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At least 847 records · Page 47

Scalable thin graphene oxide membranes enabled by polydopamine gutter layer

Two-dimensional (2D) nanosheets have been widely used to fabricate thin-film composite membranes for dye desalination. However, they often need to be thick to mitigate the defects resulting from their random stacking and rough support surface. Herein, bio-adhesive polydopamine (PDA) is used as a gutter layer to prepare graphene oxide (GO)-based membranes by improving the adhesion between the GO and porous support and providing a smooth surface to form thin, highly selective layers. For example, the PDA priming reduces the GO layer thickness by 57 %, from 447 to 190 nm, while achieving similar dye desalination properties. The effect of the dopamine concentration, exposure time, and GO layer thickness on the membrane structure and desalination performance are thoroughly investigated using various techniques, such as scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS), and x-ray diffraction (XRD). The PDA gutter layer is also applied for hollow fiber membranes, achieving water permeance of 79 L m -2 h −1 bar−1 and rejection of ∼99 % for Direct red 80. The membranes were challenged by simulated dye/salt mixtures to elucidate the complicated effect of the compositions on the desalination performance. Furthermore, this study unveils a new avenue to improve separation performance and large-scale manufacturability of 2D material-based membranes.

Dye desalination↗

Iridium-cobalt oxide synthesized via surfactant-assisted Adams fusion for efficient oxygen evolution in acidic and alkaline media

A series of iridium-cobalt (Ir-Co) oxide catalysts were synthesized using a modified surfactant-assisted Adams fusion method and evaluated for the oxygen evolution reaction (OER) in both acidic and alkaline media. The effect of varying the Ir/Co ratio was systematically studied and compared with commercial Ir black and pure IrO 2 samples. The actual elemental ratios were quantified using X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDS), and inductively coupled plasma-mass spectrometry (ICP-MS). Among the synthesized samples, the Ir 6 Co 4 catalyst exhibited the best performance in acidic media, achieving an iR-corrected overpotential of 292 mV. In alkaline conditions, it demonstrated comparable activity to Ir black, with an iR-corrected overpotential of 263 mV. XPS and electron energy loss spectroscopy analyses revealed that increasing Co content led to a higher fraction of metallic Ir (Ir 0 ) in the catalyst. In addition, the role of Ir 3+ in enhancing OER activity was explored. A strong correlation was observed between higher Ir 3+ content and improved OER performance in acidic conditions.

Adams fusion↗

Effects of pH on potassium sulfite based alkali pretreatment of corn stover under mild conditions

Sulfite salt-based alkali pretreatment is increasingly recognized as an effective method for biomass pretreatment under mild temperature conditions. However, the effects of pH on the pretreatment process are not yet fully understood. In this study, the pretreatment of corn stover using potassium sulfite (KS) combined with aqueous ammonia (AA) at 80 °C was investigated within a pH range of 9–14. Results demonstrated that high pH environment established by combining KS with AA is critical for enhancing sulfonation modifications, effectively removing lignin, facilitating deacetylation, and significantly improving the total sugar yield. For example, when comparing KS alone at pH 9.7, AA alone at pH 13, and KS combined with AA at pH 13, the delignification rates were 13.82 %, 67.71 %, and 71.27 %, respectively; the deacetylation rates were 25.84 %, 81.19 %, and 82.54 %, respectively; and the total sugar yields were 24.85 %, 78.96 %, and 92.12 %, respectively. The X-ray photoelectron spectroscopy (XPS) results confirmed that sulfonation reactions occurred under low-temperature and high pH conditions, leading to enhanced delignification efficiency. Results also showed that the cellulase adsorption, water retention, and the enzymatic digestibility of the pretreated solids increased along with rising pH. Moreover, nuclear magnetic resonance (NMR) analysis revealed that KS-based alkali pretreatment retained more β-O-4 native bonds in the pretreated lignin-rich hydrolysate than alkali pretreatment alone did, providing promising opportunities for the subsequent upgrading of lignin into high-value products.

