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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.

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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Emerging Modification Technologies of Lignin-based Activated Carbon toward Advanced Applications

Lignin-based activated carbon (LAC) is a promising high-quality functional material due to high surface area, abundant porous structure, and various functional groups. Modification is the most important step to functionalize LAC by altering its porous and chemical properties. Here, this Review summarizes the state-of-the-art modification technologies of LAC toward advanced applications. Promising modification approaches are reviewed to display their effects on the preparation of LAC. The multiscale changes in the porosity and the surface chemistry of LAC are fully discussed. Advanced applications are then introduced to show the potential of LAC for supercapacitor electrode, catalyst support, hydrogen storage, and carbon dioxide capture. Finally, the mechanistic structure-function relationships of LAC are elaborated. These results highlight that modification technologies play a special role in altering the properties and defining the functionalities of LAC, which could be a promising porous carbon material toward industrial applications.

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

Post-Modification of Crystalline Peptoid Nanomembranes with Active Nanoparticles for Efficient Photooxidation of a Mustard Gas Simulant

Peptoids (or poly-N-substituted glycines) hold immense potential for assembling into hierarchically structured functional materials via controlled molecular interactions. To create self-assembled materials with tailored functionalities, peptoid sequences are often conjugated with reactive or recognition motifs to enable applications including specific binding, biomimetic catalysis, and fluorescence imaging. However, the direct integration of bulky functional motifs into peptoid sequences can disrupt assembly processes and structural outcomes. Herein, we present a post-modification strategy for functionalizing pre-formed 2D crystalline assemblies. Through introducing clickable active sites, such as azide, alkyne, or thiol groups into a peptoid sequence, site-specific conjugation is achieved post-assembly via efficient “click”-type reactions. This strategy enables the ordered alignment of functional groups and gold nanoparticles (Au NPs) on the surface of 2D peptoid nanomaterials with controlled density, while preserving their high crystallinity and structural integrity. Furthermore, we demonstrated that nanomembranes functionalized with both Au NPs and porphyrins enhance the efficiency and selectivity of the photooxidation of 2-chloroethyl ethyl sulfide, a simulant of sulfur mustard. This innovative strategy lays the groundwork for advancing peptoid-based functional materials across diverse applications, from catalysis to biomedicine.

Chemistry↗
DOE OSTI2025

Subnanometer Thick Native sp 2 Carbon on Oxidized Diamond Surfaces

Oxygen-terminated diamond has a wide breadth of applications, which include stabilizing near-surface color centers, semiconductor devices, and biological sensors. Despite the vast literature on characterizing functionalization groups on diamond, the chemical composition of the shallowest portion of the surface (<1 nm) is challenging to probe with conventional techniques like XPS and FTIR. In this work, we demonstrate the use of angleresolved XPS to probe the first ten nanometers of both oxygen and hydrogen terminated (100) single-crystalline diamond grown via chemical vapor deposition (CVD). With the use of consistent peakfitting methods, the peak identities and relative peak binding energies were identified for sp 2 carbon, ether, hydroxyl, carbonyl, and C−H groups for both of these diamond surface terminations. For the oxygen-terminated sample, we also quantified the thickness of the sp 2 carbon layer situated on top of the bulk sp 3 diamond bonded carbon to be 0.3 ± 0.1 nm, based on the analysis of the Auger electron spectra and D-parameter calculations. These results indicate that the majority of the oxygen is bonded to the sp 2 carbon layer on the diamond, and not directly to the sp 3 diamond bonded carbon.

