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At least 991 records · Page 55
All sourcesNASA NTRSDOE OSTI
DOE OSTI2012

Synthesis and characterization of NiO nanoparticles by thermal decomposition of nickel linoleate and their optical properties

Well dispersed nickel oxide nanoparticles have been synthesized successfully by direct calcination of nickel linoleate. The structure, morphology and properties of the nanoparticles were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy and ultraviolet-visible spectroscopy. Transmission electron microscopic studies show that nickel oxide nanoparticles are uniform with an average size of 14-20 nm. The optical band gap of 3.8 eV is obtained using UV-Visible spectroscopy which exhibits the red shift compared with the bulk counterpart. - Highlights: Black-Right-Pointing-Pointer Synthesis of metal oxide nanoparticles by using metal complexes as precursors. Black-Right-Pointing-Pointer Characterization of isolated nanoparticles using XRD, FTIR, SEM, TEM and HRTEM data. Black-Right-Pointing-Pointer The expected optical properties of these nanoparticles are clarified.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2012

Optical properties of tin oxide nanoparticles prepared by laser ablation in water: Influence of laser ablation time duration and laser fluence

Colloidal tin oxide nanoparticles are prepared by laser (having a wavelength of 1064 nm) ablation of tin metallic target immersed in pure deionized water. The influences of laser ablation time and laser fluence on the size and optical properties of the synthesized nanoparticles are studied. Prepared tin oxide nanoparticles are characterized by transmission electron microscope, selected area electron diffraction and UV-Visible absorption spectroscopy. The morphology of prepared tin oxide nanoparticles is found to be mostly spherical and with sizes in the nanometric range (mean radius of 3.2 to 7.3 nm). The measured UV-Visible absorption spectra show the presence of absorption peaks in the ultraviolet region. The band gap energy of samples prepared with different laser ablation time duration is calculated and is found to be increased with decrease in size (radius) of the prepared nanoparticles. Photoluminescence emission measurements at room temperature show that all the samples exhibit photoluminescence in the visible region. The peak photoluminescence emission intensity in the sample prepared with 50 min of laser ablation time is 3.5 times larger than that obtained in the sample prepared with 10 min of laser ablation time. - Highlights: Black-Right-Pointing-Pointer SnO{sub 2} nanoparticles (6.4-14.6 nm) are prepared by laser ablation in liquid technique. Black-Right-Pointing-Pointer The influences of laser ablation time and laser fluence are studied. Black-Right-Pointing-Pointer Samples are characterized by TEM and UV-Visible absorption spectroscopy. Black-Right-Pointing-Pointer UV-Visible absorption spectra exhibit quantum confinement effect. Black-Right-Pointing-Pointer Samples exhibit enhanced photoluminescence emissions in the visible region.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Morphological and electrochemical characterization of electrodeposited Zn–Ag nanoparticle composite coatings

Silver nanoparticles with an average size of 23 nm were chemically synthesized and used to fabricate Zn–Ag composite coatings. The Zn–Ag composite coatings were generated by electrodeposition method using a simple sulfate plating bath dispersed with 0.5, 1 and 1.5 g/l of Ag nanoparticles. Scanning electron microscopy, X-ray diffraction and texture co-efficient calculations revealed that Ag nanoparticles appreciably influenced the morphology, micro-structure and texture of the deposit. It was also noticed that agglomerates of Ag nanoparticles, in the case of high bath load conditions, produced defects and dislocations on the deposit surface. Ag nanoparticles altered the corrosion resistance property of Zn–Ag composite coatings as observed from Tafel polarization, electrochemical impedance analysis and an immersion test. Reduction in corrosion rate with increased charge transfer resistance was observed for Zn–Ag composite coatings when compared to a pure Zn coating. However, the particle concentration in the plating bath and their agglomeration state directly influenced the surface morphology and the subsequent corrosion behavior of the deposits. - Highlights: • Synthesis of Ag nanoparticles with an average size of 23 nm • Fabrication of Zn/nano Ag composite coating on mild steel • Composite coatings showed better corrosion resistance. • Optimization of particle concentration is necessary.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Extracellular synthesis of silver nanoparticles using the leaf extract of Coleus amboinicus Lour

