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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 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Low-temperature upcycling of polyolefins into liquid alkanes via tandem cracking-alkylation

Selective upcycling of polyolefin waste has been hampered by the relatively high temperatures that are required to cleave the carbon-carbon (C–C) bonds at reasonably high rates. We present a distinctive approach that uses a highly ionic reaction environment to increase the polymer reactivity and lower the energy of ionic transition states. Combining endothermic cleavage of the polymer C–C bonds with exothermic alkylation reactions of the cracking products enables full conversion of polyethylene and polypropylene to liquid isoalkanes (C 6 to C 10 ) at temperatures below 100°C. Both reactions are catalyzed by a Lewis acidic species that is generated in a chloroaluminate ionic liquid. The alkylate product forms a separate phase and is easily separated from the reactant catalyst mixture. The process can convert unprocessed postconsumer items to high-quality liquid alkanes with high yields.

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

Binding, Release and Functionalization of Intact Pnictogen Tetrahedra Coordinated to Dicopper Complexes

The bridging MeCN ligand in the dicopper(I) complexes [(DPFN)Cu 2 (μ,η 1 : η 1 -MeCN)][X] 2 (X=weakly coordinating anion, NTf 2 (1 a), FAl[OC 6 F 10 (C 6 F 5 )] 3 (1 b), Al[OC(CF 3 ) 3 ] 4 (1 c)) was replaced by white phosphorus (P 4 ) or yellow arsenic (As 4 ) to yield [(DPFN)Cu 2 (μ,η 2 : η 2 -E 4 )][X] 2 (E=P (2 a-c), As (3 a-c)). The molecular structures in the solid state reveal novel coordination modes for E 4 tetrahedra bonded to coinage metal ions. Experimental data and quantum chemical computations provide information concerning perturbations to the bonding in coordinated E 4 tetrahedra. Reactions with N-heterocyclic carbenes (NHCs) led to replacement of the E 4 tetrahedra with release of P 4 or As 4 and formation of [(DPFN)Cu 2 (μ,η 1 : η 1 - Me NHC)][X] 2 (4 a,b) or to an opening of one E-E bond leading to an unusual E 4 butterfly structural motif in [(DPFN)Cu 2 (μ,η 1 : η 1 -E 4 Dipp NHC)][X] 2 (E=P (5 a,b), E=As (6)). With a cyclic alkyl amino carbene ( Et CAAC), cleavage of two As-As bonds was observed to give two isomers of [(DPFN)Cu 2 (μ,η 2 : η 2 -As 4 Et CAAC)][X] 2 (7 a,b) with an unusual As 4 -triangle+1 unit.

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

Nitroarene Photoactivation Promotes Oxidative Deconstruction of Olefinic Polymers

Photoactivation of nitroarenes has been recently reported to induce the transformation of alkenyl bonds into carbonyl functionalities. Capitalizing on this unique photochemical mechanism, this study explores the use of nitroarenes to achieve oxidative cleavage of olefinic polymers under visible light irradiation. The degradation of various olefinic polymers, including commercially available polybutadiene, polynorbornene, both linear and cyclic poly(phenylacetylene), as well as backbone-modified polyacrylates with alkenyl functionality was investigated. To elucidate the efficacy of this methodology, a series of nitroarene derivatives bearing variable substituents were screened for their degradative efficiency on polybutadiene. Varying nitroarene stoichiometry, reaction temperature, and pos-treaction workup conditions were investigated to optimize degradation conditions. Furthermore, the results demonstrated that photoexcited nitroarenes enable efficient oxidative degradation of olefinic polymers in a safe and sustainable manner, providing a novel strategy for mild macromolecular deconstruction.

Bond cleavage↗
DOE OSTI2025

Structural and Mechanistic Advances in the Chemistry of Methyl-Coenzyme M Reductase (MCR)

