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Results for “Acid etching”

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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17 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Influence of AA6061 surface preparation on the resistance to surface degradation of thermally grown boehmite films

Understanding substrate–coating interactions is crucial for designing durable, corrosion-resistant systems. This study investigates the effects of surface treatments— polishing, acid etching, and alkaline etching—on AA6061 aluminum alloy and its thermally grown boehmite coatings. Surface treatments were found to significantly alter boehmite film properties by modifying the alloy’s surface composition. X-ray photoelectron spectroscopy revealed a 10% alumina drop after acid etching alongside chemisorbed species formation in wet treatments. Structural analysis, including grazing incidence X-ray diffraction and TEM, showed α-Al 2 O 3 formation on polished surfaces, improving wear resistance but inducing cathodic E corr shifts, pointing to higher corrosion susceptibility. In contrast, acid and alkaline etching produced anodic E corr shifts with stable, pit-free films observed via potentiodynamic scans. Electrochemical impedance spectroscopy highlighted reduced oxide resistance with extended boehmite growth. The findings emphasize the role of surface pre-treatments and boehmite optimization in balancing durability and corrosion resistance for AA6061 substrates.

AA6061↗
DOE OSTI2025

Exploring the Structure–Function Relationship in Iridium–Cobalt Oxide Catalyst for Oxygen Evolution Reaction across Different Electrolyte Media

Renewable hydrogen generation from water electrolysis offers a viable path to decarbonization if the costs can be reduced. The iridium-based anode catalyst is one of the most expensive components in electrolyzers. We propose reducing iridium usage by substituting Ir with Co, a more affordable metal, in the mixed oxide phase to enhance the catalytic activity while minimizing Ir consumption. A modified surfactant-assisted Adams fusion synthesis technique was developed as a scalable method for producing IrCo oxide nanoparticles. The synthesized material outperforms the commercial baseline, iridium oxide with carbon (IrOx_C), in both acidic and alkaline media. Acid etching (IrCo_ae) further enhances activity by selectively removing Co to expose more active sites. IrCo_ae achieved a significantly lower overpotential at 10 mA/cm 2 compared to IrOx_C, with reductions of approximately 18% under acidic conditions and 14% under alkaline conditions. This work demonstrates that the proposed synthesis method enables efficient Ir utilization and can be adapted to enhance catalyst stability for renewable hydrogen production.

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

Etch Products of Copper Atomic Layer Etching by Oxidation and Formic Acid Vapor

Atomic layer etching (ALE) of metals offers a path to greater control of selectivity, etch rate, and etch profile. However, tailoring a process to meet these demands requires an understanding of the volatile etch product, which is challenging to detect due to low product concentrations and the paramagnetism of many metalorganic products. Here, in this work, several complementary analysis techniques were used to determine the volatile etch product and residual surface species of a Cu ALE process based on plasma oxidation and formic acid vapor etching of the oxidized layer. It was shown that the volatile product was copper formate with a Cu 2+ paramagnetic center, in concordance with prior density functional theory (DFT) calculations. While copper formate tetrahydrate was formed, it was determined that the tetrahydrate product was confined to the surface, with anhydrous copper formate being the volatile etch product.

Smith, Taylor G. [Univ. of California, Los Angeles↗
DOE OSTI2025

Etching-assisted upcycling of Ni-lean to Ni-rich cathode materials

Upcycling is recognized as a sustainable recycling approach for spent lithium-ion batteries. However, existing upcycling methods typically involve intricate pretreatment or post-treatment steps, complicating their practical application. Here, in this study, we propose a straightforward, etching-assisted upcycling method that effectively transforms polycrystalline Ni-lean cathodes into high-performance single crystal Ni-rich cathodes. During the etching step, nickel acetate was dissolved into acetic acid and then polycrystalline NMC111 are etched in the solution. Finally, polycrystalline NMC111 are converted into single crystal particles coated with amorphous nickel acetate. This significantly enhances elemental diffusion during subsequent sintering by minimizing both particle size and the contact distance between NMC111 and nickel acetate. As elemental diffusion is improved and acetate ions decompose completely during sintering, the process requires neither additional pretreatment nor post-treatment. The resulting cathode materials (Etched-UP622) exhibit superior structural and electrochemical properties compared to the Control622, achieving an energy density of 719.7 Wh/kg, approximately 56.7 mAh/g higher than Control622 and 125.5 Wh/kg higher than NMC111. Etched-UP622 also delivers higher discharge capacity, improved rate performance and cycling stability, surpassing Control622 and NMC111. Meanwhile, NMC811 also can be synthesized by the proposed strategy, and the discharge capacity can reach 166.9 mAh/g at 1C, similar to 14 mAh/g higher than Control811. Overall, this etching-assisted strategy simplifies the upcycling process and offers a scalable, sustainable route for producing high-quality cathode materials.