Carbon↗
DOE OSTI2025

New Insights into Nonthermal Plasma-Assisted Poly(vinyl alcohol) Depolymerization Catalyzed by TiO 2

Here, in this study, we investigated the solid residual poly(vinyl alcohol) (PVA) and TiO 2 after nonthermal air, CO 2 , and N 2 plasma depolymerization in the absence and presence of TiO 2 . Scanning electron microscopy studies showed the absence of highly viscous tar and carbonaceous residues on the surfaces of PVA and TiO 2 . In the absence of TiO 2 , PVA particles exhibited micron-sized holes on their surfaces, whereas in the presence of TiO 2 , the surface roughness of PVA particles was observed at the submicron scale. These observations suggest that TiO 2 facilitates the even distribution of nonthermal plasma at a submicron scale, leading to a more uniform depolymerization of PVA surfaces. Raman, Fourier transform infrared spectroscopy, and X-ray absorption spectroscopy showed that (i) the surface of residual PVA contains mainly ketone functional groups and less C-H bonds than the pristine PVA and (ii) further confirmed the absence of highly viscous tar and carbonaceous residues on both used TiO 2 and residual PVA. The nuclear magnetic resonance and mass spectroscopy suggested that the PVA is growing back to poly polyvinyl acetate by the esterification reaction, and the ethers are produced by the acetal reaction between PVA and aldehyde. The transmission electron microscopy and X-ray diffraction analysis indicated no major crystal structural change of the TiO 2 catalyst after the plasma reactions. This study demonstrates that nonthermal plasma-assisted depolymerization is a viable alternative to thermal depolymerization, offering the unique advantage of converting polymer wastes into gaseous small organic molecules without generating recalcitrant viscous tar and carbonaceous residues on the surfaces of the polymer and TiO 2 catalysts.

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

Electroplated Polymer‐Modified Carbon Fiber for Performance‐Enhancing Composite Interfaces

Carbon fiber composite performance relies on the fiber-matrix interface for effective load transfer. To enhance interfacial properties between the fiber and matrix, often carbon fiber surfaces are oxidatively and covalently modified to incorporate chemical functional groups. By contrast, here, noncovalent electrodeposition of functional polyelectrolyte is applied onto conducting carbon fibers from aqueous solutions. A natural polymer, chitosan (CS), is electro-deposited onto the fiber surface, which undergoes multi-scale physical interactions. The bound CS layer with abundant amine functionalities reacts with epoxy moieties within the matrix to improve the interfacial properties. The scalable and energy-efficient electrodeposition eliminates traditional functionalization and sizing requirements of carbon fiber while delivering significantly higher mechanical performance with enhanced consistency. For continuous fiber reinforced composites, compared to conventional fibers, apparent interlaminar shear strength increases by 27%, reaching ≈86 MPa. The short fiber composites with only 2–11 wt.% fibers exhibit ≈20% increase in tensile strength with a peak performance of 120 MPa. Unlike traditionally treated and sized carbon fiber, this approach delivers coated fibers with long shelf-life and allows recovery of both CS in electrolyte form and carbon fiber by continuous electrochemical processing of the modified fibers with inverse polarity; thus, it promotes overall fiber recyclability.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Statistical analysis of HAADF-STEM images to determine the surface coverage and distribution of immobilized molecular complexes

The surface immobilization of molecular catalysts is attractive because it combines the benefits of homogeneous and heterogeneous catalysis. However, determining the surface coverage and distribution of a molecular catalyst on a solid support is often challenging, inhibiting our ability to design improved catalytic systems. Here, in this work, we demonstrate that the combination of scanning transmission electron microscopy (STEM) and image analysis of the individual positions of heavy atoms in transition metal complexes via a convolutional neural network (CNN) allows statistically robust determination of the surface coverage and distribution of immobilized molecular catalysts. These observations provide information about how changes in the functionalization conditions, attachment group, and structure of the molecular catalyst affect the surface coverage and distribution, providing insight into the chemical mechanism of surface immobilization. The method could be generally valuable for correlating the surface coverage and distribution to the activity, selectivity, and stability of a catalytic system.

