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At least 1,261 records · Page 70
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Mechanistic Investigations of Gas-Phase Catalytic Hydrogenation in Metal–Organic Frameworks: Cooperative Activity of the Metal and Linker Sites in Cu x Rh 3– x (BTC) 2

We report the Cu x Rh 3–x (BTC) 2 catalyst (abbreviated CuRhBTC, BTC 3– = benzene tricarboxylate) provides excellent dispersion of active metal sites coupled with well-defined, robust structures for propylene hydrogenation reactions. This material therefore serves as a unique prototype for understanding catalytic activity in metal organic frameworks (MOFs). The mechanism of gas-phase hydrogenation at the bimetallic metal nodes of a MOF has been investigated in detail for the first time using in situ spectroscopy and diffraction experiments combined with density functional theory (DFT) calculations. The reaction occurs via a cooperative process in which the metal and linker sites play complementary roles; specifically, H 2 is dissociated at a Rh 2+ site with a missing Rh–O bond, while protonation of the decoordinated carboxylate linker stabilizes the active sites and promotes H 2 dissociation. In situ X-ray diffraction experiments show that the crystalline structure of the MOF is retained under reaction conditions at 20–100 °C. In situ Raman spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments demonstrate that propylene adsorbs at both Rh 2+ and Cu 2+ sites via π bonding. Cu 2+ is catalytically inactive, but at Rh 2+ sites, a propyl intermediate is observed when H 2 is introduced into the propylene feed. Furthermore, the appearance of the O–H stretch of COOH at ~3690 cm –1 in the DRIFT spectra is characteristic of defects consisting of missing Rh–O bonds. These experimental results are in general agreement with a reaction mechanism proposed by DFT, in which the decoordinated carboxylate linker is protonated, and the active Rh 2+ site remains available for readsorption of reactants in the subsequent catalytic cycle.

36 MATERIALS SCIENCE↗
DOE OSTI2017

A Combined Probe-Molecule, Mössbauer, Nuclear Resonance Vibrational Spectroscopy, and Density Functional Theory Approach for Evaluation of Potential Iron Active Sites in an Oxygen Reduction Reaction Catalyst

While non-precious metal M-N-C (M = Fe or Co) catalysts have been developed that are effective for the oxygen reduction reaction in polymer electrolyte fuel cells, no consensus has yet been reached regarding the nature of the M sites in these heterogeneous catalysts that are responsible for reaction with dioxygen (O 2 ). While multiple studies have developed correlations between Fe distributions in as-prepared catalysts and ORR activity, the direct identification of sites reactive towards O 2 or O 2 -analog molecules remains a significant challenge. In the present study, we demonstrate a new approach to identifying and characterizing potential Fe active sites in complex ORR catalysts that combines an effective probe molecule (NO (g) ) Mössbauer spectroscopy and nuclear resonance vibrational spectroscopy (NRVS) with density functional theory (DFT) calculations. Mössbauer spectroscopic studies demonstrate that NO (g) treatment of electrochemically reduced PANI-57Fe-C leads to selective reaction with only a sub-set of the Fe species present. Nuclear resonance vibrational spectroscopic studies identified new Fe-ligand vibrations associated with the site reactive towards NO (g) . DFT calculations of vibrational properties of a small selection of previously proposed active site structures suggest that graphene zig-zag edge hosted Fe-N structures may be responsible for the observed vibrational behavior with NO (g) probe molecules. Moreover, such sites are likely also reactive to O 2 , possibly serving as the ORR active sites in the synthesized materials.