09 BIOMASS FUELS↗

Effect of dilute Rh on oxygen dissociation, spillover, and the oxidation of Cu across many orders of magnitude pressure

Knowledge of how trace amounts of more reactive metals influence the oxidation rate and mechanism of Cu surfaces is essential for developing strategies to optimize the performance of Cu-based catalysts. We find that the addition of 1% Rh to Cu(111) increases the initial O 2 dissociation rate by approximately 9-fold. CO poisoning experiments reveal that single Rh atoms activate O 2 and facilitate the spillover of atomic oxygen to Cu sites. Scanning tunneling microscopy (STM) and in situ X-ray photoelectron spectroscopy (XPS) support this mechanism, showing enhanced surface oxygen near Rh atoms. Here, a density functional theory (DFT)-based model demonstrates that Rh binds the O 2 precursor 0.15 eV more strongly than Cu(111) and lowers the O 2 dissociation barrier by 0.02 eV. Both single-crystal and nanoparticle experiments show that at low oxygen pressures, Rh enhances Cu oxidation, whereas at higher pressures, it inhibits deeper oxidation, as evidenced by in situ ultraviolet-visible (UV-vis) spectra.

36 MATERIALS SCIENCE↗

Mineral-specific heterogeneous neptunium sorption onto geological repository rocks in oxic and anoxic conditions and various temperatures

Neptunium poses challenges for radioactive wastes management due to its long half-life and ingrowth from americium decay, as well as its high mobility in water in its oxidized forms. Np(V)-bearing aqueous solutions were contacted with polished and crushed gneiss and dolerite from the Yeniseisky site, Russia, which is under consideration as a location for an underground repository, both in oxic and anoxic conditions at 20 and 90 °C. Neptunium sorption on crushed gneiss and dolerite in oxic conditions at 20 °C was quite low, but increased substantially in anoxic conditions. Autoradiography on samples treated at 20 °C revealed that sorbed Np was associated mostly with dark colored iron-bearing minerals, and solvent extraction indicated partial reduction of Np(V) to Np(IV). Sorption of Np from aqueous solutions contacted with dolerite and gneiss at 90 °C was in all cases higher than at the lower temperature. Autoradiography of polished rock samples treated in anoxic conditions at 90 °C revealed that Fe-bearing minerals had 3–4 orders of magnitude more Np sorbed on them than the quartz and feldspar grains. X-ray photoelectron spectroscopy indicated this sorbed Np was present as NpO 2 . This study supports the concept that the geologic conditions present at the planned repository site will retard Np migration.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Effects of Co doping on the structure and physicochemical properties of hausmannite (Mn 3 O 4 ) and its transformation during aging

Hausmannite is a common low-valence manganese oxide mineral with a distorted spinel structure in surficial sediments. Although natural Mn oxides often contain various transition metal (TM) impurities, few studies have addressed the substitution mechanisms of TMs, such as cobalt (Co), with hausmannite and induced changes in the mineral physicochemical properties. In this study, Co-doped hausmannites with final Co/Mn molar ratios of 0.05 and 0.11 were synthesized and characterized by wet chemical analysis, powder X-ray diffraction (XRD), Fourier transformed infrared spectra (FTIR), high resolution transmission electron microscope (HRTEM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure spectroscopy (XAFS). Co-doped samples have larger crystallite sizes and smaller specific surface areas than those of the hausmannite without Co. The Co cations exist in a mixed-valence of +3 and + 2. Powder XRD and acid dissolution experiments indicate that Co incorporates into the mineral structures, and increases the mineral structural stability. Co K-edge extended X-ray adsorption fine structure (EXAFS) analysis demonstrates that Co likely substitutes for lattice Mn(III). After aging at room temperature for three years, 14.1 ± 1.9% of pure hausmannite is transformed to manganite while only 2.6 ± 0.7% of manganite appears in the aged Co-doped sample with an initial Co/Mn molar ratio of 0.10. Finally, these results provide new insights into the incorporation mechanisms of TMs into low valence Mn oxides, and the stability of these minerals in natural environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Propane Dehydrogenation on Single-Site [PtZn4] Intermetallic Catalysts

Propane dehydrogenation (PDH) is a commercial propylene production technology that has received much attention, but high reaction temperature results in decrease of propylene selectivity and catalyst stability. This paper describes a single-site [PtZn 4 ] catalyst by assembling atomically ordered intermetallic alloy (IMA) as a selective and ultrastable PDH catalyst. The catalyst enables more than 95% propylene selectivity from 520 to 620 oC. No obvious deactivation is observed within 160-hours test, superior to PtSn/Al 2 O 3 and state-of-the-art Pt-based catalysts. Additionally, based on in situ X-ray absorption fine-structure, X-ray photoelectron spectroscopy measurements and density functional theory calculations, we reveal that the surface [PtZn 4 ] ensembles in PtZn IMAs serve as the key active site structures, wherein the geometry-isolated and electron-rich Pt1 site in [PtZn 4 ] ensembles readily promotes the first and second C–H cleavage of propane, but inhibits further dehydrogenation of surface-bounded propylene. This significantly improves the selectivity and stability by prohibiting coke side reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of plasma treatment on LMPAEK/CF tape and composites manufactured by automated tape placement (ATP)

