Project description:Zr-based metal-organic frameworks (MOFs) have been shown to be excellent catalyst supports in heterogeneous catalysis due to their exceptional stability. Additionally, their crystalline nature affords the opportunity for molecular level characterization of both the support and the catalytically active site, facilitating mechanistic investigations of the catalytic process. We describe herein the installation of Co(II) ions to the Zr6 nodes of the mesoporous MOF, NU-1000, via two distinct routes, namely, solvothermal deposition in a MOF (SIM) and atomic layer deposition in a MOF (AIM), denoted as Co-SIM+NU-1000 and Co-AIM+NU-1000, respectively. The location of the deposited Co species in the two materials is determined via difference envelope density (DED) analysis. Upon activation in a flow of O2 at 230 °C, both materials catalyze the oxidative dehydrogenation (ODH) of propane to propene under mild conditions. Catalytic activity as well as propene selectivity of these two catalysts, however, is different under the same experimental conditions due to differences in the Co species generated in these two materials upon activation as observed by in situ X-ray absorption spectroscopy. A potential reaction mechanism for the propane ODH process catalyzed by Co-SIM+NU-1000 is proposed, yielding a low activation energy barrier which is in accord with the observed catalytic activity at low temperature.
Project description:Oxidative dehydrogenation of propane is a promising technology for the preparation of propene. Boron-based nonmetal catalysts exhibit remarkable selectivity toward propene and limit the generation of COx byproducts due to unique radical-mediated C-H activation. However, due to the high barrier of O-H bond cleavage in the presence of O2, the radical initialization of the B-based materials requires a high temperature to proceed, which decreases the thermodynamic advantages of the oxidative dehydrogenation reaction. Here, we report that the boron oxide overlayer formed in situ over metallic Ni nanoparticles exhibits extraordinarily low-temperature activity and selectivity for the ODHP reaction. With the assistance of subsurface Ni, the surface specific activity of the BOx overlayer reaches 93 times higher than that of bare boron nitride. A mechanistic study reveals that the strong affinity of the subsurface Ni to the oxygen atoms reduces the barrier of radical initiation and thereby balances the rates of the BO-H cleavage and the regeneration of boron hydroxyl groups, accounting for the excellent low-temperature performance of Ni@BOx/BN catalysts.
Project description:Possible universal dynamics of a many-body system far from thermal equilibrium are explored. A focus is set on meta-stable non-thermal states exhibiting critical properties such as self-similarity and independence of the details of how the respective state has been reached. It is proposed that universal dynamics far from equilibrium can be tuned to exhibit a dynamical transition where these critical properties change qualitatively. This is demonstrated for the case of a superfluid two-component Bose gas exhibiting different types of long-lived but non-thermal critical order. Scaling exponents controlled by the ratio of experimentally tuneable coupling parameters offer themselves as natural smoking guns. The results shed light on the wealth of universal phenomena expected to exist in the far-from-equilibrium realm.
Project description:Oxidative dehydrogenation (ODH) of light alkanes to olefins-in particular, using vanadium-based catalysts-is a promising alternative to the dehydrogenation process. Here, we investigate how the activity of the vanadium phase in ODH is related to its dispersion in porous matrices. An attempt was made to synthesize catalysts in which vanadium was deposited on a microporous faujasite zeolite (FAU) with the hierarchical (desilicated) FAU as supports. These yielded different catalysts with varying amounts and types of vanadium phase and the porosity of the support. The phase composition of the catalysts was confirmed by X-ray diffraction (XRD); low temperature nitrogen sorption experiments resulted in their surface area and pore volumes, and reducibility was measured with a temperature-programmed reduction with a hydrogen (H2-TPR) method. The character of vanadium was studied by UV-VIS spectroscopy. The obtained samples were subjected to catalytic tests in the oxidative dehydrogenation of propane in a fixed-bed gas flow reactor with a gas chromatograph to detect subtract and reaction products at a temperature range from 400-500 °C, with varying contact times. The sample containing 6 wt% of vanadium deposited on the desilicated FAU appeared the most active. The activity was ascribed to the presence of the dispersed vanadium ions in the tetragonal coordination environment and support mesoporosity.
Project description:PtCu single-atom alloys (SAAs) open an extensive prospect for heterogeneous catalysis. However, as the host of SAAs, Cu suffers from severe sintering at elevated temperature, resulting in poor stability of catalysts. This paper describes the suppression of the agglomeration of Cu nanoparticles under high temperature conditions using copper phyllosilicate (CuSiO3) as the support of PtCu SAAs. Based on quasi in situ XPS, in situ CO-DRIFTS, in situ Raman spectroscopy and in situ XRD, we demonstrated that the interfacial Cu+-O-Si formed upon reduction at 680 °C serves as the adhesive between Cu nanoparticles and the silicon dioxide matrix, strengthening the metal-support interaction. Consequently, the resistance to sintering of PtCu SAAs was improved, leading to high catalytic stability during propane dehydrogenation without sacrificing conversion and selectivity. The optimized PtCu SAA catalyst achieved more than 42% propane conversion and 93% propylene selectivity at 580 °C for at least 30 hours. It paves a way for the design and development of highly active supported single-atom alloy catalysts with excellent thermal stability.
