Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “stabilization”

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 1,171 records · Page 65
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Computation-guided discovery of coating materials to stabilize the interface between lithium garnet solid electrolyte and high-energy cathodes for all-solid-state lithium batteries

All-solid-state batteries with a lithium metal anode, enabled by lithium garnet solid electrolytes such as Li 7 La 3 Zr 2 O 12 (LLZO), are a promising next-generation energy-storage technology. The further development of all-solid-state battery requires the integration of high-energy cathodes such as LiNi 1-x-y Mn x Co y O 2 (NMC) with the garnet solid electrolyte with stable and low-resistance interfaces, which requires a coating layer to stabilize the interface during high-temperature sintering and electrochemical cycling. In order to guide the future development of interfacial coatings, we perform high-throughput thermodynamic analyses based on first-principles computation to investigate the stability of LLZO garnet and high-energy NMC cathodes with a wide range of materials chemistries. Here our study reveals the factors governing the materials stability with LLZO garnet and NMC cathodes, and identifies the mechanisms of good coating layers stable with LLZO and NMC. In addition to classifying known coating layers, our study provides detailed guiding charts and multiple new materials systems as promising coatings for stabilizing LLZO—NMC interfaces to enable high-energy-density garnet-based all-solid-state batteries. Our demonstrated computation scheme and high-throughput analyses are generally applicable to investigate and screen coating materials for stabilizing interfaces in energy-related applications.

25 ENERGY STORAGE↗
DOE OSTI2015

Stability of engineered nanomaterials in complex aqueous matrices: Settling behaviour of CeO{sub 2} nanoparticles in natural surface waters

The stability of engineered nanoparticles (ENPs) in complex aqueous matrices is a key determinant of their fate and potential toxicity towards the aquatic environment and human health. Metal oxide nanoparticles, such as CeO{sub 2} ENPs, are increasingly being incorporated into a wide range of industrial and commercial applications, which will undoubtedly result in their (unintentional) release into the environment. Hereby, the behaviour and fate of CeO{sub 2} ENPs could potentially serve as model for other nanoparticles that possess similar characteristics. The present study examined the stability and settling of CeO{sub 2} ENPs (7.3±1.4 nm) as well as Ce{sup 3+} ions in 10 distinct natural surface waters during 7 d, under stagnant and isothermal experimental conditions. Natural water samples were collected throughout Flanders (Belgium) and were thoroughly characterized. For the majority of the surface waters, a substantial depletion (>95%) of the initially added CeO{sub 2} ENPs was observed just below the liquid surface of the water samples after 7 d. In all cases, the reduction was considerably higher for CeO{sub 2} ENPs than for Ce{sup 3+} ions (<68%). A first-order kinetics model was able to describe the observed time-dependant removal of both CeO{sub 2} ENPs (R{sup 2}≥0.998) and Ce{sup 3+} ions (R{sup 2}≥0.812) from the water column, at least in case notable sedimentation occurred over time. Solution-pH appeared to be a prime parameter governing nanoparticle colloidal stability. Moreover, the suspended solids (TSS) content also seemed to be an important factor affecting the settling rate and residual fraction of CeO{sub 2} ENPs as well as Ce{sup 3+} ions in natural surface waters. Correlation results also suggest potential association and co-precipitation of CeO{sub 2} ENPs with aluminium- and iron-containing natural colloidal material. The CeO{sub 2} ENPs remained stable in dispersion in surface water characterized by a low pH, ionic strength (IS), and TSS content, indicating the eventual stability and settling behaviour of the nanoparticles was likely determined by a combination of physicochemical parameters. Finally, ionic release from the nanoparticle surface was also examined and appeared to be negligible in all of the tested natural waters. - Highlights: • Solution-pH appeared to be a key factor determining CeO{sub 2} ENPs colloidal stability. • A 1st-order kinetics model could describe the time-dependant settling of CeO{sub 2} ENPs. • Suspended solids content affected the settling rate and residual cerium fraction. • CeO{sub 2} ENPs remained stable in dispersion in water with low pH, IS, and TSS content. • Ionic release from the CeO{sub 2} ENPs appeared negligible in all surface waters.

