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At least 865 records · Page 48
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Nickel hydroxide–nickel carbonate competitive growth on carbonate surfaces

The thermodynamic and kinetic factors controlling the competitive heterogeneous nucleation and growth of ubiquitous metal carbonate and hydroxide phases are poorly understood. In this work, calcite (CaCO 3 ) and magnesite (MgCO 3 ) powders were reacted with NiCl 2 (0–600 μM) for 7 days at 22 °C and 5 °C. The reacted powders were analyzed with X-ray photoelectron spectroscopy (XPS), scanning electron microscopy, and energy-dispersive X-ray spectroscopy to characterize the Ni surface precipitates formed. Evidence from these techniques pointed to the formation of mixed Ni carbonate-Ni hydroxide amorphous surface precipitates. On calcite, XPS detected primarily Ni(OH) 2 despite the initial solutions being more supersaturated with respect to gaspéite (NiCO 3 ) than to theophrastite (Ni(OH) 2 ) by a factor of 17–18. In contrast, NiCO 3 was the dominant component detected by XPS on magnesite in the same conditions. Decreasing the temperature had the effect of increasing the proportion of NiCO 3 to the detriment of Ni(OH) 2 . The experimental observations were consistent with low lattice/cation size mismatch favoring NiCO 3 nucleation and temperature most influencing Ni(OH) 2 nucleation. Comparison to previous work on Co-reacted powders indicated the differences in lattice/cation size mismatch and/or water exchange rate impacted the composition of the surface precipitates more than the relative thermodynamic stabilities of the competing minerals. This work explored the heterogeneous growth regime of Ni carbonate and hydroxide phases on carbonate surfaces and shed light on the factors that control the competition between surface precipitates when mineral surfaces are in contact with aqueous solutions supersaturated with respect to multiple mineral phases. In conclusion, these results contribute to geochemists’ efforts toward interpreting data from geochemical systems with elevated Ni concentrations, improving Ni environmental remediation and recovery strategies, and predicting the fate and transport of Ni in geochemical systems.

Heterogeneous nucleation↗
DOE OSTI2021

Alteration of pool boiling heat transfer on metallic surfaces by in situ oxidation

The critical heat flux during pool boiling has been investigated for a range of applications including electrical power generation and thermal management. Reported experimental CHF values during pool boiling of water on flat metallic surfaces, however, show a large discrepancy across studies. Here, we address this discrepancy in CHF values by accounting for oxidation of metallic surfaces during boiling. We studied the effect of in situ oxidation on flat Cu and Ni surfaces by changing the duration that samples were held in saturated water before conducting boiling experiments. The morphology and chemical composition of surfaces after the boiling experiments were analyzed by atomic force microscopy and X-ray photoelectron spectroscopy, respectively. Cu surfaces showed gradually increasing CHF values as the duration in saturated water increased, which could be attributed to the increase in roughness due to the formation of Cu 2 O nanostructures. Conversely, Ni surfaces showed relatively stable CHF and morphology as a nearly flat layer of NiO formed, with one exception: formation of a highly wetting hydroxide, Ni(OH) 2 , on a Ni coupon held in saturated water for 24 h resulted in a uniquely high CHF value, signifying the importance of surface chemistry in addition to morphology. Finally, the fundamental mechanisms resulting in the wide spread of CHF values on metallic surfaces elucidated in this work will lead to more accurate estimation of CHF as well as a deeper mechanistic understanding of CHF values on engineered surfaces.

42 ENGINEERING↗
DOE OSTI2020

Surface oxidation and crystallization of FeNi-Based soft magnetic nanocrystalline and amorphous nanocomposite alloys

