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At least 1,675 records · Page 93
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Effect of surface strain on oxygen adsorption on Zr (0001) surface

The effect of surface strain on oxygen adsorption on Zr (0 0 0 1) surface is investigated by density functional theory (DFT) calculations. It is demonstrated that both surface strain and interactions between oxygen adsorbates influence the adsorption process. Oxygen binding to zirconium becomes stronger as the strain changes from compressive to tensile. When oxygen coverage is low and the oxygen interactions are negligible, surface face-centered cubic sites are the most stable for O binding. At high coverage and under compression, octahedral sites between second and third Zr layers become most favorable because the interactions between adsorbates are weakened by positive charge screening. Calculations with both single-layer adsorption model and multiple-layer adsorption model demonstrate that compressive strain at the Zr/oxide interface will provide a thermodynamic driving force for oxygen to incorporate from the surface into the bulk of Zr, while binding oxygen to the Zr surface will be easier when tensile strain is applied.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Analysis of hydrogen adsorption and surface binding configuration on tungsten using direct recoil spectrometry

In our work, we apply low energy ion beam analysis to examine directly how the adsorbed hydrogen concentration and binding configuration on W(1 0 0) depend on temperature. We exposed the tungsten surface to fluxes of both atomic and molecular H and D. We then probed the H isotopes adsorbed along different crystal directions using 1–2 keV Ne + ions. At saturation coverage, H occupies two-fold bridge sites on W(1 0 0) at 25 °C. Moreover, the H coverage dramatically changes the behavior of channeled ions, as does reconstruction of the surface W atoms. For the exposure conditions examined here, we find that surface sites remain populated with H until the surface temperature reaches 200 °C. Then, we observe H rapidly desorbing until only a residual concentration remains at 450 °C. Development of an efficient atomistic model that accurately reproduces the experimental ion energy spectra and azimuthal variation of recoiled H is underway.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2019

First-principles study of the surface properties of y-LiAlO2: Stability and tritium adsorption

y-LiAlO2 enriched with 6Li isotope exhibits excellent performance under neutron radiation and is used in tritium-producing burnable absorber rods (TPBARs) to produce tritium (T, 3H) in pressurized water reactor (PWR). To better understand the 3H formation and diffusion on the surfaces, the first-principles calculations are performed to study the stability of y-LiAlO2 surface and the 3H adsorption on the surface. By considering all possible symmetrical stoichiometric and nonstoichiometric low-index surfaces, two most stable surfaces, one stoichiometric (100) and one nonstoichiometric (101), were identified. The 3H adsorption and diffusion on the most stable (100) surface were further explored, and the obtained results show that there are four stable sites (three O and one Al atop) for 3H adsorption. The calculated Bader charges of atoms reflect that 3H adsorption on the top of O site is a reduction process, while on the top of Al site is an oxidation one. Under low adsorption coverage of 1/4 per surface unit cell, 3H atoms are adsorbed on the most stable OA atop site. With increasing 3H diffused from bulk to surface, the AlG site is the second choice for 3H adsorption, and then the OB site. The coverage of 2/4 is the most favorable 3H adsorption state due to the counteracted charge transfer. When the coverage is up to 4/4, the interaction between 3H atoms leads to partial formation of T2 molecule that desorbs from surface. Therefore, T2 molecule should be the main product from the perfect surface of y-LiAlO2 at high 3H coverage.

Stability of y-LiAlO2 surface, Tritium-producing b↗
DOE OSTI2017

Self-assembled Li 3 V 2 (PO 4 ) 3 /reduced graphene oxide multilayer composite prepared by sequential adsorption

Here in this paper, we report on Li 3 V 2 (PO 4 ) 3 (LVP)/reduced graphene oxide (rGO) multilayer composites prepared via a sequential adsorption method and subsequent heat treatment, and their use as cathodes for high-rate lithium-ion batteries. The sequential adsorption process includes adsorbing oppositely charged components of anionic inorganic species and cationic head of a surfactant adsorbed to graphite oxide sheets, which is a key step in the fabrication of the LVP/rGO multilayer composites. The multilayer structure has open channels between the highly conductive rGO layers while achieving a relatively high tap density, which could effectively improve the rate capability. Consequently, the LVP/rGO multilayer composites exhibit a high tap density (0.6 g cm -3 ) and good electrochemical properties. Specifically, in the voltage range of 3.0–4.3 V, the composite exhibits a specific capacity of 131 mAh g -1 at 0.1C, a good rate capabilities (88% capacity retention at 60C), and long cycling performance (97% capacity retention after 500 cycles at 10C). Moreover, in the extended voltage range of 3.0–4.8 V, it exhibits a high specific capacity of 185 mAh g -1 at 0.2C, a good rate capability (66% capacity retention at 30C), and stable cycling performance (96% capacity retention after 500 cycles at 10C).