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

Hourglass control in staggered-grid hydrodynamics using virtual element stabilization techniques

Numerical simulations using the staggered-grid hydrodynamics (SGH) discretization suffer from hourglass instabilities. In this work, we develop a stabilization method to suppress the hourglass instabilities using techniques from the virtual element method (VEM). The stiffness matrix of the VEM consists of two terms: the consistency matrix which is rank deficient and the stability matrix. Here, we first show that in two dimensions and on general polygons, the stiffness matrix of the SGH is identical to the consistency matrix of the linear VEM for both the diffusion equation and the linear elasticity equation. These analyses explain the origin of the hourglass instabilities of the SGH discretization method, and establish a theoretical foundation for our proposed stabilization method by augmenting the stiffness matrix of the SGH discretization using the VEM stability matrix. Then, we present numerical examples using Lagrangian SGH simulations. The numerical experiments demonstrate that the proposed VEM stabilization method is effective at eliminating hourglass modes in the SGH discretization.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

Hidden transformations in entropy-stabilized oxides

We report entropy-stabilized oxides (ESO) display a reversible entropy-driven phase transformation that can be leveraged to produce a continuum of metastable phase states, allowing for property optimization and novel functionalities. X-ray absorption spectroscopy reveals that entropic stabilization extends to the electronic structure (valence state and cation coordination) in sintered (Co,Cu,Mg,Ni,Zn)O, manifesting as a tunable lattice distortion in the entropy-stabilized phase. Co, Cu, and Zn ions reversibly transform from six-fold to four-fold coordinated structures and from low to high valence states due to the competition between electronic structures that are equilibrium and enthalpy-driven or metastable and entropy-driven. The segregation of a Cu-rich tenorite phase and a Co-rich spinel phase influences the electronic structure evolution. ESOs can adjust their electronic structures through heat treatment, providing a powerful tool for developing functional properties. These results indicate that the definition of entropy stabilization should include entropy-stabilized electronic structures, providing motivation to reassess previously studied HEO materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Effects of electrolytes and surfactants on the morphology and stability of advanced silver nano-materials

Highlights: ► Stoichiometric ratio of S{sub 2}O{sub 3}{sup 2−} and Ag{sup +} ions are responsible to the formation of prefect transparent yellow colored silver sol. ► Higher S{sub 2}O{sub 3}{sup 2−} concentrations has damping effect. ► Head group of the surfactants and nature of the electrolytes have significant effect on the stability of silver nanoparticles. - Abstract: The impact of electrolytes, stabilizing and/or capping agents on morphology of colloidal silver nano-materials (AgNPs) has been studied spectroscopically. Sodium thiosulfate acts as reducing-, stabilizing- and damping-agents. Stoichiometric ratios of S{sub 2}O{sub 3}{sup 2−} and Ag{sup +} ions were responsible to the formation stable and prefect transparent dark yellow colored AgNPs. The S{sub 2}O{sub 3}{sup 2−}-stabilized AgNPs were significantly more stable in inorganic electrolytes (NaNO{sub 3}, Na{sub 2}SO{sub 4}, Na{sub 2}CO{sub 3} and KBr). S{sub 2}O{sub 3}{sup 2−} is adsorbed more strongly than the used other anions. The addition of cetyltrimethylammonium bromide (CTAB) and sodium dodecylsulfate (SDS) has significant effects on the absorbance of S{sub 2}O{sub 3}{sup 2−}-stabilized AgNPs which can be rationalized in terms of electrostatic attraction and repulsion between the adsorbed S{sub 2}O{sub 3}{sup 2−} ions on to the surface of AgNPs and cationic and/or anionic head groups of used surfactants, respectively. Transmission electron microscopy images suggest that AgNPs are polydispersed, spherical and exhibiting an interesting irregular morphology.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Effect of surface loading and bulk doping of La{sup 3+} on the thermal stability and photocatalytic activity of Bi{sub 2}O{sub 2}CO{sub 3}