In this work, we present characterization of surface oxidation and crystallization behavior of Metal Amorphous Nanocomposite (MANC) (Fe 70 Ni 30 ) 80 Nb 4 Si 2 B 14 alloys via complementary x-ray diffraction, electron microscopy, and x-ray photoelectron spectroscopy techniques. An adherent amorphous oxide of roughly 15–20 nm in thickness is observed on the wheel side of the ribbon, enriched in Fe relative to Ni and with significant content of Si and Nb as would be expected based upon a comparison of the Gibbs free energy of formation of the stable oxide phases. The amorphous character of the oxide is likely to result from the significant Si-content coupled with the amorphous and nanocrystalline character of the underlying metallic layer. Higher density of FeNi-enriched nanocrystals is also observed within ~100 nm of the wheel-side surface, presumably due to reduction in local glass former concentration. A rough, crystalline copper oxide layer is also present and forms through contact between the copper wheel and the solidifying melt during the rapid solidification process. On the air side of the ribbon, a crystalline oxide layer of ~15–20 nm is formed as well as intergranular oxidation that penetrates along the grain boundaries between highly textured surface crystallites of ~50–100 nm in size. The crystalline nature of the oxide on these surfaces is asserted to result from the lack of significant Si-content and the pre-existing surface crystallites that form during the rapid solidification process which promote a crystalline oxide surface layer. Furthermore, these results shed new insights into the details of surface oxidation and can help to inform processing and alloy composition adjustments which seek to tailor surface properties.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Unraveling the nature of Fe-doping mediated inter- and intra-chain interactions in Ca 3 Co 2 O 6

The structural and magnetic properties of quasi-one-dimensional (1D) spin-chain compounds Ca 3 Co 2-x Fe x O 6 (x = 0, 0.1, 0.2 and 0.3) synthesized by a sol-gel method have been systematically studied by means of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), neutron powder diffraction (NPD), dc and ac magnetization measurements. The samples adopt a rhombohedral crystal structure with the space group R-3c in a temperature range of 5–100 K. Fe ions are found to locate at the trigonal prism Co2 crystallographic sites. Fe doping converts some of low-spin Co 3+ ions at Co1 octahedral sites into Co 2+ ions. For the high-temperature paramagnetic phase, the Curie paramagnetic temperature θp changes its sign from positive to negative at x = 0.2, implying that the dominant magnetic interaction is driven from ferromagnetic (FM) to antiferromagnetic (AFM) upon Fe substitution. A partial low-spin to high-spin state crossover of the Co1 ions is observed at high Fe-doping level x = 0.3. All the samples exhibit a long-range spin-density wave (SDW) AFM ordering below TN, followed by a spin-glass-like transition at Tf. These low-temperature magnetic phases were significantly suppressed upon Fe doping. The Fe substitution in Ca 3 Co 2-x Fe x O 6 weakened both intrachain and interchain magnetic interactions, caused by enhanced magnetic disorder due to the different magnetic characters of Ising Co and Heisenberg Fe spins.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Competing magnetic interactions and emergent phase diagrams in double perovskite Y 2 Ni x Co 1–x MnO 6

We present a comparative study of double perovskites Y 2 Ni x Co 1–x MnO 6 for x = 1, 0.5, and 0. The polycrystalline samples of Y 2 Ni x Co 1–x MnO 6 with space group P2 1 /n were synthesized via sol-gel technique. X-ray photoelectron spectroscopy (XPS) confirms the presence of majority Ni 2+ /Mn 4+ in Y 2 NiMnO 6 (YNMO) and a mixed valence state Ni 2+/3+ /Co 2+/3+ /Mn 4+/3+ in co-doped Y 2 Ni 0.5 Co 0.5 MnO 6 (YNCMO). The temperature dependent magnetization results suggest homogeneous substitution of Ni ions with Co ions with minimal contribution of 3+ cationic magnetic interactions in YNCMO. The superexchange ferromagnetic (FM) interaction has a major contribution to the magnetism of YNMO. The strength of antiferromagnetic (AFM) coupling resulting from the antiphase boundaries in Y 2 Ni x Co 1–x MnO 6 increases with the increase in the Co concentration. The AC susceptibility (AC-χ) study further validates the presence of higher density of antiphase boundaries, which is reflected by the dynamics of domain walls in YNCMO. The isothermal magnetic entropy change (ΔS M ) as functions of temperature and magnetic field is exploited to assess the stabilization of different magnetic phases. Finally, the findings of ΔS M (T,µ 0 H) lead to the proposed new magnetic phase diagrams for Y 2 Ni x Co 1–x MnO 6 for x = 1 and 0.5, in comparison with the previously established phase diagram of Y 2 CoMnO 6 .

