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Results for “cooperative and bifunctional materials”

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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8 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Direct Conversion of CO 2 to Olefins over a Cr 2 O 3 /ZSM-5@CaO Cooperative and Bifunctional Material Under Isothermal Conditions

Direct conversion of point-source CO 2 into fine chemicals over cooperative and bifunctional materials (BFMs) – composed of adsorbents and catalysts – has emerged as a promising approach to improve the energy efficiency of the carbon capture and conversion processes. In this study, a bifunctional material consisting of Cr 2 O 3 /ZSM-5 catalyst and CaO adsorbent was developed and tested in the CO 2 -oxidative dehydrogenation of propane (CO 2 –ODHP) for reactive capture of CO 2 in a fixed bed reactor. First, CaO was prepared using two distinct methods: solid-state and citrate sol–gel. The citrate sol–gel method resulted in small and finely-distributed CaO particles, allowing more accessible sites for CO 2 adsorption. Consequently, a high CO 2 adsorption capacity of ~14 mmol/g was achieved with fast adsorption kinetics compared to CaO prepared by the solid-state method. The CaO adsorbent was then combined with the Cr 2 O 3 /ZSM-5 catalyst for BFM synthesis and tested in the CO 2 –ODHP process, targeting propylene production. The BFM was extensively characterized to provide insights into the BFM’s surface chemistry, morphology, and reaction mechanism in the reactive capture process of CO 2 –ODHP. The results revealed that under isothermal adsorption–reaction conditions at 600 °C, a propane conversion of 22.5%, a propylene selectivity of 55.3%, and an olefin selectivity of 67.3% were achieved. The excellent propylene selectivity was attributed to the catalyst acidity and redox property of the Cr 2 O 3 /ZSM-5 catalyst, which facilitated the reaction pathway of propane dehydrogenation in the process of CO 2 –ODHP. Overall, this study renders Cr 2 O 3 /ZSM-5@CaO as promising BFMs with high CO 2 capture capacity and catalytic activity for integrated CO 2 capture and conversion in the ODHP reaction.

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

Reactive Carbon Capture: Cooperative and Bifunctional Adsorbent-Catalyst Materials and Process Integration for a New Carbon Economy

To say the least, releasing CO 2 into the atmosphere is reaping undue environmental consequences given the ever-present increase in severe global weather events over the past five years. However, it can be argued that–at least in the confines of current technological capabilities–the atmospheric release of CO 2 is somewhat unavoidable given that even shifting toward clean energy sources–such as solar, nuclear, wind, battery, or H 2 power–incurs an initial carbon requirement by way of manufacturing the very production abilities through which “clean” energy is generated. Even years from now, experts agree that energy production will be diversified and–as the global population continues to drive the growth of global energy consumption–thermal power derived from carbon combustion is likely to remain one intrinsic energetic source, of which CO 2 will always be a byproduct. In this context, it is the responsibility of the scientific community to devise improved pathways of carbon management such that (i) the consequences of combustion on the global environment are reduced and (ii) carbon fuels can be leveraged in a sustainable fashion. In this Account, we discuss a pivotal perspective shift on CO 2 emissions derived from a considerable breakthrough in material science from our work on shape engineering of nanoporous adsorbents and catalysts. This account details the development of materials which no longer vilify CO 2 emissions as a valueless combustion byproduct, instead providing a path for them to become a potential feedstock. In more specific terms, this work details the development of structured, cooperative “bifunctional” materials (BFMs) comprised of (i) a high-temperature adsorbent and (ii) a heterogeneous catalyst that enable single-bed CO 2 capture and utilization in oxidative ethane dehydrogenation (ODHE), oxidative propane dehydrogenation (ODHP), and dry methane reforming (DMR) processes. This Account begins with the conceptual development of the BFMs in the powdered state, followed by detailing the first-ever reports of structuring the materials into facile honeycomb contactors by 3D printing. The Account then summarizes the impressive performance of the 3D-printed BFMs, specifically focusing on how their catalysts (metal oxides and perovskites) influence their reactive CO 2 capture performances in ODHE, ODHP, and DMR processes. Such promise of CO 2 -as-fuel offers a glimpse into the future of a diversified energy economy, in which CO 2 /fuel looping can play an important role. A major factor in achieving this future is, of course, developing an appropriately active catalyst; an account of whose first breakthroughs in material science are detailed herein.

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

Cooperative and bifunctional Ga-Ca-Cr 2 O 3 @CaO structured monoliths as versatile platform for reactive capture of CO 2 and its subsequent conversion to ethylene

Cooperative and bifunctional materials (BFMs) that integrate adsorbents and catalysts offer a promising strategy for the reactive capture of CO 2 to produce valuable fuels and chemicals. In this study, we developed structured BFMs via 3D printing that combine CaO as an adsorbent with Ga–Ca–Cr 2 O 3 metal oxides as the catalyst for the reactive capture of CO 2 and its subsequent conversion to C 2 H 4 via the oxidative dehydrogenation of C 2 H 6 (CO 2 -ODHE). Three different Ga–Ca compositions were used to modify the catalyst surface characteristics and enhance C 2 H 4 selectivity. In these formulations, Ga ions stabilize the oxygen lattice of the BFM, while Ca ions interact strongly with Cr to form CaCrO 4 , thereby altering the oxygen species and enhancing the material’s basic properties. Under adsorption–reaction conditions at 600–650 °C, the optimal BFM achieved an excellent C 2 H 4 selectivity of 96.4 %, attributed to a balanced redox process and improved basicity that facilitate efficient C 2 H 6 conversion and rapid desorption of C 2 H 4 without excessive oxidation. Overall, this work provides new insights into the formulation of BFMs monoliths and highlights the critical role of catalytic surface modification in enhancing C 2 H 4 selectivity in the CO 2 -ODHE reactive capture process.

