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Results for “Heterogenous 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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Probing the Structure and Dynamics of Fluid Mixtures in Porous Materials Through Ultrafast Vibrational Spectro-Microscopy and Many-Body Molecular Dynamics

This research program focused on the characterization of both molecular structure and dynamics of aqueous solutions in various metal-organic frameworks (MOFs) and organic polymers that have recently been proposed for applications in water treatment technologies. This was accomplished by integrating ultrafast vibrational spectroscopy and microscopy, which are sensitive to local environments, molecular orientation, and dynamical couplings, with many-body molecular dynamics (MB-MD) simulations, which enable realistic modeling of aqueous systems and porous materials under different thermodynamic conditions. Our studies allowed for identifying the physical mechanisms and characterizing the underlying molecular interactions between water and host materials that determine the adsorption and transport processes of water in various MOFs and β-cyclodextrin polymers – prototypical examples of porous materials and polymers, that have recently been proposed for technological applications in water purification. By combining bulk- and surface-sensitive, spatially resolved ultrafast vibrational spectroscopy with MB-MD simulations, it was possible to gain broad insight into the structure and mobility of water under heterogeneous confinement at various length scales. In particular, measurements of surface- and bulk-sensitive vibrational spectra at single crystal level, integrated with MB-MD simulations were used to characterize domain-specific, structure–binding affinity relationships. Besides providing specific information about the behavior of aqueous solutions in prototypical MOFs and organic polymers for potential applications in water treatment technologies, our studies also provided fundamental insights into the properties of aqueous solutions in confined heterogeneous environments, which have broad implications in many areas, ranging from heterogeneous catalysis to oil recovery, ion transport processes, and reaction-diffusion processes in crowded systems.

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

Spin-selective photocatalysis and quantum transport using ab initio density-matrix dynamics

The overarching goal of this research program is to quantitatively predict out-of-equilibrium quantum dynamics and transport with electrons and spin degrees of freedom coupled to phonons, photons, defects and liquid environments, specifically targeting spin-selective chemistry. Spin polarized carriers, which can be generated at room temperature by circularly-polarized light, provide unique opportunities for creating new reaction pathways and increasing selectivity towards specific pathways. If realized, this can substantially increase the level of reaction control possible in the field of heterogeneous catalysis. Spin, a quantum mechanical entity without a classical counterpart, requires quantum dynamics. Capturing both coherent and incoherent dynamics and accurate correlation of spins, electrons and phonon environments are essential to quantitative description of generation, relaxation and transport, as well as chemical reaction of spin-polarized carriers in molecules and materials promising for spin-photocatalysis.

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

A Review of Microwave-Assisted Synthesis-Based Approaches to Reduce Pd-Content in Catalysts

This review article focuses on the latest advances in the synthesis of inorganic nano-catalysts using microwave heating, which has progressed significantly since its initial implementation in the mid-1980s. Over the years, nanoparticles (NPs), which inherently offer better surface accessibility for heterogeneous catalysis, have been synthesized using a wide array of heating methods. Microwave heating is one such method and employs a unique heating mechanism that can have several benefits for catalysis. When compared to conventional form of heating which relies on inter-layer mixing via convection, microwave heating operates through the chemical polarity in the target chemicals leading to an “inside-out” mode of heating. This heating mechanism is more targeted and therefore results in rapid synthesis of catalytically active NPs. Platinum group metals (PGM) have classically been the focus of nano-catalysis; however, recent efforts have also applied non-PGM group metals with the goals of lower costs, and ideally, improved catalytic reactivity and durability. This is especially of interest with respect to Pd because of its current historically high cost. Investigations into these new materials have primarily focused on new/improved synthetic methods and catalytic compositions, but it is important to note that these approaches must also be economic and scalable to attain practical relevance. With this overarching goal in mind, this review summarizes notable recent findings with a focus on Pd-dilution and microwave heating in a chronological fashion.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Three-Dimensional Imaging and Quantification of Gas Storativity in Nanoporous Media via X-rays Computed Tomography