Graphical abstract: The Bi{sub 2}O{sub 2}O{sub 3} modified La{sup 3+} was synthesized using two methods of co-precipitation (La-Bi{sub 2}O{sub 2}O{sub 3}) and wet impregnation (La/Bi{sub 2}O{sub 2}O{sub 3}). As compared with La-Bi{sub 2}O{sub 2}O{sub 3}, Bi{sub 2}O{sub 2}CO{sub 3} can be effectively stabilized by impregnation method, as La{sup 3+} is mainly dispersed onto the surface of Bi{sub 2}O{sub 2}O{sub 3}. In photocatalytic degradation of MO, it is found that the surface modification with La{sup 3+} can enhance the photocatalytic efficiency of Bi{sub 2}O{sub 2}O{sub 3}. The surface loading La{sup 3+} could act as an effective electron scavenger to trap the CB electrons of Bi{sub 2}O{sub 2}CO{sub 3} to reduce the recombination of electrons and holes in the surface. - Highlights: • The effect of La{sup 3+} on the thermal stability of Bi{sub 2}O{sub 2}CO{sub 3} is different for the impregnation method and coprecipitation method. • Bi2O2CO3 can be effectively stabilized by impregnation method, as La3+ is mainly dispersed onto the surface of Bi2O2O3. • Surface loading La3+ is benefit for the improvement in the photocatalytic activity of Bi2O2CO3. • Surface modification of La3+ greatly suppresses the charge recombination of photogenerated electron–hole pairs in Bi2O2CO3. - Abstract: The Bi{sub 2}O{sub 2}O{sub 3} modified La{sup 3+} was synthesized using two methods of co-precipitation (La-Bi{sub 2}O{sub 2}O{sub 3}) and wet impregnation (La/Bi{sub 2}O{sub 2}O{sub 3}). The effects of the above two modification methods on the stability of Bi{sub 2}O{sub 2}CO{sub 3} after calcination and the physicochemical properties of Bi{sub 2}O{sub 2}CO{sub 3} were investigated by XRD, SEM, BET, and XPS. As compared with La-Bi{sub 2}O{sub 2}O{sub 3}, it is observed that Bi{sub 2}O{sub 2}CO{sub 3} can be effectively stabilized by impregnation method, as La{sup 3+} is mainly dispersed onto the surface of Bi{sub 2}O{sub 2}O{sub 3}. The photocatalytic activities for the methyl orange degradation for the La/Bi{sub 2}O{sub 2}CO{sub 3} and the La-Bi{sub 2}O{sub 2}CO{sub 3} samples were tested, and the results showed that surface doping (impregnation method) is benefit for the improvement in the photocatalytic activity, as compared with bulk doping (coprecipitation method). PL characterization revealed the differences in the photocatalytic process for surface doping and bulk doping. The surface modification of La{sup 3+} greatly suppresses the charge recombination of photogenerated electron−hole pairs in Bi{sub 2}O{sub 2}CO{sub 3}, which would be beneficial to improve their photocatalytic activity.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Al-doped ZnS shell as a surface shield for enhancing the stability of Cu:ZnInS/ZnS/ZnS:Al quantum dots and their application in light emitting diodes

