal-catalysed carbenoid insertion of hydroxyl groups represents a robust and versatile method to forge C–O bonds. Achieving site-selective functionalization of alcohols using this transformation has undoubted synthetic value but remains challenging. Here we report a strategy for selective carbenoid O–H insertion that exploits an engineered heterogeneous iridium single-atom catalyst, thus providing opportunities for organic transformations by merging material science and catalysis. This catalytic protocol delivers excellent selectivities (up to 99:1) for the functionalization of aliphatic over phenolic O–H bonds, whereas the analogous homogeneous catalyst, Ir(ttp)COCl (ttp = 5,10,15,20-tetra-p-tolylporphyrinato), provided modest preferences. Density-functional-theory calculations suggest that the site-selectivity derives from the lower oxidation state of the iridium metal centre in the heterogeneous catalyst and its impact on the absorption energies of the reactants. These results showcase an example of a heterogeneous single-atom catalyst providing superior site-selectivity and provide a complementary strategy to address challenges in catalysis for organic synthesis. [Figure not available: see fulltext.]

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

State of the Art in Thermal Catalytic Upgrading of Biomass and Biomass-Derived Intermediates

Biomass-derived energy sources represent a promising domestic route for fuel and chemical production, taking advantage of largely underutilized biological and waste resources. Heterogeneous catalysis plays a key role in these biomass conversion processes, as reflected by all American Society for Testing and Materials–approved pathways for producing sustainable aviation fuel proceeding through a catalytic step. This concise review seeks to establish the state of the art in thermal catalytic process development for various biomass-derived feedstocks and the current enabling capabilities that aid this development. Research needs are identified and described throughout the article, as further advancements in heterogeneous catalysis are required to improve the affordability and realize the full potential of biomass-derived products.

09 BIOMASS FUELS↗

DOE OSTI2026

Data for Photoenzymatic Stereoablative Enantioconvergence of γ-chiral Oximes via Hydrogen Atom Transfer

Producing enantioenriched molecules from racemic mixtures is essential for manufacturing. Traditional methods such as resolution, deracemization and enantioconvergent catalysis primarily involve separating or converting enantiomers without altering their structures, or functionalization of stereocentres at or proximal to functional groups. However, there are challenges in enantioselectively forging C–H bonds that are remote from functional groups via hydrogen atom transfer (HAT) with these methods. Here we introduce a strategy for the photoenzymatic stereoablative enantioconvergence of γ-chiral oximes using repurposed flavin-dependent ene-reductases. A photoinduced single-electron reduction of the γ-chiral oxime by an ene-reductase generates an iminyl radical, which then undergoes stereoablative 1,5-HAT at the γ-stereocentre. Subsequent chiral reconstruction through enzymatic HAT and spontaneous imine hydrolysis yields the γ-chiral ketone with high enantioselectivity. This work provides a robust method for remote stereoablative enantioconvergent HAT and broadens the synthetic utility of photobiocatalysis.

Bioproducts↗

DOE OSTI2024

Unveiling Highly Sensitive Active Site in Atomically Dispersed Gold Catalysts for Enhanced Ethanol Dehydrogenation

Developing a desirable ethanol dehydrogenation process necessitates a highly efficient and selective catalyst with low cost. Herein, we show that the “complex active site” consisting of atomically dispersed Au atoms with the neighboring oxygen vacancies (Vo) and undercoordinated cation on oxide supports can be prepared and display unique catalytic properties for ethanol dehydrogenation. The “complex active site” Au–Vo–Zr 3+ on Au 1 /ZrO 2 exhibits the highest H 2 production rate, with above 37,964 mol H 2 per mol Au per hour (385 g H 2 $\text{g}^{-1}_{\text{Au}} \text{h}^{–1}$) at 350 °C, which is 3.32, 2.94 and 15.0 times higher than Au 1 /CeO 2 , Au 1 /TiO 2 , and Au 1 /Al 2 O 3 , respectively. Combining experimental and theoretical studies, we demonstrate the structural sensitivity of these complex sites by assessing their selectivity and activity in ethanol dehydrogenation. Our study sheds new light on the design and development of cost-effective and highly efficient catalysts for ethanol dehydrogenation. Fundamentally, atomic-level catalyst design by colocalizing catalytically active metal atoms forming a structure-sensitive “complex site”, is a crucial way to advance from heterogeneous catalysis to molecular catalysis. Finally, our study advanced the understanding of the structure sensitivity of the active site in atomically dispersed catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Zeolite‐Based Catalysts for Conversion of Oxygenated Polymer Waste by Positron Annihilation

