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At least 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Machine Learning-Accelerated First-Principles Molecular Dynamics Explains Anomalous Lattice Thermal Expansion in BaZr 0.78 Y 0.22 O 3-δ

Fuel cells are a vital clean energy technology that converts chemical energy directly into electricity with high efficiency, making them a cornerstone of a sustainable energy future. Herein we investigate the thermal and chemical lattice expansion behavior of hydrated BaZr 0.78 Y 0.22 O 3-δ using machine learning-accelerated ab initio molecular dynamics simulations. Here, our results reproduce the experimentally observed non-monotonic and anomalous temperature dependence of lattice expansion, which we attribute to the competing effects of thermal expansion and dehydration—two mechanisms that influence the lattice expansion in opposite directions. The importance of this work lies in its detailed demonstration of how advanced computational techniques can accurately capture complex environmental effects, providing a valuable framework for modeling similar phenomena in a variety of material systems and applications.

Proton conducting fuel cell↗
DOE OSTI2025

All-Atom Modeling and Simulation of Biopolymer Interface: Dual Role of Antifouling Polymer Brushes

Antifouling polymer brushes are well-known for their exceptional resistance to unwanted protein adsorption. While experimental studies have extensively characterized protein–polymer brush interactions, computational investigations remain limited, largely due to the challenges in accurately modeling and integrating these complex, multicomponent systems without resorting to oversimplification. To address this challenge, this study presents one of the most comprehensive and realistic model systems to date, comprising the substrate, grafted polymers, and proteins. Our work interprets the interactions between polymer brush and protein based on realistic modeling without simplification. In particular, this study utilizes molecular modeling and simulation of polycationic and polyzwitterionic brushes─poly(dimethylaminoethyl methacrylate) (PDMAEMA), poly(2-(N-oxide-N,N-dimethylamino)ethyl methacrylate) (PNOMA), and poly(2-(N-3-sulfopropyl-N,N-dimethylammonium)ethyl methacrylate) (PSBMA)─grafted onto α-quartz substrates via polymerization initiator linkers. The brush models were developed to closely replicate experimentally synthesized samples and to provide detailed insights into structural and dynamical changes at the molecular level during protein adsorption. Using steered molecular dynamics simulations, we show that the PSBMA brush, due to its high local density, exhibits the greatest resistance to protein insertion. Cα root-mean-square deviation and interaction pattern analyses further reveal that the PSBMA brush also induces the most significant destabilization of lysozyme, while the PDMAEMA brush enhances protein stability through ion-mediated interactions. The PNOMA brush, while requiring the lowest force for protein adsorption, induces greater protein destabilization than the PDMAEMA brush, primarily due to electrostatic repulsion caused by a short carbon spacer length. Hydration analysis reveals that both the PSBMA brush and the lysozyme interacting with it exhibit the most rapid dehydration, attributed to the brush’s high local chain density, which results in the greatest lysozyme destabilization and the highest adsorption force. These findings highlight the dual role of antifouling polymer brushes: resisting protein adsorption and modulating protein structural dynamics. In conclusion, this study provides valuable insights for the rational design of next-generation antifouling materials and offers a framework for realistic model development in complex multicomponent systems.

Adsorption↗
DOE OSTI2020

Dueling Backbones: Comparing Peptoid and Peptide Analogues of a Mussel Adhesive Protein

Ensembles of amino acid side chains often dominate the interfacial interactions of intrinsically disordered proteins; however, backbone contributions are far from negligible. Using a combination of nanoscale force measurements and molecular dynamics simulations, we demonstrated with analogous mussel-mimetic adhesive peptides and peptoids both 34 residues long that highly divergent adhesive/cohesive outcomes can be achieved on mica surfaces by altering backbone chemistry only. The Phe, Tyr, and Dopa containing peptoid variants used in this study deposited as dehydrated and incompressible films that facilitated analysis of peptoid side chain contributions to adhesion and cohesion. For example, whereas Phe and Dopa peptoids exhibited similar cohesion, Dopa peptoids were ~3 times more adhesive than Phe peptoids on mica. Compared with the peptides, Phe peptoid achieved only ~20% of Phe containing peptide adhesion, but the Dopa peptoids were >2-fold more adhesive than the Dopa peptides. Cation-π interactions accounted for some but not all of the cohesive interactions. Finally, our results were corroborated by molecular dynamics simulations and highlight the importance of backbone chemistry and the potential of peptoids or peptoid/peptide hybrids as wet adhesives and primers.