This study provides the engineering science underpinnings for improved characterization and quantification of the interplay of gases with kerogen and minerals in shale. Natural nanoporous media such as shale (i.e., mudstone) often present with low permeability and dual porosity, making them difficult to characterize given the complex structural and chemical features across multiple scales. These structures give nanoporous solids a large surface area for gas to sorb. In oil and gas applications, full understanding of these media and their sorption characteristics are critical for evaluating gas reserves, flow, and storage for enhanced recovery and CO 2 sequestration potential. Other applications include CO 2 capture from industrial plants, hydrogen storage on sorbent surfaces, and heterogeneous catalysis in ammonia synthesis. Therefore, high-resolution experimental procedures are demanded to better understand the gas–solid behavior. In this study, CT imaging was applied on the sub-millimeter scale to shale samples (Eagle Ford and Wolfcamp) to improve quantitative agreement between CT-derived and pulse decay (mass balance) derived results. Improved CT imaging formulations are presented that better match mass balance results, highlighting the significance of gas sorption in complex nanoporous media. The proposed CT routine implemented on the Eagle Ford sample demonstrated a 17% error reduction (22% to 5%) when compared to the conventional CT procedure. These observations are consistent in the Wolfcamp sample, emphasizing the reliability of this technique for broader implementation of digital adsorption studies in nanoporous geomaterials.

42 ENGINEERING↗
DOE OSTI2020

Nanoporous Catalysts for Biomass Conversion

Transforming plant biomass to biofuel and chemicals has become a global effort as results of increasing fuel demand but diminishing fossil-based energy preservation and rising concerns of climate and environmental impact. Various conversion routes involving thermochemical and biological conversions have been established and well-studied. Heterogeneous catalysis is playing a critical role in the biomass conversion and, with some unique catalytic properties, nanoporous catalysts have been extensively utilized in catalytic process of biomass conversion and exhibited exciting catalytic performance. This chapter will be devoted to nanoporous catalysts used in biomass conversion. It will start with a brief introduction of current biomass conversion technologies and then a detailed review of the application of various nanoporous materials in a large diversity of catalytic reactions in biomass conversion. The nanoporous materials include zeolites and zeotypes, metal-organic frameworks (MOFs), nanoporous carbons and carbon nitrides, nanoporous oxides, hydroxides and complex oxide forms, porous organic polymers (POPs), and porous metals.

Shi, Hui↗
DOE OSTI2021

Pt Catalysts Modified with Manganese Oxide through Atomic Layer Deposition for CO Oxidation: Establishing a Coating Layer above or below Pt

The effect of atomic layer deposition (ALD) of manganese oxide on CO oxidation over Pt/Al2O3 is investigated. Two types of catalysts with a thin MnOx layer coated on or under the Pt nanoparticles (NPs) are prepared, and a pristine Pt/Al2O3 catalyst is used as a reference sample. The addition of the ALD layers improves the catalyst durability and both catalysts with MnOx exhibit greater stability after thermal aging at 1073-K. Besides, MnOx promotes CO oxidation through active Pt-MnOx interfacial sites, showing a reaction rate up to 35-fold faster than that of unmodified Pt. Interestingly, the CO adsorption ability of the Pt catalysts with MnOx overcoats is greatly suppressed after the high-temperature calcination; however, the reaction rate of CO oxidation is still excellent. This phenomenon is because the uniformly covered MnOx with two atomic layers diminishes the exposed Pt surface, but the reaction near the Pt-MnOx interfacial site still occurs. Our results guide the effective use of ALD, which is actively applied to heterogeneous catalysis, and provide a novel direction to control metal-assisted interactions.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Pynta v. 1.0.0

SAND2021-1508 O The Pynta code is designed to automatically characterize chemical reactions relevant to heterogeneous catalysis in which gas-phase molecules interact with crystal facets of a solid. It organizes multiple quantum chemistry calculations to carry out this task. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.