Highlights: {yields} Synthesis of AgNPs using the leaf extract of Coleus amboinicus L. was described. {yields} UV-vis absorption spectra showed the formation of isotrophic AgNPs at 437 nm in 6 h. {yields} XRD analysis showed intense peaks corresponding to fcc structure of AgNPs. {yields} HR-TEM analysis revealed the formation of stable anisotrophic and isotrophic AgNPs. -- Abstract: In the present investigation, Coleus amboinicus Lour. leaf extract-mediated green chemistry approach for the synthesis of silver nanoparticles was described. The nanoparticles were characterized by ultraviolet-visible (UV-Vis) spectroscopy, X-ray diffraction (XRD), energy dispersive X-ray analysis (EDAX), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). The influence of leaf extract on the control of size and shape of silver nanoparticles is reported. Upon an increase in the concentration of leaf extract, there was a shift in the shape of nanoparticles from anisotrophic nanostructures like triangle, decahedral and hexagonal to isotrophic spherical nanoparticles. Crystalline nature of fcc structured nanoparticles was confirmed by XRD spectrum with peaks corresponding to (1 1 1), (2 0 0), (2 2 0) and (3 1 1) planes and bright circular spots in the selected-area electron diffraction (SAED). Such environment friendly and sustainable methods are non-toxic, cheap and alternative to hazardous chemical procedures.

36 MATERIALS SCIENCE↗
DOE OSTI2011

A spectroscopic study on the interaction between gold nanoparticles and hemoglobin

Highlights: Black-Right-Pointing-Pointer The interaction was studied using UV-vis and fluorescence spectroscopy. Black-Right-Pointing-Pointer Gold nanoparticles quench the fluorescence emission of hemoglobin solution. Black-Right-Pointing-Pointer The binding and thermodynamic constants were calculated. Black-Right-Pointing-Pointer Major impact: electrochemical applications of the complex onto a substrate. -- Abstract: The interaction between horse hemoglobin and gold nanoparticles was studied using optical spectroscopy. UV-vis and fluorescence spectra show that a spontaneous binding process occurred between hemoglobin and gold nanoparticles. The Soret band of hemoglobin in the presence of gold nanoparticles does not show significant changes, which proves that the protein retained its biological function. A shift to longer wavelengths appears in the plasmonic band of gold nanoparticles upon the attachment of hemoglobin molecules. Gold nanoparticles quench the fluorescence emission of tryptophan residues in the structure of hemoglobin. The Stern-Volmer quenching constant, the binding constant and the number of binding sites were also calculated. Thermodynamic parameters indicate that the binding was mainly due to hydrophobic interactions.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Structural transformation from Mn{sub 3}O{sub 4} nanorods to nanoparticles and band gap tuning via Zn doping

Highlights: Black-Right-Pointing-Pointer Successful doping of Zn in Mn{sub 3}O{sub 4} nanorod has been done by simple hydrothermal method. Black-Right-Pointing-Pointer Increase of Zn doping encouraged the formation of Mn{sub 3}O{sub 4} nanoparticle out of Mn{sub 3}O{sub 4} nanorod. Black-Right-Pointing-Pointer The energy band gap of Mn{sub 3}O{sub 4} nanorod increased continuously with the increase of Zn doping concentration. -- Abstract: Synthesis of undoped and Zn doped hausmannite Mn{sub 3}O{sub 4} nanorods was achieved through a simple hydrothermal route. Scanning electron microscopic studies showed that due to in situ Zn doping a structural deformation from Mn{sub 3}O{sub 4} nanorods to a mixture of Mn{sub 3}O{sub 4} nanorods and nanoparticles occurred. The amount of nanoparticles in the mixture increased with the increase of doping percentage. X-ray diffraction studies, transmission electron microscopy and selected area electron diffraction pattern revealed that both the nanorods and the nanoparticles were hausmannite Mn{sub 3}O{sub 4}. X-ray photoelectron spectroscopic studies confirmed successful zinc doping in Mn{sub 3}O{sub 4}. Microscopic studies revealed that the average diameters of Mn{sub 3}O{sub 4} nanorods and nanoparticles were of 200 nm and 70 nm, respectively. The possible growth mechanism and the reasons behind the formation of nanoparticles along with nanorods are discussed briefly. UV-vis spectroscopic studies showed a continuous increase in the energy bandgap of Mn{sub 3}O{sub 4} with the increase in Zn doping percentage.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Zn-doped and undoped SnO{sub 2} nanoparticles: A comparative structural, optical and LPG sensing properties study

