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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Poison or Promoter? Investigating the Dual-Role of Carbon Monoxide in Pincer-Iridium-Based Alkane Dehydrogenation Systems via Operando Diffuse Reflectance Infrared Fourier Transform Spectroscopy

Pincer-ligated iridium complexes of the form [( R 4 PCP)IrL] ( R 4 PCP = κ 3 -C 6 H 3 -2,6-(XPR 2 ) 2 ; X = CH 2 , O; R = tBu, iPr) have previously been shown competent for acceptorless alkane dehydrogenation when supported on silica. It was observed by postcatalysis solid-state NMR that silica-tethered [(≡SiO- tBu 4 POCOP)Ir(C 2 H 4 )] (3-C 2 H 4 ) was converted fully to [(≡SiO- tBu 4 POCOP)Ir(CO)] (3-CO) at 300 °C. In this work, the characterization of species under dehydrogenation reaction conditions far from equilibrium between butane and butenes (approach to equilibrium Q/K eq = 0.3 at 300 °C) is performed with operando Diffuse Reflectance Infrared Fourier–Transform Spectroscopy (DRIFTS) to show the kinetics of species conversion from 3-C 2 H 4 to 3-CO. It is further found that [(≡SiO- tBu 4 POCOP)IrHCl] (3-HCl), a species considered to be a precatalyst for alkane dehydrogenation, is also fully converted to 3-CO. Here, a mechanism of decomposition is proposed that implicates surface silanol groups, while carbon monoxide acts as a “stabilizer” for the catalyst by promoting their reductive elimination and maintaining the complex in the I oxidation state.

02 PETROLEUM↗
DOE OSTI2021

Identifying the Catalytic Active Site for Propylene Metathesis by Supported ReO x Catalysts

A series of supported ReO x catalysts were investigated that allowed identifying the unique surface anchoring sites on oxide supports responsible for activating the surface ReO 4 sites for propylene metathesis (the catalytic active site). The catalysts were synthesized by incipient-wetness impregnation of aqueous HReO 4 onto the oxide supports (Al 2 O 3 , ZrO 2 , TiO 2 , SiO 2 and CeO 2 ), characterized under dehydrated and propylene metathesis reaction conditions with in situ spectroscopy (Raman, DRIFTS, UV-Vis and NAP-XPS), and chemically probed (CH 3 CH=CH 2 -TPSR, CH 2 =CH 2 /CH 3 CH=CHCH 3 titration and steady-state self-metathesis of propylene to ethylene and 2-butene). The initially calcined supported rhenia species anchor as isolated surface Re 7+ O 4 sites on the oxide supports by reacting with the surface hydroxyls (terminal S-OH, bridged S-OH-S and tricoordinated S 3 -OH) of the oxide supports. The specific oxide support was found to control the number of activated sites (Al 2 O 3 >> ZrO 2 > CeO 2 > TiO 2 > SiO 2 ) and propylene metathesis activity (Al 2 O 3 >> ZrO 2 >> TiO 2 ~ CeO 2 ~ SiO 2 ) revealing that the oxide support action is a potent ligand for the surface ReO x sites. The activation and specific activity of the surface ReO x sites depend on several factors (nature of surface hydroxyls (S 3 -OH > S-OH-S > S-OH), coordination of the oxide support surface cation (ZrO 7 , AlO 6 , CeO 4 ) and electronegativity of the oxide support cation (SiO 2 > Al 2 O 3 > TiO 2 > ZrO 2 > CeO 2 ). No relationships exist between olefin metathesis activity and acid strength of surface Lewis and Brønsted sites. Here, prior studies primarily focused on supported ReO x /Al 2 O 3 and the lack of examination of non-Al 2 O 3 supported rhenia catalysts precluded comparison between efficient and inefficient olefin metathesis catalysts, which prevented identifying the catalytic active site for olefin metathesis by supported ReO x catalysts.