HAADF-STEM↗
DOE OSTI2025

Morphology Effects on Free Energies of Proton-Coupled Electron Transfer in Polyoxotungstates

Polyoxotungstates have previously been established to facilitate the hydrogenation of small molecule substrates via hydrogen atom transfer from reactive hydroxyl groups formed at the assembly surface. Understanding structure−function relationships that dictate the thermochemistry and kinetics of protoncoupled electron transfer is key to controlling this chemistry. In this work, we combine comprehensive electrochemical experiments and density functional theory calculations to address how different polyoxotungstate morphologies, specifically W 6 O 19 −2 , W 10 O 32 −4 , SiW 12 O 40 −4 , and P 2 W 18 O 62 −6 , affect the bond dissociation free energies of surface hydroxides (BDFE(O−H)) formed upon reduction of the assembly in acidic media. Our results reveal increasing hydroxide bond strengths with increasing cluster size, and that anisotropic cluster geometries result in substantial thermodynamic differentiation of H-binding sites. We demonstrate an excellent agreement between theory and experiments on the reported BDFE(O−H) values and, importantly, we elucidate how cluster size and shape affect electronic properties (local charges and frontier molecular orbitals), giving rise to sites with increased preference for hydrogen binding, demonstrated in higher BDFE(O−H). Overall, this work aids the understanding and design of polyoxometalates exhibiting surface sites with tailored interaction strengths.

anions↗
DOE OSTI2025

Solution‐Like Water Transport Across Molecular to Macroscopic Length Scales in Crosslinked Poly(Ethylene Glycol Diacrylate) Networks With Tailored Sidechains

Poly(ethylene glycol) (PEG)‐based materials, like PEG‐diacrylate (PEGDA), are prized for their hydrophilic, inert properties, and leveraged in hydrogels and as membrane mimics. While network chemistry is often tuned for selective transport and antifouling, fundamental understanding of water dynamics at the network surface and the impact on bulk transport is limited. We utilize Overhauser dynamic nuclear polarization (ODNP) to measure nanoscale water diffusivity near a tethered spin label at the water‐polymer surface and compare it to bulk water diffusivity from pulsed field gradient (PFG) NMR. Via active ester chemistry, spin labels and varied sidechain chemistries are introduced, modulating network hydrophilicity. Tuning network hydration through crosslinker content and functional groups further impacts water diffusivity. Results show rapid nanoscale water transport at the polymer surface, reflecting network volumetric water content, with further modulation by sidechain functionality. These findings demonstrate PEGDA's utility as a membrane mimic and the critical impact of network chemistry on water transport.

hydrogels↗
DOE OSTI2025

Polyhalohydrins: Investigating Vicinal Functionalities by Ring-Opening of Epoxides on Polyolefins

Halohydrins are functional groups that are underexplored in polymer science. This study synthesized and examined structure–property relationships of halohydrin-functionalized polymers derived from polycyclooctene (PCOE), which was obtained via ring-opening metathesis polymerization (ROMP). The polyhalohydrins, including polychlorohydrin, polybromohydrin, and polyiodohydrin, were produced through a two-step process involving epoxidation of PCOE followed by epoxide ring-opening using hydrochloric, hydrobromic, or hydroiodic acid. These stereoirregular and regioirregular polymers are amorphous as measured by differential scanning calorimetry and X-ray scattering. Lap joint shear testing revealed an enhanced adhesive performance in polychlorohydrin and polybromohydrin, with the former demonstrating nearly three times the ultimate shear stress compared to a model polyethylene, hydrogenated PCOE. Additionally, contact angle measurements and surface free energy analysis showed an increase in hydrophilicity and polarity from iodine- to bromine- to chlorine-functionalized polyhalohydrins, aligning with trends in adhesion strength. Furthermore, these results underscore the potential of halohydrin functionalization as a versatile approach for tuning surface properties, offering new opportunities for polymer-to-polymer transformations.