Graphical abstract: The X-ray diffraction (XRD) analyses confirm that all the materials prepared are polycrystalline SnO{sub 2} possessing tetragonal rutile structure. On Zn-doping, the crystallite size has been found to decrease from 25 nm (undoped sample) to 13 nm (1 at% Zn-doped sample). Display Omitted Highlights: ► Zn-doped SnO{sub 2} nanoparticles show smaller crystallite size (11–17 nm). ► Optical band gap in SnO{sub 2} nanoparticles increases on Zn-doping. ► 2 at% Zn-doped sample show minimum room temperature resistivity. ► LPG response of the Zn-doped SnO{sub 2} nanoparticles increases considerably. ► 1 at% Zn-doped sample shows maximum response (87%) at 300 °C to 1 vol% concentration. -- Abstract: SnO{sub 2} nanoparticles were prepared by the co-precipitation method with SnCl{sub 4}·5H{sub 2}O as the starting material and Zn(CH{sub 3}COO){sub 2}·2H{sub 2}O as the source of dopant. All the materials prepared have been found to be polycrystalline SnO{sub 2} possessing tetragonal rutile structure with crystallite sizes in the range 11–25 nm. Optical analyses reveal that for the SnO{sub 2} nanoparticles, both undoped and Zn-doped, direct transition occurs with the bandgap energies in the range 3.05–3.41 eV. Variation in the room temperature resistivity of the SnO{sub 2} nanoparticles as a function of dopant concentration has been explained on the basis of two competitive processes: (i) replacement of Sn{sup 4+} ion by an added Zn{sup 2+} ion, and (ii) ionic compensation of Zn{sup 2+} by the formation of oxygen vacancies. Among all the samples examined for LPG sensing, the 1 at% Zn-doped sample exhibits fast and maximum response (∼87%) at 300 °C for 1 vol% concentration of LPG in air.

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

A simple way to synthesize well-dispersed Gd{sub 2}O{sub 3} nanoparticles onto reduced graphene oxide sheets

Graphical abstract: Display Omitted Highlights: ► A simple approach to obtain Gd{sub 2}O{sub 3} nanoparticles onto RGO sheets. ► Gd{sub 2}O{sub 3} nanoparticles could be bonded with RGO by the residual C-OH or COOH groups. ► The as-prepared Gd{sub 2}O{sub 3} nanoparticles are well-dispersed and in the size of 10–50 nm. -- Abstract: High quality and dispersible rare-earth oxides (RE{sub 2}O{sub 3}) nanocrystals have drawn great attention because of their potential applications in the optical, electrical and biological fields. Here, we demonstrated a simple approach for the production of gadolinium oxide (Gd{sub 2}O{sub 3}) nanoparticles onto the surface of reduced graphene oxide (RGO) sheets by the chemical and the subsequent thermal reduction reactions. The residual oxygen functionalities derived from the reduction of graphene oxide (GO) played an important role to complex Gd{sub 2}O{sub 3} nanoparticles with RGO sheets. And the as-synthesized Gd{sub 2}O{sub 3} nanoparticles are uniform and well-dispersed with their particle size in the range of 10–50 nm. The approach would open up a new window for simple and effective synthesis of high quality RE{sub 2}O{sub 3} in nano scale.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Green synthesis of silver nanoparticles from aqueous Aegle marmelos leaf extract

