Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “N”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,027 records · Page 57
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Contribution of decomposing plant roots to N 2 O emissions by water absorption

The “sponge effect”, or water absorption by incorporated plant leaf residues, was recently identified as one of the mechanisms that drives activity in microbial hotspots. We explored the presence of the sponge effect in plant root residues, and its role in root decomposition and associated N 2 O and CO 2 emissions. Young soybean (Glycine max) plants were grown in microcosms with two soil materials dominated by (i) large (>30 μm Ø) and (ii) small (<10 μm Ø) pores. After termination, the microcosms with the decomposing roots were incubated at 50% and 75% water-filled pore space (WFPS) soil moisture levels. Root decomposition, water absorption by the decomposing roots, and water redistribution were quantified using X-ray computed micro-tomography (μCT), including dual-energy scanning. The results demonstrated occurrence of the sponge effect in young, in-situ grown soybean roots and sharp gradients in the distribution of the added liquid within ~150 µm distance from the decomposing roots. At 50% WFPS the large pore soil emitted 185% more N 2 O than the small pore soil; and, during the first 5 days of incubation, more N 2 O than the large pore soil at 75% WFPS. This finding indicates that the decomposing roots acted as hotspots of N 2 O production, potentially due to sponge effect and associated anoxic conditions. This study suggests that the interactions between pore characteristics and soil moisture can play a significant role in defining the contribution of detritusphere, specifically, decomposing young roots, to soil biogeochemical processes, including microbial activity and denitrification dynamics.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Structure sensitivity of n -butane hydrogenolysis on supported Ir catalysts

Hydrogenolysis of alkanes has been widely reported as structure sensitive reaction on transition metal heterogeneous catalysts with metal particle sizes ranging between 1 and 20 nm. In this work, a series of Ir/MgAl 2 O 4 and Ir/SiO 2 catalysts with different Ir particle sizes ranging from subnanometer clusters (<1 nm) to nanoparticles (1–3 nm) were prepared and tested for n-butane hydrogenolysis. Our results show that the activity towards n-butane hydrogenolysis increases as Ir particle size increases in the lower particle size range, goes through a maximum at ~1.4–1.6 nm and then drops with a further increase in particle size. In this work, the product distribution at low temperature (170–190 °C) is dominated by central and terminal CAC bond cleavage of n-butane, and less by two CAC bond cleavage or further hydrogenolysis of the propane and ethane products. The selectivity to central CAC bond cleavage is highly dependent on the size of Ir and increases with a decrease in particle size down to ~1.4 nm but remains constant with further decrease in size. The results show that an Ir size of ~1.4 nm is optimum for n-butane hydrogenolysis activity and selectivity towards ethane.

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

Polysulfide regulation by defect-modulated Ta 3 N 5- x electrocatalyst toward superior room-temperature sodium-sulfur batteries

Resolving low sulfur reaction activity and severe polysulfide dissolution remains challenging in metal-sulfur batteries. Motivated by a theoretical prediction, herein, we strategically propose nitrogen-vacancy tantalum nitride (Ta 3 N 5-x ) impregnated inside the interconnected nanopores of nitrogen-decorated carbon matrix as a new electrocatalyst for regulating sulfur redox reactions in room-temperature sodium-sulfur batteries. Through a pore-constriction mechanism, the nitrogen vacancies are controllably constructed during the nucleation of Ta 3 N 5-x . Further, the defect manipulation on the local environment enables well-regulated Ta 5d-orbital energy level, not only modulating band structure toward enhanced intrinsic conductivity of Ta-based materials, but also promoting polysulfide stabilization and achieving bifunctional catalytic capability toward completely reversible polysulfide conversion. Moreover, the interconnected continuous Ta 3 N 5-x -in-pore structure facilitates electron and sodium-ion transport and accommodates volume expansion of sulfur species while suppressing their shuttle behavior. Due to these attributes, the as-developed Ta 3 N 5-x -based electrode achieves superior rate capability of 730 mAh g -1 at 3.35 A g -1 , long-term cycling stability over 2000 cycles, and high areal capacity over 6 mAh cm -2 under high sulfur loading of 6.2mgcm -2 . This work not only presents a new sulfur electrocatalyst candidate for metal-sulfur batteries, but also sheds light on the controllable material design of defect structure in hopes of inspiring new ideas and directions for future research.

