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The amide NH group decreases the overpotential of Mn-based CO 2 reduction catalysts by promoting the dimer and protonation-first pathways in the presence of H 2 O and enhances the CO 2 electroreduction activity by facilitating C–OH bond cleavage.
To activate methane at low or medium temperatures is a difficult task and a pre-requisite for the conversion of this light alkane into high value chemicals. In this work, we report the preparation and characterizations of novel SnO x /Cu 2 O/Cu(111) interfaces that enable low-temperature methane activation. Scanning tunneling microscopy identified small, well-dispersed SnO x nanoclusters on the Cu 2 O/Cu(111) substrate with an average size of 8 Å, and such morphology was sustained up to 450 K in UHV annealing. Ambient pressure X-ray photoelectron spectroscopy showed that hydrocarbon species (CH x groups), the product of methane activation, were formed on SnO x /Cu 2 O/Cu(111) at a temperature as low as 300 K. An essential role of the SnO x –Cu 2 O interface was evinced by the SnO x coverage dependence. Systems with a small amount of tin oxide, 0.1–0.2 ML coverage, produced the highest concentration of adsorbed CH x groups. Calculations based on density functional theory showed a drastic reduction in the activation barrier for C–H bond cleavage when going from Cu 2 O/Cu(111) to SnO x /Cu 2 O/Cu(111). On the supported SnO x , the dissociation of methane was highly exothermic (ΔE ~ –35 kcal mol –1 ) and the calculated barrier for activation (~20 kcal mol –1 ) could be overcome at 300–500 K, target temperatures for the conversion of methane to high value chemicals.
The proliferation of increasingly useful reactions for hydrogen transfer in organic synthesis has included the introduction of many new homogeneous catalysts into the organic synthesis lexicon. Unlike the proliferation of palladium-based cross-coupling reactions in which the mechanism is generally conserved, we are learning that these emerging hydrogen transfer catalysts have a rich diversity of mechanisms for catalyst activation, speciation, C–H bond cleavage and formation, and ultimately deactivation. We find that an underappreciated commonality in the catalytic activation for some of these systems is the generation of a (carbonyl)metal group, which dominates the downstream speciation of the catalyst system. In this mini-review we highlight a few well-documented cases of this phenomenon as food for thought for those who are designing new catalytic systems to introduce into this dynamic and impactful area.
Here, we report the synthesis and oxygen-atom transfer (OAT) photochemistry of [Cu(tpa)BrO 3 ]ClO 4 . In situ spectroscopy and in crystallo experiments indicate OAT proceeds from a Cu–O fragment generated by sequential Cu–O bond cleavage and OAT from BrO x to [Cu(tpa)] + . Furthermore, these results highlight synthetic opportunities in M–O photochemistry and demonstrate the utility of in crystallo experiments to evaluating photochemical reaction mechanisms.
Synthetic design has enabled increasing power conversion efficiency advances in organic photovoltaics (OPV). One continuing knowledge gap is detailed understanding of single-material chemical (photo)stability. Many considerations are based on prior OPV-relevant donor homopolymer systems rather than the next-generation push–pull architectures. Generally, energetic offsets between the lowest occupied molecular orbital of the donor and molecular oxygen are assumed to dictate kinetics of photo-induced charge transfer to a super oxide radical. Herein we determine the ambient-induced photo-degradation pathways, presented as proposed site-specific arrow-pushing mechanisms, for five donor polymers all containing the same push unit – alkylthienyl-substituted-benzodithiophene (BDTT) – but with chemically distinct pull units. The donor-only polymer films were subject to controlled photobleaching in air as an accelerated degradation approach, coupled with simultaneous monitoring of absorptance. Sample subsets were periodically removed and analyzed with X-ray photoelectron spectroscopy, to evaluate near-surface chemical composition and oxygen additions to hetero reporter atoms on either the BDTT push unit or distinct pull unit (i.e., sulphur and nitrogen). Here, this methodology allows us to distinguish between different mechanisms of bond cleavage and formation. Overall, we find that neither polymer redox properties nor individual push or pull unit stability are sufficient to predict photo-oxidative degradation of these polymers. Rather, there is a greater dependence on the susceptibility of unique structural groups within a polymeric system. Alkyl chain oxygen addition is generally the first attack site and direct sulfur oxidation on the conjugated backbone occurs after saturation of the alkyl chain initiation sites. This work provides a standard that could be used to evaluate relative photo-oxidative (in)stability for new OPV materials quickly – prior to time-consuming device optimization – and demonstrates an effective methodology for correlating optical degradation with chemical structure alterations via spectroscopic signatures to guide synthetic design.