Graphical abstract: Silver nanoparticles capped with polyphenols present in Aegle marmelos leaf extract. Display Omitted Highlights: ► Silver nanoparticles are synthesized using Aegle marmelos leaf extract in aqueous media. ► Reduction reaction is fast and occurs at room temperature. ► The presence of polyphenols acts as in situ capping agent. -- Abstract: Synthesis of nanoparticles by green route is an emerging technique drawing more attention recently because of several advantages over the convention chemical routes. The present study reports one-pot synthesis and in situ stabilization of silver nanoparticles using Aegle marmelos leaf extract. Nanoparticles of almost uniform spherical size (∼60 nm) were synthesized within ∼25 min reaction time at room temperature. The size of particles depends on the ratio of AgNO{sub 3} and leaf extract. The crystallinity, size, and shape of the nanoparticles were characterized by X-ray diffraction, dynamic light scattering, and scanning electron microscopy respectively. The size stability was attained by the capping effect of polyphenolic tannin compound, procatacheuate in the extract. The capped polyphenols can be removed from the particle surface by simple NaOH/methanol wash. The involvement of phenolic compounds in metal ion reduction and capping were supported by UV–visible spectroscopy, infrared spectroscopy, high performance liquid chromatography, and zeta potential measurements.

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

Facilely preparation and microwave absorption properties of Fe{sub 3}O{sub 4} nanoparticles

Highlights: ► A bran-new method is firstly used to fabricate Fe{sub 3}O{sub 4} nanoparticles. ► The detailed analysis of formation mechanism is discussed. ► The electromagnetic absorption properties are defined. ► The effect of nanometer-sized is considered for the excellent microwave absorption. - Abstract: The Fe{sub 3}O{sub 4} nanoparticles were prepared by a novel wet-chemical method which shows its highly synthesizing efficiency and controllability. A possible formation mechanism was also proposed to explain the synthesizing process. X-ray diffraction (XRD) and transmission electron microscope (TEM) were employed and yielded an examination of an average diameter of 77 nm of the as-synthesized Fe{sub 3}O{sub 4} nanoparticles with face-centered cubic structure. Vibrating sample magnetometer (VSM) and vector network analyzer were employed to measure the magnetic property and electromagnetic parameters of the nanoparticles, then reflection losses (RL (dB)) were calculated in the frequency range of 2–18 GHz. A large saturation magnetization (72.36 emu/g) and high coercivity (95 Oe) were determined and indicated that the Fe{sub 3}O{sub 4} nanoparticles own strong magnetic performance. Following simulation results showed that the lowest reflection loss of the sample was −21.2 dB at 5.6 GHz with layer thickness of 6 mm. Effect of nanometer-sized further provided an explanation for the excellent microwave absorption behavior shown by the Fe{sub 3}O{sub 4} nanoparticles.

36 MATERIALS SCIENCE↗
DOE OSTI2013

A facile synthesis of ZnWO{sub 4} nanoparticles by microwave assisted technique and its application in photocatalysis

Highlights: ► Nanocrystalline ZnWO{sub 4} particles were successfully prepared by a microwave method. ► Spherical morphology with a 10 nm size. ► The band is 3.4 eV. ► The photodegradation of RhB was 95% within 25 min. - Abstract: A simple microwave assisted technique has been successfully developed to synthesize ZnWO{sub 4} nanoparticles. The X-ray diffraction results indicated that the synthesized nanoparticles exhibited only wolframite structure. Structural, morphological and optical properties of ZnWO{sub 4} nanoparticles have been analyzed by XRD, SEM, TEM EDAX, UV–vis and FT-IR spectral measurements. The transmission electron microscopy (TEM) image revealed that particle size of ZnWO{sub 4} nanoparticles was found to be 10 nm, the band-gap of ZnWO{sub 4} nanoparticles was found to be 3.4 eV. The photocatalytic activities for aqueous Rhodamine B and Methylene Blue samples were investigated and observed that ZnWO{sub 4} nanoparticles exhibited highly enhanced photocatalytic activity towards RhB than MB.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Electrochemical synthesis and characterization of zinc oxalate nanoparticles

