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Results for “heterogeneous catalysis”

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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At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Nanoconfinement and mass transport in metal–organic frameworks

The ubiquity of metal–organic frameworks in recent scientific literature underscores their highly versatile nature. MOFs have been developed for use in a wide array of applications, including: sensors, catalysis, separations, drug delivery, and electrochemical processes. Often overlooked in the discussion of MOF-based materials is the mass transport of guest molecules within the pores and channels. Given the wide distribution of pore sizes, linker functionalization, and crystal sizes, molecular diffusion within MOFs can be highly dependent on the MOF-guest system. In this paper, we discuss the major factors that govern the mass transport of molecules through MOFs at both the intracrystalline and intercrystalline scale; provide an overview of the experimental and computational methods used to measure guest diffusivity within MOFs; and highlight the relevance of mass transfer in the applications of MOFs in electrochemical systems, separations, and heterogeneous catalysis.

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

A Perspective on Multiscale Modeling of Explicit Solvation-Enabled Simulations of Catalysis at Liquid–Solid Interfaces

Catalysis at liquid-solid interfaces is profoundly influenced by the interfacial solvent structure, which affects catalytic activity, selectivity, and reaction pathways. This perspective discusses state-of-the-art multiscale modeling methods that integrate quantum mechanics and molecular mechanics approaches to apply explicit solvent molecules to capture these interfacial phenomena. Specifically, the construction of multiscale models, the importance of capturing the interfacial solvent structure, and the computational strategies used to achieve this are explored, and the challenges in balancing chemical accuracy with computational expense are highlighted. Additionally, this perspective addresses the limitations of current methods. Opportunities for integrating machine learning are proposed. Here, by advancing the efficiency and user friendliness of multiscale modeling, it is argued that deeper insights into heterogeneous catalysis in liquid phases can be provided, which will ultimately contribute to the development of more efficient catalytic processes.

Ab initio molecular dynamics↗
DOE OSTI2024

Synthesis of aviation biofuel precursors from biomass-derived ketones: Substrate adsorption configuration-catalytic activity

The production of aviation biofuel precursors from biomass-derived ketones by heterogeneous catalysis has been hindered by the low catalytic activity. Herein, a series of Cu-doped metal oxide catalysts were prepared for the conversion of biomass-derived ketones to aviation biofuel precursors. Solvent-free cyclopentanone conversion via aldol condensation reached 91.1 % over Cu/Al 2 O 3 with 100 % selectivity toward dimer and trimer oxygenated species, all of which are aviation biofuel precursors. This catalyst primarily contains Cu 2 O and Cu nanoparticles which are uniformly dispersed across the Al 2 O 3 surface. From in situ DRIFTS and DFT results, the incorporation of Cu species onto Al 2 O 3 not only increased the diversity of Lewis acidic sites, but also changed the adsorption of C = O groups, which lead to the increased aldol condensation activity of Cu/Al 2 O 3 . In conclusion, this study provides insight on the design of heterogeneous catalysts suitable for the solvent-free synthesis of aviation biofuel precursors from biomass-derived ketones.

Adsorption configuration↗
DOE OSTI2024

Mechanistic study of direct coupling of CO 2 and C 2 H 4 over atomically dispersed metal at graphene edges

Direct coupling of CO 2 and ethylene (hereinafter DCCE) to acrylic acid is valuable for valorizing CO 2 to manufacture acrylate-derived products. However, previous studies in DCCE have been limited on molecular catalysts with challenges in improving catalytic performance. In this work, we employed density functional theory calculations and ab initio molecular dynamics simulations to investigate the heterogeneous catalysis of DCCE over atomically dispersed metal centers at nitrogen-doped zigzag edge of graphene. Based on competitive adsorption and structural stability, Mo, Cr, V, Ru, and Ni active sites are chosen to explore the reaction kinetics. Here, we find that the activation barriers are determined by the charge redistribution at transition states, which explains the trend of activity for the C-C coupling and the hydrogen transfer, two key steps in DCCE. Furthermore, we show that the intramolecular hydrogen transfer (rate-limiting step) is hindered due to the lack of local coordinate at the active sites. We thus propose to use co-adsorbed water as a “proton-exchanger” following a water-assisted route, and show that the activation barriers are reduced over all metal centers. Particularly, water promotes the hydrogen transfer over metals with strong CO 2 -ethylene co-activation and facile C-C coupling kinetics, which could be considered promising for DCCE. In both mechanisms, the stability of metallactone intermediate can be used to predict the catalytic activity. It is anticipated that the insights from this work can provide guidelines for mimicking well-defined multifunctional active sites in molecular catalysts to design heterogeneous catalysts for such C-C coupling, which advances catalytic utilization of CO 2 .