Acid etching↗
DOE OSTI2025

Surface Manipulation on Pt 2.2 Ni(111) Nanocatalysts for Boosting Their ORR Performance in Alkaline Media

We have previously shown that Pt–Ni alloy nano-octahedra with {111} facets exhibit outstanding electrochemical performance in the oxygen reduction reaction (ORR) in acidic media when their surfaces are finely tailored at the atomic level. Here, in this investigation, we further refine the surface structure of Pt 2.2 Ni octahedral nanocatalysts to improve ORR performance in a 0.1 M KOH solution using diverse surface manipulation techniques. Through systematic analysis using electrochemical CO stripping, cyclic voltammetry, and X-ray photoelectron spectroscopy, we examined the surfaces of Pt 2.2 Ni octahedral nanocatalysts pretreated with various methods, including etching in acetic acid or perchloric acid, and subsequent electrochemical activation in an alkaline solution or an acidic solution. Among these treatments, those involving acidic media, particularly electrochemical cycling in acidic electrolytes, demonstrated significantly enhanced ORR activity in 0.1 M KOH. The latter exhibited a mass activity of 2.95 A/mg pt and a specific activity of 8.71 mA/cm 2 at 0.90 V, surpassing state-of-the-art Pt/C by 12-fold and 34-fold, respectively. Furthermore, this identified nanocatalyst displayed robust stability, with negligible activity decay observed after 10,000 cycles. This study suggests that the improved ORR activity can be attributed to the Pt-rich surfaces with well-preserved {111} lattices on the surface-modified Pt–Ni nano-octahedra.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Cosmogenic 3 He exposure dating in mafic rocks by “Virtual mineral separation” of pyroxene

We describe a “virtual mineral separation” method for measuring the cosmogenic 3 He concentration in pyroxene in mafic rocks that consist mainly of plagioclase and pyroxene, without physically separating the minerals. This approach is significantly faster and more cost-effective than the conventional method, which requires physical separation and purification of pyroxene grains by time-consuming and labor-intensive crushing, acid cleaning, magnetic separation, HF etching, and handpicking under a microscope. The premise of the method is that helium diffusivity is much higher in plagioclase than in pyroxene, so controlled preheating of a mixed whole-rock sample can degas 3 He from plagioclase while retaining all 3 He in pyroxene. A second heating step releases all 3 He from pyroxene for measurement. To then obtain a 3 He concentration in pyroxene rather than the whole rock, we determine the pyroxene weight fraction in the sample using X-ray computed tomography (CT). A comparison of 3 He concentrations in pyroxene measured using virtual mineral separation with those measured in the same samples by physical mineral separation in previous work shows no evidence of systematic bias between the methods. Virtual mineral separation greatly simplifies the workflow for 3 He exposure-dating of mafic rocks, reduces time, effort, and cost, and permits measurements on very small samples. This enables new emerging applications of exposure dating, such as quantifying stochastic surface processes, ecosystem studies, and potential subglacial bedrock exposure dating.