Automated tape placement (ATP) process is widely used in aerospace for its advanced process control and multi-axis capabilities but faces issues like limited choice of materials and suboptimal tape consolidation. This study investigates air plasma treatment on ATP carbon fiber thermoplastic feedstock tape to address these challenges. The effects on low melt Polyaryletherketone/carbon fiber unidirectional tape (LMPAEK/CF UD tape) were analyzed. Treated and untreated tapes were used to fabricate composites and evaluated for physical, thermal, mechanical, and interfacial properties. Atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) analyses revealed surface roughness changes (on LMPAEK), extent of oxidation, and the presence of hydroxyl/carboxyl groups. Composites from plasma-treated tapes showed a 7.6% increase in tensile strength, 8% in tensile modulus, 18% in flexural strength, and 8.3% in flexural modulus. Further, the interlaminar shear strength improved by 18.7%. Failure analysis showed untreated composites failed via inter-ply and fiber-matrix delamination, while treated composites experienced matrix cracking and fiber breakage. This study highlights atmospheric plasma treatment as a solution to ATP’s limitations, significantly enhancing LMPAEK/CF UD tape composites’ properties.

36 MATERIALS SCIENCE↗

Assessment of DFT methods for the prediction of detachment energies and electronic structures of complex and multiply charged anions

Here, in this work, we assess the ability of different density functional theory methods to reproduce the vertical/adiabatic detachment energies (VDEs/ADEs) of a series of 40 anions, including monoanion versus multiply charged anions (MCAs) and covalent versus noncovalent interaction. The statistical analysis of errors is firstly performed by comparing the theoretical values with the experimental benchmark data obtained from the negative ion photoelectron spectroscopy (NIPES). The proposed optimally tuned range-separated (OTRS) functionals are proved to not only well reproduce the experimental VDEs/ADEs, but also simulate experimental NIPES. The result implies a more serious issue of delocalization error for MCAs and a balanced description of electron-rich/- deficient region of anions is necessary. The radius of the spherically symmetric average electron localization function (ELF) region is demonstrated as a useful descriptor for the characterization of electronic structure of anionic systems and a quasilinear fitting model is proposed to efficiently obtain their OTRS parameters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical stability, physical, and electronic properties of thermally pre-formed oxide compared to artificially sputtered oxide on Fe thin films in aqueous chloride

Here the electrochemical stability and corrosion behavior of the thermally pre-oxidized and sputter deposited variant of an oxide single-crystalline Fe thin film were compared. Thermal oxides formed Fe 2 O 3 over an inner layer of Fe 3 O 4 while the sputtered oxides were found to have grown Fe 3 O 4 instead of the target stoichiometry of Fe 2 O 3 . Oxide films of both types were stable in pH=9.3 borate buffer solution, however, were altered in pH=9.3, 0.1 M NaCl solution in the case of thermally pre-oxidized Fe thin film. The stability of the oxide differed in pH=4, 0.1 M NaCl where sputtered Fe films were more stable against acidic chemical dissolution than the thermally formed Fe oxide film. These differences were traced by AC/DC electrochemical analysis including electronic defect densities, and molecular identity characterized by ex-situ X-ray photoelectron spectroscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The interaction of acetonitrile with H-terminated and depassivated (100) diamond surfaces

Molecular adsorption on reactive semiconductor surfaces may enable novel surface functionalisation and atomically-precise dopant formation. In this work synchrotron-based x-ray photoelectron spectroscopy and near edge x-ray absorption spectroscopy are used to examine the interaction between acetonitrile and diamond (100) surfaces under ultrahigh vacuum (UHV) conditions. We observe two surface-bound nitrogen species on hydrogen terminated surfaces after thermal depassivation or following synchrotron radiation and subsequent exposure to acetonitrile, but find no evidence of nitrogen adsorption on the hydrogen-terminated diamond surface, at room temperature. Subsequent measurements explore the stability of the surface-bound nitrogen under various temperature conditions and with atmospheric exposure. While the nitrogen coverage achieved in this study is low, this study serves as a proof-of-concept demonstration of a UHV molecular dosing approach to selective nitrogen functionalisation of diamond surfaces as an alternative to plasma-based approaches. This development may be critical for proposed surface-based fabrication workflows using atomic placement of nitrogen-vacancy centres to create quantum devices.

