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All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Synthesis and Evaluation of Cu-SAPO-34 Catalysts for Ammonia Selective Catalytic Reduction. 1. Aqueous Solution Ion Exchange

SAPO-34 molecular sieves are synthesized using various structure directing agents (SDAs). Cu-SAPO-34 catalysts are prepared via aqueous solution ion exchange. Catalysts are characterized with surface area/pore volume measurements, temperature programmed reduction (TPR), electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectroscopies. Catalytic properties are examined using standard ammonia selective catalytic reduction (NH3-SCR) and ammonia oxidation reactions. During solution ion exchange, different SAPO-34 samples undergo different extent of structural damage via irreversible hydrolysis. Si content within the samples (i.e., Al-O-Si bond density) and framework stress are key factors that affect irreversible hydrolysis. Even using very dilute Cu acetate solutions, it is not possible to generate Cu-SAPO-34 samples with only isolated Cu2+ ions. Small amounts of CuOx species always coexist with isolated Cu2+ ions. Highly active and selective Cu-SAPO-34 catalysts for NH3-SCR are readily generated using this synthesis protocol, even for SAPO-34 samples that degrade substantially during solution ion exchange. High-temperature aging is found to improve the catalytic performance. This is likely due to reduction of intracrystalline mass-transfer limitations via formation of additional porosity in the highly defective SAPO-34 particles formed after ion exchange. The authors gratefully acknowledge the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Office of Vehicle Technologies for the support of this work. The research described in this paper was performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle Memorial Institute under contract number DE-AC05-76RL01830.

chabazite↗
DOE OSTI2023

Bimolecular Reductive Elimination of Ethane from Pyridine(diimine) Iron Methyl Complexes: Mechanism, Electronic Structure, and Entry into [2+2] Cycloaddition Catalysis

The application of bimolecular reductive elimination to the activation of iron catalysts for alkene–diene cycloaddition is described. Key to this approach was the synthesis, characterization, electronic structure determination, and ultimately solution stability of a family of pyridine(diimine) iron methyl complexes with diverse steric properties and electronic ground states. Both the aryl-substituted, ( Me PDI)FeCH 3 and ( Et PDI)FeCH 3 ( R PDI = 2,6-(2,6-R 2 -C 6 H 3 N=CMe) 2 C 5 H 3 N), and the alkyl-substituted examples, ( Cy APDI)FeCH 3 ( Cy APDI = 2,6-(C 6 H 11 N=CMe) 2 C 5 H 3 N), have molecular structures significantly distorted from planarity and S = 3/2 ground states. The related N-arylated derivative bearing 2,6-di-isopropyl aryl substituents, ( iPr PDI)FeCH 3 , has an idealized planar geometry and exhibits spin crossover behavior from S = 1/2 to S = 3/2 states. At 23 °C under an N 2 atmosphere, both ( Me PDI)FeCH 3 and ( Et PDI)FeCH 3 underwent reductive elimination of ethane to form the iron dinitrogen precatalysts, [( Me PDI)Fe(N 2 )] 2 (μ-N 2 ) and [( Et PDI)Fe(N 2 )] 2 (μ-N 2 ), respectively, while ( iPr PDI)FeCH 3 proved inert to C–C bond formation. By contrast, addition of butadiene to all three iron methyl complexes induced ethane formation and generated the corresponding iron butadiene complexes, ( R PDI)Fe(η 4 -C 4 H 6 ) (R = Me, Et, i Pr), known precatalysts for the [2+2] cycloaddition of olefins and dienes. Kinetic, crossover experiments, and structural studies were combined with magnetic measurements and Mössbauer spectroscopy to elucidate the electronic and steric features of the iron complexes that enable this unusual reductive elimination and precatalyst activation pathway. Furthermore, transmetalation of methyl groups between iron centers was fast at ambient temperature and independent of steric environment or spin state, while the intermediate dimer underwent the sterically controlled rate-determining reaction with either N 2 or butadiene to access a catalytically active iron compound.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Turning on the protonation-first pathway for electrocatalytic CO 2 reduction by manganese bipyridyl tricarbonyl complexes