36 MATERIALS SCIENCE↗
DOE OSTI2023

Impact of titanium content on the thermo-mechanical and oxidation response of TiAlTa

This study aimed to analyze how the addition of titanium (Ti) to TiAlTa alloys affects their mechanical properties (Young’s modulus and hardness) and oxidation behavior. Alloys with three different Ti additions and equi-atomic Al and Ta were fabricated with nominal compositions of 33Ti-33Al-33Ta at%, 50Ti-25Al-25Ta at%, and 70Ti-15Al-15Ta at%. Phase identification of as-processed and compositionally homogenized alloys was conducted by coupling various electron microscopy, diffraction, and chemical analysis techniques. Composition and structures were modeled using CALPHAD-based phase predictions and compared with experimental results. Each of the alloys exhibited a unique set of microstructures with distinctly different ordered precipitates, dependent on cooling rate and chemical composition. Subsequently, nanoindentation tests were performed at temperatures of 25°C, 250°C, 500°C, and 750°C. Oxidation studies were conducted under static air at 750°C for up to 200 h. 33Ti-33Al-33Ta at% and 70Ti-15Al-15Ta at% alloys showed higher hardness and modulus than 50Ti-25Al-25Ta at% at room temperature. The 50Ti-25Al-25Ta at% alloy exhibited higher hardness and modulus values but lower oxidation resistance at 750°C when compared with the other specimens. The X-ray photoelectron spectroscopy experiments were conducted to further analyze the oxides present in the samples. Despite each sample displaying combinations of mixed oxide layers, TiO 2 was the preferred oxide forming in the 50Ti-25Al-25Ta composition, while the other samples preferred to form Al 2 O 3 . In conclusion, the findings from this systematic exploration of phase evolution in the TiAlTa alloy space provide insights for optimized material chemistries, processing, and properties.

36 MATERIALS SCIENCE↗
DOE OSTI2026

The presence of Ru metal modifies the behavior of deuterium bound to pyridinic nitrogen in doped graphene-like materials

We used a combination of x-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) to investigate how the presence of a ruthenium (Ru) metal substrate modifies the N-D bond strength of the pyridinic nitrogen species in nitrogen (N)-doped graphene (Gr) on Ru(0001) compared to metal-free highly-oriented pyrolytic graphite (HOPG) substrate. The N-dopants were introduced through low-energy N+/N2+ irradiation. N is embedded in the carbon materials in two predominant configurations: as graphitic N (GN: N substituted in the hexagonal C lattice) and pyridinic N (PN: substitutional N adjacent to a C vacancy). XPS data showed that upon atomic deuterium (D) exposure at 220 K, the PN peak shifted to a higher binding energy by +1.2 eV for HOPG and +1.0 eV for N-doped graphene on Ru(0001), while the GN peak remained unchanged, indicating that the D atoms bound solely to pyridinic N. 85% of PN sites on HOPG can be saturated with D atoms, whereas only ~30% of pyridinic N sites are able to bind D atoms in N-doped Gr/Ru(0001). Our DFT analysis shows that this difference is due to the coordination of PN to Ru atoms, which necessitates bond cleavage of the N-Ru interaction prior to D atom adsorption. D begins desorbing from N-HOPG at ~573 K and is fully desorbed by ~973 K, whereas desorption from N-doped graphene on Ru(0001) begins at ~290 K, with complete desorption observed at ~700 K, indicating that the Ru metal weakens the N-D bond strength. We also studied a high-surface-area, layered, and porous N-doped carbon material, internally labeled NC900, which was synthesized by pyrolysis of glucose and graphitic carbon nitride (g-C3N4) at 1173 K. D exposure caused a +1.1 eV PN peak shift in NC900, with no change in the GN peak. Moreover, the NC900 exhibited the same desorption behavior as HOPG, demonstrating that well-defined model systems can effectively capture the behavior of more complex N-doped carbon materials.