Gierada, Maciej↗
DOE OSTI2025

Single-atom Zr promoter boosts oxygen activation on ceria-supported Pt catalysts

Activation of surface lattice oxygen and chemisorbed oxygen on catalyst surfaces constitutes a pivotal step in heterogeneous oxidative catalysis. Herein, we report a strategy for enhancing oxygen activation by rational design of catalysts with single-atom promoters. Single-site Zr species in CeO 2 (Zr 1 -CeO 2 ) are synthesized using the atom-trapping method. The Zr 1 -CeO 2 -supported Pt catalyst exhibits enhanced catalytic performance over the CeO 2 -supported Pt catalyst in the oxidation of CO, C 3 H 8 , and C 3 H 6 , achieving significantly lower T 50 values (temperature required to reach 50% conversion). This enhanced catalytic activity is attributed to the formation of an asymmetric Zr 1 -O-Pt 1 structure, which favors the activation of the adjacent surface lattice oxygen and chemisorbed molecular oxygen. This work exemplifies that incorporating single-site atoms into oxide support facilitates oxygen activation, providing new insights into the role of atomically dispersed promoters in heterogeneous catalysis.

Science & Technology - Other Topics↗
DOE OSTI2020

Heterogeneous Nature of Electrocatalytic CO/CO 2 Reduction by Cobalt Phthalocyanines

Molecular catalysts for electrochemical CO 2 reduction have traditionally been studied in their dissolved states. However, the heterogenization of molecular catalysts has the potential to deliver much higher reaction rates and enable the reduction of CO 2 by more than two electrons. In light of the recently discovered reactivity of heterogenized cobalt phthalocyanine molecules to catalyze CO 2 reduction into methanol, direct comparison is needed to uncover the distinct catalytic activity and selectivity in homogeneous catalysis versus heterogeneous catalysis. In this work, soluble cobalt phthalocyanine derivatives were synthesized, and their catalytic activities in the homogeneous solutions were evaluated. The results show that the observed catalytic activities for both CO 2 -to-CO and CO-to-methanol conversions in aqueous solutions of the cobalt phthalocyanines are predominantly heterogeneous in nature through the adsorbed species on the electrode.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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

Regioselective Gas–Phase n –Butane Transfer Dehydrogenation via Silica–Supported Pincer–Iridium Complexes

The production of olefins via on-purpose dehydrogenation of alkanes allows for a more efficient, selective and lower cost alternative to processes such as steam cracking. Silica-supported pincer-iridium complexes of the form [(≡SiO– R4 POCOP)Ir(CO)] ( R4 POCOP=κ 3 -C 6 H 3 -2,6-(OPR 2 ) 2 ) are effective for acceptorless alkane dehydrogenation, and have been shown stable up to 300 °C. However, while solution-phase analogues of such species have demonstrated high regioselectivity for terminal olefin production under transfer dehydrogenation conditions at or below 240 °C, in open systems at 300 °C, regioselectivity under acceptorless dehydrogenation conditions is consistently low. In this work, complexes [(≡SiO– tBu4 POCOP)Ir(CO)] (1) and [(≡SiO– iPr4 PCP)Ir(CO)] (2) were synthesized via immobilization of molecular precursors. These complexes were used for gas-phase butane transfer dehydrogenation using increasingly sterically demanding olefins, resulting in observed selectivities of up to 77 %. Finally, the results indicate that the active site is conserved upon immobilization.