Methane represents 34% of U.S. energy consumption and is a major greenhouse gas related to the global carbon cycle and energy production. However, current industrial practices significantly increase atmospheric methane levels, necessitating a deeper understanding of its biosynthesis and oxidation. Methyl-coenzyme M reductase (MCR) is central to biological methane metabolism, catalyzing the final step of methanogenesis and the first step in anaerobic methane oxidation. It is also a key target for strategies to capture and transform methane into value-added chemicals.The active site of MCR is a buried Ni-based cofactor only accessible by the substrates via a 50 Å long tunnel. Although the Ni(I) state is required to initiate catalysis, capturing this state remains a challenge for the current structural techniques. Recent advances in structural biology using X-ray Free-Electron Laser serial crystallography have provided insights into MCR's inactive Ni(II) state at room temperature and show promise for capturing its active Ni(I) form.Our team has established several critical aspects of the MCR mechanism using a combination of experimental and computational studies. MCR uses CH 3 -SCoM and CoBSH as substrates, producing methane and a disulfide product CoMSSCoB. Kinetic analysis showed that productive substrate binding requires CH 3 -SCoM to bind first, inducing conformational changes that optimize the active site for subsequent CoBSH binding. Following substrate binding, four proposed methane production/oxidation mechanisms were examined, establishing whether the reaction proceeds through an organometallic methyl-nickel(III), methyl anion ion, or methyl radical intermediate. Experimental measurements using CoBSH analogs successfully slowed the reaction, allowing for mechanistic insight that demonstrated the methyl radical pathway, where the initial interactions involve homolytic cleavage of the methyl-sulfur bond, generating a methyl radical that quickly abstracts the thiol hydrogen atom of CoBSH to form methane. Computational studies further confirmed that, compared to other mechanisms, the methyl radical mechanism is thermodynamically more favorable and accessible under physiological conditions.Spectroscopic and computational studies challenged the conventional understanding of substrate binding in MCR by proposing an alternative positioning of CH 3 -SCoM and CoMSSCoB in the active site pocket. The research suggested that CH 3 -SCoM (substrate) and CoMSSCoB (product) bind via their sulfonate groups to the Ni(I) center of cofactor F 430 . This binding allows for the reaction without substrate reorganization in the pocket but would require a long-range electron transfer. Altogether, the work summarized in this review reflects our current understanding of the enzyme's catalytic mechanism and structural dynamics. This is essential for developing efficient methane conversion technologies that could mitigate its environmental impact while harnessing energy-storage properties.

03 NATURAL GAS↗
DOE OSTI2020

Reactivity, Mechanism, and Assembly of the Alternative Nitrogenases

Biological nitrogen fixation is catalyzed by the enzyme nitrogenase, which facilitates the cleavage of the relatively inert triple bond of N 2 . Nitrogenase is most commonly associated with the molybdenum–iron cofactor called FeMoco or the M-cluster, and it has been the subject of extensive structural and spectroscopic characterization over the past 60 years. In the late 1980s and early 1990s, two “alternative nitrogenase” systems were discovered, isolated, and found to incorporate V or Fe in place of Mo. These systems are regulated by separate gene clusters; however, there is a high degree of structural and functional similarity between each nitrogenase. Limited studies with the V- and Fe-nitrogenases initially demonstrated that these enzymes were analogously active as the Mo-nitrogenase, but more recent investigations have found capabilities that are unique to the alternative systems. In this review, we will discuss the reactivity, biosynthetic, and mechanistic proposals for the alternative nitrogenases as well as their electronic and structural properties in comparison to the well-characterized Mo-dependent system. Studies over the past 10 years have been particularly fruitful, though key aspects about V- and Fe-nitrogenases remain unexplored.

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

Manganese Catalyzed Partial Oxidation of Light Alkanes

The catalytic partial oxidation of methane is achieved at low temperatures (<200 °C) using manganese oxides and manganese salts in mixtures of trifluoroacetic acid and trifluoroacetic anhydride. Dioxygen is used as the in situ terminal oxidant. For Mn oxides (e.g., MnO 2 , Mn 2 O 3 , and Mn 3 O 4 ), we studied stoichiometric methane partial oxidation in HTFA (TFA = trifluoroacetate). Using a Mn trifluoroacetate salt, at 180 °C and under 25 psig of methane, product selectivity for the mono-oxidized product methyl trifluoroacetate (MeTFA) is observed to be >90% at ~35% methane conversion at approximately 6 turnovers. Under our catalytic methane oxidation reaction conditions, MeTFA is stable against overoxidation, which explains the likely high selectivity at conversions >15%. Using combined experimental studies and DFT calculations, a mechanism involving soluble and molecular Mn species in the catalytic cycle is proposed. The proposed reaction pathway involves initial activation of Mn II by dioxygen, cleavage of a methane C–H bond by a Mn III hydroxo intermediate, rebound of the methyl radical to generate MeTFA, and finally regeneration of the starting Mn II complex. Also, this process is shown to be applicable to the oxidation of ethane, favoring the mono-oxidized product ethyl trifluoroacetate (EtTFA) and reaching ~46% conversion.