Positron Annihilation Lifetime Spectroscopy (PALS) has been employed to investigate the catalysts HZSM-5 and MESO−Y, which play a pivotal role in catalyzing and upgrading plastics, with a primary focus on oxygenated polymers, thereby transforming existing plastic materials into simpler, higher-quality value-added products. Here, in this study, PALS was systematically compared with other complementary analytical techniques. The research outcomes have successfully demonstrated the efficacy of PALS in elucidating the morphology and topology of zeolites at micro/meso-meter scales. The first experiment focuses on H-ZSM-5 zeolite subjected to treatments involving polyurethane and polypropylene. The second experiment delves into H-ZSM-5 zeolites with varying Si/Al ratios, both before and after conversion. The third experiment investigates Y zeolites that are surfactant templated to induce meso-porosity, examining their fresh state as well as their post-conversion condition. The PALS analysis was supplemented by BET (Brunauer-Emmett-Teller) analysis and NMR (Nuclear Magnetic Resonance) spectroscopies. Notably, PALS exhibits superior sensitivity, at the sub-nanometer scale, suggesting its potential as a preferred complementary method for catalysis studies. In conclusion, the integration of PALS into the repertoire of analytical tools enhances our understanding of catalyst behavior and catalytic processes, offering valuable insights for the advancement of plastic recycling and catalysis research.

32 - ENERGY CONSERVATION, CONSUMPTION, AND UTILIZA↗

DOE OSTI2022

Recent progress toward catalyst properties, performance, and prediction with data-driven methods

Herein, data-driven approaches are currently renovating the field of heterogenous catalysis and open a door to advance catalyst design. Their success depends heavily on the synergy among machine learning (ML), experimental data, and quantum mechanical (QM) calculations. In this brief survey of recent progress, we examine catalysis informatics in the context of (1) ML-aided catalyst characterizations, (2) knowledge extractions from experimental data, (3) predictions of catalytic properties and constructions of reaction networks, and (4) ML-enabled large-scale QM simulations. An outlook on the current challenges of this rapidly evolving field is also provided.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Catalytic materials for lithium-sulfur batteries: mechanisms, design strategies and future perspective

Lithium-sulfur batteries (LSBs) are attractive candidates for post-lithium-ion battery technologies because of their ultrahigh theoretical energy density and low cost of active cathode materials. However, the commercialization of LSBs remains extremely challenging primarily due to poor cycling performance and safety concerns, which are inherently caused by low conductivity of S 8 and Li 2 S, severe polysulfide shuttling, and high polarization by solid Li 2 S 2 /Li 2 S deposition. Catalytic materials could facilitate the large-scale practical application of LSBs by overcoming all these challenges. In this review, we investigate the sulfur species evolution in LSBs and explore the roles of catalytic materials in charge/discharge processes, highlighting the catalysis of solid S 8 to liquid polysulfides and solid Li 2 S 2 to Li 2 S. Furthermore, we offer systematic strategies from atomic to macro levels, including defect engineering, morphology engineering and catalyst compositing, to enhance catalysis efficiency in terms of sulfur supercooling, fast charge transfer, thiosulfate generation, disulfide bond cleavage, tuneable Li 2 S growth and Li 2 S decomposition enhancement. Finally, the design and availability of the proposed catalytic materials will further advance LSB technology from coin cells and pouch cells to the subsequent commercialization scale.