Geosciences↗
DOE OSTI2025

Deposition-Dependent Coverage and Performance of Phosphonic Acid Interface Modifiers in Halide Perovskite Optoelectronics

In this work, we study the effect of various deposition methods for phosphonic acid interface modifiers commonly pursued as self-assembled monolayers in high-performance metal halide perovskite photovoltaics and light-emitting diodes. We compare the deposition of (2-(3,6-diiodo-9H-carbazol-9-yl)ethyl)phosphonic acid onto indium tin oxide (ITO) bottom contacts by varying three parameters: the method of deposition, specifically spin coating or prolonged dip coating; ITO surface treatment via HCl/FeCl3 etching; and use in combination with a second modifier, 1,6-hexylenediphosphonic acid. We demonstrate that varying these modification protocols can impact time-resolved photoluminescence carrier lifetimes and quasi-Fermi level splitting of perovskite films deposited onto the phosphonic acid-modified ITO. Ultraviolet photoelectron spectroscopy shows an increase in the effective work function after phosphonic acid modification and clear evidence for photoemission from carbazole functional groups at the ITO surface. We used X-ray photoelectron spectroscopy to probe differences in phosphonic acid coverage on the metal oxide contact and show that perovskite samples grown on ITO with the highest phosphonic acid coverage exhibit the longest carrier lifetimes. Finally, we establish that device performance follows these same trends. These results indicate that the reactivity, heterogeneity, and composition of the bottom contact help to control recombination rates and therefore power conversion efficiencies. ITO etching, prolonged deposition times for phosphonic acids via dip coating, and the use of a secondary, more hydrophilic bisphosphonic acid all contribute to improvements in surface coverage, carrier lifetime, and device efficiency. Furthermore, these improvements each have a positive impact, and we achieve the best results when all three strategies are implemented.

contact engineering↗
DOE OSTI2025

Carboxylic acid induced restructuring of the Fe 3 O 4 (001) surface

The redox properties of Fe 3 O 4 surfaces are central to many catalytic processes and enable dynamic, reduction-induced morphological restructuring during reactions. Here, we investigate the structural changes of the Fe 3 O 4 (001) surface during the decomposition of formic and acetic acids using scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory (DFT) calculations. Both acids readily deprotonate, forming ordered carboxylate overlayers on the surface. Product formation pathways involve the removal of lattice oxygen, resulting in extensive surface restructuring. For formic acid, only a modest level of surface oxygen removal (∼3%) is observed, resulting in elongated pits along the octahedral Fe rows and exhibiting an aspect ratio of ∼3. In contrast, acetic acid induces more extensive reduction, with the removal of ∼20% of surface oxygen, yielding significantly larger pits while maintaining a similar aspect ratio. Repeated exposure to acetic acid further enlarges the pits, indicating preferential etching at step edges. DFT calculations reveal a mechanistic sequence in which lattice oxygen removal destabilizes adjacent Fe atoms, promoting their migration into the bulk and subsequent pit propagation and step edge formation. Together, these findings provide atomistic insights into the coupling between carboxylic acid conversion and oxide surface restructuring, underscoring the strong interplay between redox chemistry and morphological changes on catalytically active Fe 3 O 4 surfaces.

Ortiz-Garcia, José J. [Pacific Northwest National ↗
DOE OSTI2026

Role of Surface Hydroxyls and Lattice Oxygen in Governing Selectivity and Restructuring During Acetic Acid Conversion on Fe 3 O 4 (001)

Understanding the reactivity of carboxylic acids on metal oxide surfaces is critical for elucidating ketonization mechanisms relevant to biomass upgrading. Here, we investigate the adsorption and thermal decomposition of acetic acid (CH 3 COOH) on Fe 3 O 4 (001) using scanning tunneling microscopy (STM), temperature-programmed reaction spectroscopy (TPRS), and X-ray photoelectron spectroscopy (XPS). At room temperature, acetic acid adsorbs dissociatively to form ordered bidentate acetate (CH 3 COO) overlayer that lifts the (√2 × √2)R 45° surface reconstruction. TPRS reveals ketene (CH 2 CO) as the dominant product, along with CO, CO 2 , and H 2 O, the latter evolving via a Mars–van Krevelen (MvK) mechanism. Isotopic labeling shows preferential CO 2 formation from the carboxyl carbon and a more balanced CO/CO 2 ratio from the methyl carbon, suggesting distinct oxidation pathways. STM imaging reveals embedded acetate intermediates filling surface oxygen vacancies created in MvK steps. Upon product formation completion (~700 K), extensive surface etching is observed, with pits elongated along the octahedral Fe rows. Approximately 20% of the surface oxygen is removed, consistent with vacancy formation stoichiometry inferred from product distributions. These findings demonstrate that carboxylate-induced restructuring of Fe 3 O 4 (001) involves both surface healing and reduction processes, offering mechanistic insights relevant to ketonization and broader carboxylic acid chemistry on metal oxides.