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

Gold-like activity copper-like selectivity of heteroatomic transition metal carbides for electrocatalytic carbon dioxide reduction reaction

An overarching challenge of the electrochemical carbon dioxide reduction reaction (eCO 2 RR) is finding an earth-abundant, highly active catalyst that selectively produces hydrocarbons at relatively low overpotentials. Here, we report the eCO 2 RR performance of two-dimensional transition metal carbide class of materials. Our results indicate a maximum methane (CH 4 ) current density of -421.63 mA/cm 2 and a CH 4 faradic efficiency of 82.7% ± 2% for di-tungsten carbide (W 2 C) nanoflakes in a hybrid electrolyte of 3 M potassium hydroxide and 2 M choline-chloride. Powered by a triple junction photovoltaic cell, we demonstrate a flow electrolyzer that uses humidified CO 2 to produce CH 4 in a 700-h process under one sun illumination with a CO 2 RR energy efficiency of about 62.3% and a solar-to-fuel efficiency of 20.7%. Density functional theory calculations reveal that dissociation of water, chemisorption of CO 2 and cleavage of the C-O bond—the most energy consuming elementary steps in other catalysts such as copper—become nearly spontaneous at the W2C surface. This results in instantaneous formation of adsorbed CO—an important reaction intermediate—and an unlimited source of protons near the tungsten surface sites that are the main reasons for the observed superior activity, selectivity, and small potential.

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

Rehybridization dynamics into the pericyclic minimum of an electrocyclic reaction imaged in real-time

Abstract Electrocyclic reactions are characterized by the concerted formation and cleavage of both σ and π bonds through a cyclic structure. This structure is known as a pericyclic transition state for thermal reactions and a pericyclic minimum in the excited state for photochemical reactions. However, the structure of the pericyclic geometry has yet to be observed experimentally. We use a combination of ultrafast electron diffraction and excited state wavepacket simulations to image structural dynamics through the pericyclic minimum of a photochemical electrocyclic ring-opening reaction in the molecule α-terpinene. The structural motion into the pericyclic minimum is dominated by rehybridization of two carbon atoms, which is required for the transformation from two to three conjugated π bonds. The σ bond dissociation largely happens after internal conversion from the pericyclic minimum to the electronic ground state. These findings may be transferrable to electrocyclic reactions in general.

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

Ultrafast Events in Electrocyclic Ring-Opening Reactions

Electrocyclic reactions are characterized by the concerted formation and cleavage of multiple σ and π bonds in a molecular system and have been extensively studied since they were introduced by Robert Burns Woodward and Roald Hoffmann in 1965. Recent advances and the integration of time-resolved experiments and nonadiabatic quantum molecular dynamics simulations have transformed the traditional understanding of electrocyclic reactions beyond the Woodward–Hoffmann rules. In this review, we focus on recent studies of 1,3-cyclohexadiene and two of its derivatives, α-phellandrene and α-terpinene, to shed light on the underlying mechanisms of electrocyclic photochemical reactions. We highlight recent progress in ultrafast electron diffraction techniques and the simulation approach of ab initio multiple spawning. Together, these approaches can elucidate molecular structure dynamics from femtosecond to picosecond timescales as well as nuclear and electronic responses at conical intersections.

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

Unifying principles for catalytic hydrotreating processes (Final Technical Report)