Homogeneous earth abundant transition-metal electrocatalysts capable of carbon dioxide (CO 2 ) reduction to generate value-added chemical products are a possible strategy to minimize rising anthropogenic CO 2 emissions. Previously, it was determined that Cr-centered bipyridine-based N 2 O 2 complexes for CO 2 reduction are kinetically limited by a proton-transfer step during C–OH bond cleavage. Therefore, it was hypothesized that the inclusion of pendent relay groups in the secondary coordination sphere of these molecular catalysts could increase their catalytic activity. Here, it is shown that the introduction of a pendent methoxy group favorably impacts a pre-equilibrium protonation prior to the catalytic resting state, resulting in a significant increase in catalytic activity without a loss of product selectivity for generating carbon monoxide (CO) from CO 2 . Interestingly, combining the pendent methoxy group with a cationic acid causes a positive shift of the catalytic reduction potential of the system, while maintaining increased activity and quantitative selectivity. This work suggests that tuning the secondary coordination sphere with respect to cationic proton sources can result in activity improvements by modifying the kinetic and thermodynamic aspects of proton transfer in the catalytic cycle.
A structural and functional biomimetic Ni( ii )N 3 O complex, capable of O 2 mediated dioxygenase like C–C bond cleavage, via a putative high-valent Ni intermediate.
Conducting a comprehensive molecular-level evaluation of a photoacid generator (PAG) and its subsequent impact on lithography performance can facilitate the rational design of a promising 193 nm photoresist tailored to specific requirements. In this study, we integrated spectroscopy and computational techniques to meticulously investigate the pivotal factors of three prototypical PAG anions, p-toluenesulfonate (pTS - ), 2-(trifluoromethyl)benzene-1-sulfonate (TFMBS - ), and triflate (TF - ), in the lithography process. Our findings reveal a significant redshift in the absorption spectra caused by specific PAG anions, attributed to their involvement in electronic transition processes, thereby enhancing the transparency of the standard PAG cation, triphenylsulfonium (TPS + ), particularly at ~193 nm. Furthermore, the electronic stability of PAG anions can be enhanced by solvent effects with varying degrees of strength. Here we observed the lowest vertical detachment energy of 6.6 eV of pTS - in PGMEA solution based on the polarizable continuum model, which prevents anion loss at 193 nm lithography. In addition, our findings indicate gas-phase proton affinity values of 316.4 kcal/mol for pTS - , 308.1 kcal/mol for TFMBS - , and 303.2 kcal/mol for TF - , which suggest the increasing acidity strength, yet even the weakest acid pTS - is still stronger than strong acid HBr. The photolysis of TPS + -based PAG, TPS + ·pTS - , generated an excited state leading to homolysis bond cleavage with the lowest reaction energy of 83 kcal/mol. Overall, the PAG anion pTS - displayed moderate acidity, possessed the lowest photolysis reaction energy, and demonstrated an appropriate redshift. These properties collectively render it a promising candidate for an effective acid producer.
Significance Direct ethanol fuel cells are attracting growing attention as portable power sources due to their advantages such as higher mass-energy density than hydrogen and less toxicity than methanol. However, it is challenging to achieve the complete electrooxidation to generate 12 electrons per ethanol, resulting in a low fuel utilization efficiency. This manuscript reports the complete ethanol electrooxidation by engineering efficient catalysts via single-atom modification. The combined electrochemical measurements, in situ characterization, and density functional theory calculations unravel synergistic effects of single Rh atoms and Pt nanocubes and identify reaction pathways leading to the selective C–C bond cleavage to oxidize ethanol to CO 2 . This study provides a unique single-atom approach to tune the activity and selectivity toward complicated electrocatalytic reactions.