Electrocatalytic reduction of CO 2 to CO is reported for the complex, { fac -Mn I ([(MeO) 2 Ph] 2 bpy)(CO) 3 (CH 3 CN)}(OTf), containing four pendant methoxy groups, where [(MeO) 2 Ph] 2 bpy = 6,6'-bis(2,6-dimethoxyphenyl)-2,2'-bipyridine. In addition to a steric influence similar to that previously established for the 6,6'-dimesityl-2,2'-bipyridine ligand in [ fac -MnI(mes 2 bpy)(CO) 3 (CH 3 CN)](OTf), which prevents Mn 0 –Mn 0 dimerization, the [(MeO) 2 Ph] 2 bpy ligand introduces an additional electronic influence combined with a weak allosteric hydrogen-bonding interaction that significantly lowers the activation barrier for C–OH bond cleavage from the metallocarboxylic acid intermediate. This provides access to the thus far elusive protonation-first pathway, minimizing the required overpotential for electrocatalytic CO 2 to CO conversion by Mn(I) polypyridyl catalysts, while concurrently maintaining a respectable turnover frequency. Comprehensive electrochemical and computational studies here confirm the positive influence of the [(MeO) 2 Ph] 2 bpy ligand framework on electrocatalytic CO 2 reduction and its dependence upon the concentration and p K a of the external Bronsted acid proton source (water, methanol, trifluoroethanol, and phenol) that is required for this class of manganese catalyst. Linear sweep voltammetry studies show that both phenol and trifluoroethanol as proton sources exhibit the largest protonation-first catalytic currents in combination with { fac -Mn I ([(MeO) 2 Ph] 2 bpy)(CO) 3 (CH 3 CN)}(OTf), saving up to 0.55 V in overpotential with respect to the thermodynamically demanding reduction-first pathway, while bulk electrolysis studies confirm a high product selectivity for CO formation. As a result, to gain further insight into catalyst activation, time-resolved infrared (TRIR) spectroscopy combined with pulse-radiolysis (PR-TRIR), infrared spectroelectrochemistry, and density functional theory calculations were used to establish the v (CO) stretching frequencies and energetics of key redox intermediates relevant to catalyst activation.

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

Evaluating the Role of Metastable Surfaces in Mechanochemical Reduction of Molybdenum Oxide

Mechanochemistry and mechanocatalysis are gaining increasing attention as environmentally friendly chemical processes because of their solvent-free nature and scalability. Significant effort has been devoted for studying continuum-scale phenomena in mechanochemistry, such as temperature and pressure gradients, but the atomic-scale mechanisms remain relatively unexplored. In this work, we focus on the mechanochemical reduction of MoO3 as a case study. We use experimental techniques to determine the mechanochemical reduction conditions and density functional theory (DFT) simulations to establish an atomistic framework for identifying the metastable surfaces that are most likely to enable this process. Our results show that metastable surfaces can significantly lower or remove thermodynamic barriers for surface reduction and that kinetic energy from milling can facilitate the formation of metastable surfaces that have high surface fracture energies and are not thermally accessible. These findings indicate that metastable surfaces are an important aspect of mechanochemistry along with hot spots and other continuum-scale phenomena.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Chirality-induced spin selectivity as a mechanism to control product selectivity during electrochemical CO 2 reduction

Electrocatalytic CO 2 reduction often suffers from competition with the hydrogen evolution reaction (HER), which lowers efficiency and limits product selectivity. Recent studies suggest that electron spin, when controlled at an electrode surface, can influence reaction pathways, but direct evidence linking spin effects to suppressed HER has been limited. Here, in this work, we show that helical chiral copper (Cu) electrodes reduce competing HER during CO 2 reduction, consistent with spin polarization induced via the chiral-induced spin selectivity effect. The helically structured Cu electrodes are fabricated by electrodeposition with a chiral templating reagent. Time-resolved Kerr ellipticity measurements, which track spin-polarized carriers generated by an ultrafast Seebeck current, confirm spin accumulation at the chiral Cu surface. This spin polarization disfavours H—H bond formation, thereby suppressing HER and enabling formate production alongside CO. These findings demonstrate that chirality-based spin control offers a strategy for steering selectivity in CO 2 reduction and other reactions where HER is an undesired competitor.

14 SOLAR ENERGY↗
DOE OSTI2015

Enhanced electrocatalytic activity and stability of Pd 3 V/C nanoparticles with a trace amount of Pt decoration for the oxygen reduction reaction