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

Mechanism and kinetics of light alkane dehydrogenation and cracking over isolated Ga species in Ga/H-MFI

The objective of this study is to examine the mechanisms and kinetics of C2H6 dehydrogenation and n-C4H10 dehydrogenation and cracking over isolated Ga species in Ga/HMFI and to compare these results to those reported previously for C3H8 dehydrogenation and cracking. C2H6 dehydrogenation is found to be catalyzed by both [GaH]2+ and [GaH2]+ cations at similar turnover frequencies. Rate measurements over Ga/H-MFI containing predominantly [GaH2]+ cations reveal that C2H6 dehydrogenation rates exhibit a Langmuir.Hinshelwood dependence on C2H6 partial pressure at elevated temperatures (>730 K), consistent with the involvement of chemisorbed [C2H5.GaH]+ species. The reaction kinetics suggest that C2H6 dehydrogenation proceeds via heterolytic C-H cleavage of adsorbed C2H6 by [GaH2]+ cations to form H2 and [C2H5-GaH]+ species, which further decompose via β-hydride elimination to form C2H4. By contrast, C4H10 dehydrogenation and both terminal and central cracking are catalyzed exclusively by [GaH]2+ cations. All three reactions exhibit a Langmuir-Hinshelwood dependence on C4H10 partial pressure and are inhibited by H2. Ratios of dehydrogenation to cracking (total) and terminal to central cracking are approximately independent of C4H10 partial pressure consistent with the involvement of a common C4H10-derived surface intermediate. The observed reaction kinetics are consistent with an alkyl-mediated mechanism occurring over [GaH]2+, analogous to that reported previously for C3H8 dehydrogenation/cracking over Ga/H-MFI (Phadke, N. M.; et al. J. Am. Chem. Soc. 2019, 141, 1614-1627). The mechanism proceeds via facile, heterolytic dissociation of adsorbed C4H10 to form [C4H9-GaH]+-H+ cation pairs via methyl C-H-activated pathways. Dehydrogenation then proceeds via β-hydride elimination, respectively, forming butene, while terminal and central cracking proceed via C-H-activated H+ attack. Methylene activation was also considered but found to occur at a significantly lower rate. Theoretical analysis of the proposed reaction pathways leads to apparent activation enthalpies in good agreement with values extracted from the measured kinetics, thereby supporting the proposed pathways and the roles of [GaH]2+ and [GaH2]+ cations in the dehydrogenation and cracking of light alkanes on Ga/H-MFI.

Phadke, NM↗
DOE OSTI2022

Dehydrogenation of Propane and n -Butane Catalyzed by Isolated PtZn 4 Sites Supported on Self-Pillared Zeolite Pentasil Nanosheets

Propene and 1,3-butadiene are important building-block chemicals that can be produced by dehydrogenation of propane and butane over Pt catalysts. The challenge is to develop highly active and selective catalysts that are resistant to deactivation by Pt sintering and coke formation. We have recently shown that these objectives can be met for propane dehydrogenation using atomically dispersed Pt atoms anchored to neighboring ≡SiOZn-OH groups bonded to the framework dealuminated zeolite BEA. In the present study, we demonstrate that significantly superior performance can be achieved by using self-pillared pentasil (SPP) zeolite nanosheets. Following catalyst reduction in H 2 , atomic-resolution, scanning transmission electron microscopy (STEM) and X-ray absorption spectroscopy (XAS) indicate that Pt is stabilized in structures well approximated as (≡Si-O-Zn) 4-5 Pt. These species are highly active, selective, and stable for propane dehydrogenation (PDH) to give propene and for n-butane dehydrogenation (BDH) to give 1,3-butadiene. No catalyst deactivation was observed after 12 days of time on stream, and the selectivity remained at nearly 100% for PDH conducted at 823 K and a weight hourly space velocity (WHSV) of 1,350 h -1 . The apparent rate coefficient for PDH over this catalyst is significantly higher than that reported previously for Pt-containing catalysts. For BDH at 823 K and a WHSV of 3560 h -1 , the selectivity to butene isomers and 1,3-butadiene is 98.9%, and the selectivity to 1,3-butadiene is 45%. Here, we propose that the high catalyst stability observed during PDH and BDH is a consequence of a large fraction of the Pt-containing centers being located on the external surface of the zeolite nanosheets, where nascent coke precursors can desorb before condensing to form coke.