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

Periodic Trends in Adsorption Energies around Single-Atom Alloy Active Sites

Single-atom alloys (SAAs) make up a special class of alloy surface catalysts that offer well-defined, isolated active sites in a more inert metal host. The dopant sites are generally assumed to have little or no influence on the properties of the host metal, and transport of chemical reactants and products to and from the dopant sites is generally assumed to be facile. Here, by performing density functional theory calculations and surface science experiments, we identify a new physical effect on SAA surfaces, whereby adsorption is destabilized by ≤300 meV on host sites within the perimeter of the reactive dopant site. We identify periodic trends for this behavior and demonstrate a zone of exclusion around the reactive sites for a range of adsorbates and combinations of host and dopant metals. Experiments confirm an increased barrier for diffusion of CO toward the dopant on a RhCu SAA. Furthermore, this effect offers new possibilities for understanding and designing active sites with tunable energetic landscapes surrounding them.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Dialing in Catalytic Sites on Metal Organic Framework Nodes: MIL-53(Al) and MIL-68(Al) Probed with Methanol Dehydration Catalysis

Many metal organic frameworks (MOFs) incorporate metal oxide clusters as nodes. Node sites where linkers are missing can be catalytic sites. We now show how to dial in the number and occupancy of such sites in MIL-53 and MIL-68, which incorporate aluminum-oxide-like nodes. Here, the methods involve modulators used in synthesis and postsynthesis reactions to control the modulator-derived groups on these sites. We illustrate the methods using formic acid as a modulator, giving formate ligands on the sites, and these can be removed to leave μ 2 -OH groups and open Lewis acid sites. Methanol dehydration was used as a catalytic reaction to probe these sites, with infrared spectra giving evidence of methoxide ligands as reaction intermediates. Control of node surface chemistry opens the door for placement of a variety of ligands on a wide range of metal oxide cluster nodes for dialing in reactivity and catalytic properties of a potentially immense class of structurally well-defined materials.

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

Computational Investigation of the Role of Active Site Heterogeneity for aSupported Organovanadium(III) Hydrogenation Catalyst

A crucial consideration for supported heterogeneous catalysts is the nonuniformity of the active sites, particularly for supported organometallic catalysts. Standard spectroscopic techniques, such as X-ray absorption spectroscopy, reflect the nature of the most populated sites, which are often intrinsically structurally distinct from the most active catalytic sites. Additionally, with computational models, often, only a few representative structures are used to depict catalytic active sites on a surface, even though there are numerous observable factors of surface heterogeneity that contribute to the kinetically favorable active species. A previously reported study on the mechanism of a surface organovanadium-(III) catalyst [(SiO 2 )V III (Mes)(THF)] for styrene hydrogenation yielded two possible mechanisms: heterolytic cleavage and redox cycling. These two mechanistic scenarios are challenging to differentiate experimentally since the kinetic readouts of the catalyst are identical. To showcase the importance of modeling surface heterogeneity and its effect on catalytic activity, density functional theory (DFT) computational models of a series of potential active sites of [(SiO 2 )V III (Mes)(THF)] for the reaction pathways are applied in combination with kinetic Monte Carlo (kMC) simulations. Computed results were then compared to the previously reported experimental kinetic study: (1) DFT free-energy reaction pathways indicated the likely active site and pathway for styrene hydrogenation, a heterolytic cleavage pathway requiring a bare tripodal vanadium site. (2) From the kMC simulations, a mixture of different bond lengths from the support oxygen to the metal center was required to qualitatively describe the experimentally observed kinetic aspects of a supported organovanadium(III) catalyst for olefin hydrogenation. This work underscores the importance of modeling surface heterogeneity in computational catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Discovery and Characterization of Non-ATP Site Inhibitors of the Mitogen Activated Protein (MAP) Kinases