Graphical abstract: The normalized electroluminescence spectra of Cu:ZnInS@ZnS:Al (a) and Cu:ZnInS@ZnS quantum dot based LEDs under an injection current of 10 mA for various operation times are presented. The quantum dots were mixed with same amount of silicone resin and treated at 50 °C for 30 min. - Highlights: • The self-passivated Cu:ZnInS@ZnS:Al quantum dots were synthesized successfully. • The thermal and current stability of Cu:ZnInS@ZnS:Al quantum dots were improved. • The Cu:ZnInS@ZnS:Al quantum dots had a small reduction of 20% in PL lifetime under thermal annealing from 50 °C to 250 °C. • The Cu:ZnInS@ZnS:Al quantum dot based LED had a 3% luminescence enhancement under 10 mA injection current for a long time. - Abstract: Cu:ZnInS/ZnS/ZnS:Al quantum dots (QDs) with a Cu-doped inner core and an Al-doped outer shell were synthesized in this work, exhibiting improved stability of luminescence, compared with Cu:ZnInS/ZnS/ZnS QDs. The X-ray diffraction patterns and photoluminescence spectra confirmed that the Al ions were doped into the ZnS shell. The stability of Cu:ZnInS/ZnS/ZnS:Al QDs under various thermal annealing temperatures was studied by steady-state and time resolved photoluminescence spectroscopy. The Cu:ZnInS/ZnS/ZnS:Al QDs had a relatively small reduction of 20% in photoluminescence lifetime from 167 ns under thermal annealing at 50 °C to 132.8 ns at 250 °C, compared to a 55% drop for the undoped ones, indicating less thermal effect on the photoluminescence of the QDs with an Al-doped shell. The Cu:ZnInS/ZnS/ZnS:Al QD-based light emitting diodes (LEDs) had a 3% luminescence enhancement under injection current of 10 mA for 30 h, compared to a 13% reduction for the undoped QDs, suggesting improved thermal stability of photoluminescence for the QDs with Al-doped shell. Finally, Cu:ZnInS/ZnS/ZnS:Al QD-based white LEDs with good color rendering index (>80) and correlated color temperature (<4500 K) were fabricated by combining with green emitting CuInS{sub 2}/ZnS QDs. The self-passivated QDs show promises for enhancing thermal stability of QD-based LEDs in the conserved energy lighting industry.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Magnetic well and Mercier stability of stellarators near the magnetic axis

We have recently demonstrated that by expanding in small distance from the magnetic axis compared with the major radius, stellarator shapes with low neoclassical transport can be generated efficiently. To extend the utility of this new design approach, here we evaluate measures of magnetohydrodynamic interchange stability within the same expansion. In particular, we evaluate the magnetic well, Mercier's criterion, and resistive interchange stability near a magnetic axis of arbitrary shape. In contrast to previous work on interchange stability near the magnetic axis, which used an expansion of the flux coordinates, here we use the ‘inverse expansion’ in which the flux coordinates are the independent variables. Reduced expressions are presented for the magnetic well and stability criterion in the case of quasisymmetry. The analytic results are shown to agree with calculations from the VMEC equilibrium code. Finally, we show that near the axis, Glasser, Greene and Johnson's stability criterion for resistive modes approximately coincides with Mercier's ideal condition.

Physics↗
DOE OSTI2022

Tuning Enzyme Thermostability via Computationally Guided Covalent Stapling and Structural Basis of Enhanced Stabilization

Enhancing the thermostability of enzymes without impacting their catalytic function represents an important yet challenging goal in protein engineering and biocatalysis. We recently introduced a novel method for enzyme thermostabilization that relies on the computationally guided installation of genetically encoded thioether “staples” into a protein via cysteine alkylation with the noncanonical amino acid O-2-bromoethyl tyrosine (O2beY). Here, we demonstrate the functionality of an expanded set of electrophilic amino acids featuring chloroacetamido, acrylamido, and vinylsulfonamido side-chain groups for protein stapling using this strategy. Using a myoglobin-based cyclopropanase as a model enzyme, our studies show that covalent stapling with pchloroacetamido-phenylalanine (pCaaF) provides higher stapling efficiency and enhanced stability (thermodynamic and kinetic) compared to the other stapled variants and the parent protein. Interestingly, molecular simulations of conformational flexibility of the cross-links show that the pCaaF staple allows fewer energetically feasible conformers than the other staples, and this property may be a broader indicator of stability enhancement. Using this strategy, pCaaF-stapled variants with significantly enhanced stability against thermal denaturation (ΔT m ' = +27 °C) and temperature-induced heme loss (ΔT 50 = +30 °C) were obtained while maintaining high levels of catalytic activity and stereoselectivity. Crystallographic analyses of singly and doubly stapled variants provide key insights into the structural basis for stabilization, which includes both direct interactions of the staples with protein residues and indirect interactions through adjacent residues involved in heme binding. This work expands the toolbox of protein stapling strategies available for protein stabilization.