This project builds on the hypothesis that the hydrotreating processes for the removal of oxygen and sulfur are fundamentally similar at the atomic-scale and existing knowledge from the treatment of petroleum derived feedstock can be leveraged for the design of novel catalysts for the upgrade of bio-oil. We tested this hypothesis by comparing computed potential energy diagrams for hydrodesulfurization (HDS) of thiophene over MoS 2 with hydrodeoxygenation (HDO) of furan over MoO 3 and concluded that certain aspects, such as catalyst promotion with transition metals, are valid strategies for both reactions. On the other hand, we also noticed significant differences in the mechanism for hydrogen (H 2 ) activation, which requires sites with metallic character. While MoS 2 is known to have metallic edge states that can catalyze H 2 dissociation, this elementary step is prohibitively slow on defect-free oxides. Only in the presence of vacancies or by creating metal/oxide interfaces can efficient H 2 activation sites during HDO be formed. The need for bifunctional catalyst when it comes to efficient and selective HDO or dehydrogenation reactions was further corroborated in joint experimental and theoretical studies of the Guerbet reaction for the coupling of biomass derived oxygenates over PdCu alloys, nitrate reduction over In-promoted Pd nanoparticles, and ethylene dehydroaromatization over Ga-exchanged ZSM-5 zeolites. All of these catalytic systems have in common that catalytic sites with distinct functional requirements are needed to create a working catalyst. Detailed computational studies were carried out for HDO of m -cresol and phenol on Ru-modified TiO 2 surfaces, which allowed us to attribute catalytic activity to the metal/oxide interface. A surprising finding was that heterolytic cleavage of the H-H bond across the Ru/TiO 2 interface was critically important, despite lower barriers for homolytic H 2 activation on Ru metal. The explanation lies in the high barriers for hydrogen spillover from Ru to TiO 2 , which becomes unnecessary in the heterolytic activation pathway. Moreover, we also reported that proton transfer steps between metal and oxide sites are mediated by weakly adsorbed surface water. During attempts to develop and validate a kinetic Monte Carlo (kMC) model for HDO reactions at the Ru/TiO 2 interface, it became clear that lateral interactions are paramount to describe realistic surface chemistry and without these interactions, the reduction and hydroxylation behavior from our simulations was inconsistent with reported experiments. To assess the importance of lateral interactions in popular computational catalyst design strategies relying on the identification of reactivity descriptors, which can be used along with Brønsted–Evans–Polanyi (BEP) and scaling relations as input to a microkinetic model (MKM) to make predictions for activity or selectivity trends, we compared predicted trends with those obtained from descriptor-based kMC models. We critically evaluated the benefits of kMC over MKM in terms of trend predictions and computational cost when using only a small set of input parameters. After confirming that in the absence of lateral interactions the kMC and MKM approaches yield identical trends and mechanistic information, we observed substantial differences between the two kinetic models when lateral interactions were introduced. The mean-field implementation applies coverage corrections directly to the descriptors, causing an artificial overprediction of the activity of strongly binding metals. In contrast, the cluster expansion in kMC implementation can differentiate among the highly active metals but it is very sensitive to the set of included interaction parameters. Considering that computational screening relies on a minimal set of descriptors, for which MKM makes reasonable trend predictions at a ca. three orders of magnitude lower computational cost than kMC, we concluded that the MKM approach does provide an overall better entry point for computational catalyst design. Overall, this project has led to 11 peer-reviewed publications, and their scientific is impact is well illustrated by their combined 702 citations.

08 HYDROGEN↗
DOE OSTI2022

A photosensitive sustainable lignin nanoplatform for multimodal image-guided mitochondria-targeted photodynamic and photothermal therapy

Photoactivated nanocarriers exhibit significant potential for anticancer therapy, but complex design strategies, unsustainable substrates, and short wavelengths limit their practical application. Here, we designed a new lignin-derived photoactivated nanomaterial that exploits the sensitivity of the β-O-4 bond of lignin to singlet oxygen. This sustainable product was loaded with mitochondria-targeting chlorin e6 and black phosphorus quantum dots (BPQDs) to produce BPQDs@N-LgC NPs, which were used for mitochondria-targeted fluorescence/photoacoustic-guided photothermal and photodynamic therapy. When irradiated at 808 nm, the BPQDs in BPQDs@N-LgC NPs exhibited good photothermal conversion, which allowed photoacoustic imaging and inhibited tumor growth. When irradiated at 660 nm, the BPQDs@N-LgC NPs generated fluorescence and reactive oxygen species, which allowed photoluminescence imaging and further inhibited tumor growth. Cleavage of the β-O-4 bond of lignin by photo-triggered reactive oxygen species degraded the NPs and released the BPQDs, facilitating rapid excretion of the therapeutic nanomaterials. Our rationally designed BPQDs@N-LgC NPs exhibited good therapeutic efficacy, both in vitro and in vivo.