Alupothe Gedara, Buddhika S.↗
DOE OSTI2026

Crystal structure, magnetism, and specific heat of lightly depleted layered honeycomb oxides, Na$_2$(Ni$_{2-x}$D$_x$)TeO$_6$ ($D$ = Mg, Ga, Co; 0.10 ≤ $x$ ≤ 0.25)

Layered oxides, in which transition metal atoms form a honeycomb lattice, are known for complex magnetic phase diagrams. In this work we study the doped compounds, Na$_2$(Ni$_{2-x}$D$_x$)TeO$_6$, $D$ = Mg, Ga, and Co (0.10 ≤ $x$ ≤ 0.25), to understand how chemical dilution at the nickel site influences the stability of magnetic exchanges within the honeycomb layer of the parent, Na$_2$ Ni$_2$ TeO$_6$. Here, the studied compounds were found to crystallize in $P6_3/mcm$ space group common to P2 type layered oxides. In general, the lattice parameters and the unit cell volume expanded with increased doping. The oxidation states determined from X-ray photoelectron spectroscopy were consistent with bond valence sum estimates, that confirmed the presence of Ni$^{2+}$, Mg$^{2+}$, Ga$^{3+}$, Co$^{2+}$ in our samples. Irrespective of magnetic or non-magnetic doping, the magnetic phase transition temperature ($T_N$) of the doped compounds were reduced from that of Na$_2$ Ni$_2$ TeO$_6$ or Na$_2$ Co$_2$ TeO$_6$, and lay between 21.7 K and 26.8 K. The effective paramagnetic moments extracted from Curie–Weiss analysis were in the range 3.17 μ B to 3.84 μ B and the Weiss temperatures were between $-15$ K and $-25$ K, suggesting antiferromagnetism. Mg- and Ga-doped compounds showed free spin formation, indicated by Curie–Weiss tails in their magnetic susceptibility. Our results suggest emergence of short-range magnetic correlations in Na$_2$(Ni$_{2-x}$D$_x$)TeO$_6$, enhanced due to the depletion of the Ni honeycomb lattice.

75 - CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY A↗
DOE OSTI2024

Hydrogen activation by rhodium under the cover of a copper oxide thin film

Here, the activation of reactants by catalytically active metal sites at metal-oxide interfaces is important for understanding the effect of metal-support interactions on nanoparticle catalysts and for tuning activity and selectivity. Using a combined experimental and theoretical approach, we studied the activation of H 2 and the effect of CO poisoning on isolated Rh atoms completely or partially covered by a copper oxide (Cu 2 O) thin film. Temperature-programmed desorption (TPD) experiments conducted in ultra-high vacuum (UHV) show that neither a partially nor a fully oxidized Cu 2 O layer grown on a Rh/Cu(111) single-atom alloy can activate hydrogen in UHV. However, in situ ambient pressure X-ray photoelectron spectroscopy (AP-XPS) experiments performed at elevated H 2 pressures reveal that Rh significantly accelerates the reduction of these Cu 2 O thin films by hydrogen. Remarkably, the fastest reduction rate is observed for the fully oxidized sample with all Rh sites covered by Cu 2 O. Both TPD and AP-XPS data demonstrate that these covered Rh sites are inaccessible to CO, indicating that Rh under Cu 2 O is active for H 2 dissociation but cannot be poisoned by CO. In contrast, an incomplete oxide film leaves some of the Rh sites exposed and accessible to CO, and hence prone to CO poisoning. Density functional theory calculations demonstrate that unlike many reactions in which hydrogen activation is rate limiting, the rate-determining step in the dissociation of H 2 on thin-film Cu 2 O with Rh underneath is the adsorption of H 2 on the buried Rh site, and once adsorbed, the dissociation of H 2 is barrierless. These calculations also explain why H 2 can only be activated at higher pressures. Together, these results highlight how different the reactivity of atomically dispersed Rh in Cu can be depending on its accessibility through the oxide layer, providing a way to engineer Rh sites that are active for hydrogen activation but resilient to CO poisoning.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Enhancement of oxidative dehydrogenation over cerium-doped nickel niobium catalysts and analysis of batch-to-batch variability