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

Unusual Electrochemical Activity of Thin SiO 2 Layers Leads to Instability of Molecular Attachment in Hybrid Photoelectrodes

Hybrid photoelectrodes, comprised of a light-absorbing semiconductor and a surface-integrated molecular catalyst, are attractive for applications in artificial photosynthesis, since they combine the advantages of broadband semiconductor light absorption with the selectivity of molecular catalysis. A widely used class of hybrid photoelectrodes is based on Si substrates passivated by a thin (<3 nm) layer of silicon oxide, which is commonly prepared by controlled chemical or thermal oxidation, resulting in chemical oxide (ChO) or thermal oxide (ThO) layers, respectively. However, the electrochemical stability of these oxide layers, and the chemical stability of the semiconductor-molecule assembly in hybrid photoelectrodes, are not well understood, with evidence that covalently-bound molecules detach from the oxide surface upon application of cathodic bias. We have examined the intrinsic electrochemical reactivity of silicon oxide layers and how it affects the attachment of molecular monolayers. We determined that the surface of Si|ThO is primarily terminated with hydrophobic siloxane moieties, whereas that of Si|ChO contains a higher concentration of hydrophilic silanol groups. Initial high current densities for Si|ChO under applied bias up to -2 V vs. Ag/AgCl, decrease during repeated cyclic voltammetry scans, due to the consumption of surface-bound water. This is manifested by a reversible wave around -0.5 V in CH 3 CN solution, and a similar pH-dependent wave in water, revealing the pK a of the silanol groups to be ~4. Here, our combined observations support the electrochemically-induced dehydration of the SiO 2 surface, which converts silanol groups to siloxanes and proceeds through an H-atom intermediate that is most likely stabilized by pentavalent Si. We propose that similar reactivity is responsible for the electrochemical loss of alkylsiloxane-attached molecules under cathodic bias, which has important implications for the choice of catalyst attachment strategy in hybrid photoelectrodes.

14 SOLAR ENERGY↗
DOE OSTI2022

Selective Hydration of Rutile TiO 2 as a Strategy for Site-Selective Atomic Layer Deposition

In this report the feasibility of a site-selective hydration strategy that enables site-selective atomic layer deposition (ALD) is investigated among four rutile TiO 2 facets [(110), (100), (101) and (001)] and their most prevalent step edges. First-principles simulations of asymmetric slab models were utilized to create accurate representations of pristine terrace and step edge sites. The adsorption free energies for molecular and dissociative adsorption of H 2 O were calculated to evaluate this strategy as a viable route to step edge selectivity. We predict that selective hydroxylation is possible on the 110 and 001 step edges and further computationally evaluate three metalorganic ALD precursors for their compatibility with the selective hydration strategy. Experimental evidence for delayed nucleation of ALD on rutile (001), (110), and (100) TiO2 single crystals corroborates predictions of the dehydration of the surface and suggests the possibility of site-selective ALD.

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

Tunable Solid Acid Catalyst Thin Films Prepared by Atomic Layer Deposition

Solid acid catalysts, including zeolites and amorphous silica-aluminas (ASAs), are industrially important materials widely used in the fuel and petrochemical industries. The versatility of zeolites is due to the Brønsted acidity of the bridging hydroxyl and shape selectivity that can be tailored during and after synthesis. This is in contrast to amorphous silica-alumina, where tailoring acidity is a major challenge as the Brønsted acid structure in ASA is still debated. In both cases, however, the pore size and acidity cannot be tuned independently, and this is particularly limiting in the application of biomass conversion, where zeolite pores are too small for the molecules of interest. Herein, we present a method using atomic layer deposition (ALD) to prepare thin films of solid acid materials where the ratio of Brønsted to Lewis acid sites can be tuned precisely. This capability, combined with the sub-nm pore size control afforded by ALD yields a powerful and flexible method for synthesizing solid acid catalysts inside virtually any mesoporous host. We demonstrate the utility of these materials in two acid-catalyzed reactions relevant to biomass conversion: (1) Meerwein–Ponndorf–Verley–Oppenauer (MPVO) reaction and dehydration of fructose and (2) cascade reaction of glucose to 5-hydroxymethylfurfural. Finally, we propose a plausible structure for the Brønsted acid sites in our materials based on infrared spectroscopy and solid-state nuclear magnetic resonance measurements and density functional theory calculations and argue that this same structure might apply to conventional ASAs as well.