Functional groups↗
DOE OSTI2024

Experimental investigation into coal wettability changes caused by reactions with scCO 2 -H 2 O

Geological CO 2 sequestration (GCS) can help mitigate global warming and enhance methane recovery from coal beds. However, few studies have linked the effects of CO 2 to surface chemistry changes controlling wetting behavior in deep coal beds. Contact angles (CAs) of CO 2 /N 2 -high volatile bituminous coal-water systems were measured under different temperatures and pressures. The surface chemistry and physical structure of coals were characterized to investigate changes in physicochemical properties and their relations with wettability after reactions. For N 2 treatment, the time-dependence of static and dynamic CAs were insignificant, ranging within 4°. For gaseous CO 2 treatment, the static CAs and the average advancing angles increased slightly. With supercritical (sc) CO 2 , both the static and dynamic CAs increased significantly, and θ adv changed to intermediate-wet (92°). Reactions with minerals exposed to scCO 2 resulted in greater surface roughness and heterogeneity, greater contact angle hysteresis and more surface sites occupied by scCO 2 rather than H 2 O. Increases in hydrophobic functional groups and decreases in hydrophilicity were shown by FTIR spectra, reflecting the shedding of polar oxygen-containing functional groups, reduction of hydrogen bonds, and increasing percentage of hydrocarbons. XRD patterns obtained following scCO 2 -treatment showed that crystallite growth and molecular polymerization were higher toward graphite-like. The calculated structural parameters of functional groups and crystallites both showed elevated coal rank. Changes in crystallite structure, notably higher carbon content and decreased negative surface charge, are unfavorable for water-wetting. Finally, this study contributes to understanding surface chemistry changes responsible for decreased wettability during CO 2 -enhanced coal bed methane recovery and GCS in coal reservoirs.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2026

Engineering acid-base active sites on an N-doped biochar catalyst for microwave-assisted biodiesel production from waste cooking oil

Acid-base bifunctional catalysts play a crucial role in converting high-free fatty acid (FFA) feedstocks into biodiesel by enabling the simultaneous esterification and transesterification of triglycerides in a single step, thereby minimizing saponification and streamlining the process. In this study, we report the design and development of a novel N-doped acid-base bifunctional biochar catalyst synthesized from renewable biomass precursors- glucose and chitosan. The catalyst’s acidic sites were introduced via surface functionalization with o-sulfobenzoic acid cyclic anhydride, grafting -SO₃H groups onto the carbon framework, while basic sites were generated from amine functionalities (-NH) derived from chitosan, yielding a robust and truly bifunctional surface. The catalyst was characterized and used for the microwave-assisted transesterification of waste cooking oil, and process optimization using response surface methodology (RSM-CCD) yielding a maximum biodiesel yield of 98.8 ± 0.4% under optimal conditions (methanol-to-oil molar ratio 20:1, catalyst loading 5.7 wt%, temperature 99 °C, and reaction time 46.6 min). The catalyst demonstrated good stability, maintaining a yield of 92.2 ± 0.4% after eight reuse cycles. A Life Cycle Assessment (LCA) conducted for 1 kg of biodiesel production revealed a global warming potential of 0.85 kg CO 2 eq and human toxicity potential of 1.59 kg 1,4-DB eq, with the largest environmental contributions arising from catalyst preparation and reuse. In conclusion, this work highlights a green and circular approach to biodiesel production, combining renewable catalyst design, waste feedstock utilization, and quantitative sustainability assessment to guide future developments in sustainable catalysis and biofuel engineering.

Bifunctional catalyst↗
DOE OSTI2021

The pH-dependent orientation of N3 dye on a gold substrate is revealed using heterodyne-detected vibrational sum frequency generation spectroscopy

We report on systematic changes to the adsorption geometry of the dye N3 {[cis-bis(isothiocyanato)bis(2,2' -bipyridyl-4,4' -dicarboxylato ruthenium(II)]} on a gold substrate as the pH of the deposition environment is altered. The protonation states of the four --COOH groups of the N3 dye change according to the modified pH conditions, thus affecting the number of --COOH and --NCS functional groups that participate in the adsorption to gold. Here, we use heterodyne detected vibrational sum frequency generation (HD-VSFG) spectroscopy to obtain surface specific vibrational information on both --COOH and --NCS groups as a function of pH of the deposition conditions. Polarization-dependent HD-VSFG yields sets of complex χ (2) spectra, enabling us to perform a simultaneous fitting procedure to the polarization-dependent real and imaginary components and thus extract detailed structural information of the N3/gold interface. Overall, our results show that N3 preferentially adsorbs to gold either with two --COOH groups and one --NCS group in more acidic conditions or with one --COOH group and two --NCS groups in more basic conditions.