25 ENERGY STORAGE↗
DOE OSTI2022

Verification of stability and unraveling the electronic and physical properties of bulk and (001)-surfaces of newly synthesized Ti 2 ZnX (X = C, N) MAX phases

MAX phase family has been extended by the addition of late transition metals at the A-site with the expectation of diverse functional properties. Here, we present our systematic density functional investigation on the thermodynamic and phonon stabilities, elastic properties, including elastic constants, elastic moduli and elastic anisotropy of newly synthesized Ti 2 ZnX (X = C, N) phases in comparison with conventional Ti 2 AlX (X = C, N). Due to the smaller size of N as compared to C, the unit cell dimension is reduced when C atoms are replaced by N atoms at the X-site. Furthermore, the Ti 2 ZnC and Ti 2 ZnN are stable at the equilibrium volume of 110.84 Å 3 and 105.70 Å 3 . The thermodynamic, mechanical and dynamical stabilities are validated by estimating the formation energies, elastic constants and phonon dispersions, respectively. The elastic properties of Ti 2 ZnN are less anisotropic as compared to those of Ti 2 ZnC. To understand the thin-film characteristics in Ti 2 ZnX, the surface properties with (001)-terminated slabs are investigated. Both Ti 2 ZnX bulk and (001)-surfaces exhibit metal-like electronic structures. There is a strong covalent bonding between Ti-X and Ti-Zn atoms confirmed by the charge density map and Mulliken population analysis. Additional states are generated at the Fermi level (EF) due to the unusual d-p states hybridization between Ti and Zn atoms. The anisotropy in chemical bonding is confirmed by the cleavage energy difference between Ti-X and Ti-Zn. Here, Ti(X)-001 and Zn-001 terminations are stable surfaces; however, in terms of chemical potentials, Zn-001 termination is the most favourable in Ti 2 ZnX.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Small bimetallic clusters Agn-1M (M = Au, Co, Cu, Ni, Pd, Pt; n = 3, 9, 15): Density functional theory and genetic algorithm

We investigated the effect of size and composition on the properties of bimetallic nanoclusters. The geometric structures, stabilities, and electronic properties of size-selected Ag n-1 M (M = Au, Co, Cu, Ni, Pd, Pt; n = 3, 9, 15) bimetallic nanoclusters are systematically analyzed using spin-polarized density functional theory (DFT) within the generalized gradient approximation (GGA). We determine the most stable geometries for these clusters using a genetic algorithm (GA) in combination with DFT. Our results show that doping pure silver clusters with an M atom (transition metal), referred to as a “guest atom”, increases the stability as compared to pure Ag n (n = 3, 9, 15) clusters. The results for various properties including formation energy per atom, electronic structure, magnetic moments, and vibrational density of states (VDOS) are evaluated as a function of both size and composition of the system. The adsorption of selected bimetallic clusters on hydroxylated alumina substrate shows weak binding and minor changes in geometric properties except for Ag 8 Pt.

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

Heterogeneous M-N-C Catalysts for Aerobic Oxidation Reactions: Lessons from Oxygen Reduction Electrocatalysts

Nonprecious metal heterogeneous catalysts composed of first-row transition metals incorporated into nitrogen-doped carbon matrices (M-N-Cs) have been studied for decades as leading alternatives to Pt for the electrocatalytic O 2 reduction reaction (ORR). More recently, similar M-N-C catalysts have been shown to catalyze the aerobic oxidation of organic molecules. Here, this Focus Review highlights mechanistic similarities and distinctions between these two reaction classes and then surveys the aerobic oxidation reactions catalyzed by M-N-Cs. As the active-site structures and kinetic properties of M-N-C aerobic oxidation catalysts have not been extensively studied, the array of tools and methods used to characterize ORR catalysts are presented with the goal of supporting further advances in the field of aerobic oxidation.

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

Multiple N–H and C–H Hydrogen Atom Abstractions Through Coordination-Induced Bond Weakening at Fe-Amine Complexes