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

Insights into Dopant-Mediated Tuning of Silica-Supported Mo Metal Centers for Enhanced Olefin Metathesis

Here, we show that the electronic environment around active Mo centers supported on mesoporous silicates can be tuned by the addition of transition metals creating highly dispersed bimetallic catalysts that display enhanced activity for ethylene + 2-butene metathesis to propylene. The bimetallic catalysts are prepared by incorporating electrophilic Lewis acid metals (M) such as Nb, Ta, Zr, or Hf as dopant promoters into mesoporous KIT-6 supports using a one-pot sol–gel technique followed by impregnation of the Mo species. All the bimetallic Mo/M-KIT-6 catalysts display better activity than monometallic Mo/KIT-6 catalyst (28.7 ± 1.1 mmol (mol Mo s ) –1 ), with (Mo/Nb-KIT-6) catalysts exhibiting maximum propylene formation rates (54.2 ± 0.5 mmol (mol Mo s ) –1 ) at an identical Mo loading.

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

Ethanol Conversion to C 4+ Olefins over Bimetallic Copper- And Lanthanum-Containing Beta Zeolite Catalysts

We report ethanol conversion to C 4+ olefins remains a critical yet nonselective process for producing renewable middle distillates. Here, Cu–La/Beta catalysts composed of copper and lanthanum incorporated onto a dealuminated Beta support are reported for ethanol conversion to C 4+ olefins (73% selectivity, ~98% ethanol conversion, 623 K,<4% C 1 –C 3 hydrocarbons) which particularly favors C 5+ olefin formation (43% selectivity) as a distinction from the benchmarking Cu–Y/Beta catalyst. Monometallic Cu/Beta or La/Beta samples are insufficient to catalyze the C 4+ olefin formation and primarily form dehydration products (e.g., ethylene and diethyl ether), indicating the necessity of both Cu and La species for butene and C 5+ olefin formation. Increasing the bulk La loading at a fixed Cu content yields higher C 5+ olefins until the La/Cu molar ratio reaches 3.6. These findings indicate Cu–La/Beta as an effective ethanol conversion catalyst that facilitates multiple C–C bond formation events required for synthesizing C 5+ olefins (i.e., hexenes and octenes).

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

Cascade Reaction of Ethanol to Butadiene over Multifunctional Silica-Supported Ag and ZrO 2 Catalysts

Although butadiene is currently a by-product of naphtha cracking, interest in producing butadiene from bio-based ethanol has increased because of the lower environmental impact of the ethanol to butadiene reaction. Furthermore, this work explores a multifunctional catalyst system composed of silica-supported Ag and ZrO 2 used for the cascade reaction of ethanol to butadiene at 573 K. The Ag and ZrO 2 components were synthesized on separate support particles enabling characterization of each component without interference from the other. High selectivity to butadiene (65%) at high ethanol conversion (75%) was achieved with an appropriate ratio of Ag and ZrO 2 in the reactor. Silver catalyzed the initial dehydrogenation of ethanol to acetaldehyde while ZrO 2 catalyzed the C-C coupling and subsequent dehydration reactions. The silica-supported ZrO 2 exhibited superior selectivity relative to bulk ZrO 2 in the Ag-promoted ethanol to butadiene reaction. Results from Zr K-edge X-ray absorption spectroscopy and UV-Vis spectroscopy showed that ZrO 2 was highly dispersed on the silica support over a range of loadings. Infrared spectroscopy of adsorbed pyridine, CO, and CO 2 , and kinetics of probe reactions 1-butene double bond isomerization, 2-propanol decomposition, and ethanol hydrogenation of acetone were used to compare the acid-base nature and chemical reactivity of silica-supported ZrO 2 to bulk ZrO 2 .