In this study, carbon supported Pd 3 V bimetallic alloy nanoparticles (Pd 3 V/C) have been successfully synthesized via a simple impregnation–reduction method, followed by high temperature treatment under a H 2 atmosphere. Electrochemical tests reveal that the half-wave potential of Pd 3 V/C-500 shifts positively 40 mV compared with Pd/C. However, the catalytic activity of Pd 3 V/C-500 suffers from serious degradation after 1k cycles. By a spontaneous displacement reaction or co-reduction method, a trace amount of Pt was decorated on the surface or inside of the Pd 3 V/C nanoparticles. The catalytic activity and stability of the Pd 3 V@Pt/C and Pt-Pd 3 V/C catalysts for the oxygen reduction reaction (ORR) are enhanced significantly, and are comparable to commercial Pt/C. In addition, the Pt mass activity of Pd 3 V@Pt/C and Pt-Pd 3 V/C improves by factors of 10.9 and 6.5 at 0.80 V relative to Pt/C. Moreover, Pt-decorated Pd 3 V/C nanoparticles show almost no obvious morphology change after durability tests, because the Pt-rich shell plays an important role in preventing degradation.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Modeling of the oxygen reduction reaction for dense LSM thin films

In this study, the oxygen reduction reaction mechanism is investigated using numerical methods on a dense thin (La 1-x Sr x ) y MnO 3±δ film deposited on a YSZ substrate. This 1-D continuum model consists of defect chemistry and elementary oxygen reduction reaction steps coupled via reaction rates. The defect chemistry model contains eight species including cation vacancies on the A- and B-sites. The oxygen vacancy is calculated by solving species transportation equations in multiphysics simulations. Due to the simple geometry of a dense thin film, the oxygen reduction reaction was reduced to three elementary steps: surface adsorption and dissociation, incorporation on the surface, and charge transfer across the LSM/YSZ interface. The numerical simulations allow for calculation of the temperature- and oxygen partial pressure-dependent properties of LSM. The parameters of the model are calibrated with experimental impedance data for various oxygen partial pressures at different temperatures. The results indicate that surface adsorption and dissociation is the rate-determining step in the ORR of LSM thin films. With the fine-tuned parameters, further quantitative analysis is performed. The activation energy of the oxygen exchange reaction and the dependence of oxygen non-stoichiometry on oxygen partial pressure are also calculated and verified using the literature results.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Catalytic bias in oxidation–reduction catalysis

Cataytic bias refers to the propensity of a reaction catalyst to effect a different rate acceleration in one direction versus the other in a chemical reaction under non-equilibrium conditions. In biocatalysis, the inherent bias of an enzyme is often advantagous to augment the innate thermodynamics of a reaction to promote efficiency and fidelity in the coordination of catabolic and anabolic pathways. In industrial chemical catalysis a directional cataltyic bias is a sought after property in facilitating the engineering of systems that couple catalysis with harvest and storage of for example fine chemicals or energy compounds. Interestingly, there is little information about catalytic bias in biocatalysis likely in large part due to difficulties in developing tractible assays sensitive enough to study detailed kinetics. For oxidation–reduction reactions, colorimetric redox indicators exist in a range of reduction potentials to provide a mechanism to study both directions of reactions in a fairly facile manner. The current short review attempts to define catalytic bias conceptually and to develop model systems for defining the parameters that control catalytic bias in enzyme catalyzed oxidation–reduction catalysis.

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

Analytical model for drag reduction on liquid-infused structured non-wetting surfaces

Liquid-infused structured non-wetting surfaces provide alternating no-slip and partial slip boundary conditions to the fluid flow, resulting in reduced friction at the interface. In this paper, an analytical model is developed for the evaluation of effective slip and, in turn, friction factor and drag reduction on liquid-infused structured non-wetting surfaces. By considering the entire range of anisotropy and heterogeneity of the surface structures as well as the full range of partial slip offered by the infusion liquid, the present model eliminates empirical fitting or correlations that are inherent in previous studies. Based on the effective slip length, drag reduction and skin friction coefficient values for Newtonian flow between two infinite parallel plates and flow in round tubes are presented. Extension of Moody charts for non-wetting surfaces and design maps of surface meso/micro/nano texturing for achieving desired drag reduction are presented for a broad range of engineering applications. The paper further presents independent validation of the model across experimental and computational data from the literature and brings together several previous studies in a unified manner.

36 MATERIALS SCIENCE↗
DOE OSTI2025

From lignin to market: a technical and economic perspective of reductive depolymerization approaches

Lignin has grown into one of the main candidates to replace fossil-based resources as it is the largest renewable source of aromatic building blocks. The complex structure of polymeric lignin, however, requires depolymerization to simpler building blocks for the chemical industry. One of the most promising depolymerization approaches is reductive depolymerization of which two process configurations are currently studied in pilot scale installations for upscaling to industrial scale: (i) reductive catalytic fractionation (RCF), and (ii) reductive catalytic depolymerization (RCD). Both technical and techno-economic aspects will be covered within this review, discussing the advantages and challenges of both approaches regarding processing, production costs, product output, and applications. In this regard, RCF benefits from its decreased energy and solvent consumption linked with being a one-step process and delivers a product with a high monomer content (∼25–45 wt%). RCD, on the other hand, has the advantage of continuous processing and reduced catalyst fouling and delivers a product that mainly consists of oligomers (<10 wt% monomers). The complete overview of both processes presented here addresses their potential, and can guide future researchers, policy makers and companies to make thoughtful decisions on lignin valorization.