Inhibition of protein kinases has validated therapeutic utility for cancer, with at least seven kinase inhibitor drugs on the market. Protein kinase inhibition also has significant potential for a variety of other diseases, including diabetes, pain, cognition, and chronic inflammatory and immunologic diseases. However, as the vast majority of current approaches to kinase inhibition target the highly conserved ATP-binding site, the use of kinase inhibitors in treating nononcology diseases may require great selectivity for the target kinase. As protein kinases are signal transducers that are involved in binding to a variety of other proteins, targeting alternative, less conserved sites on the protein may provide an avenue for greater selectivity. Here we report an affinity-based, high-throughput screening technique that allows nonbiased interrogation of small molecule libraries for binding to all exposed sites on a protein surface. This approach was used to screen both the c-Jun N-terminal protein kinase Jnk-1 (involved in insulin signaling) and p38{alpha} (involved in the formation of TNF{alpha} and other cytokines). In addition to canonical ATP-site ligands, compounds were identified that bind to novel allosteric sites. The nature, biological relevance, and mode of binding of these ligands were extensively characterized using two-dimensional {sup 1}H/{sup 13}C NMR spectroscopy, protein X-ray crystallography, surface plasmon resonance, and direct enzymatic activity and activation cascade assays. Jnk-1 and p38{alpha} both belong to the MAP kinase family, and the allosteric ligands for both targets bind similarly on a ledge of the protein surface exposed by the MAP insertion present in the CMGC family of protein kinases and distant from the active site. Medicinal chemistry studies resulted in an improved Jnk-1 ligand able to increase adiponectin secretion in human adipocytes and increase insulin-induced protein kinase PKB phosphorylation in human hepatocytes, in similar fashion to Jnk-1 siRNA and to rosiglitazone treatment. Together, the data suggest that these new ligand series bind to a novel, allosteric, and physiologically relevant site and therefore represent a unique approach to identify kinase inhibitors.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2014

Evidence That the [beta] Subunit of Chlamydia trachomatis Ribonucleotide Reductase Is Active with the Manganese Ion of Its Manganese(IV)/Iron(III) Cofactor in Site 1

The reaction of a class I ribonucleotide reductase (RNR) begins when a cofactor in the {beta} subunit oxidizes a cysteine residue {approx}35 {angstrom} away in the {alpha} subunit, generating a thiyl radical. In the class Ic enzyme from Chlamydia trachomatis (Ct), the cysteine oxidant is the Mn{sup IV} ion of a Mn{sup IV}/Fe{sup III} cluster, which assembles in a reaction between O{sub 2} and the Mn{sup II}/Fe{sup II} complex of {beta}. The heterodinuclear nature of the cofactor raises the question of which site, 1 or 2, contains the Mn{sup IV} ion. Because site 1 is closer to the conserved location of the cysteine-oxidizing tyrosyl radical of class Ia and Ib RNRs, we suggested that the Mn{sup IV} ion most likely resides in this site (i.e., {sup 1}Mn{sup IV}/{sup 2}Fe{sup III}), but a subsequent computational study favored its occupation of site 2 ({sup 1}Fe{sup III}/{sup 2}Mn{sup IV}). In this work, we have sought to resolve the location of the Mn{sup IV} ion in Ct RNR-{beta} by correlating X-ray crystallographic anomalous scattering intensities with catalytic activity for samples of the protein reconstituted in vitro by two different procedures. In samples containing primarily Mn{sup IV}/Fe{sup III} clusters, Mn preferentially occupies site 1, but some anomalous scattering from site 2 is observed, implying that both {sup 1}Mn{sup II}/{sup 2}Fe{sup II} and {sup 1}Fe{sup II}/{sup 2}Mn{sup II} complexes are competent to react with O{sub 2} to produce the corresponding oxidized states. However, with diminished Mn{sup II} loading in the reconstitution, there is no evidence for Mn occupancy of site 2, and the greater activity of these 'low-Mn' samples on a per-Mn basis implies that the {sup 1}Mn{sup IV}/{sup 2}Fe{sup III}-{beta} is at least the more active of the two oxidized forms and may be the only active form.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Effects of Cofeeding Hydrogen on Propane Dehydrogenation Catalyzed by Isolated Iron Sites Incorporated into Dealuminated BEA