25 ENERGY STORAGE↗
DOE OSTI2012

Membrane contactor/separator for an advanced ozone membrane reactor for treatment of recalcitrant organic pollutants in water

An advanced ozone membrane reactor that synergistically combines membrane distributor for ozone gas, membrane contactor for pollutant adsorption and reaction, and membrane separator for clean water production is described. The membrane reactor represents an order of magnitude improvement over traditional semibatch reactor design and is capable of complete conversion of recalcitrant endocrine disrupting compounds (EDCs) in water at less than three minutes residence time. Coating the membrane contactor with alumina and hydrotalcite (Mg/Al=3) adsorbs and traps the organics in the reaction zone resulting in 30% increase of total organic carbon (TOC) removal. Large surface area coating that diffuses surface charges from adsorbed polar organic molecules is preferred as it reduces membrane polarization that is detrimental to separation. - Graphical abstract: Advanced ozone membrane reactor synergistically combines membrane distributor for ozone, membrane contactor for sorption and reaction and membrane separator for clean water production to achieve an order of magnitude enhancement in treatment performance compared to traditional ozone reactor. Highlights: Black-Right-Pointing-Pointer Novel reactor using membranes for ozone distributor, reaction contactor and water separator. Black-Right-Pointing-Pointer Designed to achieve an order of magnitude enhancement over traditional reactor. Black-Right-Pointing-Pointer Al{sub 2}O{sub 3} and hydrotalcite coatings capture and trap pollutants giving additional 30% TOC removal. Black-Right-Pointing-Pointer High surface area coating prevents polarization and improves membrane separation and life.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

First-principles study of hydrogen storage on Ti-decorated B{sub 2}C sheet

The hydrogen storage capacity of Ti decorated B{sub 2}C sheet has been investigated by first-principles plane-wave calculation. It is revealed that a single Ti atom adsorbed on the B{sub 2}C sheet can strongly bind up to four hydrogen molecules. The adsorption energy is in the range of -0.36--0.82 eV/H{sub 2}, which is suitable for ambient temperature hydrogen storage. Considering the fact that Ti can be loaded on both sides of B{sub 2}C sheet, corresponding gravimetric storage capacity of Ti/B{sub 2}C system was also calculated and it can reach to about 7.0 wt%, exceeding the minimum requirement of 6.0 wt% for applications. - Graphical abstract: We investigated the hydrogen storage capacity of Ti decorated B{sub 2}C sheet. The most favorable adsorption geometries for every number of hydrogen molecules on Ti/B{sub 2}C complex are given in the figure. Highlights: Black-Right-Pointing-Pointer Ti decorated B{sub 2}C sheet serve as hydrogen storage medium. Black-Right-Pointing-Pointer A single Ti atom adsorbed on the B{sub 2}C sheet can strongly bind up to four hydrogen molecules. Black-Right-Pointing-Pointer The adsorption energy is in moderate range of -0.36--0.82 eV/H{sub 2}.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Hexagonal phase WO{sub 3} nanorods: Hydrothermal preparation, formation mechanism and its photocatalytic O{sub 2} production under visible-light irradiation