74 ATOMIC AND MOLECULAR PHYSICS↗

Investigating the durability of a direct methanol fuel cell equipped with commercial Platinum Group Metal-free cathodic electro-catalysts

For the first time a long-term (500 h) durability study in direct methanol fuel cells (DMFCs) is carried out on a Platinum Group Metal-free (PGM-free) cathodic electro-catalyst commercially available on market. The electro-catalyst is tested for 500 h at a fixed cell voltage (0.3 V), recording the polarization curves during the operation. A drastic decrease in performance is observed after the first 100 h (from 220 to 75 mA cm –2 ); afterwards, the decrease is flatter, passing from 75 to 25 mA cm –2 (at 500 h). The causes of this performance degradation are investigated by postmortem physicochemical analyzes, such as X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) with X-ray energy dispersive analysis (EDX). Finally, possible reasons of degradation are indicated to be PGM-free catalyst aggregation, carbon and nitrogen species decrease, Ruthenium dissolution and migration from the anode to the cathode, poisoning both membrane and cathode catalyst.

25 ENERGY STORAGE↗

Electrodeposition of near-equiatomic CoCuFeNi multi-principal element alloys from an acidic glycine-citrate-triton X100 aqueous electrolyte

Understanding the composition and morphology control of electrodeposited CoCuFeNi is the first step to finding a general strategy for developing electrodeposition processes of unconventional alloys with large redox potential differences and complicated deposition mechanisms. Here, in this work, we have successfully synthesized the near-equiatomic (<5 at% error) CoCuFeNi films with ~200nm thickness by electrodeposition from glycine-citrate-Triton X-100 acidic electrolytes. This system generally follows the Principle II in Brenner’s paradigm on alloy composition control in electrodeposition. X-ray diffraction (XRD) profiles show that the films only consist of one crystalline phase, different from the deposit from ammonia-citrate-boric acid electrolytes and the equilibrium phases predicted by CALPHAD. The near-equiatomic deposits at Ru substrates were successfully annealed at 400 ° C without significant intermixing between the substrate and the deposit, in which no phase separation of the crystalline phase was observed in its XRD profile. Xray photoelectron spectroscopy (XPS) reveals that some depositing elements (mainly Fe) exist as metal oxides. Cu is dissolved in the crystalline phases, stabilized by small crystalline domain size and the amorphous metal oxides inside the CoCuFeNi deposits.

CoCuFeNi↗

The X-ray emission of cerium oxide

Using a combination of spectral simulation with FEFF and experimental data for metallic Ce, it has been possible to extract the Cerium Oxide-only M 4,5 X-ray Emission Spectrum (XES) from an experimental result, which had been produced utilizing a combined CeOxide/Ce sample. In this paper, it is shown that the XES emission for CeOxide-only is significantly different for the M 4 and M 5 edges, with the M 4 XES consistent with normal XES and the M 5 XES exhibiting a continued enhancement associated with a threshold effect, connected to Resonant Inverse Photoelectron Spectroscopy (RIPES).

36 MATERIALS SCIENCE↗

Freestanding vanadium nitride nanowire membrane as an efficient, carbon-free gas diffusion cathode for Li–CO 2 batteries

A freestanding vanadium nitride nanowire (VN-NW) membrane is employed as a carbon-free gas diffusion cathode (GDC) for high-performance Li–CO 2 batteries. Li–CO 2 cells built with the VN-NW GDC exhibit excellent electrochemical performance, achieving 100 discharge/charge cycles with an ultralow round-trip overpotential of <1 V. The VN-NW GDC also delivers vastly improved capacity and rate capability compared to a conventional multiwalled carbon nanotube GDC. The morphology of the discharge products (Li 2 CO 3 + C) is greatly improved with the VN-NW GDC compared to the carbon-based cathode, allowing for facile decomposition on charge. Furthermore, the absence of carbon in the VN-NW GDC allows for easy characterization of the discharge products with a variety of techniques, including transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The impressive performance of the hierarchically structured VN-NW GDC in Li–CO 2 batteries justifies further investigation into noble metal-free and carbon-free materials for gas diffusion cathodes.