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

Kβ X-ray Emission Spectroscopy of Cu(I)-Lytic Polysaccharide Monooxygenase: Direct Observation of the Frontier Molecular Orbital for H 2 O 2 Activation

Lytic polysaccharide monooxygenases (LPMOs) catalyze the degradation of recalcitrant carbohydrate polysaccharide substrates. These enzymes are characterized by a mononuclear Cu(I) active site with a three-coordinate T-shaped “His-brace” configuration including the N-terminal histidine and its amine group as ligands. Here, this study explicitly investigates the electronic structure of the d 10 Cu(I) active site in a LPMO using Kβ X-ray emission spectroscopy (XES). The lack of inversion symmetry in the His-brace site enables the 3d/p mixing required for intensity in the Kβ valence-to-core (VtC) XES spectrum of Cu(I)-LPMO. These Kβ XES data are correlated to density functional theory (DFT) calculations to define the bonding, and in particular, the frontier molecular orbital (FMO) of the Cu(I) site. These experimentally validated DFT calculations are used to evaluate the reaction coordinate for homolytic cleavage of the H 2 O 2 O–O bond and understand the contribution of this FMO to the low barrier of this reaction and how the geometric and electronic structure of the Cu(I)-LPMO site is activated for rapid reactivity with H 2 O 2 .

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

Hydrogenolysis of n -eicosane over Ru-based catalysts in a continuous flow reactor

The hydrogenolysis of n-eicosane (C 20 H 42 ) was studied under differential conditions over Ru-based catalysts including Ru/SiO 2 , Ru/TiO 2 , and Ru/SBA-15, using a continuous flow reactor that was specially designed for large hydrocarbon reactants that are solids at room temperature. Similar rates and product distributions were obtained for Ru/SiO 2 and Ru/SBA-15 at 433 K, with the most abundant products being C 1 and C 19 hydrocarbons and smaller amounts of C 8 to C 18 also being produced. The higher yield of C 1 and C 19 indicates that cleavage of the terminal C-C bond is somewhat more facile than an internal C-C bond. At 473 K the product distribution shifted to mostly C 1 suggesting that, at this temperature, the adsorbed alkyl fragments undergo complete C-C bond scission prior to desorbing. Here, the conversion was also found to be inversely proportional to the H 2 pressure. Similar results were obtained for Ru/TiO 2 except this catalyst was found to be less active than both Ru/SiO 2 and Ru/SBA-15.

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

CFM-ID 4.0: More Accurate ESI MS/MS Spectral Prediction and Compound Identification

In the field of metabolomics, mass spectrometry (MS) is the method most commonly used for identifying and annotating metabolites. As this typically involves matching a given MS spectrum against an experimentally acquired reference spectral library, this approach is limited by the coverage and size of such libraries (which typically number in the thousands). These experimental libraries can be greatly extended by predicting the MS spectra of known chemical structures (which number in the millions) to create computational reference spectral libraries. To facilitate the generation of predicted spectral reference libraries we developed CFM-ID, a computer program that can accurately predict ESI-MS/MS spectrum for a given compound structure. CFM-ID is one of the best-performing methods for compound-to-mass-spectrum prediction, and also one of the top tools for in silico mass-spectrum-to-compound identification. This work improves CFM-ID’s ability to predict ESI-MS/MS spectra from compounds by: (1) learning parameters from features based on the molecular topology, (2) adding a new approach to ring cleavage that models such cleavage as a sequence of simple chemical bond dissociations and (3) expanding its hand-written rule-based predictor to cover more chemical classes, including acylcarnitines, acylcholines, flavonols, flavones, flavanones, and flavonoid glycosides. We demonstrate that this new version of CFM-ID (version 4.0) is significantly more accurate than previous CFM-ID versions, in terms of both EI-MS/MS spectral prediction and compound identification. CFM-ID 4.0 is available at http://cfmid4.wishartlab.com/ as a webservice and docker images can be downloaded at https://hub.docker.com/r/wishartlab/cfmid

Wang, Fei↗
DOE OSTI2026

Understanding Electrochemical Alcohol Hydrogenolysis Enabled by Carbonyl Reduction in Lignocellulosic Biomass-Derived Aromatic Oxygenates