C2H4 production↗
DOE OSTI2020

Bifunctional Heterometallic Metal-Organic Frameworks for Solvent-Free Heterogeneous Cascade Catalysis

A family of heterometallic metal-organic frameworks (MOFs) (CPM200s) harmoniously coexisting as Lewis acids and base (azo) sites were prepared. Seven CPM200s were employed as multifunctional heterogeneous cascade catalysts for the one-pot deacetalization-Knoevenagel reaction in a solvent-free system. Benefiting from the cooperation between Lewis acids from the open metal sites and base sites from the ligands, the CPM200s showed high activity and selectivity for the tandem reaction. The heterometallic 3D porous framework reported here not only offers a combination of two opposite active sites in the same framework of materials but also increases mass transfer of the substrate, thus maximizing the efficiency and substrate selectivity of the bifunctional catalysts. The CPM200s showed the highest turnover frequency (TOF), outperforming that of the reported MOFs in tandem with the deacetalization-Knoevenagel reaction. A strong correlation between the TOF and charge-to-radius ratio (z/r) of metal ions in the CPM200s was observed for the first time. The bifunctional CPM200s catalysts can be reused five times without significant loss of activity.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Comment on Improved CO 2 Hydrogenation on Ni–ZnO/MCM-41 Catalysts with Cooperative Ni and ZnO Sites

A recent publication from Murthy et al.1 describes experiments in which they proposed the hypothesis that a bifunctional catalyst consisting of adlineated,2 nanometer-sized domains of Ni and ZnO, confined within the pores of MCM-41, hydrogenates carbon dioxide adsorbed on the ZnO using hydrogen atoms produced by the Ni-catalyzed dissociation of H2. The reanalysis of their data presented below suggests that the reaction rates they employed to test their hypothesis, when properly normalized, show little to no effect of bifunctionality. This closer inspection of their data raises the possibility that the observed effects may instead arise from experimental artifacts (e.g., different levels of conversion, finite rates of mass transport) or morphological correlations that were not considered by the authors.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Cooperativity in the Aldol Condensation Using Bifunctional Mesoporous Silica–Poly(styrene) MCM-41 Organic/Inorganic Hybrid Catalysts

This work explores the efficacy of silica/organic hybrid catalysts, where the organic component is built from linear aminopolymers appended to the silica support within the support mesopores. Specifically, the role of molecular weight and polymer chain composition in amine-bearing atom transfer radical polymerization-synthesized poly(styrene-co-2-(4-vinylbenzyl)isoindoline-1,3-dione) copolymers is probed in the aldol condensation of 4-nitrobenzaldehyde and acetone. Controlled polymerization produces protected amine-containing poly(styrene) chains of controlled molecular weight and dispersity, and a grafting-to thiol–ene coupling approach followed by a phthalimide deprotection step are used to covalently tether and activate the polymer hybrid catalysts prior to the catalytic reactions. Site-normalized batch kinetics are used to assess the role of polymer molecular weight and chain composition in the cooperative catalysis. Lower-molecular-weight copolymers are demonstrated to be more active than catalysts built from only molecular organic components or from higher-molecular-weight chains. Molecular dynamics simulations are used to probe the role of polymer flexibility and morphology, whereby it is determined that higher-molecular-weight hybrid structures result in congested pores that inhibit active site cooperativity and the diffusivity of reagents, thus resulting in lower rates during the reaction.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Unraveling the Cooperative Activity of Hydrophilicity, Conductivity, and Interfacial Active Sites in Alginate‐CNT‐Cuo Self‐Standing Electrodes with Benchmark‐Close Activity for Alkaline Water Splitting

Designing electrocatalysts that excel in hydrogen and oxygen electrochemistry is crucial for sustainable hydrogen generation through electrochemical water splitting. This study presents a novel tricomponent catalyst composed of an alginate hydrogel (AL) infused with single-walled carbon nanotubes (CNTs) and copper oxide (CuO) nanoparticles. The catalyst exhibits benchmark-close bifunctional activity toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) under alkaline conditions. The aerophobic nature of the AL-gel facilitates superior bubble release from the electrode, while the inclusion of CNTs mitigates charge transfer resistance. Moreover, heterojunctions of CuO and CNTs create unique interfacial active sites, culminating in high electrocatalytic water-splitting activity. The structural rigidity of the composite permits its use as self-standing electrodes (SSE) without using substrates or binders, enabling a direct evaluation of its activity. The composite electrode demonstrates exceptional electrocatalytic HER activity in an alkaline solution, with onset potentials of 93 mV and moderate OER activity with an onset of 155 mV. Furthermore, a water electrolysis cell featuring the bifunctional SSE exhibits an open circuit voltage of 1.85 V at 100 mA.cm −2 , and only 8% efficiency loss after 100 h marking this a significant stride in developing self-standing nonprecious electrocatalysts with impressive catalytic performance.

36 MATERIALS SCIENCE↗