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

Mechanistic Insights on Permeation of Water over Iron Cations in Nanoporous Silicon Oxide Films for Selective H 2 and O 2 Evolution

Electrocatalysts encapsulated by an ultrathin and semipermeable oxide layer offer a promising avenue for efficient, selective, and cost-effective production of hydrogen through photoelectrochemical water splitting. This architecture is especially attractive for Z-scheme water splitting, for which a nanoporous oxide film can be leveraged to mitigate undesired, yet kinetically facile, reactions involving redox shuttles, such as aqueous iron cations, by limiting transport of these species to catalytically active sites. In this work, molecular dynamics simulations were combined with electrochemical measurements to provide a mechanistic understanding of permeation of water and Fe(III)/Fe(II) redox shuttles through nanoporous SiO 2 films. It is shown that even for SiO 2 pores with a width as small as 0.8 nm, water does not experience any energy barrier for permeating into the pores due to a favorable interaction with hydrophilic silanol groups on the oxide surface. In contrast, permeation of Fe(III) and Fe(II) into microporous SiO 2 pores is limited due to high energy barriers, which stem from a combination of distortion and dehydration of the second and third ion solvation shells. Furthermore, our simulations and experimental results show that SiO 2 coatings can effectively mitigate undesired Fe(III)/Fe(II) redox reactions at underlying electrodes by attenuating permeation of iron cations, while allowing water to permeate and thus participate in water splitting reactions. In a broader context, our study demonstrates that selectivity of solvated cations can be manipulated by controlling the pore size and surface chemistry of oxide films.

14 SOLAR ENERGY↗
DOE OSTI2020

Understanding Cation Selectivity in Carbon Nanopores with Hybrid First-Principles/Continuum Simulations: Implications for Water Desalination and Separation Technologies

Understanding ion adsorption in porous carbons is crucial for a range of technologies, including water desalination and energy storage. In this work, we combined density functional theory with a continuum solvation model to investigate thermodynamics and kinetics of the adsorption process of alkali metal ions from aqueous solutions into carbon nanopores with different sizes and geometries. We found that cations with a larger ionic radius are more favorable to enter the nanopores because of a lower energy penalty of dehydration. In addition, the pore size and geometry were found to have a significant impact on the ion–pore interaction under confinement and cation selectivity. Our study highlights a complex interplay among nanopore geometry, ion size, and hydration on the cation adsorption selectivity, suggesting that tuning the porosity could represent a general strategy for improving ion separations.

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

Synthesis and Characterization of Amorphous Lawsone Polymer Dots for Fluorescent Applications

In this work, a two-step hydrothermal/solvothermal process was developed to generate highly fluorescent lawsone polymer dots (LPDs) utilizing an inexpensive and abundant starting material, 2-hydroxy-1,4-napththoquinone (lawsone). This hydrothermal/solvothermal process produces LPDs that have excitation independent emission with well-defined electronic transitions. This two-step protocol provides a straightforward approach to remove unwanted small molecular fluorescence, which has plagued carbon dot systems, without the need for advanced chromatographic purification methods or steps. A series of spectroscopic, electrochemical, and theoretical experiments suggest that this process proceeds via a sequential dehydration and dehydrogenation pathway to cross-link the lawsone into a carbon dot structure. This polymerization process helps to stabilize and favor certain electronic transitions inherently present in the lawsone monomer. The generation of the LPDs results in a 2 order of magnitude increase in the emission intensity and a quantum yield of 37%. This behavior is likely the result of the cross-linked structure shielding these electronic states from deactivation caused by nonradiative processes such as vibrational coupling and excited state quenching from thermal deactivation and solvent collisions. This finding is consistent with a cross-linked enhanced emission (CEE) mechanism, as previously observed for other similar systems. The LPDs were then incorporated into a TiO2 photoanode and utilized as a photosensitizer in a dye-sensitized solar cell (DSSC) which showed an enhancement in photocurrent density over pure TiO2. We also prepared a derivative of the LPDs utilizing a diethylene triamine additive (nitrogen-doped lawsone polymer dots (N-LPDs)) using the same two-step protocol and demonstrated its potential as a fluorescence microscopy dye for imaging MDA-MB-231 cancer cells.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Resonance-Promoted Formic Acid Oxidation via Dynamic Electrocatalytic Modulation

It is a truth universally acknowledged that faster catalysts enable more efficient transformation of molecules to useful products and enhance the utilization of natural resources. However, the limit of static catalyst performance defined by the Sabatier principle has motivated a dynamic approach to catalyst design, whereby catalysts oscillate between varying energetic states. In this work, the concept of dynamic catalytic resonance was experimentally demonstrated via the electrocatalytic oxidation of formic acid over Pt. Oscillation of the electrodynamic potential between 0 and 0.8 V NHE via a square waveform at varying frequency (10 –3 < f < 10 3 Hz) increased the turnover frequency to ~20 s –1 at 100 Hz, over one order of magnitude (20×) faster than optimal potentiostatic conditions. We attribute the accelerated dynamic catalysis to nonfaradaic formic acid dehydration to surface-bound carbon monoxide at low potentials, followed by surface oxidation and desorption to carbon dioxide at high potentials.