09 BIOMASS FUELS↗
DOE OSTI2025

Active Site Dynamics in Molybdenum-Based Silica-Supported Olefin Metathesis Catalysts: Site Renewal and Decay Beyond the Chauvin Cycle

Heterogeneous olefin metathesis catalysts exhibit low active site densities and unpredictable kinetics due to dynamic active site formation and decay processes. Here, in this study, we establish a quantitative framework that captures active site generation, renewal, and decay in olefin metathesis over silica-supported molybdenum oxide catalysts, enabling a mechanistic explanation of catalytic behavior and strategies to achieve high, stable activity. Steady-state active site titrations reveal that 2,3-dimethyl-butene isomers (4MEs) cofeeding increases active site density by up to 4.3-fold, directly correlating with enhanced metathesis rates. Spectroscopic studies demonstrate that 4MEs facilitate Mo(VI) reduction to Mo(IV) and interact strongly with surface Si–OH groups, generating labile protons that promote active site formation via a 1,2-proton shift mechanism. Kinetic modeling indicates that ethylene acts as a decay promoter, shifting kinetic control away from the Chauvin cycle and suppressing metathesis activity. Comparative studies on catalysts with varying Mo loading reveal that promotion is most effective for dispersed molybdate species, with a decline at higher Mo loadings. These findings provide a unified mechanistic framework for heterogeneous olefin metathesis, offering new strategies to enhance active site accessibility, mitigate deactivation, and optimize catalyst design.

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

Olefin Coupling Catalyzed by (Pybox)Os Complexes via Osmacyclopentane Intermediates: Comparison with Isoelectronic (Phebox)Ir

(Pybox)Os is found to catalyze alkene hydrovinylation, effecting the dimerization of ethylene, tail-to-tail coupling of propene and 1-butene, and cross-coupling of ethylene with higher α-olefins. This reactivity contrasts with the previously reported dehydrogenative coupling of ethylene to give butadiene catalyzed by the isoelectronic fragment (Phebox)Ir. The reaction mechanism was investigated through computational and experimental means. Both the Os- and Ir-catalyzed reactions proceed through a [2 + 2 + 1] cyclization of the corresponding bis-olefin complex to yield an experimentally observed metallacyclopentane intermediate. In both cases, the metallacyclopentane undergoes β- H elimination, via a dechelated κ 2 -pincer-ligated intermediate, to yield a σ−π-but-3-enyl hydride complex or derivative. Both the greater reactivity and the distinct chemoselectivity of the Os system relative to the Ir system are attributable to C−H reductive elimination by the σ−π-but-3-enyl hydride having a barrier for Os much lower than that for Ir. This lower barrier to C−H elimination for Os is unexpected given that the thermodynamic driving force for elimination is much less for Os than for Ir. Computational studies of model complexes were conducted, comparing (Pybox)Os(L)(CH 3 )(H) with the isoelectronic (Phebox)Ir(L)(CH 3 )(H). The results indicate that the more facile kinetics with Os relative to Ir may be general for C−H elimination from six-coordinate d 6 complexes of the two metals, as well as for the microscopic reverse, i.e., C−H addition to the corresponding four-coordinate d 8 species.

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

A Single Compartment Relaxed Eddy Accumulation Method

The relaxed eddy accumulation (REA) method is a widely-known technique that measures turbulent fluxes of scalar quantities. The REA technique has been used to measure turbulent fluxes of various compounds, such as methane, ethene, propene, butene, isoprene, nitrous oxides, ozone, and others. The REA method requires the accumulation of scalar concentrations in two separate compartments that conditionally sample updrafts and downdraft events. It is demonstrated here that the assumptions behind the conventional or two-compartment REA approach allow for one-compartment sampling, therefore called a one compartment or 1-C-REA approach, thereby expanding its operational utility. The one-compartment sampling method is tested across various land cover types and atmospheric stability conditions, and it is found that the one-compartment REA can provide results comparable to those determined from conventional two-compartment REA. This finding enables rapid expansion and practical utility of REA in studies of surface-atmosphere exchanges, interactions, and feedbacks.