Molecules derived from lignocellulosic biomass are oxygenates with multiple oxygen-containing functional groups, such as hydroxyl and carbonyl groups. Therefore, the ability to selectively reduce a specific oxygenate group is essential for the reductive upgrading of such molecules. Previous studies on electrochemical biomass conversion have shown that alcohol hydrogenolysis, which involves cleavage of the σ(C–O alcohol ) bond, is extremely challenging for furfural and 5-hydroxymethylfurfural (HMF) derivatives, including furfuryl alcohol, 5-methylfurfuryl alcohol (MFA), and 2,5-bis(hydroxymethyl)furan (BHMF). In contrast, HMF itself undergoes alcohol hydrogenolysis relatively easily in acidic aqueous media. Considering that the only structural difference between HMF and BHMF or MFA is the presence of a carbonyl group, this observation raises the question of whether the carbonyl group in HMF facilitates alcohol hydrogenolysis. In this study, we designed systematic experiments to provide a coherent explanation of when and how a carbonyl group enables hydrogenolysis of a copresent alcohol group. Specifically, we show that alcohol hydrogenolysis in HMF proceeds via reduction of the carbonyl group to a ketyl radical, followed by a spin-center shift (SCS) through extended π conjugation. We also elucidate the effect of pH on the selectivity between carbonyl hydrogenation and alcohol hydrogenolysis, both of which share the ketyl radical intermediate. This mechanistic understanding enhances our ability to predict and control alcohol hydrogenolysis in the reductive upgrading of biomass-derived oxygenates.

alcohols↗
DOE OSTI2024

AP-XPS Study of the Reaction of O 2 and CO 2 with Zn–Au(111) Surface Alloys: Activation of O–O/C–O Bonds and the Formation of ZnO

Synchrotron-based ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) was used to study the dissociation of O 2 and CO 2 on Zn-Au(111) alloys which contained 0.2-0.3 monolayers of zinc. Although Au(111) is inert, the alloys displayed a high activity for the cleavages of O-O and C-O bonds at room temperature with the formation of ZnO x species. Dissociative adsorption of O 2 at 300 K destroyed the alloys and the results of AP-XPS pointed to the co-existence of two types of oxygen species on the surface: ZnO x and chemisorbed O atoms (O chem ) on Au or the Au-ZnO interface. Annealing from room temperature to 600 K induced a O chem → ZnO x transformation that reflected the poor stability of O atoms on Au(111). The Zn-Au(111) systems exhibited a reactivity towards CO 2 that was much larger than that seen for Au(111), Cu(111) or surfaces of late transition metals like, Ni, Pd or Pt. At 300 K, CO 2 underwent partial dissociation depositing large amounts of O chem on the surface with minor formation of ZnO x . In addition, the deposited O chem reacted with CO 2 to form surface carbonate groups. Dosing of CO 2 at 500-600 K mainly led to the formation of ZnO x and the surface carbonate almost disappeared. In the presence of hydrogen, i.e. reaction feeds with a CO 2 to H 2 ratio of 1:3, the surface chemistry at 300 K was very similar to that seen for pure CO 2 with the formation of ZnO x and carbonate groups. In contrast, at 500-600 K, reaction with hydrogen induced the removal of ZnO x and CO 3 /HCOO species. Finally, our AP-XPS results are consistent with the idea that CO 2 hydrogenation on AuZn alloys involves a redox process where there is sequential oxidation by CO 2 and reduction by H 2 to yield methanol.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Skeletal Ni electrode-catalyzed C-O cleavage of diaryl ethers entails direct elimination via benzyne intermediates

Diaryl ethers undergo electrocatalytic hydrogenolysis (ECH) over skeletal Ni cathodes in a mild, aqueous process that achieves direct C-O cleavage without initial benzene ring saturation. Mechanistic studies find that aryl phenyl ethers with a single para or meta functional group (methyl, methoxy, or hydroxy) are selectively cleaved to the substituted benzene and phenol, in contrast to recently reported homogeneous catalytic cleavage processes. Ortho positioning of substituents reverses this C-O bond selectivity, except for the 2-phenoxyphenol case. Together with isotope labeling and co-solvent studies, these results point to two distinct cleavage mechanisms: (a) dual-ring coordination and C-H activation, leading to vicinal elimination to form phenol and a surface-bound aryne intermediate which is then hydrogenated and released as the arene; and (b) surface binding in keto form by the phenolic ring of the hydroxy-substituted substrates, followed by direct displacement of the departing phenol. Notably, acetone inhibits the well-known reduction of phenol to cyclohexanol, affording control of product ring saturation. A byproduct of this work is the discovery that the ECH treatment completely defluorinates substrates bearing aromatic C-F and C-CF 3 groupings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