02 PETROLEUM↗
DOE OSTI2025

Tungsten-dioxo single-site heterogeneous catalyst on carbon: synthesis, structure, and catalysis

This study investigates the application of a novel third-row metal, tungsten, to carbon-supported single-site metal-oxo heterogeneous catalysis. Tungsten is a green and earth-abundant metal, but an unexplored candidate in this role. The carbon (AC = activated carbon)-supported tungsten dioxo complex, AC/WO 2 was prepared via grafting of (DME)WO 2 Cl 2 (DME = 1,2-dimethoxyethane) onto high-surface-area activated carbon. AC/WO 2 was fully characterized by ICP-OES, XPS, EXAFS, XANES, SMART-EM, and DFT. W 4d 7/2 XPS and W L III -Edge XANES assign the oxidation state as W(VI), while EXAFS reveals two W=O double and two W–O single bonds at distances of 1.73 and 1.92 Å, respectively. These data align well with DFT computational results, supporting the structure as Carbon(–μ-O–) 2 M(=O) 2 . SMART-EM verifies that single W(VI) catalytic sites are bonded in an out-of-plane manner. The catalytic performance of air- and water-stable AC/WO 2 is compared to that of AC/MoO 2 . AC/WO 2 is more active and selective than the molybdenum analog in mediating alcohol dehydration of various substrates, and is recyclable. Notably, AC/WO 2 is an effective and recyclable catalyst for primary aliphatic alcohol dehydration and forms no dehydrogenation side products in contrast to AC/MoO 2 . However, AC/WO 2 is less effective in epoxidation and PET depolymerization. Overall, this work demonstrates the potential of carbon-supported third row metals for future studies.

02 PETROLEUM↗
DOE OSTI2022

Sulfated Zirconium Metal–Organic Frameworks as Well-Defined Supports for Enhancing Organometallic Catalysis

Understanding heterogeneous catalysts is a challenging pursuit due to surface site nonuniformity and aperiodicity in traditionally-used materials. One example is sulfated metal oxides, which function as highly-active catalysts and as supports for organometallic complexes. These applications are due to traits such as acidity, ability to act as a weakly coordinating ligand, and aptitude for promoting transformations via radical cation intermediates. Research is ongoing about the structural features of sulfated metal oxides that imbue the aforementioned properties, such as sulfate geometry and coordination. To better understand these materials, metal–organic frameworks (MOFs) have been targeted as structurally-defined analogs. Composed of inorganic nodes and organic linkers, MOFs possess features such as high porosity and crystallinity, which make them attractive for mechanistic studies of heterogeneous catalysts. In this work, a Zr 6 -based MOF NU-1000 is sulfated and characterized using atomically-precise techniques such as single crystal X-ray diffraction (SCXRD) in addition to diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Here, the dynamic nature of the sulfate binding motif is found to transition from monodentate, to bidentate, to tridentate depending on the degree of hydration, as supported by density functional theory (DFT) calculations. Heightened Brønsted acidity compared to the parent MOF was observed upon sulfation, and probed through trimethylphosphine oxide (TMPO) physisorption, ammonia sorption, in-situ ammonia DRIFTS, and DFT studies. With the support structure benchmarked, an organoiridium complex was chemisorbed onto the sulfated MOF node and the efficacy of this supported catalyst was demonstrated for stoichiometric and catalytic activation of benzene-d6 and toluene with structure-activity relationships derived.

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

Leveraging Exchange Kinetics for the Synthesis of Atomically Precise Porous Catalysts

Metal-organic frameworks (MOFs) have attracted significant attention as porous catalyst platforms due to the synthetic modularity of these materials and the diversity of lattice-confined catalytic active sites that are readily embedded within periodic crystalline frameworks. MOFs offer platforms to heterogenize molecular catalysts, stabilize novel coordination motifs, and leverage confinement effects in catalysis. Crystallinity allows diffraction-based methods to be employed in the characterization of these catalysts. Access to crystalline MOFs typically requires reversible construction of the metal-ligand (M-L) bonds that connect the SBUs, which provides a mechanism to anneal defects during crystallization. While the required M-L bond reversibility is often promoted by synthesis at elevated temperature, access to crystalline materials based on either transition metals with characteristic slow exchange kinetics or highly basic donor ligands remains a synthetic challenge. Here in this paper, we highlight synthetic strategies that leverage M-L exchange kinetics to access MOFs based on kinetically inert ions and extensions of these strategies to the assembly of atomically precise multimetallic materials.