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

Modulating Chemical Environments of Metal–Organic Framework-Supported Molybdenum(VI) Catalysts for Insights into the Structure–Activity Relationship in Cyclohexene Epoxidation

Solid supports are crucial in heterogeneous catalysis due to their profound effects on catalytic activity and selectivity. However, elucidating the specific effects arising from such supports remains challenging. We selected a series of metal–organic frameworks (MOFs) with 8-connected Zr 6 nodes as supports to deposit molybdenum(VI) onto to study the effects of pore environment and topology on the resulting Mo-supported catalysts. As characterized by X-ray absorption spectroscopy (XAS) and single-crystal X-ray diffraction (SCXRD), we modulated the chemical environments of the deposited Mo species. For Mo-NU-1000, the Mo species monodentately bound to the Zr 6 nodes were anchored in the microporous c-pore, but for Mo-NU-1008 they were bound in the mesopore of Mo-NU-1008. Both monodentate and bidentate modes were found in the mesopore of Mo-NU-1200. Cyclohexene epoxidation with H 2 O 2 was probed to evaluate the support effect on catalytic activity and to unveil the resulting structure–activity relationships. SCXRD and XAS studies demonstrated the atomically precise structural differences of the Mo binding motifs over the course of cyclohexene epoxidation. No apparent structural change was observed for Mo-NU-1000, whereas the monodentate mode of Mo species in Mo-NU-1008 and the monodentate and bidentate Mo species in Mo-NU-1200 evolved to a new bidentate mode bound between two adjacent oxygen atoms from the Zr 6 node. This work demonstrates the great advantage of using MOF supports for constructing heterogeneous catalysts with modulated chemical environments of an active species and elucidating structure–activity relationships in the resulting reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Synthesis and Structure–Activity Characterization of a Single-Site MoO 2 Catalytic Center Anchored on Reduced Graphene Oxide

Molecularly derived single-site heterogeneous catalysts can bridge the understanding and performance gaps between conventional homogeneous and heterogeneous catalysis, guiding the rational design of next-generation catalysts. While impressive advances have been made with well-defined oxide supports, the structural complexity of other supports and the nature of the grafted surface species present an intriguing challenge. In this study, single-site Mo(=O) 2 species grafted onto reduced graphene oxide (rGO/MoO 2 ) are characterized by XPS, DRIFTS, powder XRD, N 2 physisorption, NH 3 -TPD, aqueous contact angle, active site poisoning assay, Mo EXAFS, model compound single-crystal XRD, DFT, and catalytic performance. NH 3 -TPD reveals that the anchored MoO 2 moiety is not strongly acidic, while Mo 3d 5/2 XPS assigns the oxidation state as Mo(VI), and XRD shows little rGO periodicity change on MoO 2 grafting. Contact angle analysis shows that MoO 2 grafting consumes rGO surface polar groups, yielding a more hydrophobic surface. The rGO/MoO 2 DRIFTS assigns features at 959 and 927 cm –1 to the symmetric and antisymmetric Mo=O stretching modes, respectively, of an isolated cis-(O=Mo=O) moiety, in agreement with DFT computation. Moreover, the Mo EXAFS rGO/MoO 2 structural data are consistent with isolated (C–O) 2– Mo(=O) 2 species having two Mo=O bonds and two Mo–O bonds at distances of 1.69(3) and 1.90(3) Å, respectively. rGO/MoO 2 is also more active than the previously reported AC/MoO 2 catalyst, with reductive carbonyl coupling TOFs approaching 1.81 × 10 3 h –1 . rGO/MoO 2 is environmentally robust and multiply recyclable with 69 ± 2% of the Mo sites catalytically significant. Altogether, rGO/MoO 2 is a structurally well-defined and versatile single-site Mo(VI) dioxo heterogeneous catalytic system.

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

Activity of Silica-Alumina for the Conversion of Polyethylene into Tunable Aromatics Below Pyrolytic Temperatures

Plastic waste is a mounting problem that lacks global strategy, largely due to inadequate recycling capabilities. One alternative gaining traction in the heterogeneous catalysis community is the upcycling of polyolefins into value-added products, such as hydrogen-free conversion to alkylaromatic compounds over Pt/Al 2 O 3 . Here, we examined the activity of nominally metal-free, mesoporous silica-alumina mixed oxide materials (SiO 2 –Al 2 O 3 ) for the conversion of polyethylene into aromatic compounds at temperatures of and below 280 °C. Yields with the silica-alumina catalysts are comparable to those obtained over Pt(1 wt %)/Al 2 O 3 under identical conditions, and product selectivity can be tuned by altering reaction conditions or the acid site density of the SiO 2 –Al 2 O 3 . Notably, the fraction of polyaromatic products increases with the Brønsted acid site density of the catalyst, as does the degree of polymer deconstruction. These catalysts can be reused without regeneration, and their activity improves with each recycling event, producing soluble product yields up to 83%. Preliminary work on the mechanism of the reaction suggests that acid sites are responsible for initiating depolymerization and aromatization reactions, in analogy to previous work in the literature. Finally, this work showcases the activity of SiO 2 –Al 2 O 3 for polyolefin deconstruction/aromatization at subpyrolytic temperatures and lays the foundation for future studies involving solid acid and bifunctional catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Manipulating Surface Termination of Perovskite Manganate for Oxygen Activation