We report the use of the reported Fe-phthalocyanine complex, PcFe (1; Pc = 1,4,8,11,15,18,22,25-octaethoxy-phthalocyanine), to generate PcFe–amine complexes 1-(NH 3 ) 2 , 1-(MeNH 2 ) 2 , and 1-(Me 2 NH) 2 . Treatment of 1 or 1-(NH 3 ) 2 to an excess of the stable aryloxide radical, 2,4,6-tritert-butylphenoxyl radical ( t Bu ArO•), under NH 3 resulted in catalytic H atom abstraction (HAA) and C–N coupling to generate the product 4-amino-2,4,6-tritert-butylcyclohexa-2,5-dien-1-one (2) and t Bu ArOH. Exposing 1-(NH 3 ) 2 to an excess of the trityl (CPh 3 ) variant, 2,6-di-tert-butyl-4-tritylphenoxyl radical ( Tr ArO • ), under NH 3 did not lead to catalytic ammonia oxidation as previously reported in a related Ru-porphyrin complex. However, pronounced coordination-induced bond weakening of both α N–H and β C–H in the alkylamine congeners, 1-(MeNH 2 ) 2 and 1-(Me 2 NH) 2 , led to multiple HAA events yielding the unsaturated cyanide complex, 1-(MeNH 2 )(CN), and imine complex, 1-(MeN=CH 2 ) 2 , respectively. Subsequent C–N bond formation was also observed in the latter upon addition of a coordinating ligand. Detailed computational studies support an alternating mechanism involving sequential N–H and C–H HAA to generate these unsaturated products.

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

Using Substituted [Fe 4 N(CO) 12 ] – as a Platform To Probe the Effect of Cation and Lewis Acid Location on Redox Potential

The impact of cationic and Lewis acidic functional groups installed in the primary or secondary coordination sphere (PCS or SCS) of an (electro)catalyst is known to vary depending on the precise positioning of those groups. However, it is difficult to systematically probe the effect of that position. In this report we probe the effect of the functional group position and identity on the observed reduction potentials (E p,c ) using substituted iron clusters, [Fe 4 N(CO) 11 R] n , where R = NO + , PPh 2 -CH 2 CH 2–9 BBN, ( Me PTA + ) 2 , ( Me PTA + ) 4 , and H + , where n = 0, -1, +1, or +3 (9-BBN is 9-borabicyclo(3.3.1)nonane and Me PTA + is 1-methyl-1 azonia-3,5-diaza-7-phosphaadamantane). The cationic NO + and H + ligands cause anodic shifts of 700 and 320 mV, respectively, in E p,c relative to unsubstituted [Fe 4 N(CO) 12 ] – . Infra-red absorption band data, νCO, suggests that some of the 700 mV shift by NO + results from electronic changes to the cluster core. Furthermore, this contrasts with the effects of cationic MePTA + and H + which cause primarily electrostatic effects on E p,c . Lewis acidic 9-BBN in the SCS had almost no effect on E p,c .

14 SOLAR ENERGY↗
DOE OSTI2023

Rare Earth Nitrate Hybrid Double Perovskites [Me 4 N] 2 [MLn(NO 3 ) 6 ] (M = Na–Cs; Ln = La–Gd, ex. Pm)

An exploration of the synthetic and structural phase space of rare earth hybrid double perovskites A 2 B'BX 6 (A = organocation, B' = M + , B = M 3+ , X = molecular bridging anion) that include X = NO 3 – and B' = alkali metal is reported, complementing earlier studies of the [Me 4 N] 2 [KB(NO 3 ) 6 ] (B = Am, Cm, La–Nd, Sm–Lu, Y) (Me 4 N = (CH 3 ) 4 N + ) compounds. In the present efforts, the synthetic phase space of these systems is explored by varying the identity of the alkali metal ion at the B'-site. Herein, we report three new series of the form [Me 4 N] 2 [B'B(NO 3 ) 6 ] (B = La–Nd, Sm–Gd; B' = Na, Rb, Cs). The early members of the Na-series crystallize in the trigonal space group R3̅ from La to Nd where a phase transition occurs in the phase between 273 and 300 K, going from R3̅ to the high-symmetry, cubic space group Fm3̅m. The preceding trigonal members of the Na-series also undergo phase transitions to cubic symmetry at temperatures above 300 K, establishing a decreasing trend in the phase-transition temperature. The remainder of the Na-series, as well as the Rb- and Cs-series, all crystallize in Fm3̅m at 300 K. The temperature-dependent phase behavior of the synthesized phases is studied via variable-temperature spectroscopic methods and high-resolution powder X-ray diffractometry. All phases were characterized via single-crystal and powder X-ray diffraction and Fourier transform infrared (FT-IR) and Raman spectroscopic methods. These results demonstrate the versatility of the perovskite structure type to include rare earth ions, nitrate ions, and a suite of alkali metal ions and serve as a foundation for the design of functional rare earth hybrid double perovskite materials such as those possessing useful multiferroic, optical, and magnetic properties.