Banerjee, T.↗
DOE OSTI2023

Nature-inspired methylated polyhydroxybutyrates from C1 and C4 feedstocks

Polyolefin plastics are widely used due to their low cost and outstanding properties, but their environmental persistence presents a major societal challenge. Polyhydroxyalkanoates (PHA) are biodegradable substitutes for polyolefins, but their high cost and thermal instability are impediments to their widespread application. Here we report a series of methylated polyhydroxybutyrates, poly(3-hydroxy-2-methylbutyrate)s, which are structurally inspired by natural PHAs. The cis homopolymers exhibit tacticity-independent crystallinity, which allows for the discovery of high-melting, thermally stable and mechanically tough copolymers, and a full range of polyolefin-like properties can be further achieved by tailoring the cis/trans ratio of the repeating units. Moreover, these materials can be synthesized from inexpensive carbon monoxide and 2-butene feedstocks, and they can be chemically recycled or upcycled at their end of life. As a result, the versatile properties, abundant feedstocks and end-of-life utility of this family of polyesters will enable a powerful platform for the discovery of sustainable alternatives to polyolefin plastics.

36 MATERIALS SCIENCE↗
DOE OSTI2020

An Experimental and Theoretical Study of the High Temperature Reactions of the Four Butyl Radical Isomers

The high temperature gas phase chemistry of the four butyl radical isomers (n-butyl,sec-butyl, iso-butyl, andtert-butyl) was investigated in a combined experimental and theoretical study. Organic nitrites were used as convenient and clean sources of each of the butyl radical isomers. Rate coefficients for dissociation of each nitrite were obtained experimentally and are at, or close to, the high pressure limit. Low pressure experiments were performed in a diaphragmless shock tube with laser schlieren densitometry at post-shock pressures of 65, 130, and 260 Torr and post-shock temperatures of 700-1000 K. Additional experiments were conducted with iso-butyl radicals at 805 K and 8.7 bar to elucidate changes in mechanism at higher pressures. These experiments were performed in a miniature shock tube with synchrotron-based photoionization mass spectrometry. The mass spectra confirmed that scission of the O-NO bond is the primary channel by which the precursors dissociate, but they also provided evidence of a minor channel (<7.7%) through HNO loss and formation of an aldehyde. These high pressure experiments were also used to determine the disproportionation/recombination ratio for iso-butyl radicals as 0.3. Reanalysis of the lower-temperature literature and the present data yielded rate constants for the disproportionation reaction, iso-butyl + iso-butyl = iso-butene + iso-butane. A chemical kinetics model was developed for the reactions of the butyl isomers that included new paths for highly energized adducts. These adducts are formed by the addition of H, CH 3 or C 2 H 5 to the butyl radicals. Accompanying theoretical investigations show that chemically activated pathways are competitive with stabilization of the adduct by collision under the conditions of the laser schlieren experiments. These calculations also show that at 10 bar and T< 1000 K stabilization is the only important reaction, but at higher temperatures, even at 10 bar, chemically activated product channels should also be considered. Branching fractions and rate coefficients are presented for these reactions. Furthermore, this study also highlights the importance of the radical structure for determining branching ratios for disproportionation and recombination of alkyl radicals, and these were facilitated by theoretical calculations of recombination rate coefficients for the four butyl radical isomers. Overall, the results reveal previously unknown features of butyl radical chemistry under conditions that are relevant to a wide range of applications and reaction mechanisms are presented that incorporate pressure dependent rate coefficients for the key steps.