Highlights: ► Synthesis of zinc oxalate nanoparticles via electrolysis of a zinc plate anode in sodium oxalate solutions. ► Design of a Taguchi orthogonal array to identify the optimal experimental conditions. ► Controlling the size and shape of particles via applied voltage and oxalate concentration. ► Characterization of zinc oxalate nanoparticles by SEM, UV–vis, FT-IR and TG–DTA. - Abstract: A rapid, clean and simple electrodeposition method was designed for the synthesis of zinc oxalate nanoparticles. Zinc oxalate nanoparticles in different size and shapes were electrodeposited by electrolysis of a zinc plate anode in sodium oxalate aqueous solutions. It was found that the size and shape of the product could be tuned by electrolysis voltage, oxalate ion concentration, and stirring rate of electrolyte solution. A Taguchi orthogonal array design was designed to identify the optimal experimental conditions. The morphological characterization of the product was carried out by scanning electron microscopy. UV–vis and FT-IR spectroscopies were also used to characterize the electrodeposited nanoparticles. The TG–DTA studies of the nanoparticles indicated that the main thermal degradation occurs in two steps over a temperature range of 350–430 °C. In contrast to the existing methods, the present study describes a process which can be easily scaled up for the production of nano-sized zinc oxalate powder.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Synthesis of amino-silane modified superparamagnetic Fe{sub 3}O{sub 4} nanoparticles and its application in immobilization of lipase from Pseudomonas fluorescens Lp1

Highlights: ► Magnetic nanoparticles were synthesized by chemical co-precipitation method. ► Surface was functionalized with amino-silane and used for lipase immobilization. ► Characterized through TEM, SEM, XRD, FT-IR and VSM analysis. ► The functionalization and immobilization did not affect the magnetite properties. ► The immobilized lipase showed greater functional property than free lipase. - Abstract: Superparamagnetic nanoparticles (Fe{sub 3}O{sub 4}–magnetite) were prepared by chemical co-precipitation method and their surface was functionalized with 3-aminopropyltriethoxysilane via silanization reaction to obtain amino functionalized magnetic nanoparticles. The purified lipase from Pseudomonas fluorescens Lp1 was immobilized onto functionalized magnetite using glutaraldehyde as the coupling agent. The characterization of the nanoparticles was done by scanning electron microscopy, transmission electron microscopy, powder X-ray diffraction, vibrating sample magnetometry and Fourier transformed infrared spectroscopy. The size of the magnetite was measured about 10–30 nm. The results of characterization study revealed the successful immobilization of lipase on to functionalized magnetite. The saturation magnetization of magnetic nanoparticles was found to be 28.34 emu/g whereas the immobilized magnetic nanoparticle was 17.074 emu/g. The immobilized lipase had greater activity at 50 °C and thermal stability upto 70 °C. It exhibited excellent reusability for 4 cycles and storage stability upto 15 days by retaining 75% of its initial activity.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Application of a new coordination compound for the preparation of AgI nanoparticles

