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Connecting cation site location to alkane dehydrogenation activity in Ni/BEA catalysts
Ni-modified beta zeolite (Ni/BEA) catalysts activate carbon-hydrogen bonds in light alkanes, as demonstrated through isobutane reaction testing. Controlled synthesis of Ni/BEA allows for efficient introduction of ion-exchanged Ni sites at varying Ni loadings (0.43% - 1.8%). These catalysts exhibit site time yields (STY) for H2 production that increase with increasing Ni loading. A detailed analysis of secondary reactions and carbon deposition based on the relative molar flowrates of product C and H indicates that the observed increase in H2 STY with increasing Ni loading is likely attributed to both increasing alkane activation activity and increasing formation of hydrogen-deficient aromatic products retained within the catalyst pores. In situ diffuse-reflectance UV-visible-NIR absorbance and X-ray absorption spectroscopies indicate isolated, 4-coordinate Ni(2+) species for all loadings. Quantum mechanics/molecular mechanics modeling identifies two distinct Ni(2+) sites consistent with the structural characterization, but with differing relative stabilities due to their coordination environment. Computed reaction energetics for isobutane dehydrogenation demonstrate that the more stable Ni(2+) species at a six-membered 4Si-2Al ring, Ni-6MR, is less active for isobutane dehydrogenation than the less stable Ni(2+) at the five-membered 3Si-2Al ring, Ni-5MR. The differing local structure of the isolated cationic Ni sites in Ni/BEA offers a possible rationalization for the increased H2 STY observed at greater Ni loadings.
Splitting Mono- and Di-Branched Alkane Isomers by a Robust Aluminum-Based Metal-Organic Framework Material with Optimal Pore Dimensions
The separation of alkanes with different degrees of branching, particularly mono- and dibranched isomers, represents a challenging yet important industrial process for the production of premium gasoline blending components with high octane number. We report here the separation of linear/monobranched and dibranched alkanes through complete molecular sieving by a robust aluminum-based MOF material, Al-bttotb (H 3 bttotb = 4,4',4"-(benzene-1,3,5-triyltris(oxy))tribenzoicacid). Single- and multicomponent adsorption experiments reveal that the material adsorbs linear and monobranched alkanes, but fully excludes their dibranched isomers. Adsorption sites of alkanes within the MOF channels have been identified by single-crystal X-ray diffraction studies, and the adsorption mechanism was explored through computational calculations and modeling. The highly selective adsorption of the MOF should be attributed to its optimal pore dimensions.
Cationic Tantalum Hydrides Catalyze Hydrogenolysis and Alkane Metathesis Reactions of Paraffins and Polyethylene
Sulfated aluminum oxide (SAO), a high surface area material containing sulfate anions that behave like weakly coordinating anions, reacts with Ta(=CH t Bu)(CH 2 t Bu) 3 to form [Ta(CH 2 t Bu) 2 (O–) 2 ][SAO] (1). Subsequent treatment with H 2 forms Ta–H + sites supported on SAO that are active in hydrogenolysis and alkane metathesis reactions. In both reactions Ta–H + is more active than related neutral Ta–H sites supported on silica. This reaction chemistry extends to melts of high-density polyethylene (HDPE), where Ta–H + converts 30% of a low molecular weight HDPE (M n = 2.5 kg mol –1 ; D = 3.6) to low molecular weight paraffins under hydrogenolysis conditions. Under alkane metathesis conditions Ta–H + converts this HDPE to a high MW fraction (M n = 6.2 kDa; D = 2.3) and low molecular weight alkane products (C 13 –C 32 ). Furthermore, these results show that incorporating charge as a design element in supported d 0 metal hydrides is a viable strategy to increase the reaction rate in challenging reactions involving reorganization of C–C bonds in alkanes.
Topologically guided tuning of Zr-MOF pore structures for highly selective separation of C6 alkane isomers
Effective separation of alkane isomers is a critical step in the petroleum refining process to produce gasoline with high octane rating. Current technology relies on energy intensive distillation method. Adsorptive separation using porous solids offers an alternative route that is more cost effective, lower energy and higher efficiency. Guided by topology-directed design and synthesis, we have developed a series of zirconium-based metal-organic frameworks with optimized pore structure for efficient separation of C6 alkane isomers, Zr-bptc adsorbs a large amount of n-hexane while excluding branched isomers. The n-hexane uptake is ~70% higher than that of a benchmark adsorbent, zeolite-5A. A derivative structure, Zr-abtc, is capable of discriminating all three C6 isomers with a high separation factor for 3-methylpentane over 2,3-dimethylbutane. This property is important for producing gasoline with further improved quality.