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

Semiconducting High-Entropy Chalcogenide Alloys with Ambi-ionic Entropy Stabilization and Ambipolar Doping

Entropy stabilization is a novel materials-design paradigm to realize new compounds with widely tunable properties. However, almost all entropy-stabilized materials so far are either conducting metals or insulating ceramics, with a clear dearth in the semiconducting regime. Here, a new class of the multi-cationic and -anionic entropy-stabilized chalcogenide alloys based on the (Ge,Sn,Pb)(S,Se,Te) formula are synthesized and characterized experimentally. The con-figurational entropy from the disorder of both the anion and the cation sublattices reaches a record value of ~2.2 R mol -1 for the equimolar composition and stabilizes the single-phase solid solution. Theoretical calculations and experiments both show that the synthesized alloys are thermodynamically stable at the growth temperature and kinetically metastable at room temperature, segregating by spinodal decomposition at moderate temperatures. In conclusion, doping and electronic transport measurements verify that the synthesized materials are ambipolarly dopable semiconductors, which paves the way for the wider adoption of entropy-stabilized chalcogenide alloys in functional applications.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Improving Thermal Stability of Perovskite Solar Cells by Suppressing Ion Migration Using Copolymer Grain Encapsulation

Thermal stability of organic–inorganic hybrid perovskites (OIHPs) remains as one of the critical challenges against the stable operation of perovskite solar cells (PSCs) in direct sunlight with elevated temperatures. Here, we show that the addition of a polystyrene-co-polyacrylonitrile (SAN) copolymer can significantly enhance thermal stability of OIHPs and improve the stability of the corresponding PSCs by suppressing the migration of organic cations in OHIP. The methylammonium lead iodide (MAPI) with SAN incorporated within the perovskite layer featured a superior thermal stability compared to pure MAPI without SAN, only displaying an average of 5–15% decrease in PCE even after continuous thermal aging for 24 h at 100 °C. The secondary ion mass spectrometry revealed that the thermal degradation of the pure MAPI was largely associated with MA+ out-migration. Conducting atomic force microscopy analysis further indicated that the incorporated SAN led to a suppression of ionic currents present at the grain boundaries of the perovskite film, which was understood by high immiscibility between SAN and MA+ components as confirmed by the experimentally estimated Flory–Huggins parameter between them. This study newly identifies a potential of using polymer grain encapsulation for enhancing thermal stability of OIHPs and their solar cell performance by suppressing the out-diffusion of cationic organic components.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Magic Numbers and Stabilities of Photoionized Water Clusters: Computational and Experimental Characterization of the Nanosolvated Hydronium Ion

The stability and distributions of small water clusters generated in a supersonic beam expansion are interrogated by tunable vacuum ultraviolet (VUV) radiation generated at a synchrotron. Time-of-flight mass spectrometry reveals enhanced population of various protonated water clusters (H + (H 2 O) $n$ ) based upon ionization energy and photoionization distance from source, suggesting there are "magic" numbers below the traditional $n$ = 21 that predominates in the literature. These intensity distributions suggest that VUV threshold photoionization (11.0-11.5 eV) of neutral water clusters close to the nozzle exit leads to a different nonequilibrium state compared to a skimmed molecular beam. This results in the appearance of a new magic number at 14. Metadynamics conformer searches coupled with modern density functional calculations are used to identify the global minimum energy structures of protonated water clusters between $n$ = 2 and 21, as well as the manifold of low-lying metastable minima. New lowest energy structures are reported for the cases of $n$ = 5, 6, 11, 12, 16, and 18, and special stability is identified by several measures. These theoretical results are in agreement with the experiments performed in this work in that $n$ = 14 is shown to exhibit additional stability, based on the computed second-order stabilization energy relative to most cluster sizes, though not to the extent of the well-known $n$ = 21 cluster. Other cluster sizes that show some additional energetic stability are $n$ = 7, 9, 12, 17, and 19. To gain insight into the balance between ion-water and water-water interactions as a function of the cluster size, an analysis of the effective two-body interactions (which sum exactly to the total interaction energy) was performed. In conclusion, this analysis reveals a crossover as a function of cluster size between a water-hydronium-dominated regime for small clusters and a water-water-dominated regime for larger clusters around $n$ = 17.