For ABO 3 perovskite oxides, one of the key issues limiting their utilization in heterogeneous catalysis is the dominant presence of catalytically inactive A-site cations at the surface. The engineering of B-site terminated perovskites is considered as an effective method to address this issue, especially when dealing with Mn/Co-based perovskite catalysts. However, to date, such a strategy has not been fully successful and remains a major challenge in the field. Herein, a Mn-terminated La 0.45 Sr 0.45 MnO 3 (B-LSM) is successfully synthesized via a one-pot hydrothermal method, in which low-valence Mn ions partially occupy the A site to form the active Mn-excess phase. Additionally, experimental results and theoretical calculations reveal that the presence of the surface Mn termination in B-LSM optimizes the hybrid orbitals of Mn 3d-O 2p and promotes the activation of surface lattice oxygen, where the pristine inert lattice O 2- is evolved into active and stable lattice O 2-x . Such structural optimization significantly reduces the activation energy barriers on going from O 2 ⁻ species to important intermediate O - species during O 2 activation. Moreover, this results in good stability and Pt-like activity for the B-LSM during CO oxidation. This work offers a new chemical route for the design of advanced perovskite-type oxides possessing novel functions.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Atomically Precise Single Metal Oxide Cluster Catalyst with Oxygen–Controlled Activity

Single cluster catalysts (SCCs) consisting of atomically precise metal nanoclusters dispersed on supports represent a new frontier of heterogeneous catalysis. However, the ability to synthesize SCCs with high loading and to precisely introduce non-metal atoms to further tune their catalytic activity and reaction scope of SCCs have been longstanding challenges. In this work, a new interface confinement strategy is developed for the synthesis of a high density of atomically precise Ru oxide nanoclusters (Ru 3 O 2 ) on reduced graphene oxide (rGO), attributed to the suppression of diffusion-induced metal cluster aggregation. Ru 3 O 2 /rGO exhibits a significantly enhanced activity for oxidative dehydrogenation of 1,2,3,4-tetrahydroquinoline (THQ) to quinoline with a high yield (≈86%) and selectivity (≈99%), superior to Ru and RuO 2 nanoparticles, and homogeneous single/multiple-site Ru catalysts. In addition, Ru 3 O 2 /rGO is also capable of efficiently catalyzing more complex oxidative reactions involving three reactants. The theoretical calculations reveal that the presence of two oxygen atoms in the Ru 3 O 2 motif not only leads to a weak hydrogen bonding interaction between the THQ reactant and the active site, but also dramatically depletes the density of states near the Fermi level, which is attributed to the increased positive valence state of Ru and the enhanced oxidative activity of the Ru 3 O 2 cluster for hydrogen abstraction.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Zero-Valent Palladium Single-Atoms Catalysts Confined in Black Phosphorus for Efficient Semi-Hydrogenation

Single-atom catalysts (SACs) represent a new frontier in heterogeneous catalysis due to their remarkable catalytic properties and maximized atomic utilization. However, single atoms often bond to the support with polarized electron density and thus exhibit a high valence state, limiting their catalytic scopes in many chemical transformations. In this study, it is demonstrated that 2D black phosphorus (BP) acts as giant phosphorus (P) ligand to confine a high density of single atoms (e.g., Pd 1 , Pt 1 ) via atomic layer deposition. Unlike other 2D materials, BP with relatively low electronegativity and buckled structure favors the strong confinement of robust zero-valent palladium SACs in the vacancy site. Metallic Pd 1 /BP SAC shows a highly selective semi-hydrogenation of phenylacetylene toward styrene, distinct from metallic Pd nanoparticles that facilitate the formation of fully hydrogenated products. Density functional theory calculations reveal that Pd atom forms covalent-like bonding with adjacent P atoms, wherein H atoms tend to adsorb, aiding the dissociative adsorption of H 2 . Zero-valent Pd in the confined space favors a larger energy gain for the synthesis of partially hydrogenated product over the fully hydrogenated one. This work provides a new route toward the synthesis of zero-valent SACs on BP for organic transformations.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Photoinduced Electron and Energy Transfer Pathways and Photocatalytic Mechanisms in Hybrid Plasmonic Photocatalysis