WO{sub 3} with various morphologies and crystal phases were prepared via a hydrothermal process in the presence of different Na{sub 2}SO{sub 4} concentrations. Experimental results indicated that the preferred growth face ((200) crystal plane) of hexagonal WO{sub 3} could adsorb abundant Na{sup +}, which induced the WO{sub 3} growing along [001] crystal direction to form nanorods, and hexagonal phase WO{sub 3} nanorods with diameter of 30-150 nm and length of 0.5-5 {mu}m were obtained in the presence of 0.25 M Na{sub 2}SO{sub 4}, while excessive Na{sub 2}SO{sub 4} led to a mixed crystal consisting of cubic H{sub 2}W{sub 2}O{sub 7} and hexagonal WO{sub 3}. The photoactivities for O{sub 2} evolution for various products were investigated by using Fe(NO{sub 3}){sub 3} as a sacrificial reagent under visible-light irradiation, and the hexagonal phase WO{sub 3} nanorods show a better photoactivity than the other products with different morphologies and crystal phases due to its fast three-dimensional photogenerated carrier transfer along its special rod-shaped structure. - Graphical abstract: As a preferred growth plane, (200) plane of h-WO{sub 3} can adsorb abundant of Na{sup +}, which induces the WO{sub 3} growing along [001] direction to form nanorods with high length-diameter ratio. Highlights: Black-Right-Pointing-Pointer WO{sub 3} with various morphologies were hydrothermally prepared. Black-Right-Pointing-Pointer Hexagonal WO{sub 3} nanorods with diameter of 30-150 nm can be obtained from 0.25 M Na{sub 2}SO{sub 4} solution. Black-Right-Pointing-Pointer Hexagonal WO{sub 3} nanorods show a better photoactivity than the other products. Black-Right-Pointing-Pointer The good photoactivity can be due to its fast carrier transfer along its rod-shaped structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Mechanism for high hydrogen storage capacity on metal-coated carbon nanotubes: A first principle analysis

The hydrogen adsorption and binding mechanism on metals (Ca, Sc, Ti and V) decorated single walled carbon nanotubes (SWCNTs) are investigated using first principle calculations. Our results show that those metals coated on SWCNTs can uptake over 8 wt% hydrogen molecules with binding energy range -0.2--0.6 eV, promising potential high density hydrogen storage material. The binding mechanism is originated from the electrostatic Coulomb attraction, which is induced by the electric field due to the charge transfer from metal 4s to 3d. Moreover, we found that the interaction between the H{sub 2}-H{sub 2} further lowers the binding energy. - Graphical abstract: Five hydrogen molecules bound to individual Ca decorated (8, 0) SWCNT : a potential hydrogen-storage material. Highlights: Black-Right-Pointing-Pointer Each transition metal atom can adsorb more than four hydrogen molecules. Black-Right-Pointing-Pointer The interation between metal and hydrogen molecule is electrostatic coulomb attraction. Black-Right-Pointing-Pointer The electric field is induced by the charge transfer from metal 4s to metal 3d. Black-Right-Pointing-Pointer The adsorbed hydrogen molecules which form supermolecule can further lower the binding energy.

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

Calcium-decorated graphyne nanotubes as promising hydrogen storage media: A first-principles study

First principles calculations based on density functional theory are carried out to study the hydrogen storage properties of Ca-decorated graphyne nanotubes. The results show that Ca atoms can be adsorbed stably on the acetylenic ring of the graphyne nanotube (GNT) without Ca atom clustering. Both the polar interactions and the orbital hybridizations contribute to the adsorption of H{sub 2} molecules. The average adsorption energy is in the range of 0.13-0.33 eV/H{sub 2} which is almost independent of the tube diameter. Each Ca atom can adsorb up to four H{sub 2} molecules due to the steric hindrance of the H{sub 2} molecules. With a hydrogen uptake of 7.44-8.96 wt%, the Ca-decorated GNT is an optimal choice for hydrogen recycling at near ambient conditions. - Graphical abstract: 2D contour of charge density of Ca decorated GNT2 and the side view of Ca decorated GNT2 with full loaded H{sub 2} molecules. Highlights: Black-Right-Pointing-Pointer Ca decorated graphyne nanotubes as hydrogen storage media. Black-Right-Pointing-Pointer The gravimetric density of H{sub 2} is 7.44-8.96 wt%. Black-Right-Pointing-Pointer The average adsorption energy of hydrogen molecule is 0.13-0.33 eV/H{sub 2}. Black-Right-Pointing-Pointer It can operate under ambient thermodynamic conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Controlled release of ibuprofen by meso–macroporous silica