Iron sites dispersed on nonacidic siliceous supports have been reported to be catalytically active for propane dehydrogenation (PDH), yet the precise relationship between site structure and catalytic activity remains elusive. Here, this study provides a comprehensive understanding of the catalytic performance of iron supported on dealuminated BEA (DeAlBEA) zeolites for PDH. Using XAS, UV-vis, and IR spectroscopy of adsorbed pyridine and deuterated acetonitrile, it was found that, at an Fe/Al 0 of 0.04, isolated Fe sites form. These isolated sites exhibit a forward rate of PDH of 213 mol propene/mol Fe·h at 823 K and a feed containing 15 kPa propane. When 15 kPa of H 2 is added to the feed, the forward rate of PDH rises to 391 mol of propene/mol of Fe·h. In both cases, the propene selectivity is over 99%. IR spectroscopy of d 3 -acetonitrile suggests that the open Lewis acid site ((-Si-O-) 2 Fe 3+ -OH) serves as the active site responsible for PDH, while Brønsted acid sites (≡Fe 3+ -O(H)-Si≡) contribute to propane cracking with increasing Fe/Al 0 ratios. Kinetic analysis of the effects of H 2 addition to the propane feed on PDH kinetics shows that H 2 enhances the activity of 0.04FeDeAlBEA primarily by enhancing the strength of the propane adsorption.

Alghannam, Afnan [University of California, Berkel↗
DOE OSTI2019

Dynamic Reorganization and Confinement of Ti IV Active Sites Controls Olefin Epoxidation Catalysis on Two-Dimensional Zeotypes

The effect of dynamic reorganization and confinement of isolated Ti IV catalytic centers supported on silicates is investigated for olefin epoxidation. Active sites consist of grafted single-site calix[4]arene–Ti IV centers or their calcined counterparts. Their location is synthetically controlled to be either unconfined at terminal T-atom positions (denoted as type-(i)) or within confining 12-MR pockets (denoted as type-(ii); diameter ~7 Å, volume ~185 Å 3 ) composed of hemispherical cavities on the external surface of zeotypes with *-SVY topology. Electronic structure calculations (density functional theory) indicate that active sites consist of cooperative assemblies of TiIV centers and silanols. When active sites are located at unconfined type-(i) environments, the rate constants for cyclohexene epoxidation (323 K, 0.05 mM TiIV, 160 mM cyclohexene, 24 mM tert-butyl hydroperoxide) are 9 ± 2 M –2 s –1 ; whereas within confining type-(ii) 12-MR pockets, there is a ~5-fold enhancement to 48 ± 8 M –2 s –1 . When a mixture of both environments is initially present in the catalyst resting state, the rate constants reflect confining environments exclusively (40 ± 11 M–2 s–1), indicating that dynamic reorganization processes lead to the preferential location of active sites within 12-MR pockets. While activation enthalpies are ΔH ‡ app = 43 ± 1 kJ mol–1 irrespective of active site location, confining environments exhibit diminished entropic barriers (ΔS ‡ app = -68 J mol –1 K –1 for unconfined type-(i) vs -56 J mol –1 K –1 for confining type-(ii)), indicating that confinement leads to more facile association of reactants at active sites to form transition state structures (volume ~ 225 Å 3 ). These results open new opportunities for controlling reactivity on surfaces through partial confinement on shallow external-surface pockets, which are accessible to molecules that are too bulky to benefit from traditional confinement within micropores.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Dual-Site Cascade Oxygen Reduction Mechanism on SnO x /Pt–Cu–Ni for Promoting Reaction Kinetics

Designing highly active oxygen reduction reaction (ORR) catalysts is crucial to boost the fuel cell economy. Previous research has mainly focused on Pt-based alloy catalysts in which surface Pt is the solely active site and the activity improvement was challenged by the discovered scaling relationship. In this paper, we report a new concept of utilizing dual active sites for the ORR and demonstrate its effectiveness by synthesizing a SnO x /Pt-Cu-Ni heterojunctioned catalyst. A maximum of 40% enhancement in the apparent specific activity, which corresponds to 10-fold enhancement on interface sites, is measured compared with pure Pt-Cu-Ni. Detailed investigations suggest an altered dual-site cascade mechanism wherein the first two steps occur on SnO x sites and the remaining steps occur on adjacent Pt sites, allowing a significant decrease in the energy barrier. This study with the suggested dual-site cascade mechanism shows the potential to overcome the ORR energy barrier bottleneck to develop highly active catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