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

Prediction of Hydroxymethylfurfural Yield in Glucose Conversion through Investigation of Lewis Acid and Organic Solvent Effects

Hydroxymethylfurfural (HMF) is one of the important renewable platform compounds that can be obtained from biomass feedstocks through glucose conversion catalyzed by Brønsted and Lewis acids. However, it is challenging to enhance the HMF yield due to side reactions. In this study, a systematic approach combining theory and experiment was performed to investigate the influence of Lewis acids and organic solvents on the HMF yield. For the Lewis acid effect, a relationship between chemical hardness and experimental HMF yields was found in the rate-limiting step of glucose-to-fructose isomerization for six metal chlorides; HMF production was promoted when the metal chloride and a substrate had a similar chemical hardness. To study the organic solvent effect, a multivariate model was developed based on the insights gained from the mechanistic study of fructose dehydration, to predict HMF yields in a given water-organic cosolvent system. It showed a reliable accuracy in evaluating HMF yields with a mean absolute error (MAE) of 3.0% with respect to experimental HMF yields for 13 solvents, and also predicted HMF yields with a MAE of 10.7% for four new solvents. Chemical interpretation of the model revealed that it is desirable to use a solvent capable of stabilizing the carbocation intermediates with low proton transfer activity and high hydrogen bond basicity, to maximize the HMF yield. This multivariate model informs experimentalists about rational selection of solvents with very low computational costs needed to calculate only six variables for each solvent. It can be expanded to other catalytic systems such as heterogeneous Brønsted–Lewis bifunctional catalysts and enables optimization of reaction conditions to obtain other useful platform molecules through biomass conversion.

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

Identifying the Catalytic Active Site for Propylene Metathesis by Supported ReO x Catalysts

A series of supported ReO x catalysts were investigated that allowed identifying the unique surface anchoring sites on oxide supports responsible for activating the surface ReO 4 sites for propylene metathesis (the catalytic active site). The catalysts were synthesized by incipient-wetness impregnation of aqueous HReO 4 onto the oxide supports (Al 2 O 3 , ZrO 2 , TiO 2 , SiO 2 and CeO 2 ), characterized under dehydrated and propylene metathesis reaction conditions with in situ spectroscopy (Raman, DRIFTS, UV-Vis and NAP-XPS), and chemically probed (CH 3 CH=CH 2 -TPSR, CH 2 =CH 2 /CH 3 CH=CHCH 3 titration and steady-state self-metathesis of propylene to ethylene and 2-butene). The initially calcined supported rhenia species anchor as isolated surface Re 7+ O 4 sites on the oxide supports by reacting with the surface hydroxyls (terminal S-OH, bridged S-OH-S and tricoordinated S 3 -OH) of the oxide supports. The specific oxide support was found to control the number of activated sites (Al 2 O 3 >> ZrO 2 > CeO 2 > TiO 2 > SiO 2 ) and propylene metathesis activity (Al 2 O 3 >> ZrO 2 >> TiO 2 ~ CeO 2 ~ SiO 2 ) revealing that the oxide support action is a potent ligand for the surface ReO x sites. The activation and specific activity of the surface ReO x sites depend on several factors (nature of surface hydroxyls (S 3 -OH > S-OH-S > S-OH), coordination of the oxide support surface cation (ZrO 7 , AlO 6 , CeO 4 ) and electronegativity of the oxide support cation (SiO 2 > Al 2 O 3 > TiO 2 > ZrO 2 > CeO 2 ). No relationships exist between olefin metathesis activity and acid strength of surface Lewis and Brønsted sites. Here, prior studies primarily focused on supported ReO x /Al 2 O 3 and the lack of examination of non-Al 2 O 3 supported rhenia catalysts precluded comparison between efficient and inefficient olefin metathesis catalysts, which prevented identifying the catalytic active site for olefin metathesis by supported ReO x catalysts.