The enzyme soybean lipoxygenase (SLO) provides a prototype for deep tunneling mechanisms in hydrogen transfer catalysis. This work combines room temperature X-ray studies with extended hydrogen–deuterium exchange experiments to define a catalytically-linked, radiating cone of aliphatic side chains that connects an active site iron center of SLO to the protein–solvent interface. Employing eight variants of SLO that have been appended with a fluorescent probe at the identified surface loop, nanosecond fluorescence Stokes shifts have been measured. We report a remarkable identity of the energies of activation ( E a ) for the Stokes shifts decay rates and the millisecond C–H bond cleavage step that is restricted to side chain mutants within an identified thermal network. These findings implicate a direct coupling of distal protein motions surrounding the exposed fluorescent probe to active site motions controlling catalysis. While the role of dynamics in enzyme function has been predominantly attributed to a distributed protein conformational landscape, the presented data implicate a thermally initiated, cooperative protein reorganization that occurs on a timescale faster than nanosecond and represents the enthalpic barrier to the reaction of SLO.
We employed cryogenic X-ray Raman spectroscopy to investigate the early-stage decomposition of the high explosive molecule hexanitrohexaazaisowurtzitane (CL-20). By systematically varying the radiation dose under cryogenic conditions, we induced the decomposition of the molecule using ionizing radiation and observed the evolution of spectral features at the carbon, nitrogen, and oxygen K edges. Through extensive first-principles calculations, we identified key intermediates in the early stages of the decomposition process, resulting from C–C and C–N bond cleavage which leads to the opening of the internal cage structure. A detailed analysis of spectral trends and fingerprints provided evidence supporting N–NO 2 homolytic cleavage as the primary initial decomposition pathway. The combination of advanced core-level spectroscopy methods and state-of-the-art theoretical calculations enabled a comprehensive characterization of the molecular changes induced by controlled radiation dose exposures. In conclusion, our findings establish a benchmark for understanding the decomposition chemistry of high-explosive materials, offering important insights into their stability and reactivity under extreme conditions.
Highly selective oxidation of methane to methanol has long been challenging in catalysis. Here, we reveal key steps for the promotion of this reaction by water when tuning the selectivity of a well-defined CeO 2 /Cu 2 O/Cu(111) catalyst from carbon monoxide and carbon dioxide to methanol under a reaction environment with methane, oxygen, and water. Ambient-pressure x-ray photoelectron spectroscopy showed that water added to methane and oxygen led to surface methoxy groups and accelerated methanol production. These results were consistent with density functional theory calculations and kinetic Monte Carlo simulations, which showed that water preferentially dissociates over the active cerium ions at the CeO 2 –Cu 2 O/Cu(111) interface. The adsorbed hydroxyl species blocked O-O bond cleavage that would dehydrogenate methoxy groups to carbon monoxide and carbon dioxide, and it directly converted this species to methanol, while oxygen reoxidized the reduced surface. Water adsorption also displaced the produced methanol into the gas phase.