09 BIOMASS FUELS↗
DOE OSTI2025

Electrochemical reduction of ammonia-captured CO 2 to CO over a nickel single-atom catalyst

Carbon reactive capture and conversion offers a sustainable route to valuable chemicals and fuels while aiding Green House Gas (GHG) reduction. Direct electrochemical conversion of capture solutions like bicarbonate avoids the energy demands of conventional CO 2 regeneration. Ammonium bicarbonate (NH 4 HCO 3 ) is particularly attractive due to its low decomposition temperature and ability to supply in situ CO 2 from dilute sources without requiring purified CO 2 . Meanwhile, single-atom catalysts (SACs) with nitrogen-coordinated metal sites further enhance CO 2 reduction efficiency using Earth-abundant materials. In this study, we demonstrate a nickel single-atom catalyst (Ni-SAC)-based electrolyzer that utilizes NH 4 HCO 3 as the CO 2 source, achieving significantly improved CO production performance compared to the conventional silver cathodes used in the CO 2 reduction reaction (CO 2 RR) to produce CO. The Ni-SAC cathode exhibited a Faradaic efficiency of 60.1% for CO production at −200 mA cm −2 , while the silver cathode achieved a Faradaic efficiency of only 2%, likely due to ammonium-induced poisoning. Furthermore, the integration of a customized microporous layer onto the electrode significantly increased the Faradaic efficiency from 64% to 83% at −100 mA cm −2 , emphasizing the crucial role of electrode structure optimization in enhancing CO selectivity. These findings demonstrate a sustainable and economically viable strategy for green CO production directly from CO 2 capture solutions.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2014

Direct printing and reduction of graphite oxide for flexible supercapacitors

We report direct printing and photo-thermal reduction of graphite oxide (GO) to obtain a highly porous pattern of interdigitated electrodes, leading to a supercapacitor on a flexible substrate. Key parameters optimized include the amount of GO delivered, the suitable photo-thermal energy level for effective flash reduction, and the substrate properties for appropriate adhesion after reduction. Tests with supercapacitors based on the printed-reduced GO showed performance comparable with commercial supercapacitors: the energy densities were 1.06 and 0.87 mWh/cm{sup 3} in ionic and organic electrolytes, respectively. The versatility in the architecture and choice of substrate makes this material promising for smart power applications.

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

A systematic way for the cost reduction of density fitting methods

We present a simple approach for the reduction of the size of auxiliary basis sets used in methods exploiting the density fitting (resolution of identity) approximation for electron repulsion integrals. Starting out of the singular value decomposition of three-center two-electron integrals, new auxiliary functions are constructed as linear combinations of the original fitting functions. The new functions, which we term natural auxiliary functions (NAFs), are analogous to the natural orbitals widely used for the cost reduction of correlation methods. The use of the NAF basis enables the systematic truncation of the fitting basis, and thereby potentially the reduction of the computational expenses of the methods, though the scaling with the system size is not altered. The performance of the new approach has been tested for several quantum chemical methods. It is demonstrated that the most pronounced gain in computational efficiency can be expected for iterative models which scale quadratically with the size of the fitting basis set, such as the direct random phase approximation. The approach also has the promise of accelerating local correlation methods, for which the processing of three-center Coulomb integrals is a bottleneck.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Opening gates to oxygen reduction reactions on Cu(111) surface

Electrocatalytic reduction of oxygen is composed of multiple steps, including the diffusion-adsorption-dissociation of molecular oxygen. This study explores the role of electrical double layer in aqueous medium in quantifying the rate of these coupled electrochemical processes at the electrode interface during oxygen reduction. The electronic, energetic, and configurational aspects of molecular oxygen diffusion and adsorption onto Cu(111) in water are identified through density functional theory based computations. The liquid phase on Cu(111) is modeled with hexagonal-ordered water bilayers, at two slightly different structures, with O–H bonds either facing the vacuum or the metal surface. The results indicate that the energetically preferred structure of water bilayers and adsorption configuration of O{sub 2} are different in cathodic and anodic potentials. The diffusion of O{sub 2} is found to be heavily hindered at the water/metal interface because of the ordering of water molecules in bilayers as compared to the bulk liquid. The unique correlations of diffusion and adsorption kinetics with water structure identified in this work can provide clues for improving oxygen reduction efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Investigation of optimal route to fabricate submicron-sized Sm{sub 2}Fe{sub 17} particles with reduction-diffusion method