Graphical abstract: Silver iodide nanoparticles have been sonochemically synthesized by using silver salicylate complex, [Ag(HSal)], as silver precursor. A series of control experiments were carried out to investigate the effects of solvent, surfactant concentration, sonication time and temperature on the morphology of AgI nanostructures. - Highlights: • Silver salicylate as a new precursor was applied to fabricate γ-AgI nanoparticles. • To further decrease the particle size of AgI, SDS was used as surfactant. • The effect of preparation parameters on the particle size of AgI was investigated. - Abstract: AgI nanoparticles have been sonochemically synthesized by using silver salicylate, [Ag(HSal)], as silver precursor. To investigate the effects of solvent, surfactant concentration, sonication time and temperature on the morphology of AgI nanostructures, several experiments were carried out. The products were characterized by SEM, TEM, XRD, TGA/DTA, UV–vis, and FT-IR. Based on the experimental findings in this research, it was found that the size of AgI nanoparticles was dramatically dependent on the silver precursor, sonochemical irradiation, and surfactant concentration. Sodium dodecyl sulfate (SDS) was applied as surfactant. When the concentration of SDS was 0.055 mM, very uniform sphere-like AgI nanoparticles with grain size of about 25–30 nm were obtained. These results indicated that the high concentration of SDS could prevent the aggregation between colloidal nanoparticles due to its steric hindrance effect.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Diffusion mediated agglomeration of CdS nanoparticles via Langmuir–Blodgett technique

Graphical abstract: - Highlights: • Diffusion mediated agglomeration of CdS nanoparticles are discussed. • Formation of CdS nanoparticles are confirmed by the change of chain length in XRD. • AFM shows the agglomeration of particles with a film swelling of about 5 Å. • UV–vis absorbance suggests that the grown particles show quantum confinement. • Hexagonal form of particle was confirmed by UV–vis reflectivity. - Abstract: We have reported a diffusion mediated agglomeration of cadmium sulphide (CdS) nanoparticles within cadmium arachidate (CdA{sub 2}) film matrix. The structural morphology and formation of CdS nanoparticles are characterized by X-ray diffraction (XRD), X-ray reflectivity (XRR), atomic force microscopy (AFM) and ultraviolet-visible spectroscopy techniques. X-ray diffraction (XRD) results show a change in bilayer difference from 53.04 Å to 43 Å after the sulphidation. An epitaxial growth of the films by ∼5 Å after sulphidation is confirmed from atomic force microscopy studies. The particle size calculated form UV–vis absorption edges are found to be varying from 2.6 nm to 3.3 nm for the different layers. A lateral dimension of 72–80 nm from AFM measurements and a size of 2.6–3.3 nm have confirmed one side flat pseudo two-dimensional disk-like nanoparticles. UV–vis reflectivity peak at E{sub 1} (A) confirms the formation of hexagonal CdS nanoparticles along the c-axis.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Cytotoxicity of monodispersed chitosan nanoparticles against the Caco-2 cells

Published toxicology data on chitosan nanoparticles (NP) often lack direct correlation to the in situ size and surface characteristics of the nanoparticles, and the repeated NP assaults as experienced in chronic use. The aim of this paper was to breach these gaps. Chitosan nanoparticles synthesized by spinning disc processing were characterised for size and zeta potential in HBSS and EMEM at pHs 6.0 and 7.4. Cytotoxicity against the Caco-2 cells was evaluated by measuring the changes in intracellular mitochondrial dehydrogenase activity, TEER and sodium fluorescein transport data and cell morphology. Cellular uptake of NP was observed under the confocal microscope. Contrary to established norms, the collective data suggest that the in vitro cytotoxicity of NP against the Caco-2 cells was less influenced by positive surface charges than by the particle size. Particle size was in turn determined by the pH of the medium in which the NP was dispersed, with the mean size ranging from 25 to 333 nm. At exposure concentration of 0.1%, NP of 25 ± 7 nm (zeta potential 5.3 ± 2.8 mV) was internalised by the Caco-2 cells, and the particles were observed to inflict extensive damage to the intracellular organelles. Concurrently, the transport of materials along the paracellular pathway was significantly facilitated. The Caco-2 cells were, however, capable of recovering from such assaults 5 days following NP removal, although a repeat NP exposure was observed to produce similar effects to the 1st exposure, with the cells exhibiting comparable resiliency to the 2nd assault. -- Highlights: ► Chitosan nanoparticles reduced mitochondrial dehydrogenase activity. ► Cellular uptake of chitosan nanoparticles was observed. ► Chitosan nanoparticles inflicted extensive damage to the cell morphology. ► The transport of materials along the paracellular pathway was facilitated.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2025