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

Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI) 2 in Diglyme: Implications for Multivalent Electrolytes

In this paper, we reveal the general mechanisms of partial reduction of multivalent complex cations in conditions specific for the bulk solvent and in the vicinity of the electrified metal electrode surface and disclose the factors affecting the reductive stability of electrolytes for multivalent electrochemistry. Using a combination of ab initio techniques, we clarify the relation between the reductive stability of contact-ion pairs comprising a multivalent cation and a complex anion, their solvation structures, solvent dynamics, and the electrode overpotential. We found that for ion pairs with multiple configurations of the complex anion and the Mg cation whose available orbitals are partially delocalized over the molecular complex and have antibonding character, the primary factor of the reductive stability is the shape factor of the solvation sphere of the metal cation center and the degree of the convexity of a polyhedron formed by the metal cation and its coordinating atoms. We focused specifically on the details of Mg (II) bis(trifluoromethanesulfonyl)imide in diethylene glycol dimethyl ether (Mg(TFSI) 2 )/diglyme) and its singly charged ion pair, MgTFSI + . In particular, we found that both stable (MgTFSI) + and (MgTFSI) 0 ion pairs have the same TFSI configuration but drastically different solvation structures in the bulk solution. This implies that the MgTFSI/dyglyme reductive stability is ultimately determined by the relative time scale of the solvent dynamics and electron transfer at the Mg–anode interface. In the vicinity of the anode surface, steric factors and hindered solvent dynamics may increase the reductive stability of (MgTFSI) + ion pairs at lower overpotential by reducing the metal cation coordination, in stark contrast to the reduction at high overpotential accompanied by TFSI decomposition. By examining other solute/solvent combinations, we conclude that the electrolytes with highly coordinated Mg cation centers are more prone to reductive instability due to the chemical decomposition of the anion or solvent molecules. Finally, the obtained findings disclose critical factors for stable electrolyte design and show the role of interfacial phenomena in reduction of multivalent ions.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Trends in the thermodynamic stability of ultrathin supported oxide films

The formation of thin oxide films on metal supports is an important phenomenon, especially in the context of strong metal support interaction (SMSI). Computational predictions of the stability of these films are hampered by their structural complexity and a varying lattice mismatch with different supports. In this study, we report a large combination of supports and ultrathin oxide films studied with density functional theory (DFT). Trends in stability are investigated through a descriptor-based analysis. Since the studied films are bound to the support exclusively through metal–metal interaction, the adsorption energy of the oxide-constituting metal atom can be expected to be a reasonable descriptor for the stability of the overlayers. If the same supercell is used for all supports, the overlayers experience different amounts of stress. Using supercells with small lattice mismatch for each system leads to significantly improved scaling relations for the stability of the overlayers. Finally, this approach works well for the studied systems and therefore allows the descriptor-based exploration of the thermodynamic stability of supported thin oxide layers.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Influence of Interligand Interactions and Core-Charge Distribution on Gold Cluster Stability: Enthalpy vs Entropy

Understanding the formation and stability of ligated gold clusters is necessary to direct the scalable solution-phase synthesis of atomically-precise clusters with predetermined properties. Gas-phase studies provide molecular-level insight into ligandgold cluster interactions that control ligand exchange and growth/etching reactions in solution. Here we report a joint experimental and theoretical study of a series of eight gold atom, mixed phosphine, di-cationic clusters using time- and energy-resolved surface induced dissociation (SID) experiments and high-level calculations. Gold clusters were prepared by reduction of a gold salt precursor containing triphenylphosphine (PPh3). Subsequent ligand exchange reactions with methyldiphenylphosphine (MePPh2) generated a distribution of mixed-phosphine gold clusters. Experimentally-derived ligand binding energies and activation entropies for the mixed-ligand gold clusters were compared with ligand removal energies obtained from theoretical calculations. The results show that the exchange ligand, MePPh2, has a lower binding energy to the gold core than PPh3. In addition, both ligands are more strongly bound to the mixed-ligand clusters than to any of the pure PPh3-ligated gold clusters. Larger ligand binding energies in the mixed-ligand clusters are associated with large activation entropies, which become a competing factor determining cluster stability. This study reveals, for the first time, that ligand-ligand Van der Waals interactions contribute substantially to gold cluster stability and may be partially responsible for the large ligand dissociation entropies observed in SID experiments. We propose that ligand-ligand interactions in conjunction with changes in the charge distribution of the gold cores upon ligand removal bring about kinetically-driven fragmentation pathways, which may be responsible for the fast ligand exchange reactions observed in solution. These findings have broad implications for understanding what factors determine the stability of ligated metal clusters as certain ligands may have similar enthalpic and entropic components contributing to overall cluster stability.