Recent Advances in the Understanding of Boron-Containing Catalysts for the Selective Oxidation of Alkanes to Olefins
The production of ethylene and propylene through aerobic alkane oxidation without significant coproduction of CO and CO 2 (CO x ) presents a challenge to academic and industrial researchers alike. Recently, boron-containing materials such as hexagonal boron nitride (hBN) have been identified as active and selective catalysts for the oxidative dehydrogenation (ODH) of propane to propylene with minimal CO x selectivity. Additionally, high olefin selectivity is also obtained in the oxidation of other alkanes and other materials such as metal borides and supported B/SiO 2 have been successfully applied to this transformation. Here, recent advances in the understanding of these catalysts in the oxidation of light alkanes are presented here providing a framework for further study of this exciting field.
Electrophilic Impact of High-Oxidation State Main-Group Metal and Ligands on Alkane C–H Activation and Functionalization Reactions
High-oxidation state main-group metal complexes are potential alternatives to transition metals for electrophilic alkane C–H functionalization reactions. Yet, there is little known about how selection of the p-block, main-group metal and ligand impact alkane C–H activation and functionalization thermodynamics and reactivity. This work reports density functional theory calculations used to determine qualitative and quantitative features of C–H activation and metal-methyl functionalization energy landscapes for reaction between high-oxidation state d 10 s 0 In III , Tl III , Sn IV , and Pb IV carboxylate complexes with methane. While the main-group metal influences the C–H activation barrier height in a periodic manner, the carboxylate ligand has a much larger quantitative impact on C–H activation with stabilized carboxylate anions inducing the lowest barriers. For metal-methyl reductive functionalization reactions, the main-group metal dramatically influences the barrier heights, which are correlated to reaction thermodynamics and bond heterolysis energies as a model for two-electron reduction energies. Generally, this work begins to outline which main-group metals and carboxylate ligands could be useful for alkane functionalization systems that utilize electrophilic C–H activation and metal-alkyl functionalization reactions.
Alkane dehydrogenation catalyst and methods of converting alkanes to alkenes
Provided herein is an alkane dehydrogenation catalyst, a method of manufacturing an alkane dehydrogenation catalyst, and a method of converting alkanes to alkenes.
Serendipity in Catalysis Research: Boron-Based Materials for Alkane Oxidative Dehydrogenation
In this Account, we will first present our initial discovery of boron nitride (BN) as an unexpected catalyst for the oxidative dehydrogenation of light alkanes. Beyond its surprising activity, BN also drew interest due to its low selectivity to carbon oxides. This observation made BN distinct from previously studied metal oxide catalysts for selective alkane oxidation. Here, we narrowed down its unique reactivity to the oxygen functionalization of the catalyst surface, particularly the formation of B–O species as probed by various spectroscopic techniques. In investigating the critical role of each of the structural elements during ODH, we discovered that not only BN but an entire class of boron-containing compounds are active and selective for the formation of propylene from propane.
Hydrolysis of zeolite framework aluminum and its impact on acid catalyzed alkane reactions
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Structure, Dynamics, and Reactivity for Light Alkane Oxidation of Fe(II) Sites Situated in the Nodes of a Metal–Organic Framework
Metal organic frameworks (MOFs), with their crystalline, porous structures, can be synthesized to incorporate a wide range of catalytically active metals in tailored surroundings. These materials have potential as catalysts for conversion of light alkanes, feedstocks available in large quantities from shale gas that are changing the economics of manufacturing commodity chemicals. Mononuclear high-spin (S = 2) Fe(II) sites situated in the nodes of the MOF MIL-100(Fe) convert propane via dehydrogenation, hydroxylation, and overoxidation pathways in reactions with the atomic oxidant N 2 O. Pair distribution function analysis, N 2 adsorption isotherms, X-ray diffraction patterns, and infrared and Raman spectra confirm the single-phase crystallinity and stability of MIL-100(Fe) under reaction conditions (523 K in vacuo, 378–408 K C 3 H 8 + N 2 O). Density functional theory (DFT) calculations illustrate a reaction mechanism for the formation of 2-propanol, propylene, and 1-propanol involving the oxidation of Fe(II) to Fe(III) via a high-spin Fe(IV)$=$O intermediate. The speciation of Fe(II) and Fe(III) in the nodes and their dynamic interchange was characterized by in situ X-ray absorption spectroscopy and ex situ Mössbauer spectroscopy. Furthermore, the catalytic relevance of Fe(II) sites and the number of such sites were determined using in situ chemical titrations with NO. N 2 and C 3 H 6 production rates were found to be first-order in N 2 O partial pressure and zero-order in C3H8 partial pressure, consistent with DFT calculations that predict the reaction of Fe(II) with N 2 O to be rate determining. DFT calculations using a broken symmetry method show that Fe-trimer nodes affecting reaction contain antiferromagnetically coupled iron species, and highlight the importance of stabilizing high-spin (S = 2) Fe(II) species for effecting alkane oxidation at low temperatures (<408 K).