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

Operando identification of site-dependent water oxidation activity on ruthenium dioxide single-crystal surfaces

Understanding the nature of active sites is central to controlling (electro)catalytic activity. Here we employed surface X-ray scattering coupled with density functional theory and surface-enhanced infrared absorption spectroscopy to examine the oxygen evolution reaction on RuO 2 surfaces as a function of voltage. At 1.5 V RHE , our results suggest that there is an –OO group on the coordinatively unsaturated ruthenium (Ru CUS ) site of the (100) surface (and similarly for (110)), but adsorbed oxygen on the Ru CUS site of (101). Density functional theory results indicate that the removal of –OO from the Ru CUS site, which is stabilized by a hydrogen bond to a neighbouring –OH (–OO–H), could be the rate-determining step for (100) (similarly for (110)), where its reduced binding on (100) increased activity. A further reduction in binding energy on the Ru CUS site of (101) resulted in a different rate-determining step (–O + H 2 O – (H + + e - ) → –OO–H) and decreased activity. Our study provides molecular details on the active sites, and the influence of their local coordination environment on activity.

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

Swelling-Assisted Sequential Infiltration Synthesis of Nanoporous ZnO Films with Highly Accessible Pores and Their Sensing Potential for Ethanol

Here, we report a swelling-assisted sequential infiltration synthesis (SIS) approach for the design of highly porous zinc oxide (ZnO) films by infiltration of block copolymer templates such as polystyrene-block- polyvinyl pyridine with inorganic precursors followed by UV ozone-assisted removal of the polymer template. We show that porous ZnO coatings with the thickness in the range between 140 and 420 nm can be obtained using only five cycles of SIS. The pores in ZnO fabricated via swelling-assisted SIS are highly accessible, and up to 98% of pores are available for solvent penetration. The XPS data indicate that the surface of nanoporous ZnO films is terminated with -OH groups. Density functional theory calculations show a lower energy barrier for ethanol-induced release of the oxygen restricted depletion layer in the case of the presence of -OH groups at the ZnO surface, and hence, it can lead to higher sensitivity in sensing of ethanol. We monitored the response of ZnO porous coatings with different thicknesses and porosities to ethanol vapors using combined mass-based and chemiresistive approaches at room temperature and 90 °C. The porous ZnO conformal coatings reveal a promising sensitivity toward detection of ethanol at low temperatures. In conclusion our results suggest the excellent potential of the SIS approach for the design of conformal ZnO coatings with controlled porosity, thickness, and composition that can be adapted for sensing applications.

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

Hydrophobic Lightweight Cement with Thermal Shock Resistance and Thermal Insulating Properties for Energy-Storage Geothermal Well Systems

This study assessed the possibility of using polymethylhydrosiloxane (PMHS)-treated fly ash cenospheres (FCS) for formulating a thermally insulating and thermal shock (TS)-resistant cementitious blend with calcium aluminate cement. To prevent FCS degradation in an alkaline cement environment at high temperatures, the cenospheres were pre-treated with sodium metasilicate to form silanol and aluminol groups on their surface. These groups participated in a dehydrogenation reaction with the functional ≡Si–H groups within PMHS with the formation of siloxane oxygen-linked M-FCS (M: Al or Si). At high hydrothermal temperatures of 175 and 250 °C, some Si–O–Si and SiCH 3 bonds ruptured, causing depolymerization of the polymer at the FCS surface and hydroxylation of the raptured sites with the formation of silanol groups. Repolymerization through self-condensation between the silanol groups followed, resulting in the transformation of siloxane to low crosslinked silicon-like polymer as a repolymerization-induced product (RIP) without carbon. The RIP provided adequate protection of FCS from pozzolanic reactions (PR), which was confirmed by the decline in zeolites as the products of PR of FCS. Cements with PMHS-treated FCS withstood both hydrothermal and thermal temperature of 250 °C in TS tests, and they also showed improved compressive strength, toughness, and water repellency as well as decreased thermal conductivity. The lubricating properties of PMHS increased the fluidity of lightweight slurries.