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

Coupled Cluster Study of the Interactions of AnO 2 , AnO 2 + , and AnO 2 2+ (An = U, Np) with N 2 and CO

We report thermochemical and spectroscopic properties for actinyl complexes involving UO 2 2+/1+/0 and NpO 2 2+/1+/0 with N 2 and CO, together with the UO 2 -O 2 , UO 2 + -O 2 , and UO 2 + -NO complexes, have been studied for the first time using an accurate composite coupled cluster approach. Two general bonding motifs were investigated, end-on (η 1 ) and side-on (η 2 ) relative to the metal center of the actinyls. For end-on CO complexes, both C-coordinated (An-C) and O-coordinated (An-O) structures were examined, with the former always being lower in energy. All of the η 1 complexes were calculated to be stable, with dissociation energies ranging from 2 to 36 kcal/mol, except for that of UO 2 + -O 2 (the η 1 orientation for UO 2 + -NO was not amenable to single reference coupled cluster). In agreement with a previous study, the η 2 structure for UO 2 + -O 2 was calculated to be relatively strongly bound, by 22.3 kcal/mol in this work. The closely related NO complex, however, had a calculated dissociation energy of just 4.0 kcal/mol. The binding energy of O 2 to neutral UO 2 in a η 2 orientation was calculated to be very strong, 75.4 kcal/mol, and strongly resembled a UO 2 + (O 2 – ) complex at equilibrium. The N–N and C–O bonds were found to be somewhat activated for all the side-on (η 2 ) neutral An(IV) complexes, with stretching frequencies of N 2 or CO being red-shifted by as much as 480 cm –1 with a 0.06 Å bond length elongation. Dissociation energies for the η 1 complexes are strongly correlated with the extent of electron transfer from ligand to actinyl. The nature of bonding in the actinyl complexes is examined using natural resonance theory (NRT). The correlation between bonding motif and small molecule activation is in agreement with experiments in condensed phases.

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

Determining the Ensemble N -Representability of Reduced Density Matrices

The N-representability problem for reduced density matrices remains a fundamental challenge in electronic structure theory. Following our previous work that employs a unitary-evolution algorithm based on an adaptive derivative-assembled pseudo-Trotter variational quantum algorithm to probe pure-state N-representability of reduced density matrices [J. Chem. Theory Comput. 2024, 20, 9968], in this work we propose a practical framework for determining the ensemble N-representability of a p-body matrix. This is accomplished using a purification strategy that embeds an ensemble state into a pure state defined on an extended Hilbert space, such that the reduced density matrices of the purified state reproduce those of the original ensemble. By iteratively applying variational unitaries to an initial purified state, the proposed algorithm minimizes the Hilbert-Schmidt distance between its p-body reduced density matrix and a specified target p-body matrix, which serves as a measure of the N-representability of the target. This methodology facilitates both error correction of defective ensemble reduced density matrices and quantum-state reconstruction on a quantum computer, offering a route for density-matrix refinement. We validate the algorithm with numerical simulations on systems of two, three, and four electrons in both simple models as well as molecular systems at finite temperature, demonstrating its robustness.

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

Effects of Field Strength and Silver Nanowire Size on Plasmon-Enhanced N 2 Dissociation

Dissociation of the nitrogen molecule via plasmon-enhanced catalysis using noble metal nanoparticles has been investigated both experimentally and computationally in recent years. However, the mechanism of plasmon-enhanced nitrogen dissociation is still not very clear. In this work, we apply theoretical approaches to examine the dissociation of a nitrogen molecule on atomically-thin Ag n nanowires (n = 6, 8, 10, 12) and a Ag 19 + nanorod. Ehrenfest dynamics provides information about the motion of nuclei during the dynamics process and real-time TDDFT calculations show the electronic transitions and population of electrons over the first 10s of fs time scale. The activation and dissociation of nitrogen is typically enhanced when the electric field strength increases. However, the enhancement is not always monotonic with field strength. As the length of the Ag wire increases, nitrogen is typically easier to dissociate and thus requires lower field strengths, even though the plasmon frequency is lower. The Ag 19 + nanorod leads to faster dissociation of N 2 than the atomically-thin nanowires. Altogether, our detailed study yields insights into the mechanisms involved in plasmon-enhanced N 2 dissociation, as well as provides information about factors that can be used to improve adsorbate activation.