acetic acid↗
DOE OSTI2025

Alloy selective optical sorting of mixed post-consumer aluminum scrap streams

Shredded post-consumer non-ferrous scrap stream, also known as Zorba, contains a mixture of cast and wrought aluminum pieces with very different compositions. Cast Al pieces, with their high Si, Cu and Fe content, are a major contaminant in wrought scrap fraction, which results in downcycling of the mixed cast + wrought scrap into non-structural cast Al alloys and parts. Here, in this paper, we introduce a chemical treatment method to color-code scrap aluminum pieces by alloy family and demonstrate low-cost optical sorting of cast from wrought pieces to upgrade the scrap stream. We utilized non-acidic chemical solutions that react with (i.e., etch) the scrap pieces to produce colors based on the Al alloy chemistry of a given piece. Cast pieces with high Si and Cu fractions turned black, whereas the much leaner wrought pieces remained unreacted. We showed > 95% sorting efficiency of mixed cast and wrought pieces using a repurposed low-cost optical sorter originally designed for food sorting. We also colored wrought Al pieces by alloy families, such as 5xxx and 6xxx, using a two-step chemical etching technique, which has the potential to create a circular supply chain in which wrought aluminum alloys are sorted from the mixed scrap stream and recycled back to high-value wrought products such as sheets, extrusions, and forgings with minimal contamination from cast scrap.

Aluminum↗
DOE OSTI2025

Nb 2 O 5 Protection Layers for Hydrogen Evolution by p-InP Photocathodes in Acidic Electrolytes

Coatings of HfO 2 , Ta 2 O 5 , TiO 2 , and Nb 2 O 5 were evaluated as protection layers for p-InP photocathodes in aqueous acidic electrolytes. Each candidate protection layer was characterized based on interfacial conduction of photogenerated electrons, the thermodynamic and kinetic stability of the overlayer over the relevant potential and pH range for cathodic fuel-forming half-reactions, and inhibition of the primary anodic and/or chemical dissolution processes that limit electrode stability. The conduction of photogenerated electrons and inhibition of anodic oxidation was evaluated using V 3+ / 2+ in 5.0 M HCl(aq) as a one-electron redox couple with a potential close to that of hydrogen evolution in acidic media. Failure modes due to cathodic plating of metal, as well as anodic dissolution and chemical dissolution processes, were evaluated for photocathodes made from etched p-InP, platinized p-InP, and p-InP photoelectrodes that had been coated with the various oxide films and then platinized for use in photoelectrochemical hydrogen evolution in acidic aqueous electrolytes. Nb 2 O 5 best met all of the criteria, contrasting with TiO 2 , which is thermodynamically and kinetically unstable in acid over the potential range relevant for the hydrogen evolution and/or CO 2 reduction electrochemical half-reactions. Furthermore, these protocols should be useful for other materials and semiconductors to determine the effectiveness of protection layers for photocathodes.

Electrodes↗
DOE OSTI2026

Robust photocatalytic hydrogen generation from CdSe nanoplatelets

Mercaptopropionic acid (MPA) capped-CdSe NPLs in-conjunction with a nickel-dihydrolipoic acid (Ni-DHLA) co-catalyst, yielded a robust output of photocatalytically generated hydrogen (H 2 ) at low concentrations of nanoplatelets. Furthermore, etching led to increased catalytic efficiency, suggesting that exposed catalytically active sites are primarily responsible for photocatalytic activity.