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

Metallic and ferromagnetic carbon allotrope discovered using molecular precursors

Although carbon materials are known for their versatile structures and properties, a crystalline phase of carbon being both metallic and ferromagnetic is yet to be found. Here, using an organic molecular precursor 3,3-dimethyl-1-butene ( C 6 H 12 ) and a comprehensive theoretical study, we have discovered a metastable crystalline carbon phase that is both metallic and ferromagnetic under ambient conditions. The new carbon structures, produced by stacking puckered layers of 4,6-membered rings, are found to exhibit exotic electronic, magnetic, and mechanical properties originating from a special s p 2 − s p 3 bonding topology. These findings open the prospect of realizing the metallic and ferromagnetic carbon allotrope in practice. Published by the American Physical Society 2025

Fang, Hong (ORCID:0000000209688687)↗
DOE OSTI2022

Anaerobic Biohydrogenation of Isoprene by Acetobacterium wieringae Strain Y

Isoprene is a ubiquitously distributed, biogenic, and climate-active organic compound. Microbial isoprene degradation in oxic environments is fairly well understood; however, studies exploring anaerobic isoprene metabolism remain scarce, with no isolates for study available. Here, we obtained an acetogenic isolate, designated Acetobacterium wieringae strain Y, which hydrogenated isoprene to a mixture of methyl-1-butenes at an overall rate of 288.8 ± 20.9 μM day -1 with concomitant acetate production at a rate of 478.4 ± 5.6 μM day -1 . Physiological characterization demonstrated that isoprene was not utilized in a respiratory process; rather, isoprene promoted acetogenesis kinetically. Bioinformatic analysis and proteomics experiments revealed the expression of candidate ene-reductases responsible for isoprene biohydrogenation. Notably, the addition of isoprene to strain Y cultures stimulated the expression of proteins associated with the Wood-Ljungdahl pathway, indicating unresolved impacts of isoprene on carbon cycling and microbial ecology in anoxic environments (e.g., promoting CO 2 plus H 2 reductive acetogenesis while inhibiting methanogenesis). Our new findings advance understanding of microbial transformation of isoprene under anoxic conditions and suggest that anoxic environments are isoprene sinks.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Materials Data on NiC14S2N2O3 by Materials Project

(C)6NiC8N2S2O3 crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of four 1-butene molecules, four ethyne molecules, and two NiC8N2S2O3 clusters. In each NiC8N2S2O3 cluster, Ni2+ is bonded to two N3-, one S2-, and three O2- atoms to form distorted edge-sharing NiSN2O3 octahedra. There are one shorter (2.11 Å) and one longer (2.12 Å) Ni–N bond lengths. The Ni–S bond length is 2.38 Å. There are a spread of Ni–O bond distances ranging from 2.10–2.16 Å. There are eight inequivalent C1+ sites. In the first C1+ site, C1+ is bonded in a single-bond geometry to one C1+ and one N3- atom. The C–C bond length is 1.39 Å. The C–N bond length is 1.26 Å. In the second C1+ site, C1+ is bonded in a 2-coordinate geometry to two C1+ atoms. There is one shorter (1.31 Å) and one longer (1.37 Å) C–C bond length. In the third C1+ site, C1+ is bonded in a single-bond geometry to one N3- atom. The C–N bond length is 1.26 Å. In the fourth C1+ site, C1+ is bonded in a distorted bent 120 degrees geometry to two C1+ atoms. The C–C bond length is 1.36 Å. In the fifth C1+ site, C1+ is bonded in a single-bond geometry to one N3- atom. The C–N bond length is 1.41 Å. In the sixth C1+ site, C1+ is bonded in a 2-coordinate geometry to one C1+ atom. In the seventh C1+ site, C1+ is bonded in a single-bond geometry to one N3- atom. The C–N bond length is 1.41 Å. In the eighth C1+ site, C1+ is bonded in a 2-coordinate geometry to two C1+ atoms. There are two inequivalent N3- sites. In the first N3- site, N3- is bonded in a distorted trigonal planar geometry to one Ni2+ and two C1+ atoms. In the second N3- site, N3- is bonded in a distorted trigonal planar geometry to one Ni2+ and two C1+ atoms. There are two inequivalent S2- sites. In the first S2- site, S2- is bonded in a trigonal non-coplanar geometry to one S2- and three O2- atoms. The S–S bond length is 2.02 Å. There are a spread of S–O bond distances ranging from 1.45–1.57 Å. In the second S2- site, S2- is bonded in a 1-coordinate geometry to one Ni2+ and one S2- atom. There are three inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted L-shaped geometry to one Ni2+ and one S2- atom. In the second O2- site, O2- is bonded in a 3-coordinate geometry to two equivalent Ni2+ and one S2- atom. In the third O2- site, O2- is bonded in a single-bond geometry to one S2- atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