One-of-a-kind: a microporous metal–organic framework capable of adsorptive separation of linear, mono- and di-branched alkane isomers via temperature- and adsorbate-dependent molecular sieving
Clean separation of linear, monobranched, and dibranched alkanes is achieved using a flexible, microporous metal–organic framework (MOF).
Testing of the reliability of alkanes as biological indicators and development of reference data on alkanes of various origins Final report
Alkane reliability as biological indicators, and sensitive analytical methods for determining contamination
Ammonia-Assisted Light Alkane Anti-coke Reforming on Isolated ReO x Sites in Zeolite
The conventional reforming produces H 2 with stoichiometric amounts of CO and CO 2 from hydrocarbons. Here, we show that CO x -free H 2 can be produced from ammonia-assisted reforming (ammoreforming) of natural gas liquids (C n H 2n+2 + nNH 3 = nHCN + (2n + 1) H 2 , n = 2 or 3) at the same conditions as the steam reforming. Such a process co-produces HCN, which can be easily separated from H 2 and used as value-added chemicals or for NH 3 recycling through hydrolysis. In addition, the ammoreforming of ethane and propane was realized over the Re-modified HZSM-5 zeolite rather than the traditional Pt-based catalyst for the BMA process (methane ammoreforming). The specific activity of the Re/HZSM-5 catalysts at 650 °C is up to 1 mol H2 /g Re /min (or 180 min –1 ) during ethane ammoreforming. The catalyst is highly coke resistant and shows only slight deactivation with a time-on-stream up to 20 h. Characterization of the fresh and used catalysts by X-ray absorption and Raman spectroscopies suggested that the isolated ReO x site grafted by AlO 4 – tetrahedral in the zeolite framework is responsible for the outstanding catalytic activity and coke resistibility.
A comprehensive multi-omics approach uncovers adaptations for growth and survival of Pseudomonas aeruginosa on n-alkanes
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One-Pot Process for Hydrodeoxygenation of Lignin to Alkanes Using Ru-Based Bimetallic and Bifunctional Catalysts Supported on Zeolite Y
The synthesis of high-efficiency and low-cost multifunctional catalysts for hydrodeoxygenation (HDO) of waste lignin into advanced biofuels is crucial for enhancing current biorefinery processes. Inexpensive transition metals, including Fe, Ni, Cu, Zn, were severally co-loaded with Ru on HY zeolite to form bimetallic and bifunctional catalysts. These catalysts were subsequently tested for HDO conversion of softwood lignin and several lignin model compounds. Results indicated that the inexpensive earth abundant metals could modulate the hydrogenolysis activity of Ru and decrease the yield of low molecular weight gaseous side-products. Among all the prepared catalysts, Ru-Cu/HY showed the best HDO performance, giving the highest selectivity to hydrocarbon products. The improved catalytic performance of Ru-Cu/HY was probably due to the following three factors: (1) high total and strong acid sites, (2) good dispersion of metal species and limited segregation, (3) high adsorption capacity for polar fractions, including hydroxyl groups and ether bonds. Moreover, all the bifunctional catalysts were proven to be superior over the combination catalysts of Ru/Al2O3 and HY zeolite, and this could be attributed to the “intimacy criterion”. The practical use of the designed catalysts would be promising in lignin valorization.