Project description:Fluctuations arise universally in nature as a reflection of the discrete microscopic world at the macroscopic level. Despite their apparent noisy origin, fluctuations encode fundamental aspects of the physics of the system at hand, crucial to understand irreversibility and nonequilibrium behavior. To sustain a given fluctuation, a system traverses a precise optimal path in phase space. Here we show that by demanding invariance of optimal paths under symmetry transformations, new and general fluctuation relations valid arbitrarily far from equilibrium are unveiled. This opens an unexplored route toward a deeper understanding of nonequilibrium physics by bringing symmetry principles to the realm of fluctuations. We illustrate this concept studying symmetries of the current distribution out of equilibrium. In particular we derive an isometric fluctuation relation that links in a strikingly simple manner the probabilities of any pair of isometric current fluctuations. This relation, which results from the time-reversibility of the dynamics, includes as a particular instance the Gallavotti-Cohen fluctuation theorem in this context but adds a completely new perspective on the high level of symmetry imposed by time-reversibility on the statistics of nonequilibrium fluctuations. The new symmetry implies remarkable hierarchies of equations for the current cumulants and the nonlinear response coefficients, going far beyond Onsager's reciprocity relations and Green-Kubo formulas. We confirm the validity of the new symmetry relation in extensive numerical simulations, and suggest that the idea of symmetry in fluctuations as invariance of optimal paths has far-reaching consequences in diverse fields.
Project description:The inherent variability and insufficiencies in the co-production of propylene from steam crackers has raised concerns regarding the global propylene production gap and has directed industry to develop more on-purpose propylene technologies. The oxidative dehydrogenation of propane by CO2 (CO2-ODHP) can potentially fill this gap while consuming a greenhouse gas. Non-precious FeNi and precious NiPt catalysts supported on CeO2 have been identified as promising catalysts for CO2-ODHP and dry reforming, respectively, in flow reactor studies conducted at 823?K. In-situ X-ray absorption spectroscopy measurements revealed the oxidation states of metals under reaction conditions and density functional theory calculations were utilized to identify the most favorable reaction pathways over the two types of catalysts.
Project description:It's of paramount importance to develop renewable nanocarbon materials to replace conventional precious metal catalysts in alkane dehydrogenation reactions. Graphene-based materials with high surface area have great potential for light alkane dehydrogenation. However, the powder-like state of the graphene-based materials seriously limits their potential industrial applications. In the present work, a new synthetic route is designed to fabricate nitrogen-doped graphene-based monolith catalysts for oxidative dehydrogenation of propane. The synthetic strategy combines the hydrothermal-aerogel and the post thermo-treatment procedures with urea and graphene as precursors. The structural characterization and kinetic analysis show that the monolithic catalyst well maintains the structural advantages of graphene with relatively high surface area and excellent thermal stability. The homogeneous distributed nitrogen species can effectively improve the yield of propylene (5.3% vs. 1.9%) and lower the activation energy (62.6 kJ mol-1 vs. 80.1 kJ mol-1) in oxidative dehydrogenation of propane reaction comparing with un-doped graphene monolith. An optimized doping amount at 1:1 weight content of the graphene to urea precursors could exhibit the best catalytic performance. The present work paves the way for developing novel and efficient nitrogen-doped graphene monolithic catalysts for oxidative dehydrogenation reactions of propane.
Project description:Propane dehydrogenation (PDH) is an on-purpose catalytic technology to produce propylene from propane that operates at high temperatures, 773-973 K. Several key industry players have been active in developing new catalysts and processes with improved carbon footprint and economics, where Pt-based catalysts have played a central role. The optimization of these catalytic systems through computational and atomistic simulations requires large-scale models that account for their reactivity and dynamic properties. To address this challenge, we developed a new reactive ReaxFF force field (2023-Pt/C/H) that enables large-scale simulations of PDH reactions catalyzed on Pt surfaces. The optimization of force-field parameters relies on a large training set of density functional theory (DFT) calculations of Pt-catalyzed PDH mechanism, including geometries, adsorption and relative energies of reaction intermediates, and key C-H and C-C bond-breaking/forming reaction steps on the Pt(111) surface. The internal validation supports the accuracy of the developed 2023-Pt/C/H force-field parameters, resulting in mean absolute errors (MAE) against DFT data of 14 and 12 kJ mol-1 for relative energies of intermediates and energy barriers, respectively. We demonstrated the applicability of the 2023-Pt/C/H force field with reactive molecular dynamics simulations of propane on different Pt surface topologies and temperatures. The simulations successfully model the formation of propene in the gas phase as well as competitive, unproductive reactions such as deep dehydrogenation and C-C bond cleavage that produce H, C1 and C2 adsorbed species responsible of catalytic deactivation of Pt surface. Results show the following reactivity order: Pt(111) < Pt(100) < Pt(211), and that for the stepped Pt(211) surface, propane activation occurs on low-coordinated Pt atoms at the steps. The measured selectivity as a function of surface topology follows the same trend as activity, the Pt(211) facet being the most selective. The 2023-Pt/C/H reactive force field can also describe the increase of reactivity with the temperature. From these simulations, we were able to estimate the Arrhenius activation energy, 73 kJ mol-1, whose value is close to those reported experimentally for PDH catalyzed by large, supported Pt nanoparticles . The newly developed 2023-Pt/C/H reactive force field can be used in subsequent investigations of different Pt topologies and of collective effects such as temperature, propane pressure, or H surface coverage.