Photoenzymes are rare biocatalysts driven by absorption of a photon at each catalytic cycle; they inspire development of artificial photoenzymes with valuable activities. Fatty acid photodecarboxylase (FAP) is a natural photoenzyme that has potential applications in the bio-based production of hydrocarbons, yet its mechanism is far from fully understood. RATIONALE To elucidate the mechanism of FAP, we studied the wild-type (WT) enzyme from Chlorella variabilis (CvFAP) and variants with altered active-site residues using a wealth of techniques, including static and time-resolved crystallography and spectroscopy, as well as biochemical and computational approaches. RESULTS A 1.8-Å-resolution CvFAP x-ray crystal structure revealed a dense hydrogen-bonding network positioning the fatty acid carboxyl group in the vicinity of the flavin adenine dinucleotide (FAD) cofactor. Structures solved from free electron laser and low-dose synchrotron x-ray crystal data further highlighted an unusual bent shape of the oxidized flavin chromophore, and showed that the bending angle (14°) did not change upon photon absorption (step 1) or throughout the photocycle. Calculations showed that bending substantially affected the energy levels of the flavin. Structural and spectroscopic analysis of WT and mutant proteins targeting two conserved active-site residues, R451 and C432, demonstrated that both residues were crucial for proper positioning of the substrate and water molecules and for oxidation of the fatty acid carboxylate by 1 FAD* (~300 ps in WT FAP) to form FAD ∙– (step 2). Time-resolved infrared spectroscopy demonstrated that decarboxylation occured quasi-instantaneously upon this forward electron transfer, consistent with barrierless bond cleavage predicted by quantum chemistry calculations and with snapshots obtained by time-resolved crystallography. Transient absorption spectroscopy in H 2 O and D 2 O buffers indicated that back electron transfer from FAD ∙– was coupled to and limited by transfer of an exchangeable proton or hydrogen atom (step 3). Unexpectedly, concomitant with FAD ∙– reoxidation (to a red-shifted form FAD RS ) in 100 ns, most of the CO 2 product was converted, most likely into bicarbonate (as inferred from FTIR spectra of the cryotrapped FAD RS intermediate). Calculations indicated that this catalytic transformation involved an active-site water molecule. Cryo-Fourier transform infrared spectroscopy studies suggested that bicarbonate formation (step 4) was preceded by deprotonation of an arginine residue (step 3). At room temperature, the remaining CO 2 left the protein in 1.5 μs (step 4'). The observation of residual electron density close to C432 in electron density maps derived from time-resolved and cryocrystallography data suggests that this residue may play a role in stabilizing CO 2 and/or bicarbonate. Three routes for alkane formation were identified by quantum chemistry calculations; the one shown in the figure is favored by the ensemble of experimental data. CONCLUSION Finally, we provide a detailed and comprehensive characterization of light-driven hydrocarbon formation by FAP, which uses a remarkably complex mechanism including unique catalytic steps. We anticipate that our results will help to expand the green chemistry toolkit.
Transition metal reactivity toward carbon–hydrogen (C–H) bonds hinges on the interplay of electron donation and withdrawal at the metal center. Manipulating this reactivity in a controlled way is difficult because the hypothesized metal-alkane charge-transfer interactions are challenging to access experimentally. Using time-resolved x-ray spectroscopy, we track the charge-transfer interactions during C–H activation of octane by a cyclopentadienyl rhodium carbonyl complex. Changes in oxidation state as well as valence-orbital energies and character emerge in the data on a femtosecond to nanosecond timescale. The x-ray spectroscopic signatures reflect how alkane-to-metal donation determines metal-alkane complex stability and how metal-to-alkane back-donation facilitates C–H bond cleavage by oxidative addition. Furthermore, the ability to dissect charge-transfer interactions on an orbital level provides opportunities for manipulating C–H reactivity at transition metals.
Polyolefins and their chlorinated derivatives such as polyvinyl chloride (PVC) are among the most prevalent plastics in global production and waste streams. Traditional waste-to-energy methods such as incineration and pyrolysis, as well as most chemical upcycling methods for PVC utilization, require thorough, high-temperature dechlorination to prevent the release of toxic chlorinated compounds. Here, we present here a strategy for upgrading discarded PVC into chlorine-free fuel range hydrocarbons and hydrogen chloride in a single-stage process catalyzed by chloroaluminate ionic liquids. This approach offsets endothermic dechlorination and carbon-carbon bond cleavage with exothermic alkylation and hydrogen transfer by isobutane or isopentane in a low-temperature tandem process. The light isoalkanes are available from refinery processes and partly from recycling of the product stream. This process is suitable for handling real-world mixed and contaminated PVC and polyolefin waste streams.