Nickel based catalysts are inexpensive and efficient for use in the oxidative dehydrogenation of ethane. NiO doped with niobium and cerium shows increased ethylene production. Small amounts of Ce doped onto a NiNb catalyst led to increased Ni activity. The catalyst that had the highest ethylene production rate per g of catalyst had 1 atom% Ce, 86 at% Ni, and 13 at% Nb (1CeNiNb) while, if surface area is incorporated into the calculation, the catalyst that had the highest ethylene production rate per m 2 was the 0.5CeNiNb catalyst. The ethylene production rates of these Ce-containing catalysts are 27 %-127 % higher than those with NiNb alone previously reported in the literature. Here, to fully understand how cerium affects the NiNb catalyst, the Ce content and effect on active sites has been fully characterized over multiple batches. In doing this, light has been shed on batch-to-batch variability. Characterization techniques such as powder X-ray diffraction, hydrogen temperature programmed reduction, X-ray photoelectron spectroscopy, synchrotron X-ray absorption spectroscopy, and methanol adsorption were used.

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

Pd-promoted reduction and restructuring of an In 2 O 3 -based catalyst for CO 2 hydrogenation at room temperature

An unconventional reaction mechanism in an In 2 O 3 /Pd(1 1 1) inverse model catalyst for the CO 2 hydrogenation reaction has been uncovered: In 2 O 3 is partially reduced at room temperature in a reaction atmosphere as a result of its direct contact with Pd(1 1 1), which is an efficient H 2 splitter. The reduction induces changes in surface free energy, leading to a dynamical restructuring at the In 2 O 3 /Pd(1 1 1) interface via formation of InO x and outward diffusion of Pd, as revealed by ambient pressure X-ray photoelectron spectroscopy, X-ray absorption spectroscopy and density functional theory simulations. This dynamical restructuring eventually promotes the growth of 2D InPd y O x nanodomains as the catalytically active phase and the exclusive formation of methanol upon hydrogenation of CO 2 at room temperature. A comparable high selectivity toward CH 3 OH was found in more realistic bulk catalytic systems (2 wt% Pd/In 2 O 3 catalyst and commercial CZA catalyst). Scanning tunneling microscopy under ultrahigh vacuum and ambient pressure reaction atmospheres further reveals the structural dynamics at the InO x /Pd(1 1 1) interface, where we follow in situ the evolution of the InO x particles on Pd(1 1 1) and the mobility of the InPd y O x nanodomains in a CO 2 + H 2 environment. The present findings of the formation of a mixed oxide phase in a dynamically restructuring metal/reducible-oxide interface indicate further implications for other heterogeneous catalytic systems beyond the present CO 2 hydrogenation example and highlight the importance of in situ investigations.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Catalytic degradation of waste rubbers and plastics over zeolites to produce aromatic hydrocarbons

Catalytic conversion of waste rubbers and plastics into aromatic hydrocarbons is a promising approach to waste management and energy recovery. In the present study, acidic HY zeolites were supported by cobalt, iron, and zirconium, and the catalysts were characterized by powder X-ray diffraction, nitrogen adsorption-desorption, ammonia temperature programmed desorption, X-ray photoelectron spectroscopy, and pyridine-Fourier transform infrared spectroscopy. Here, the catalytic degradation of waste polybutadiene rubbers (BR) was conducted to investigate the degradation mechanism and evaluate the catalytic activity of supported zeolites. Experimental results indicated that HY loaded by zirconium and iron led to a higher content of Lewis acid sites as opposed to cobalt supported one. Compared with the non-catalytic pyrolysis of BR, the zirconium supported HY (Zr/HY) led to a 10-fold increase in aromatic hydrocarbons production with a distinctively high selectivity of 97.9%. A series of waste polymers including waste tires (WT), polyethylene (PE), polycarbonate (PC), and BR, were subjected to catalytic pyrolysis to explore the effects of polymer type on aromatic hydrocarbons generation, and BR was the most effective substrate, with yield enhancement reaching 2.4 over Zr/HY. Catalytic co-pyrolysis of waste rubbers and plastics was conducted to probe the effect of polymer structure on aromatic hydrocarbons formation, where a significant synergistic effect was observed in the PE co-fed with PC run.