15 GEOTHERMAL ENERGY↗
DOE OSTI2021

Altering Linear Scaling Relationships on Metal Catalysts via Ligand–Adsorbate Hydrogen Bonding

Linear scaling relationships for adsorption energies of related molecules provide a simple tool for the prediction of catalytic properties and also reveal inherent constraints in heterogeneous catalyst design. In an effort to predict materials that preferentially stabilize intermediates capable of forming hydrogen bonds (H-bonds) and thus reduce these constraints, scaling relations for thiolate-coated fcc (111) surfaces were developed. Here, we demonstrate how ligand–adsorbate H-bonds lead to the stabilization of certain adsorbates and how this affects the linear scaling of adsorption energies for similarly bound intermediates. For H-bonds that occur remote from the surface, ligand–adsorbate H-bond strength is independent of metal composition and instead depends only on the acidities of the H-bond-forming functional groups. As the distance of H-bond-accepting groups from the surface decreases and interactions with the metal strengthen, the effect of surface composition on H-bond strength increases while additional factors, such as conformational changes and steric hinderance, can offset the stabilizing effect of the ligands. In this work, these competing factors may influence both the slope and y-intercept of adsorption strength scaling. These findings aid the rational design of enhanced catalytic materials by enabling the screening of ligand- or spectator-modified materials that do not conform to the linear scaling relations of bare metal surfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Surface Modification of a MXene by an Aminosilane Coupling Agent

MXenes, two–dimensional (2D) transition metal carbides and/or nitrides, possess surface termination groups such as hydroxyl, oxygen, and fluorine, which are available for surface functionalization. Their surface chemistry is critical in many applications. This article reports amine functionalization of Ti 3 C 2 T x MXene surface with [3–(2–aminoethylamino)–propyl]trimethoxysilane (AEAPTMS). Characterization techniques such as X–ray photoelectron spectroscopy verify the success of the surface functionalization and confirm that the silane coupling agent bonds to Ti 3 C 2 T x surface both physically and chemically. The functionalization changes the MXene surface charge from –35 to +25 mV at neutral pH, which allows for in situ preparation of self–assembled films. Further, surface charge measurements of the functionalized MXene at different pH values show that the functionalized MXene has an isoelectric point at a pH around 10.7, and the highest reported positive surface charge of +62 mV at a pH of 2.58. Furthermore, the existence of a mixture of different orientations of AEAPTMS and the simultaneous presence of protonated and free amine groups on the surface of Ti 3 C 2 T x are demonstrated. As a result, the availability of free amine groups on the surface potentially permits the fabrication of crosslinked electrically conductive MXene/epoxy composites, dye adsorbents, high–performance membranes, and drug carriers. Surface modifications of this type are applicable to many other MXenes.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Carboxyl-functionalized perovskite enables ALD growth of a compact and uniform ion migration barrier

Mixed-halide wide-band-gap perovskites are critical components of highly efficient tandem cells, but their operating stability is limited by halide migration. Metal oxides deposited via atomic layer deposition (ALD) have been shown to block halide migration; however, previously pursued methods result in inhomogeneous nucleation and growth. We hypothesized that functionalizing the perovskite surface with ALD-active carboxyl groups could promote nucleation and enable higher-temperature metal oxide growth. We find that 5-ammonium valeric acid iodide (5-AVAI) facilitates the formation of a compact and uniform aluminum oxide (Al 2 O 3 ) layer and allows growth at 100°C compared with the previous limit of 75°C. We demonstrate that halide migration into the C 60 electron transport layer is reduced by a factor of 10 compared with the reference case. Finally, Al 2 O 3 -capped perovskite solar cells with a band gap of 1.78 eV retain 90% of their initial power conversion efficiency after 1,000 h of continuous operation under 1-sun illumination at 55°C.

Al2O3↗