Ligare, Marshall R.↗
DOE OSTI2018

Improved Chemical and Colloidal Stability of Gold Nanoparticles through Dendron Capping

Nanoparticle (NP) stability is imperative for commercialization of nanotechnology. In this study, we compare the stability of Au NPs with surfaces functionalized with oleylamine, dodecanethiol, and two dendritic ligands of different generations. Dendrimer ligands provide a significant increase in the chemical stability of Au NPs when analyzed by cyanide-induced NP decomposition as well as an investigation into their colloidal stability at ambient conditions. These results were supported by absorption measurements, transmission electron microscopy, thermogravimetric analysis, nuclear magnetic resonance, and small-angle transmission X-ray scattering and show that dendrimers play a key role in improving the chemical and colloidal stability of NPs.

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

Alkaline Stability of Quaternized Diels–Alder Polyphenylenes

Alkaline stability of anion exchange membranes is an essential requirement for the practical application of alkaline membrane fuel cells. In this study, we investigate the alkaline stability of Diels-Alder polyphenylenes (DAPPs) under various stability testing conditions. Structural analysis and membrane properties of the DAPPs indicated that different chemical structural changes of quaternized DAPPs occur depending on test conditions. Benzyltrimethylammonium functionalized DAPPs degraded rapidly via nucleophilic benzyl substitution under a relatively mild condition ca. 80 °C, 4 M NaOH whereas DAPPs with hexyltrimethylammonium (HTMA DAPP) exhibited much better alkaline stability. While only crosslinking of unreacted alkyl bromides of HTMA DAPP occurred at 80 °C, we observed the degradation of the cations via β- elimination after long term testing. At higher temperature or reduced relative humidity (RH) conditions, e.g., 160 °C or RH 10%, the rapid degradation of the cation in HTMA DAPP occurred via nucleophilic methyl substitution. These results suggest that accelerated stress tests may not be a quick and straightforward alternative to prolonged alkaline stability tests of AEMs.

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

Quaternary FeCoNiMn-Based Nanocarbon Electrocatalysts for Bifunctional Oxygen Reduction and Evolution: Promotional Role of Mn Doping in Stabilizing Carbon

The intrinsic instability of carbon largely limits its use for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) as a bifunctional catalyst in reversible fuel cells or water electrolyzers. In this paper, we discovered that Mn doping has a promotional role in stabilizing nanocarbon catalysts for the ORR/OER in alkaline media. Stable nanocarbon composites are derived from an inexpensive carbon/nitrogen precursor (i.e., dicyandiamide) and quaternary FeCoNiMn alloy via a template-free carbonization process. In addition to FeCoNiMn metal alloys/oxides, the carbon composites comprise substantial carbon tube forests growing on a thick and dense graphitic substrate. The dense carbon substrate with high degree of graphitization results from Mn doping, while active nitrogen-doped carbon tubes stem from FeCoNi. Catalyst structures and performance are greatly dependent on the doping content of Mn. Various accelerated stress tests (AST) and life tests verify the encouraging ORR/OER stability of the nanocarbon composite catalyst with optimal Mn doping. Extensive characterization before and after ASTs elucidates the mechanism of stability enhancement resulting from Mn doping, which is attributed to (i) hybrid carbon nanostructures with enhanced resistance to oxidation and (ii) the in situ formation of the β-MnO 2 and FeCoNi-based oxides capable of preventing carbon corrosion and promoting activity. Note that the improvement in stability due to Mn doping is accompanied by a slight activity loss due to a decrease in surface area. Finally, this work provides a strategy to stabilize carbon catalysts by appropriately integrating transition metals and engineering carbon structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