Hybrid plasmonic nanostructures are built on plasmonic metalnanostructures surrounded by catalytic metals or metal oxides. We report that recent studies have shown that hybrid plasmonic nanocatalysts can concurrently utilize thermal energy and photon stimuli and exhibit high catalytic activity, selectivity, and stability that are not attainable in conventional purely thermally activated catalytic processes. The hybrid plasmonic photocatalytic approach has recently emerged as an attractive concept for the conversion of solar energy into chemical energy, the distributed synthesis of valuable chemicals such as ammonia with little to no requirement of external heating, and the development of coke-resistant and selective catalytic processes. The field of hybrid plasmonic photocatalysis has grown tremendously in the last decade. In this review article, the advantages of visible-light-augmented hybrid plasmonic photocatalysis over conventional pure thermally activated heterogeneous catalysis are discussed. Fundamental insights are provided into photocatalytic mechanisms by which the photoexcited charge carriers (electrons and holes) are formed and transferred to adsorbates triggering chemical transformations on the surface of hybrid plasmonic nanocatalysts. Computational modeling used for predicting and understanding the photocatalytic activity and selectivity on hybrid plasmonic nanostructures is also reviewed. The review closes with a discussion of the current challenges, new opportunities, and future outlook for hybrid plasmonic photocatalysis.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Effects of penta‐coordinated Al 3+ sites and Ni defective sites on Ni/ Al 2 O 3 for CO methanation

Abstract Engineering sophisticated structure of Al 2 O 3 and controlling the structure of counterpart metal active sites remain challenges to achieve a high catalytic‐performance in heterogeneous catalysis. Herein, we present a confinement strategy to stabilize homogeneous Ni by penta‐coordinated Al 3+ anchoring sites in Al 2 O 3 . This approach is involved in using a metal–organic framework as host to load Ni 2+ ions, by the aim of producing a confined Ni/Al 2 O 3 catalyst after a standard calcination. Metal–support interaction between Ni and Al 2 O 3 was tailored to be medium to avoid the formation of inactive NiAl 2 O 4 , which favors the generation of more available Ni active sites accessible to the reactants. The resultant Ni/Al 2 O 3 exhibited superior catalytic performance in comparison with the control Ni/Al 2 O 3 in CO methanation owing to the presence of defective sites on sufficient Ni 0 surface. Furthermore, the presence of oxygen vacancies on Al 2 O 3 and hydrogen spillover contributed toward excellent coke resistance properties in the reaction.

Engineering↗
DOE OSTI2023

C−N Coupling through Hydroaminoalkylation on a Single‐Atom Rh Heterogeneous Catalyst

Abstract C−N coupling is significant for the synthesis of fine chemicals toward various applications. Hydroaminoalkylation of olefins is a tandem reaction of C−N coupling involving first the formation of an aldehyde through hydroformylation of an olefin and then the production of amine through reductive amination of the aldehyde. Here we report a stable, supported catalyst of singly dispersed Rh 1 atoms anchored on TiO 2 (P25) nanoparticles designated as Rh 1 /P25. Its high activity for C−N coupling was demonstrated by six hydroaminoalkylations of olefins and amines with selectivity of higher than 90% for producing tertiary amines. The singly dispersed Rh 1 O 4 on P25 exhibit activity and selectivity for hydroaminoalkylation comparable or even higher than some reported molecular catalysts. In contrast to molecular catalysts, the Rh‐based single‐atom Rh heterogeneous catalysis (Rh 1 /P25) can be readily separated from reactants and products, reused for multiple runs of hydroaminoalkylation, and recycled with a low cost.

Li, Yuting↗
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 OSTI2023

C–N Coupling through Hydroaminoalkylation on a Single–Atom Rh Heterogeneous Catalyst

C–N coupling is significant for the synthesis of fine chemicals toward various applications. Hydroaminoalkylation of olefins is a tandem reaction of C–N coupling involving first the formation of an aldehyde through hydroformylation of an olefin and then the production of amine through reductive amination of the aldehyde. Here we report a stable, supported catalyst of singly dispersed Rh 1 atoms anchored on TiO 2 (P25) nanoparticles designated as Rh 1 /P25. Its high activity for C–N coupling was demonstrated by six hydroaminoalkylations of olefins and amines with selectivity of higher than 90% for producing tertiary amines. Furthermore, the singly dispersed Rh 1 O 4 on P25 exhibit activity and selectivity for hydroaminoalkylation comparable or even higher than some reported molecular catalysts. In contrast to molecular catalysts, the Rh-based single-atom Rh heterogeneous catalysis (Rh 1 /P25) can be readily separated from reactants and products, reused for multiple runs of hydroaminoalkylation, and recycled with a low cost.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