25 ENERGY STORAGE↗

Effect of Si/Al ratio of ZSM-5 support on structure and activity of Mo species in methane dehydroaromatization

The effect of the Si/Al ratio of the ZSM-5 support on the structure and activity of Mo/HZSM-5 catalysts in methane dehydroaromatization (MDA) was studied. ZSM-5 (with Si/Al = 15, 25, and 40) supported Mo oxide catalysts (MoOx/ZSM-5) with 3 and 10 wt% Mo loading were prepared by incipient wetness impregnation followed by calcination in air at 500 °C. The as-prepared catalysts were activated by temperature programmed reduction in hydrogen in order to maximize Mo dispersion. To understand the structure-activity relationship, the fresh and spent samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 adsorption isotherms, Scanning Transmission Electron Microscopy with Energy Dispersive X-Ray Spectroscopy (STEM-EDS), X-ray absorption spectroscopy (EXAFS and XANES), thermogravimetric analysis (TGA), and Raman spectroscopy. The results show that the Si/Al ratio does not influence the the local structure around the Mo centers. It does however affect the number of available Brønsted acid sites in the support and the amount of Mo species entering the zeolite channels. A lower Si/Al ratio and higher Mo loading resulted in a higher Mo occupation within the zeolite channels. The higher channel occupation directly correlated with higher benzene selectivity and yield, as well as a lower catalyst deactivation rate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In situ characterization of phase transformations in petroleum pitch by high temperature X-ray diffraction

The phase transformation from isotropic to mesophase of a petroleum-derived pitch was monitored by in situ X-ray diffraction at 410 °C. The kinetics of the transformation were characterized by monitoring the growth of a broad peak at 2θ~24° and could be described by Avrami’s equation. The volatilization of low molecular weight components originally present in the pitch, or produced during the condensation reaction, was assessed by thermal gravimetry analysis, following the same thermal history. Ex situ characterizations of the pitch precursor before and after thermal treatment provided insight into the evolution of the molecular structure associated with mesophase generation (optical polarized microscopy, molecular weight distribution by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, X-ray photoelectron spectroscopy, Auger spectroscopy, and thermal stability). Here, this investigation demonstrates the value of using complementary in situ and ex situ experimental techniques to characterize complex mechanisms during the processing of organic materials.

02 PETROLEUM↗

Reduction of uranyl and uranyl-organic complexes mediated by magnetite and ilmenite: A combined electrochemical AFM and DFT study

Reduction of mobile aqueous uranyl complexes can be hindered by the strength of the uranyl-ligand complex and the resistivity of the complexes to electron transfer. Semiconducting solids, such as magnetite (Fe 3 O 4 ) and ilmenite (FeTiO 3 ), can facilitate otherwise-slow electron transfer between the reductant and oxidant, especially if these species are adsorbed on their surfaces as inner-sphere complexes. Electrons can then be shuttled through the surface or the structure. This process can be facilitated by either finding a new electron transfer path or by weakening or destroying the ligand-uranyl complex. Using in situ electrochemical atomic force microscopy (EC-AFM), we imaged reduction products of uranyl as mediated by magnetite and ilmenite in the absence or presence of the organic ligands, ethylenediaminetetraacetate (EDTA) and oxalate. In situ images of uranyl reduction show gradual nucleation and growth of reduced uranium on the mineral surfaces with decreasing reduction potentials. X-ray photoelectron spectroscopy (XPS) measurements indicate pentavalent uranium as the dominant uranium species resulting from uranyl reduction mediated by magnetite and ilmenite. The reduction potentials of uranyl-organic species relevant to our reaction system, (U VI O 2 ∙oxalate) 0 and (U VI O 2 ∙HEDTA) - , are derived using quantum–mechanical modeling and compared with the midpoint potentials obtained from cyclic voltammetry measurements. The spectroscopic, electrochemical, and computational data suggest that the catalysis of Fe-bearing minerals facilitates the reduction of uranyl-organic complexes. U(VI)-oxalate complexes are redox-active and participate directly in the reduction mediated by magnetite. In the presence of EDTA, reduction of uranyl may proceed in concert with ligand exchange between metals (i.e., U and Fe) on the mineral surface. Finally, the proposed mechanism is the breaking of uranyl-organic bonds upon interaction with the mineral surface followed by the formation of Fe-organic bonds, thereby allowing the reduction of hexavalent uranyl to pentavalent one.

58 GEOSCIENCES↗