Structured meso–macroporous silica was successfully synthesized from an O/W emulsion using decane as a dispersed phase. Sodium silicate solution, which acts as a silica source and a poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (EO{sub 19}PO{sub 39}EO{sub 19}) denoted as P84 was used in order to stabilize the emulsion and as a mesopore template. The materials obtained were characterized through transmission electron microscopy (TEM), scanning electron microscopy (SEM), small-angle X-ray diffraction scattering (SAXS) and nitrogen adsorption–desorption isotherms. Ibuprofen (IBU) was selected as the model drug and loaded into ordered meso–macroporous materials. The effect of the materials’ properties on IBU drug loading and release was studied. The results showed that the loading of IBU increases as the macropore presence in the material is increased. The IBU adsorption process followed the Langmuir adsorption isotherm. A two-step release process, consisting of an initial fast release and then a slower release was observed. Macropores enhanced the adsorption capacity of the material; this was probably due to the fact that they allowed the drug to access internal pores. When only mesopores were present, ibuprofen was probably adsorbed on the mesopores close to the surface. Moreover, the more macropore present in the material, the slower the release behaviour observed, as the ibuprofen adsorbed in the internal pores had to diffuse along the macropore channels up to the surface of the material. The material obtained from a highly concentrated emulsion was functionalized with amino groups using two methods, the post-grafting mechanism and the co-condensation mechanism. Both routes improve IBU adsorption in the material and show good behaviour as a controlled drug delivery system. - Graphical abstract: Ibuprofen release profiles for the materials obtained from samples P84{sub m}eso (black diamonds), P84{sub 2}0% (white squares), P84{sub 5}0% (black triangles), P84{sub 7}5% (white diamonds), P84{sub 7}5% functionalized by grafting (black squares) and P84{sub 7}5% functionalized by co-condensation method (white triangles). Display Omitted - Highlights: • Ordered meso–macroporous material is used as a controlled delivery system for ibuprofen. • Incorporation of macropores in mesoporous silica improves ibuprofen adsorption. • Meso–macroporous structures provide a lower delivery than mesoporous silica. • APTES functionalization in meso–macroporous materials improves ibuprofen adsorption and delivery behaviour.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

The role of SO{sub 4}{sup 2−} surface distribution in arsenic removal by iron oxy-hydroxides

This study investigates the contribution of chemisorbed SO{sub 4}{sup 2−} in improving arsenic removal properties of iron oxy-hydroxides through an ion-exchange mechanism. An analytical methodology was developed for the accurate quantification of sulfate ion (SO{sub 4}{sup 2−}) distribution onto the surface and structural compartments of iron oxy-hydroxides synthesized by FeSO{sub 4} precipitation. The procedure is based on the sequential determination of SO{sub 4}{sup 2−} presence in the diffuse and Stern layers, and the structure of these materials as defined by the sulfate-rich environments during the reaction and the variation in acidity (pH 3–12). Physically sorbed SO{sub 4}{sup 2−}, extracted in distilled water, and physically/chemically adsorbed ions on the oxy-hydroxide's surface leached by a 5 mM NaOH solution, were determined using ion chromatography. Total sulfate content was gravimetrically measured by precipitation as BaSO{sub 4}. To validate the suggested method, results were verified by X-ray photoelectron and Fourier-transformed infrared spectroscopy. Results showed that low precipitation pH-values favor the incorporation of sulfate ions into the structure and the inner double layer, while under alkaline conditions ions shift to the diffuse layer. - Graphical abstract: An analytical methodology for the accurate quantification of sulfate ions (SO{sub 4}{sup 2−}) distribution onto the diffuse layer, the Stern layer and the structure of iron oxy-hydroxides used as arsenic removal agents. - Highlights: • Quantification of sulfate ions presence in FeOOH surface compartments. • Preparation pH defines the distribution of sulfates. • XPS and FTIR verify the presence of SO{sub 4}{sup 2−} in the structure, the Stern layer the diffuse layer of FeOOH. • Chemically adsorbed sulfates control the arsenic removal efficiency of iron oxyhydroxides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Tailoring surface properties and structure of layered double hydroxides using silanes with different number of functional groups