The Distribution of Ti3+ Surface Sites in Reduced TiO2

We describe a DFT+U study of the (110) rutile surface with oxygen vacancies (Ov). Oxygen vacancies leave behind two excess unpaired electrons per Ov the formation of two Ti3+ ions. We investigate the location of the Ti3+ ions within the first three surface layers. In total we obtained 49 unique solutions of possible Ti3+ pairs, to examine the stability of all Ti types (e.g. five-coordinated surface Ti, six-coordinated surface Ti, sub-surface sites, etc.). Our results show that sub-surface sites are preferred, but that many configurations are close in energy, up to 0.3-0.4 eV of each other. In contrast to findings in previous work, we show that sites directly adjacent to the Ov are unstable. Analysis of our results show that the two Ti3+ ions within a pair behave independent of each other, as there are little electronic interactions between the excess electrons associated with these sites. We also examined the migration of Ti3+ sites from the surface into the bulk and find the surface locations to be preferred by ~ 0.5 eV relative to the bulk. Our systematic results provide a comprehensive picture of excess electrons that indicates that they are not trapped or localized at specific sites, but are distributed across several sites due to nearly degenerate Ti3+ states. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Influence of Adsorption Site and Wavelength on the Photodesorption of NO from the (Fe,Cr) 3 O 4 (111) Mixed Oxide Surface

The photochemical properties of nitric oxide on a mixed oxide single crystal surface was examined in ultrahigh vacuum (UHV) using temperature programmed desorption (TPD), photon stimulated desorption (PSD) and low energy electron diffraction (LEED). The mixed oxide was a 75% Fe and 25% Cr corundum (0001) oxide film prepared on an α-Al2O3(0001) crystal, however its surface became terminated with a magnetite-like (111) structure after sputter/anneal cleaning, leading to a surface designated of (Fe,Cr)3O4(111). TPD of NO from the (Fe,Cr)3O4(111) surface revealed three chemisorbed states at 220, ~315 and 370 K assigned to NO binding at Fe3+, Cr3+ and Fe2+ sites, respectively. No significant thermal chemistry of NO was detected. NO photodesorption, the primary photochemical pathway in UHV, was sensitive to the adsorption site, with rates at the three adsorption sites following the trend: Fe3+ > Fe2+ > Cr3+. Multiexponential rate behavior seen in the overall NO PSD spectra was linked directly to site heterogeneity being manifested as a convolution of the individual NO photodesorption rates at the three types of surface sites. The photodesorption rate with UV light (365 nm) was ~10 times greater than that in the visible, but the per-photon rates across the visible spectrum (from 460 to 630 nm) were independent of the wavelength, which is suggestive of localized photon absorption at the adsorption site. Results in this study demonstrate that the adsorption site plays a critical role in determining photochemical rates on complex oxide surfaces. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multi-program national laboratory operated for DOE by Battelle. The research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Site-dependent reactivity of MoS2 nanoparticles in hydrodesulfurization of thiophene

The catalytically active site for the removal of S from organosulfur compounds in catalytic hydrodesulfurization has been attributed to a generic site at an S-vacancy on the edge of MoS2 particles. However, steric constraints in adsorption and variations in S-coordination means that not all S-vacancy sites should be considered equally active. Here, we use a combination of atom-resolved scanning probe microscopy and density functional theory to reveal how the generation of S-vacancies within MoS2 nanoparticles and the subsequent adsorption of thiophene (C4H4S) depends strongly on the location on the edge of MoS2. Thiophene adsorbs directly at open corner vacancy sites, however, we find that its adsorption at S-vacancy sites away from the MoS2 particle corners leads to an activated and concerted displacement of neighboring edge S. This mechanism allows the reactant to self-generate a double CUS site that reduces steric effects in more constrained sites along the edge.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Creation of discrete active site domains via mesoporous silica poly(styrene) composite materials for incompatible acid–base cascade reactions