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

Isolated Metal Sites in Cu–Zn–Y/Beta for Direct and Selective Butene-Rich C 3+ Olefin Formation from Ethanol

Direct and selective production of C 3+ olefins from bioethanol remains a critical challenge and important for the production of renewable transportation fuels such as aviation biofuels. In this study, we report a Cu–Zn–Y/Beta catalyst for selective ethanol conversion to butene-rich C 3+ olefins (88% selectivity at 100% ethanol conversion, 623 K), where the Cu, Zn, and Y sites are all highly dispersed. The ethanol-to-butene reaction network includes ethanol dehydrogenation, aldol condensation to crotonaldehyde, and hydrogenation to butyraldehyde, followed by further hydrogenation and dehydration reactions to form butenes. Cu sites play a critical role in promoting hydrogenation of the crotonaldehyde C═C bond to form butyraldehyde in the presence of hydrogen, making this a distinctive pathway from crotyl alcohol-based ethanol-to-butadiene reaction. Reaction rate measurements in the presence of ethanol and acetaldehyde (543 K, 12 kPa ethanol, 1.2 kPa acetaldehyde, 101.9 kPa H 2 ) over monometallic Zn/Beta and Y/Beta catalysts indicate that Y sites have higher C–C coupling rates than over Zn sites (initial C–C coupling rate, 6.1 × 10 –3 mol mol Y –1 s –1 vs 1.2 × 10 –3 mol mol Zn –1 s –1 ). Further, Lewis-acidic Y-site densities over Cu–Zn–Y/Beta with varied Y loadings are linearly correlated with the initial C–C coupling rates, suggesting that Lewis-acidic Y sites are the predominant sites that catalyze C–C coupling in Cu–Zn–Y/Beta catalysts. Control experiments show that the dealuminated Beta support is important to form higher density of Lewis-acidic Y sites in comparison with other supports such as silica, or deboronated MWW despite similar atomic dispersion of Y sites and Y–O coordination numbers over these supports, leading to more than 9 times higher C–C coupling rate per mole Y over dealuminated Beta relative to other supports. This study highlights the significance of unique combination of metal sites in contributing to the selective valorization of ethanol to C 3+ olefins, motivating for exploring multifunctional zeolite catalysts, where the presence of multiple sites with varying reactivities and functions allows for controlling the predominant molecular fluxes toward the desired products in complex reactions.

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

Catalytic Reduction of Esters over Zirconia-Supported Metal Catalysts

Esters are often produced as unwanted byproducts during the catalytic upgrading of ethanol to diesel fuel precursors through Guerbet coupling. Removal of esters from the product stream is important to prevent the loss of downstream catalyst activity from ester-derived carboxylic acids. In this work, we studied ester hydrogenolysis to the parent alcohols as a viable route for enhanced diesel fuel production. Specifically, we investigated the reduction of hexyl acetate in butanol over ZrO 2 -supported Ni, Co, Cu, Rh, Pd, and Pt catalysts, where Cu/ZrO 2 was the most selective catalyst for the hydrogenolysis of hexyl acetate into hexanol and ethanol. Thermodynamic analysis reveals that a 90% alcohol yield can be obtained at 200 °C, 30 bar, and a relatively high H 2 :hexyl acetate molar ratio of 480:1. Experimentally, an alcohol yield of 88% yield was obtained with a 10 wt % Cu/ZrO 2 catalyst at these conditions with a residence time of 5.4 h kg cat kmol gas –1 . Catalytic tests on the support revealed that ZrO 2 catalyzes the transesterification reaction between hexyl acetate and butanol. However, only the Cu sites can catalyze the hydrogenolysis of the esters into the final alcohols. We developed a kinetic model for our experimental results, which shows that the transesterification and hydrogenolysis reactions run at two different timescales, the former being 10 times faster than the latter. Data regression has been used to develop a model to predict the mole fraction distribution of ester hydrogenolysis products over a wide range of contact times. Cu/ZrO 2 loses half its catalytic activity after 80 h of time on stream. Modeling of deactivation data reveals that the ZrO 2 support conserves a residual activity due to external active sites, while active sites over the Cu surface deactivate at different rates. Furthermore, the catalytic conversion of esters into their parent alcohols is relevant to the production of surrogate liquid fuels since alcohols can be bimolecularly dehydrated to produce a blend of ethers with diesel fuel-like properties.