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

Dynamic and reversible transformations of subnanometre-sized palladium on ceria for efficient methane removal

Reversibly adjusting the active structures of supported metal catalysts in response to dynamic working conditions has long been pursued. Here we report the reaction-environment-modulated transformations of subnanometre-sized Pd on CeO 2 for efficient methane removal, leveraging the reaction environments at different stages of automotive exhaust aftertreatment. During the cold start of vehicles, inactive Pd 1 single atoms are readily transformed into PdO $x$ subnanometre clusters by CO even at room temperature with excess O 2 , resulting in boosted low-temperature CH 4 oxidation. At elevated temperatures, dispersion of PdO $x$ cluster into Pd 1 against metal sintering renders outstanding hydrothermal stability to the catalyst, to be activated during the next vehicle start. Combined experimental and computational studies elucidate the dynamically evolved Pd speciation on CeO 2 at an atomic level. In conclusion, modulating the reversible nature of supported metals helps overcome the long-existing trade-off between low-temperature activity and high-temperature stability, also providing a new paradigm for designing intelligent catalysts that brings single-atom/cluster catalysts closer to real applications.

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

Site heterogeneity and broad surface-binding isotherms in modern catalysis: Building intuition beyond the Sabatier principle

Learning the science of heterogeneous catalysis and electrocatalysis always starts with the simple case of a flat, uniform surface with an ideal adsorbate. It has of course been recognized for a century that real catalysts are more complicated. For the increasingly complex catalysts of the 21st century, this Perspective argues that surface heterogeneity and non-ideal binding isotherms are central features, and their implications need to be incorporated in current thinking. A variety of systems are described herein where catalyst complexity leads to broad, non-Langmuirian surface isotherms for the binding of hydrogen atoms – and this occurs even for ideal, flat Pt(111) surfaces. Modern catalysis employs nanoscale materials whose surfaces have substantial step, edge, corner, impurity, and other defect sites, and they increasingly have both metallic and non-metallic elements M n X m , including metal oxides, chalcogenides, pnictides, carbides, doped carbons, etc. The surfaces of such catalysts are often not crystal facets of the bulk phase underneath, and they typically have a variety of potential active sites. Catalytic surfaces in operando are often non-stoichiometric, amorphous, dynamic, and impure, and often vary from one part of the surface to another. Understanding of the issues that arise at such nanoscale, multi-element catalysts is just beginning to emerge. Yet these catalysts are widely discussed using Brønsted/Bell-Evans-Polanyi (BEP) relations, volcano plots, Tafel slopes, the Butler-Volmer equation, and other linear free energy relations (LFERs), which all depend on the implicit assumption that the active sites are “similar” and that surface adsorption is close to ideal. These assumptions underly the ubiquitous intuition based on the Sabatier Principle, that the fastest catalysis will occur when key intermediates have free energies of adsorption that are not too strong nor too weak. Current catalysis research often aims to minimize the complexity of non-ideal isotherms through experimental and computational design (e.g., the use of single crystal surfaces), and these studies are the foundation of the field. In contrast, this Perspective argues that the heterogeneity of binding sites and binding energies is an inherent strength of these catalysts. Here, this diversity makes many nanoscale catalysts inherently a high-throughput screen wrapped in a tiny package. Only by making the heterogeneity part of the foundation of catalysis models, sorting the types of active sites and dissecting non-ideal binding isotherms, will modern catalysis learn to harness the inherent diversity of real catalysts. Controlling and exploiting diversity rather than avoiding it will help to optimize complex modern catalysts and catalytic conditions.

Mayer, James M.↗
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.

Cavedon, Cristian↗