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

Insights into the methanol synthesis mechanism via CO 2 hydrogenation over Cu-ZnO-ZrO2 catalysts: Effects of surfactant/Cu-Zn-Zr molar ratio

In this study, we evaluated aspects of the CO 2 hydrogenation mechanism, correlating structure-activity relationships of Cu-ZnO-ZrO 2 catalysts prepared by one-pot surfactant-assisted co-precipitation with different surfactant ratios. Identifying the CO 2 hydrogenation pathway intermediates is key to controlling the reaction selectivity. Experimental evidence shows that the CO 2 is dissociating into CO* and O* onto the surface of the Cu-ZnO-ZrO 2 catalyst. The adsorption and dissociation of CO2 were evidenced by a combination of in situ ambient-pressure X-ray Photoelectron Spectroscopy (AP-XPS) and Fourier Transform Infrared Spectroscopy (FTIR) with a transmission cell. AP-XPS showed that the catalysts are composed of a Cu 2+ , Zr 3+ , and Zr 4+ mixture and two kinds of Zn 2+ species. After the H 2 reduction process, only Cu 2+ was reduced to Cu0. The Zn and Zr species were oxidized by the dissociated O* species. In situ transmission FTIR showed that CO was adsorbed onto the Cu+/0 sites. The catalyst with the higher surfactant molar ratio exhibited the highest CO 2 conversion close to the equilibrium conversion, as well as a good methanol formation rate.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A study of damage-free in-situ etching of GaN in metalorganic chemical vapor deposition (MOCVD) by tertiarybutylchloride (TBCl)

This paper reports a study of the effect of NH 3 flow rate and reactor temperature on the tertiarybutylchloride (TBCl) etching of patterned GaN-on-sapphire templates. It is found that a reduced NH 3 flow rate and an elevated reactor temperature can eliminate islands or dots on the surface, while at the same time, enhance the etching around dislocations. TBCl etching was also performed on planar bulk GaN templates with much lower dislocation density. We find an atomically flat and layer-by-layer etching behavior within the region free of dislocations. Surface kinetics analysis reveals a short diffusion length of etching products. Room-temperature photoluminescence (PL) and x-ray photoelectron spectroscopy (XPS) measurements confirm that TBCl etching is capable of removing the damage and impurities induced by plasma etching without introducing additional damage.

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

MOCVD Surface Preparation of V-Groove Si for III-V Growth

V-groove nanopatterning of Si substrates has recently demonstrated promise for achieving high-quality III-V-on-Si epitaxy while providing a lower-cost processing route than chemo-mechanical polishing to produce epi-ready planar wafers. A key factor in determining the crystalline quality of III-V buffer layers is the Si surface structure and its chemical composition. Unlike planar Si surfaces, the surfaces of V-grooves prior to growth have not been studied in detail. Here, we study the surface of V-groove Si prepared for GaP nucleation via X-ray photoelectron spectroscopy and low-energy electron diffraction. We identify several pretreatments, using both 830 and 1000 annealing under an As background pressure, as being suitable for deoxidizing and cleaning the V-groove Si surface. The V-groove Si was found to behave similarly to reference Si(0 0 1) and Si(1 1 1) planar samples, demonstrating that in situ techniques such as reflection anisotropy spectroscopy can be used on reference samples to infer the state of the V-groove surface, and indicating that the extensive research on planar Si surfaces can be directly applied to V-grooves.

III-V epitaxy↗
DOE OSTI2022

Defect redistribution along grain boundaries in SrTiO 3 by externally applied electric fields

During thermal annealing at 1425 °C nominal electric field strengths of 50 V/mm and 150 V/mm were applied along the grain boundary planes of a near 45° (100) twist grain boundary in SrTiO 3 . Electron microscopy characterization revealed interface expansions near the positive electrode around 0.8 nm for either field strength. While the interface width decreased to roughly 0.4 nm after annealing at 50 V/mm, the higher field strength caused decomposition of the boundary structure close to the negative electrode. Electron energy-loss and X-ray photoelectron spectroscopies demonstrated an increased degree of oxygen sublattice distortion at the negative electrode side, and enhanced concentrations of Ti 3+ and Ti 2+ compared to bulk for both single crystals and bicrystals annealed with an external electric field, respectively. Oxygen migration due to the applied electric field causes the observed alteration of grain boundary structures. At sufficiently high field strength the agglomeration of anion vacancies may lead to the decomposition of the grain boundary.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Production of polyacrylonitrile/ionic covalent organic framework hybrid nanofibers for effective removal of chromium(VI) from water