The Activation of Hydrogen by First-Row Transition-Metal Complexes. Final Report

We have assigned the vibrational spectra of Os 1 and Os 2 complexes of propene, butene, and acetylene, and have used them for the assignment of the vibrational frequencies of surface alkenes and alkynes. We have measured the rates of H• transfer from (C 5 R 5 )Cr(CO) 3 H to olefins of many structural types, and have learned that even one substituent on the carbon to which the H• is transferred slows down the reaction considerably. We have shown that these Cr hydrides are useful catalysts for chain transfer during radical polymerization reactions. We have determined the strengths of several M–H bonds (in particular Cr–H ones), and have confirmed that the hydrides of first-row transition metals are particularly useful for generating radicals. We have used H• transfer to terminal methylenes to generate radicals that cyclize. We have shown that (C 5 R 5 )Cr(CO) 3 H can be regenerated under H 2 and is therefore catalytic, but that (P–P)V(CO) 4 H cannot be regenerated from H 2 and therefore can only be used stoichiometrically for radical generation. (The V-H bonds are weaker than the Cr–H ones, and the H• transfer to an olefin is therefore faster.) We have found that, under five atm of H 2 pressure, cobaloximes catalyze H• transfer; they efficiently remove an H• from cyclized radicals, and therefore can be used to catalyze the cycloisomerization of some olefins. We have explored the one- and two-electron oxidation of (Ph 3 P) 6 Cu 6 H 6 . One-electron oxidation (which is reversible) generates a cation radical, whereas two-electron oxidation generates loss of a hydride (i.e., two electrons and a proton). We have found that the hydricity of (Ph 3 P) 6 Cu 6 H 6 is between 36 and 50 kcal/mol. We have shown that uncongested organic radicals (i.e., TEMPO) can catalyze H• transfer from (C 5 R 5 )Cr(CO) 3 H to congested radicals like Ar 3 C•. We have examined the one-electron oxidation of [CpV(CO 3 H] – , and have inferred from the results that the reduction of alkyl iodides with [CpV(CO 3 H] – occurs by one-electron transfer. We have been able to use that reagent to catalyze radical cyclizations from H 2 and appropriate alkyl iodides.

08 HYDROGEN↗
DOE OSTI2020

Single-reactor conversion of ethanol to 1-/2-butenes

A simplified processes for producing desired chemicals such as butenes from feedstock mixtures containing ethanol. In one set of embodiments this is performed in a single step, wherein a feed containing ethanol in a gas phase is passed over an acidic metal oxide catalyst having a transition metal dispersion of at least 5% on a metal oxide support. The ethanol content of the feedstock mixture may vary from 10 to 100 percent of the feed and in those non-eat applications the ethanol feed may contain water.

09 BIOMASS FUELS↗
DOE OSTI2021

Catalytic conversion of ethanol to 1-/2-butenes

Simple and economical conversion of aqueous ethanol feed streams into butenes by a single step method using transition metal oxides on a silica supports under preselected processing conditions. By directly producing a C4-rich olefin mixture from an ethanol containing stream various advantages are presented including, but not limited to, significant cost reduction in capital expenses and operational expenses.

Dagle, Vanessa M.↗