Impact of SO 2 on NiFe Nanoparticle Exsolution and Dissolution from LaFe 0.9 Ni 0.1 O 3 Perovskite Oxides

Ni-doped LaFeO 3 perovskite oxide is a promising cathode material for solid oxide electrolysis cells (SOECs) designed for CO 2 /H 2 O coelectrolysis. Here, the performance of LaFe 0.9 Ni 0.1 O 3 is being investigated under real-world conditions that include exposure to acid gases, such as SO 2 , relevant to SOEC operation. Experiments show that LaFe 0.9 Ni 0.1 O 3 exsolves NiFe nanoparticles, along with the formation of surface SO 4 2– and SO 3 2– after being exposed to 200 ppm of SO 2 . This suggests that the ionic diffusion of Ni 3+ and Fe 3+ between the bulk and the surface remains unaffected throughout the exsolution–dissolution–exsolution cycle. Thermochemical water splitting has been employed as a probe reaction to evaluate the catalytic properties of the exsolved NiFe nanoparticles. These nanoparticles demonstrated improved hydrogen production compared to bare perovskite oxide substrates. However, after exposure to SO 2 , the formation of Fe-rich NiFe nanoparticles led to poor thermocatalytic performance and rapid deactivation of the perovskite at elevated temperatures. Density functional theory (DFT) analysis was utilized to validate the experimental findings, indicating a significantly negative reaction energy for water splitting over exsolved Fe, as well as stronger binding of SO 2 to Fe than to Ni. Computational analysis further suggests that the presence of surface sulfate promotes the formation of Fe-rich NiFe nanoparticles, aligning with the experimental results. Overall, this study clarifies how SO 2 affects the structure of SOEC perovskite oxide candidate materials. Future engineering efforts should focus on enhancing nanoparticle exsolution and sulfur resistance, which is crucial for improving the hydrogen production capacity of La-based perovskite oxides for electro- and thermocatalytic water splitting in real environments containing acid gases.

Najimu, Musa [Univ. of Southern California, Los An↗
DOE OSTI2015

Influence of Sulfide Nanoparticles on Dissolved Mercury and Zinc Quantification by Diffusive Gradient in Thin-Film Passive Samplers

Diffusive gradient in thin-film (DGT) passive samplers are frequently used to monitor the concentrations of metals such as mercury and zinc in sediments and other aquatic environments. The application of these samplers generally presumes that they quantify only the dissolved fraction and not particle-bound metal species that are too large to migrate into the sampler. However, metals associated with very small nanoparticles (smaller than the pore size of DGT samplers) can be abundant in certain environments, yet the implications of these nanoparticles for DGT measurements are unclear. The objective of this study was to determine how the performance of the DGT sampler is affected by the presence of nanoparticulate species of Hg and Zn. DGT samplers were exposed to solutions containing known amounts of dissolved Hg(II) and nanoparticulate HgS (or dissolved Zn(II) and nanoparticulate ZnS). The amounts of Hg and Zn accumulated onto the DGT samplers were quantified over hours to days, and the rates of diffusion of the dissolved metal (i.e., the effective diffusion coefficient D) into the sampler’s diffusion layer were calculated and compared for solutions containing varying concentrations of nanoparticles. The results suggested that the nanoparticles deposited on the surface of the samplers might have acted as sorbents, slowing the migration of the dissolved species into the samplers. The consequence was that the DGT sampler data underestimated the dissolved metal concentration in the solution. In addition, X-ray absorption spectroscopy was employed to determine the speciation of the Hg accumulated on the sampler binding layer, and the results indicated that HgS nanoparticles did not appear to directly contribute to the DGT measurement. Overall, our findings suggest that the deployment of DGT samplers in settings where nanoparticles are relevant (e.g., sediments) may result in DGT data that incorrectly estimated the dissolved metal concentrations. Models for metal uptake into the sampler may need to be reconsidered.

54 ENVIRONMENTAL SCIENCES↗