This work highlights the design and synthesis of bifunctional mesoporous silicate – polymer composite dual acid–base supported cascade catalysts. Compartmentalization of the two incompatible active sites is sought by segregating acid sites on the silica surface, and base sites within polymer chains and/or polymer domains. The ability to isolate and segregate active sites via control of the mesoporous silica pore size and polymer molecular weight is probed with silica samples functionalized by a grafting-to process. Supplemental activator and reducing agent (SARA) atom transfer radical polymerization is used to synthesize random copolymers containing protected primary amines. Thiol–ene ‘click’ chemistry facilitates silica functionalization via a convergent approach, with the ene-functionalized polymer end group and silica-grafted thiols forming SBA/MCM-SH-poly(styrene-co-2-(4-vinylbenzyl)isoindoline-1,3-dione). Polymer deprotection and thiol oxidation produces primary amine/sulfonic acid containing composite catalysts. With the polymer supported Lewis base and silica grafted Brønsted acid, the two-step deacetalization – Knoevenagel condensation cascade is explored to assess the ability of these polymer/silica hybrids to segregate active sites, allowing both acid and base site accessibility. Six composite catalysts are synthesized and tested in individual and cascade reactions with kinetic results demonstrating that lower molecular weight SBA-15-P1 and MCM-41-P1 catalysts outperform (higher turnover frequencies and initial rates) their higher molecular weight analogues, as well as a polymer-free system containing molecular active sites dispersed on the silica surface. Higher molecular weight composite catalysts perform more poorly due to limited chain solubility, mass transfer limitations, and poor catalyst accessibility. In many cases, the polymer chains effectively thread into the mesopores, with higher molecular weight polymers leading to pore blockage and inhibited mass transfer.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Combining artificial intelligence and physics-based modeling to directly assess atomic site stabilities: from sub-nanometer clusters to extended surfaces

The performance of functional materials is dictated by chemical and structural properties of individual atomic sites. In catalysts, for instance, the thermodynamic stability of constituting atomic sites is a key descriptor from which more complex properties, such as molecular adsorption energies and reaction rates, can be derived. In this study, we present a widely applicable machine learning (ML) approach to instantaneously compute the stability of individual atomic sites in structurally and electronically complex nano-materials. Conventionally, we determine such site stabilities using computationally intensive first-principles calculations. With our approach, we predict the stability of atomic sites in sub-nanometer metal clusters of 3–55 atoms with mean absolute errors in the range of 0.11–0.14 eV. To extract physical insights from the ML model, we introduce a genetic algorithm (GA) for feature selection. This algorithm distills the key structural and chemical properties governing the stability of atomic sites in size-selected nanoparticles, allowing for physical interpretability of the models and revealing structure–property relationships. The results of the GA are generally model and materials specific. In the limit of large nanoparticles, the GA identifies features consistent with physics-based models for metal–metal interactions. By combining the ML model with the physics-based model, we predict atomic site stabilities in real time for structures ranging from sub-nanometer metal clusters (3–55 atom) to larger nanoparticles (147 to 309 atoms) to extended surfaces using a physically interpretable framework. Finally, we present a proof of principle showcasing how our approach can determine stable and active nanocatalysts across a generic materials space of structure and composition.

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

Highly dense atomic Fe–Ni dual metal sites for efficient CO 2 to CO electrolyzers at industrial current densities