Four silanes, trimethylchlorosilane (TMCS), dimethyldiethoxylsilane (DMDES), 3-aminopropyltriethoxysilane (APTES) and tetraethoxysilane (TEOS), were adopted to graft layered double hydroxides (LDH) via an induced hydrolysis silylation method (IHS). Fourier transform infrared spectra (FTIR) and {sup 29}Si MAS nuclear magnetic resonance spectra ({sup 29}Si MAS NMR) indicated that APTES and TEOS can be grafted onto LDH surfaces via condensation with hydroxyl groups of LDH, while TMCS and DMDES could only be adsorbed on the LDH surface with a small quantity. A combination of X-ray diffraction patterns (XRD) and {sup 29}Si MAS NMR spectra showed that silanes were exclusively present in the external surface and had little influence on the long range order of LDH. The surfactant intercalation experiment indicated that the adsorbed and/or grafted silane could not fix the interlamellar spacing of the LDH. However, they will form crosslink between the particles and affect the further surfactant intercalation in the silylated samples. The replacement of water by ethanol in the tactoids and/or aggregations and the polysiloxane oligomers formed during silylation procedure can dramatically increase the value of BET surface area (S{sub BET}) and total pore volumes (V{sub p}) of the products. - Graphical abstract: The replacement of water by ethanol in the tactoids and aggregations of LDHs, and the polysiloxane oligomers formed during silylation process can dramatically increase the BET surface area (S{sub BET}) and the total pore volume (V{sub p}) of the silylated products. - Highlights: • Silanes with multifunctional groups were grafted onto LDH surface in C{sub 2}H{sub 5}OH medium. • The number of hydrolysable groups in silanes affects the structure of grafted LDH. • Replacement of H{sub 2}O by C{sub 2}H{sub 5}OH in aggregations increases S{sub BET} and V{sub p} of grafted LDH. • Polysiloxane oligomers contribute to the increase of S{sub BET} and V{sub p} of grafted LDH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Synthesis and investigation of proton conductivity for intercalated kaolinite with 4-amidinopyridinium chloride

The proton-conducting materials have potential application in devices such as fuel cells. In this study, a mineral kaolinite-based proton conducting material, kaolinite-4-amidinopyridinium hydrochloride (K-4-APy–HCl), was synthesized by the intercalated compound kaolinite-4-amidinopyridine (K-4-APy) adsorbing volatilizing HCl. The thermogravimetric analysis (TG), powder X-ray diffraction (PXRD) and IR spectrum confirmed the HCl successfully inserting into the interlayer space of kaolinite and the 4-aminopyridine being protonated. The intercalation efficiency is estimated to be ca. 85.6%. With respect to K-4-APy, the interlayer space expends by 1.53 Å. The thermal decomposition mechanism was studied by PXRD and TG techniques. The K-4-APy–HCl shows proton conductivity with σ=3.379×10{sup −8} S cm{sup −1} at 373 K and E{sub a}=1.159 eV in the anhydrous condition, which are comparable to MOFs-based proton conducting materials. - Graphical abstract: The intercalated hybrid of mineral kaolinite with 4-amidinopyridinium hydrochloride is prepared to use as proton conducting material. - Highlights: • A new strategy is proposed for preparation of kaolinite-based proton conductor. • Intercalatied hybrid was prepared by sequentially inserting 4-amidinopyridine and adsorbing HCl. • The proton conductivity of intercalated hybrid is comparable to MOFs-based proton-conductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Influence of difference quantity La-doped TiO{sub 2} photoanodes on the performance of dye-sensitized solar cells: A strategy for choosing an appropriate doping quantity

Facilitated by TiO{sub 2} particles adsorbing lanthanide ions in hydrosol, La-doped TiO{sub 2} was produced by a hydrothermal method. The structure, optical and photoluminescence properties of down-converting photoelectrode with the La{sup 3+} were characterized by X-ray (XRD), Scanning electron microscopy (SEM), Energy dispersive X-ray detector (EDX) and N{sub 2} adsorption-desorption isotherms measurement. The photoelectric conversion efficiency of dye-sensitized solar cells (DSSCs) fabricated with 0.05 g-La/TiO{sub 2} reached 7.02%, which gave an efficiency improved by 10.36% compared with that of cells fabricated from pure TiO{sub 2}. The improvement in efficiency was ascribed to more dyes adsorbed on the surface of TiO{sub 2}. - Graphical abstract: (a) J–V curves of La-doped photoelectrodes with different La(NO{sub 3}){sub 3}·6H{sub 2}O amounts; (b) the curves of efficiency changing with the amount of La(NO{sub 3}){sub 3}·6H{sub 2}O. The photoelectric conversion efficiency of dye-sensitized solar cells (DSSCs) fabricated with 0.05 g-La/TiO{sub 2} reached 7.02%, which gave an efficiency improved by 10.36% compared with that of cells fabricated from pure TiO{sub 2}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