Phinney, Elizabeth O. [University of Rochester, NY↗
DOE OSTI2025

Etching-Chemistry-Driven Ruthenium Doping on Ti 3 C 2 T x MXene for Optimizing Electrochemical Performance

We demonstrate that the etching chemistry used during MXene synthesis from Ti 3 AlC 2 MAX phase significantly influences surface functionalization and structural vacancies, which in turn affect ruthenium (Ru) ion interactions. Using hydrofluoric acid (HF) and ammonium bifluoride (NH 4 HF 2 ) as etchants, we obtained MXene surfaces with distinct functional groups and Ti vacancies that impact Ru ion interactions and electrochemical performance. Both MXene variants (labeled MX(H) and MX(N), respectively) exhibited negative zeta potentials in their pristine state, but upon the addition of Ru the zeta potential for MX(H) reached 12.9 mV while that for MX(N) remained negative at −6.4 mV. This adsorption resulted in a 14.4-fold increase in the specific capacitance of MX(H)/Ru compared to pristine MX(H), whereas MX(N)/Ru exhibited only a 4.4-fold increase over its pristine counterpart. X-ray diffraction analysis identified the formation of ammonium titanium oxide fluoride, (NH 4 ) 3 TiOF 5 , on MX(N), which likely contributed to its reduced Ru adsorption. X-ray photoelectron spectroscopy suggested the presence of Ti vacancies in both MXene variants; however, their behavior toward Ru accommodation differed markedly, with MX(H) showing the most obvious shift in the Ti 2p peak in the XPS survey spectrum, while MX(N) showed the most obvious shift in the C 1s peak. Electron paramagnetic resonance spectroscopy further demonstrated a distinct alteration in the spectral signatures of MX(H) upon Ru addition, in contrast to the negligible changes in MX(N), indicating effective passivation of the Ti defect sites in MX(H) via vacancy-assisted Ru doping. Cyclic voltammetry showed that Ru-incorporated MX(H) nanocomposites exhibit more efficient redox-active sites, as reflected in their higher capacitance values. These findings highlight the pivotal role of MXene surface chemistry in controlling cation adsorption, providing valuable insights for the rational design of high-performance electrodes.

2D surface engineering↗
DOE OSTI2025

Immobilizing a Lehn-Type Catalyst with Nitrocyclocondensation Chemistries: CO 2 Reduction on Silicon Hybrid Photoelectrodes

Here, we present the first examples of installing a redox reporter and CO 2 reduction (CO 2 R) catalyst onto freshly HF-etched Si (photo)­electrodes using a solution-phase nitrocyclocondensation (NCC) reaction. Previous studies detailed the mechanism of NCC reactions on Si under ultrahigh vacuum conditions but have not applied these chemistries to generate functional (photo)­electrodes. Installing 4-nitrophenyl ferrocene (4-NpFc) molecules directly onto degenerately doped p + Si allowed us to evaluate the effects of different NCC reaction conditions on coverage (e.g., 3.6 ± 1.2 × 10 –11 mol/cm 2 ) and electrochemical reversibility. The 4-NpFc molecules remained immobilized under the reducing potentials (−2.0 V vs Fc +/0 in acetonitrile) needed to drive molecular CO 2 R catalysts. Installing 4-nitroaniline (4-NA) molecules onto low-doped pSi allowed us to couple Lehn-type Re­(I) catalysts with pendant carboxylic acids. The CO Faradaic efficiency of CO production under 1-sun illumination (−2.15 V vs Fc +/0 ) was 23% in CO 2 -saturated electrolyte, a value that surpasses previous examples of CO 2 R catalyst monolayers on Si. These two examples highlight the versatility of solution-phase NCC attachment chemistries for generating functional Si (photo)­electrodes.

catalysis↗
DOE OSTI2024

Lead Adsorption and Desorption at the Barite (001) Surface in the Presence of EDTA

Scaling minerals, such as barite, can cause detrimental consequences for oil/gas pipelines and water systems, but their formation can be inhibited by organic chelators such as ethylenediaminetetraacetic acid (EDTA). Here, we resolve how EDTA affects sorption and desorption of Pb at the barite (001) surface using a combination of X-ray scattering and microscopy measurements. In the presence of EDTA, Pb incorporated in the topmost part of the barite surface and adsorbed as inner-sphere complexes on the surface. In barite saturated solutions containing [Pb] ≥ 100 μM, overgrowth films grew along step edges. These films were exclusively monolayer thick, indicating that their growth was a self-limiting process. Approximately half of the Pb was removed after 14.5 h reaction with a Pb-free EDTA solution where most of the desorption occurred to adsorbed Pb rather than incorporated Pb. Dissolution proceeded primarily via step retreat and etch pit formation in EDTA, but in deionized water, the secondary phase was quickly removed within 3 min. Together these results suggest EDTA binds to both the surface and Pb in solution, which limits Pb sorption. However, EDTA binding to the surface also inhibits removal of the secondary phase that formed at higher Pb concentrations.