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

Characterizing Complex Gas–Solid Interfaces with in Situ Spectroscopy: Oxygen Adsorption Behavior on Fe–N–C Catalysts

Electrocatalysts for the oxygen reduction reaction within polymer electrolyte membrane fuel cells based on iron, nitrogen, and carbon elements (Fe–N–C) are receiving significant research attention as they offer an inexpensive alternative to catalysts based on platinum-group metals. Although both the performance and the fundamental understanding of Fe–N–C catalysts have improved over the past decade, there remains a need to differentiate the relative activity of different active sites. Toward this goal, our study is focused on characterizing the interactions between O 2 and a set of five structurally different Fe–N–C materials. Detailed characterization of the Fe speciation was performed with 57 Fe Mössbauer spectroscopy and soft X-ray absorption spectroscopy of the Fe L 3,2 -edge, whereas nitrogen chemical states were investigated with X-ray photoelectron spectroscopy (XPS). In addition to initial sXAS and XPS measurements performed in ultra-high vacuum (UHV), measurements were also performed (at the identical location) in an atmosphere of 100 mTorr of O 2 at 80 °C (O 2 -rich). XPS and sXAS results reveal the presence of several types of FeNxCy adsorption sites. FeNxCy sites that are proposed as the most active ones do not show significant change (based on the techniques used in this study) when their environment is changed from UHV to O 2 -rich. Correlation with Mössbauer and sXAS results suggests that this is most likely due to the persistence of strongly adsorbed O 2 molecules from their previous exposure to air. However, other species do show spectroscopic changes from UHV conditions to O 2 -rich. This implies that these sites have a weaker interaction with O 2 that results in their desorption in vacuum conditions and re-adsorption when exposed to the O 2 -rich environment. The nature of these weakly and strongly O 2 -adsorbing FeN x C y sites is discussed in the context of different synthetic and processing parameters employed to fabricate each of these five Fe–N–C materials.

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

Dynamics in Flexible Pillar[ n ]arenes Probed by Solid-State NMR

Pillar[n]arenes are supramolecular assemblies that can perform a range of technologically important molecular separations which are enabled by their molecular flexibility. Here, we probe dynamical behavior by performing a range of variable-temperature solid-state NMR experiments on microcrystalline perethylated pillar[n]arene (n = 5, 6) and the corresponding three pillar[6]arene xylene adducts in the 100–350 K range. This was achieved either by measuring site-selective motional averaged 13 C 1 H heteronuclear dipolar couplings and subsequently accessing order parameters or by determining 1 H and 13 C spin–lattice relaxation times and extracting correlation times based on dipolar and/or chemical shift anisotropy relaxation mechanisms. We demonstrate fast motional regimes at room temperature and highlight a significant difference in dynamics between the core of the pillar[n]arenes, the protruding flexible ethoxy groups, and the adsorbed xylene guest. Additionally, unexpected and sizable 13 C 1 H heteronuclear dipolar couplings for a quaternary carbon were observed for p-xylene adsorbed in pillar[6]arene only, indicating a strong host–guest interaction and establishing the p-xylene location inside the host, confirming structural refinements.

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

First-Principles Study of n -Butane Monomolecular Cracking and Dehydrogenation on Two-Dimensional-Zeolite Model Systems: Reaction Mechanisms and Effects of Spatial Confinement

Two-dimensional (2D) ultrathin (~0.5 nm) aluminosilicate bilayer films, consisting of hexagonal prisms (a.k.a. double 6-membered rings D6R) with acidic bridging hydroxyl groups exposed on the surface, have been previously synthesized on a Ru(0001) surface as a zeolite model system. These structures are helpful for mimicking zeolite catalysts with D6R building blocks, such as chabazite. We performed density functional theory calculations to investigate the monomolecular cracking and dehydrogenation of n-butane molecules over the acidic hydroxyl groups of the 2D model system and compared the reaction energetics with that in bulk chabazite. The intrinsic activation energy barrier is the highest for dehydrogenation and lowest for central C–C bond cracking in bulk chabazite. The trend of intrinsic energy barriers for dehydrogenation and terminal and central C–C bond cracking is reproduced on the 2D aluminosilicate film. Overall, the activation barriers are higher on the 2D film than in bulk chabazite due to the lack of confinement in the former. We further explored the effects of the zeolite channel size on the n-butane adsorption and monomolecular cracking using different bulk nanoporous zeolite frameworks (TON, MEL, MEI, and VFI). We found that as the confinement of channels decreases, n-butane adsorption becomes weaker, and the intrinsic energy barrier of terminal C–C cracking increases. The activation energy barriers (dehydrogenation and terminal and central C–C cracking) on the 2D bilayer film surface, which may be considered as zeolite cages at the infinite cage size limit, are close to that in VFI with a relatively large channel size. Comparing the reaction pathway of n-butane terminal C–C cracking in 3D nanocages and on the surface of the 2D aluminosilicate film revealed that stabilizing the transition states in the 3D nanocages is responsible for the decrease in the intrinsic energy barriers for bulk zeolites.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Excited-State Charge Distribution of a Donor–π–Acceptor Zn Porphyrin Probed by N K-Edge Transient Absorption Spectroscopy