Submicron-sized Sm{sub 2}Fe{sub 17} powder samples were fabricated by a non-pulverizing process through reduction-diffusion of precursors prepared by a wet-chemical technique. Three precursors having different morphologies, which were micron-sized porous Sm-Fe oxide-impregnated iron nitrate, acicular goethite impregnated-samarium nitrate, and a conventional Sm-Fe coprecipitate, were prepared and subjected to hydrogen reduction and reduction-diffusion treatment to clarify whether these precursors could be convert to Sm{sub 2}Fe{sub 17} without impurity phases and which precursor is the most attractive for producing submicron-sized Sm{sub 2}Fe{sub 17} powder. As a result, all three precursors were successfully converted to Sm{sub 2}Fe{sub 17} powders without impurity phases, and the synthesis route using iron-oxide particle-impregnated samarium oxide was revealed to have the greatest potential among the three routes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Unraveling driving forces explaining significant reduction in satellite-inferred Arctic surface albedo since the 1980s

The Arctic has warmed significantly since the early 1980s and much of this warming can be attributed to the surface albedo feedback. In this study, satellite observations reveal a 1.25 to 1.51% per decade absolute reduction in the Arctic mean surface albedo in spring and summer during 1982 to 2014. Results from a global model and reanalysis data are used to unravel the causes of this albedo reduction. We find that reductions of terrestrial snow cover, snow cover fraction over sea ice, and sea ice extent appear to contribute equally to the Arctic albedo decline. We show that the decrease in snow cover fraction is primarily driven by the increase in surface air temperature, followed by declining snowfall. Although the total precipitation has increased as the Arctic warms, Arctic snowfall is reduced substantially in all analyzed data sets. Light-absorbing soot in snow has been decreasing in past decades over the Arctic, indicating that soot heating has not been the driver of changes in the Arctic snow cover, ice cover, and surface albedo since the 1980s.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Novel technologies for emission reduction complement conservation agriculture to achieve negative emissions from row-crop production

Plants remove carbon dioxide from the atmosphere through photosynthesis. Because agriculture’s productivity is based on this process, a combination of technologies to reduce emissions and enhance soil carbon storage can allow this sector to achieve net negative emissions while maintaining high productivity. Unfortunately, current row-crop agricultural practice generates about 5% of greenhouse gas emissions in the United States and European Union. Here, to reduce these emissions, significant effort has been focused on changing farm management practices to maximize soil carbon. In contrast, the potential to reduce emissions has largely been neglected. Through a combination of innovations in digital agriculture, crop and microbial genetics, and electrification, we estimate that a 71% (1,744 kg CO 2 e/ha) reduction in greenhouse gas emissions from row crop agriculture is possible within the next 15 y. Importantly, emission reduction can lower the barrier to broad adoption by proceeding through multiple stages with meaningful improvements that gradually facilitate the transition to net negative practices. Emerging voluntary and regulatory ecosystems services markets will incentivize progress along this transition pathway and guide public and private investments toward technology development. In the difficult quest for net negative emissions, all tools, including emission reduction and soil carbon storage, must be developed to allow agriculture to maintain its critical societal function of provisioning society while, at the same time, generating environmental benefits.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2014

Reduction experiment of FeO-bearing amorphous silicate: application to origin of metallic iron in GEMS

Glass with embedded metal and sulfides (GEMS) are amorphous silicates included in anhydrous interplanetary dust particles (IDPs) and can provide information about material evolution in our early solar system. Several formation processes for GEMS have been proposed so far, but these theories are still being debated. To investigate a possible GEMS origin by reduction of interstellar silicates, we synthesized amorphous silicates with a mean GEMS composition and performed heating experiments in a reducing atmosphere. FeO-bearing amorphous silicates were heated at 923 K and 973 K for 3 hr, and at 1023 K for 1-48 hr at ambient pressure in a reducing atmosphere. Fe grains formed at the interface between the silicate and the reducing gas through a reduction. In contrast, TEM observations of natural GEMS show that metallic grains are uniformly embedded in amorphous silicates. Therefore, the present study suggests that metallic inclusions in GEMS could not form as reduction products and that other formation process such as condensation or irradiation are more likely.

36 MATERIALS SCIENCE↗