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

Microphase Separation of Randomly Linked Branched Polystyrene/Polylactic Acid for Formation of Cocontinuous Nanostructures

Cocontinuous polymeric nanomaterials have gained attention for their ability to preserve distinct properties of constituent microphases within a single material. Randomly linked copolymer networks have shown very wide stability windows for disordered cocontinuous phases (extending over ≈ 30 wt % in composition), but the reliance on a network architecture prevents subsequent solution- or melt-processing. Furthermore, the key factors contributing to cocontinuity have remained unclear. We recently found that randomly linked star copolymers (RSCs) can exhibit a cocontinuous window as wide as 25 wt % in the case of 4-arm stars, suggesting that while a network architecture is not essential for the formation of disordered cocontinuous phases, the presence of random elastic forces in such architectures may indeed facilitate their formation. In addition, the behavior was found to be highly sensitive to arm number, with 6-arm RSCs exhibiting almost no cocontinuous phase. These results raised a key mechanistic question regarding the contribution of random elastic forces, originating from strands that bridge between junctions, in stabilizing disordered cocontinuous phases. In the current study, we synthesized randomly linked branched copolymers (RBCs) of polystyrene (PS) and poly(D,L-lactic acid) (PLA), which represent an intermediate architecture between networks and stars. This approach allows for the introduction of elastic contributions from strands bridging between different junctions, while still maintaining the processability advantages of a non-network architecture. The cocontinuous regions of the PS/PLA RBCs, with varying polymer and linker functionalities (f p and f l , respectively), were characterized by small-angle X-ray scattering, gravimetry, and scanning electron microscopy. We found that the cocontinuous windows of RBCs typically expanded with increasing elastic contributions and exhibited reduced sensitivity to junction-functionality compared to RSCs. Notably, RBCs with f p = 1.50 and f l = 3, which had large molecular weights due to proximity to the gel point, achieved a cocontinuous window of ≈ 34 wt %, which is almost twice as wide as analogous 3-arm RSCs and comparable to randomly linked networks. Leveraging this robust cocontinuity and solution-processability, we fabricated a film of interconnected nanoporous PS.

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

Depolymerization as a Design Strategy: Depolymerization Etching of Polymerization-Induced Microphase Separations

Thermally triggered depolymerization has traditionally been viewed through the lens of sustainability and recycling, not as a constructive tool for materials design. Herein, we show that selective, thermally triggered depolymerization to gaseous monomer serves as a solvent-free strategy for generating porosity in nanostructured polymer materials, offering a means to bypass the mass transport limitations inherent in conventional solution-based etching. As a demonstration platform, we employed polymerization-induced microphase separation (PIMS) to generate disordered bicontinuous block copolymer structures with embedded depolymerizable domains. By incorporating a methacrylate block susceptible to thermal depolymerization within a cross-linked, depolymerization-resistant styrenic matrix, we developed a process we term depolymerization etching of polymerization-induced microphase separations (DEPIMS). This approach enables highly selective and efficient domain removal via reversion to monomer to produce mesoporous materials with high surface areas (>200 m 2 /g). Subsequent surface functionalization yielded mesoporous adsorbents with tunable uptake kinetics and among the highest dye adsorption capacities reported for PIMS-derived materials, demonstrating the adaptability of the DEPIMS platform for chemical separations. DEPIMS can also be extended to a gram-scale, one-pot approach to yield mesoporous materials with recoverable monomer in under 12 h. These findings reposition thermal depolymerization from a sustainability tool to a broadly enabling strategy for scalable, on-demand fabrication of functional nanostructured materials.

Depolymerization↗