Carbon-supported, atomically dispersed, nitrogen-coordinated metal sites (e.g., Fe and Ni) are arguably the most promising catalysts for the electrochemical reduction of CO 2 to CO due to their unique catalytic properties and the use of earth-abundant elements. However, conventional single metal sites are constrained by their structural simplicity, causing either too weak or too strong absorption/desorption of multiple critical intermediates (e.g., *COOH and *CO). Current catalysts also suffer from ultra-low loadings (<1.0 wt%) of atomic metal active sites in catalysts, leading to inadequate performance for CO 2 -to-CO conversion. Here, we develop dual Ni/Fe metal site catalysts with significantly increased atomically dispersed metal loadings (up to 4.8 wt%). A gas-phase chemical vapor deposition (CVD) approach to introducing single Ni sites was integrated with Fe 2 O 3 /ZIF-8 precursors, followed by an optimal thermal activation. The optimized CVD-Ni/Fe–N–C catalyst exhibited remarkable electrocatalytic performance for the CO 2 reduction to CO in a continuous membrane-electrode-assembly electrolyzer, achieving a maximum CO faradaic efficiency (FE CO ) of 96% at a current density of 700 mA cm −2 in a near-neutral electrolyte. Furthermore, a desirable but challenging acidic flow-cell electrolyzer was designed using this dual metal site catalyst to improve CO 2 utilization, accomplishing a FE CO of up to 95% at a CO partial current density close to 600 mA cm −2 . Density functional theory (DFT) calculations suggest a synergetic effect between Fe–Ni pairs facilitating *COOH intermediate formation and *CO desorption simultaneously during CO 2 to CO conversion. This is key to breaking the linear scaling relationship of conventional single-metal site catalysts during the CO 2 reduction reaction.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Site-selected luminescence of atomic europium in the solid rare gases

Site-selective excitation has been used to simplify complex emission recorded in the visible spectral region for atomic europium isolated in the solid rare gases. In addition to y{sup 8}P resonance fluorescence, excitation of the y{sup 8}P state produces emission from the z{sup 6}P state and the metastable a{sup 10}D state. Very weak emission at 690 nm is tentatively assigned to the J = 9/2 level of the z{sup 10}P state. Eu atoms isolated in the red and blue sites exhibit very different temperature dependence both spectrally and temporally. For the y{sup 8}P state emission the red site atoms exhibit small Stokes shifts and yield radiative lifetimes while the emission from the blue site loses intensity and the temporal profiles shorten dramatically between 10 and 16 K indicating very efficient non-radiative relaxation in this site. An analysis of the Stokes shifts exhibited for the y{sup 8}P state in each site supports the attributions made in a previous publication [O. Byrne and J.G. McCaffrey, J. Chem. Phys. 134, 124501 (2011)] that the smaller blue tetravacancy site has a greater repulsive interaction with the guest. With the exception of the y{sup 8}P state resonance fluorescence, the recorded decay profiles of all the other emissions exhibit multiple components. This behaviour has been attributed to the existence of multiple crystal field levels arising from the splitting of the distinct spin-orbit levels from which emission occurs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Local electronic structure analysis for brownmillerite Ca(Sr)FeO{sub 2.5} using site-resolved energy-loss near-edge structures

Oxygen K-edge and Fe L{sub 2,3}-edge electron energy-loss near-edge structures (ELNES) were measured for FeO{sub 6} octahedra and FeO{sub 4} tetrahedra in the brownmillerite Ca(Sr)FeO{sub 2.5} by focusing an electron probe at individual Fe sites using scanning transmission electron microscopy combined with electron energy-loss spectroscopy. The observed site-resolved oxygen K-ELNES showed different features reflecting the local chemical bonding around the FeO{sub 6} octahedra and FeO{sub 4} tetrahedra. A pre-peak in the O K-edge spectra, which is attributed to a transition to an unoccupied O 2p band hybridized with the Fe-3d band, shows splitting in the spectrum of the FeO{sub 6} octahedral site. Additionally, for the oxygen linking the octahedral and tetrahedral Fe sites in CaFeO{sub 2.5}, charge transfer was found to preferentially occur toward the tetrahedral Fe ions. In the case of SrFeO{sub 2.5}, charge transfer from the oxygen located in the ac plane was biased toward the tetrahedral Fe atoms. Based upon an analysis of the pre-peak intensity of the O K-ELNES, it was concluded that bonding between the oxygen and iron atoms at the tetrahedral site was more covalent in character than at the octahedral site. The strong covalent character of the tetrahedral sites would be one of the reasons for distortion in the FeO{sub 6} octahedra in Ca(Sr)FeO{sub 2.5}, as exhibited by an extension along the b-axis.

36 MATERIALS SCIENCE↗