25 ENERGY STORAGE↗

DOE OSTI2025

H-cluster Intermediates and Catalytic Properties of Clostridium pasteurianum [FeFe]-Hydrogenase III

[FeFe]-Hydrogenases are structurally diverse enzymes that catalyze reversible H2 activation at a catalytic cofactor or H-cluster. The H-cluster is a [4Fe-4S] cubane linked by a cysteine thiolate to a diiron subsite containing unique CO, CN-, and dithiomethylamine ligands. The established H-cluster resting state of [4Fe-4S]2+-[FeII-FeI], or Hox, functions in H2 binding and oxidation, or by proton-coupled reduction initiates H2 evolution. In contrast, in Clostridium pasteurianum [FeFe]-hydrogenase III (CpIII) the resting state of the H-cluster is fully oxidized, [4Fe-4S]2+-[FeII-FeII], or Hox+1. To begin to understand if Hox+1 has a role in the mechanism of CpIII, we determined the spectroscopic and redox properties of CpIII H-cluster states under catalytic conditions. CpIII poised in Hox+1 and either equilibrated under 1 atm of H2 or reduced with sodium dithionite, resulted in a mixture of reduced states including Hox (Em8 = -407 mV), Htrans-like [4Fe-4S]+-[FeII-FeII] (Em8 = -418 mV), Hred [4Fe-4S]+-[FeII-FeI], and HredH+ [4Fe-4S]2+-[FeI-FeI] (Em8 = -455-480 mV). Under H2 the population of the Htrans-like state was >20-fold higher than Hox, implicating a role in CpIII catalysis. Unlike other enzymes, there was no spectral evidence of fully reduced states, such as HsredH+ ([4Fe-4S]+-[FeI-FeI]) or Hhyd ([4Fe-4S]+-[FeII-FeII]-H-). Thus, while the H-cluster states of CpIII encompass most of the catalytic intermediates, it is either unable to form HsredH+ and Hhyd, or these states are highly destabilized in CpIII. Thus, these results demonstrate that catalytic intermediates of reduced CpIII differ from the typical intermediates of other catalytic [FeFe]-hydrogenases and may explain the catalytic preference for H2 production.

08 HYDROGEN↗

DOE OSTI2022

In Situ EXAFS-Based Nanothermometry of Heterodimer Nanocrystals under Induction Heating

The ability to heat nanocrystalline materials through magnetic induction has been used in the fields of catalysis, biomedical sciences, and polymer degradation. However, the working temperature to which the inductively coupled material rises is still poorly understood. Herein, we use extended X-ray absorption fine structure spectroscopy in conjunction with thermal imaging to improve the understanding of heating in inductively coupled systems. After extraction of the Debye–Waller factor from the spectroscopy, we obtain the temperature of inductively heated nanocrystals from the correlated Debye model. We combine carbon-supported iron oxide nanocrystals as induction heating agents with platinum nanocrystals as thermal probes. By testing these nanocrystal species as both unattached nanocrystals and heterodimers, we report that nanostructured systems show a significant temperature difference of up to 73.60 °C when compared to their local support environment. Furthermore, this result has implications for inductively heated catalysis, magnetic hyperthermia for targeted cell death, and polymer synthesis.

09 BIOMASS FUELS↗

DOE OSTI2025

Single-Walled Zeolitic Nanotube–Poly(oxazoline) Nanocomposites as Heterogeneous Catalysts for Acid–Base Cascade Reactions

Zeolites with a unique, 1-dimensional form factor were recently discovered − zeolite nanotubes (ZNTs). Here we describe the synthesis and characterization of NaH-ZNTpoly( oxazoline) composites targeting liquid-phase acid−base cascade catalysis. NaH-ZNT, a one-dimensional zeolite analogue with mesoporosity (3−4 nm) associated with nanotubes and inherent Brønsted acid sites associated with the microporous zeolite domains, is functionalized with poly(oxazoline)-based triblock copolymers with varying molecular weights (3−17 kDa). The composites are characterized using N2 sorption, STEM, FTIR, and elemental analysis, confirming successful grafting and preservation of the zeolite nanotube structure. The composites’ catalytic performance is evaluated through separate acid and base reactions, followed by a combined cascade of a deacetalization−Knoevenagel condensation for the synthesis of chalcone compounds. High initial reaction rates are demonstrated, but modest overall cascade product formation rates are observed, attributed to interactions between Brønsted acid sites and base amine groups that occur in the polymer-grafted systems. Physical mixtures of NaH-ZNT-SH and poly(oxazoline)s, lacking covalent linkages between ZNT and the polymer, support this supposition. This work demonstrates the potential of NaH-ZNT-poly(oxazoline) composites for liquid-phase cascade catalysis for synthesizing compounds of potential medicinal interest, highlighting the benefits of the grafting-to approach as well as the need for further optimization of the catalytic performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