A significant problem in biological X-ray crystallography is the radiation chemistry caused by the incident X-ray beam. This produces both global and site-specific damage. Site specific damage can misdirect the biological interpretation of the structural models produced. Cryo-cooling crystals has been successful in mitigating damage but not eliminating it altogether; however, cryo-cooling can be difficult in some cases and has also been shown to limit functionally relevant protein conformations. The doses used for X-ray crystallography are typically in the kilo-gray to mega-gray range. While disulfide bonds are among the most significantly affected species in proteins in the crystalline state at both cryogenic and higher temperatures, there is limited information on their response to low X-ray doses in solution, the details of which might inform biomedical applications of X-rays. In this work we engineered a protein that dimerizes through a susceptible disulfide bond to relate the radiation damage processes seen in cryo-cooled crystals to those closer to physiologic conditions. This approach enables a low-resolution technique, small angle X-ray scattering (SAXS), to detect and monitor a residue specific process. A dose dependent fragmentation of the engineered protein was seen that can be explained by a dimer to monomer transition through disulfide bond cleavage. This supports the crystallographically derived mechanism and demonstrates that results obtained crystallographically can be usefully extrapolated to physiologic conditions. Fragmentation was influenced by pH and the conformation of the dimer, providing information on mechanism and pointing to future routes for investigation and potential mitigation. The novel engineered protein approach to generate a large-scale change through a site-specific interaction represents a promising tool for advancing radiation damage studies under solution conditions.
Microwave co-gasification of plastics and biomass has several advantages over conventional gasification, including enhanced hydrogen production and greater solid-to-gas conversion, as opposed to undesirable char and tar -- via process electrification route. A previous study at NETL has revealed the efficient role of microwave heating, which can liberate the oxygenated free radicals and encourage bond cleavage in non-microwave active plastics, if combined with microwave-active corn stover. However, further reduction of the unwanted tar must be achieved for future process scale-up and higher energy efficiency, which can be realized via a microwave-assisted catalytic approach. This continuous study investigates a series of microwave-active Fe catalysts that can efficiently enhance H2 production and reduce tar for plastic-corn stover co-gasification. The results suggest that in presence of magnetite, hydrogen yield increase 100% as compared to non-catalytic system at similar reaction conditions.
The Overarching Goal of this proposed research is to understand and quantitively determine the interactions between non-thermal plasma (hot electrons, reactive radicals, vibrationally excited species) and surface reactions on influencing the activity and selectivity of the desired reactions via developing multi-scale model informed deep learning algorithm. Investigating non-thermal plasma-surface interaction is feasible due to the low bulk temperature in the discharge region. To investigate the role of plasma-nanoparticle interaction on enhancing the reaction kinetics, we will focus on ammonia cracking to generate clean hydrogen over earth-abundant, non-critical metallic nanoparticles, which is of great significance for decarbonization. We hypothesize that (1) reactive radicals interacting with surface reaction species via Eley–Rideal mechanism will significantly lower the energetics of the potential rate-limiting step of nitrogen formation; (2) the surface will be charged heterogeneously under non-thermal plasma conditions and the charged site will lower the energetics of ammonia cracking through Langmuir– Hinshelwood mechanism; (3) vibrationally excited ammonia will further promote the initial N-H bond cleavage. To access the hypothesis, we will (1) reveal the surface charge effects on tunning the reaction energetics via interpretable, physics-informed deep learning accelerated density functional theory (DFT) calculations; (2) determine the reactive radicals interacting with surface reaction species on tuning the reaction energetics via DFT; (3) reveal the surface charge effects on tunning the reaction energetics via DFT and deep learning models, (4) quantify how vibrationally excited species, reactive radicals, and surface charging effects on enhancing the catalysis via developing DFT-based microkinetic modeling (MKM) and active learning. Deep and active learning of plasma-nanoparticle interactions effects on enhancing ammonia cracking to generate hydrogen represents a new paradigm for designing high performance plasma materials. The fundamental science of how plasma-nanoparticle interactions will change the plasma kinetics and will improve the energy efficiency for decarbonization and sustainability. The interpretable and physics-informed machine learning model will accelerate low temperature plasma chemistry and material discovery with physics rules and model interpretation.