Zinc porphyrin solar cell dyes with donor-π–acceptor architectures combine light absorber (π), electron-donor, and electron-acceptor moieties inside a single molecule with atomic precision. The donor-π–acceptor design promotes the separation of charge carriers following optical excitation. Here, we probe the excited-state electronic structure within such molecules by combining time-resolved X-ray absorption spectroscopy at the N K-edge with first-principles time-dependent density functional theory (TD-DFT) calculations. Furthermore, customized Zn porphyrins with strong-donor triphenylamine groups or weak-donor tri-tert-butylbenzene groups were synthesized. Energetically well-separated N K-edge absorption features simultaneously probe the excited-state electronic structure from the perspectives of the macrocycle and triphenylamine N atoms. New absorption transitions between the macrocycle N atoms and the excited-state HOMO vacancy are observed, and the triphenylamine associated absorption feature blue-shifts, consistent with partial oxidation of the donor groups in the excited state.

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

Size-Dependent Onset of Nitric Acid Dissociation in Cs + ·(HNO 3 )(H 2 O) n =0–11 Clusters at 20 K

We report the water-mediated charge separation of nitric acid upon incorporation into size-selected Cs + ∙(HNO 3 )(H 2 O) n=0-11 clusters at 20 K. Dramatic spectral changes are observed in the range n=7-9 that are traced to the formation of many isomeric structures associated with intermediate transfer of the acidic proton to the water network. This transfer is complete by n=10, which exhibits much simpler vibrational band patterns consistent with those expected for a tri-coordinated hydronium ion (the Eigen motif) along with the NO stretching bands predicted for a hydrated NO 3 – anion that is directly complexed to the Cs + cation. Theoretical analysis of the n=10 spectrum indicates that the dissociated ions adopt a solvent-separated ion-pair configuration such that the Cs + and H 3 O + cations flank the NO 3 – anion in a microhydrated salt bridge. In conclusion, this charge separation motif is evidently assisted by the electrostatic stabilization of the product NO 3 – /H 3 O + ion pair by the proximal metal ion.

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

Effect of Dispersion Medium Composition and Ionomer Concentration on the Microstructure and Rheology of Fe–N–C Platinum Group Metal-free Catalyst Inks for Polymer Electrolyte Membrane Fuel Cells

In this paper, we present an investigation of the microstructure and rheological behavior of catalyst inks consisting of Fe–N–C platinum group metal-free catalysts and a perfluorosulfonic acid ionomer in a dispersion medium (DM) of water and 1-propanol ( n PA). The effects of the ionomer-to-catalyst (I/C) ratio and weight percentage of water (H 2 O %) in the DM on the ink microstructure were studied. Steady-shear and dynamic-oscillatory-shear rheology, in combination with synchrotron X-ray scattering, was utilized to understand interparticle interactions and the level of agglomeration of the inks. In the absence of the ionomer, the inks were significantly agglomerated, approaching a gel-like microstructure for catalyst concentrations as low as 2 wt %. The effect of H 2 O % in the DM on particle agglomeration was found to vary with particle concentration. In concentrated inks (≥2 wt % catalyst), increasing H 2 O % was found to increase agglomeration because of the hydrophobic nature of the catalysts. In dilute inks (<1 wt % catalyst), the trend was reversed with increasing H 2 O %, suggesting that electrostatic interactions are dominating the behavior. In inks with 5 wt % catalyst, the addition of an ionomer was found to significantly stabilize the catalyst against agglomeration. Maximum stability was observed at 0.35 I/C for all DM H 2 O % studied. At high ionomer concentrations (I/C > 0.35), interesting differences were observed between n PA-rich inks (H 2 O % ≤ 50%) and H 2 O-rich (82% H 2 O) inks. The n PA-rich inks remained predominantly stable—ink viscosity only weakly increased with I/C and the Newtonian behavior was maintained for I/C up to 0.9. In contrast, the H 2 O-rich inks exhibited a significant increase in viscoelasticity with increasing I/C, suggesting flocculation of the catalyst by the ionomer. These differences suggest that the nature of the interactions between the ionomer and catalyst is highly dependent on the H 2 O % in the DM.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