Hexavalent Cr(VI) found in industrial wastewater is a proven carcinogen which causes serious health issues in humans around the world. This study presents a novel method to enhance the Cr(VI) oxyanion removal from wastewater by polyacrylonitrile (PAN) nanofibers through incorporation of a guanidinium-based ionic covalent organic framework (BT-DG) in the nanofibers structure. In this work, simple electrospinning technique was employed to produce PAN nanofibers and BT-DG was synthesized through condensation between benzene-1,3,5-tricarbaldehyde and N,N'-diaminoguanidine monohydrochloride. In-situ polymerization of BT-DG onto PAN nanofibers resulted in generation of hybrid PAN-BT-DG nanofibers. This modified PAN-BT-DG was characterized by obtaining its point of zero charge (PZC), differential scanning calorimeter (DSC), scanning electron microscopy (SEM) morphology and surface elements and oxidation states by X-ray photoelectron spectroscopy (XPS). PAN-BT-DG exhibited positive surface charge below pH 4, making it an outstanding adsorbent, for Cr(VI) removal. Cr(VI) adsorption onto PAN-BT-DG followed pseudo second order kinetics and adsorption data fitted well to Freundlich isotherm model. Highest Cr(VI) removal was obtained at 55 °C with a maximum Langmuir adsorption capacity of 173 mg/g at pH 3. Kinetic studies revealed that Cr(VI) adsorption onto PAN-BT-DG is endothermic and thermodynamically feasible. Desorption studies were conducted on PAN-BT-DG using 1 M NaOH as the stripping solvent and PAN-BT-DG exhibited excellent regeneration after five consecutive cycles.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Complex spin structure in co-trimer-chain Li 2 Co 3 Se 4 O 12

Complex magnetic materials are extremely attractive for revealing unconventional spin states and novel magnetic excitations. Here, we report the structural, thermodynamic, and magnetic properties of a novel magnetic material Li 2 Co 3 Se 4 O 12 based on x-ray and neutron diffraction, specific heat, magnetization, and x-ray photoelectron spectroscopy measurements. X-ray and neutron diffraction refinements reveal two Co sites Co (1) and Co (2) even though both are in the octahedral environment. While they are not connected along the b and c directions, these octahedra are edge-shared forming the Co (2) – Co (1) – Co (2) trimer chain along the a direction. The magnetic susceptibility exhibits the Curie-Weiss (CW) temperature dependence at high temperatures (above ∼50 K) with the negative CW temperature, a dip centered at T ⁎ ∼ 8.0 K, and an antiferromagnetic transition at T N = 3.3 K. The specific heat confirms that there is a phase transition at T N and a hump at T ⁎ . The long-range magnetic transition at T N implies that, in addition to the intra-chain interaction, there is strong inter-chain interaction, which is likely due to polarized SeO 3 bridging between chains. Single crystal neutron diffraction refinement reveals a complex magnetic structure with the angle between Co (1) and Co (2) moments ∼105°. Within the Co (2) – Co (1) – Co (2) trimer, two Co (2) moments are parallelly aligned. Surprisingly, the Co (1) moment (1.92μB) is only half of the Co (2) moment (3.96μB). There is likely the spin-state change for Co (1) from the high-spin state at T > T ⁎ to the low-spin state at T < T ⁎ , causing a dip in the magnetic susceptibility and a hump in the specific heat. When the magnetic field is applied, multiple metamagnetic transitions are found in all directions, implying field-driven magnetic excitations. Our results demonstrate rich magnetic properties of Li 2 Co 3 Se 4 O 12 that are sensitive to the external stimuli such as the magnetic field.

Antiferromagnetism↗