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

Preventing Loss of Selectivity during the Oxidative Dehydrogenation of Propane over Supported Vanadium Catalysts

Supported vanadium materials are promising catalysts for the oxidative dehydrogenation of propane to propylene (ODHP), but a lack of mechanistic understanding limits the rational design of catalysts with improved propylene selectivity. Adding Ta to V/SiO 2 increases the propylene selectivity, as well as the activity, leading to superior performance compared to state-of-the-art boron-based systems. In this contribution, we utilize this surprising promotional effect of Ta to elucidate key elements of the mechanistic cycle. Through a combination of characterization techniques, computational modeling, and kinetic experiments, we show that the catalytic cycle over V/SiO 2 likely involves the formation of an isopropyl alcohol intermediate, the fate of which is in kinetic competition between subsequent dehydration to propylene or further oxidation. Furthermore, we show that the relatively facile propylene overoxidation observed for these materials occurs via the epoxidation of propylene by a proposed peroxovanadium intermediate, rather than the abstraction of propylene’s allylic C–H bond as previously assumed. Using these key mechanistic features, we rationalize the enhanced selectivity and activity of Ta promotion. In conclusion, our mechanistic framework offers avenues for future catalyst development to improve supported vanadium materials for ODHP.

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

Structure–Activity Relationships for Ethanol Dehydrogenation to Acetaldehyde by Silica-Supported Zinc Oxide Catalysts

Silica-supported ZnO efficiently catalyzes the nonoxidative dehydrogenation of ethanol to acetaldehyde, which is relevant for production of 1,3-butadiene from bioethanol. Characterization with in situ spectroscopies under dehydrated conditions (high sensitivity-low energy ion scattering (HS-LEIS), diffuse reflectance (DR) UV–vis, X-ray absorption spectroscopy (XAS), diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS), inelastic neutron scattering (INS), and UV Raman), and ammonia adsorption probed by temperature-programmed desorption followed by DRIFTS and mass spectrometry (DRIFTS-MS NH 3 -TPD), and DFT calculations revealed that the supported ZnO x phase was present as isolated surface ZnO x sites on SiO 2 , with the vast majority coordinated by two siloxane bonds and one silicon atom with two nonbridging oxygens ((≡SiO) 2 Zn 2+ O 2 Si=), anchored at 4-, 5-, and 6-membered siloxane rings. A minor fraction of surface ZnO x sites possessed Lewis acidity, and even fewer sites possessed a Bro̷nsted acidic Zn(OH) + Si moiety. Ethanol temperature-programmed surface reaction-mass spectrometry (TPSR-MS) with various oxidative or ethanol reaction pretreatments indicated that only sites with Lewis and Bro̷nsted acidic character (Zn(OH) + Si) were active for ethanol dehydrogenation, while the majority surface (≡SiO) 2 Zn 2+ O 2 Si= sites were inactive. Greater heterogeneity among all surface ZnO x sites, as assessed by in situ DR UV–vis spectroscopy, was associated with a greater number of ZnO x sites that were active for ethanol dehydrogenation as well as lower enthalpic barriers for acetaldehyde production among the most active surface ZnO x sites. Turnover frequencies and the apparent activation energy for ethanol dehydrogenation were determined from steady-state kinetics. Together, these findings suggested that anchoring inactive surface (≡SiO) 2 Zn 2+ O 2 Si= sites on the silica support caused a greater number of active surface ZnO x sites to adopt a more strained configuration, promoting ethanol dehydrogenation catalysis. Pretreatments and catalysts that promoted desorption of ethanol during TPSR, taken as a marker of surface dehydroxylation, were associated with an increased number of the most active surface (Zn(OH) + Si) sites. Such findings suggested that inactive surface ZnO x sites were activated for ethanol dehydrogenation by dehydroxylation of the support and/or decreased coordination to hemilabile siloxane ligands.

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

Ligand-Functionalized Polymer Membranes for Selective Ion Separations

Selective ion separations are central to technologies spanning water purification, resource recovery, and clean energy. Conventional polymer membranes, which rely on steric hindrance or Donnan exclusion, struggle to discriminate between chemically similar ions in high-ionic-strength environments. Ligand-functionalized membranes offer a transformative strategy by embedding molecular recognition directly into polymer matrices, enabling selective complexation and transport. Here, this Viewpoint highlights the structure–function relationships underlying ligand-mediated ion separation, emphasizing the interplay of dehydration penalties, ligand coordination, and nanoscale confinement. We discuss design principles, denticity, donor identity, rigidity, and spatial organization, alongside the permeability–selectivity trade-off, multicomponent effects, and stability challenges. Finally, we outline emerging strategies, from bioinspired ligands to computationally guided design, that chart a path toward next-generation membranes for precise and energy-efficient ion separations.

ions↗