A density functional theory study of the structure of pure-silica and aluminium-substituted MFI nanosheets

The layered MFI zeolite allows a straightforward hierarchization of the pore system which accelerates mass transfer and increases its lifetime as a catalyst. Here, we present a theoretical study of the structural features of the pure-silica and aluminium-substituted MFI nanosheets. We have analysed the effects of aluminium substitution on the vibrational properties of silanols as well as the features of protons as counter-ions. The formation of the two-dimensional system did not lead to appreciable distortions within the framework. Moreover, the effects on the structure due to the aluminium dopants were the same in both the bulk and the slab. The principal differences were related to the silanol groups that form hydrogen-bonds with neighbouring aluminium-substituted silanols, whereas intra-framework hydrogen-bonds increase the stability of aluminium-substituted silanols toward dehydration. Thus, we have complemented previous experimental and theoretical studies, showing the lamellar MFI zeolite to be a very stable material of high crystallinity regardless of its very thin structure. - Graphical abstract: The structure of MFI zeolite nanosheet was investigated using Density Functional Theory. The results showed no differences against the bulk-type material upon aluminium doping. The aluminium-substituted silanol dehydrates toward a more stable configuration composed by a water molecule adsorbed on a Lewis centre. - Highlights: • MFI nanosheets with variable thicknesses were characterised using DFT calculations. • The distortions in the nanosheets after Al substitution reproduced those of the bulk. • H-bonds were only observed between silanol groups when the Al substitution took place. • The kinetic of the Al-silanol dehydration is dependent on intra-framework H-bonds. • Lewis acids with adsorbed water are more stable than Al-silanols. • The proton accessibility was related to the framework O atom binding the proton.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

In-situ functionalization of mesoporous hexagonal ZnO synthesized in task specific ionic liquid as a photocatalyst for elimination of SO{sub 2}, NO{sub x}, and CO

A novel mesoporous structure of zinc oxide was synthesized in hydrothermal autocalve in the presence of a functional ionic liquid (FIL) {[CH_2CH_2] O_2 (mm)_2}. This FIL with ether groups was used simultaneously as a designer templating agent and a source of the hydroxyl radical. The presence of this ionic liquid led to producing ethylene glycol in the reaction media, which adsorb on the surface of mesoporous hexagonal ZnO plates. These mesoporous structures can adsorb pollutant gases and increase photocatalytic oxidation of pollutant gases in compare with commercial ZnO nanoparticles and agglomerated nanoparticles synthesized in this work. XPS data confirmed ethylene glycol production by the ionic liquid, which could prove a role for ionic liquids as designers. The estimated BET surface area values of ZnO hexagonal mesoporous plates and agglomerated particles were 84 m{sup 2}/g and 12 m{sup 2}/g respectively. Optical properties of the mesoporous structures were analyzed by photoluminescence spectroscopy and diffuse reflectance UV–visible spectroscopy. The performance of these structures as efficient photocatalysts was further demonstrated by their removal of NO{sub x}, SO{sub 2,} and CO under UV irradiation. The removal of NO{sub x}, SO{sub 2,} and CO under UV irradiation was 56%, 81%, and 35% respectively, after 40 min of irradiation time. Reusability of the photocatalyst was determined; the results show no significant decrease of activity of photocatalyst. after five cycles. - Highlights: • The hexagonal and mesoporous structures of ZnO were synthesized in the presence of FIL. • FIL has been used as a designer agent and a source of the hydroxyl radical. • In-situ functionalization of ZnO in presence of FIL. • The mesoporous functionalized ZnO was used as photocatalyst for removal of NOx, SO{sub 2,} and CO.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Cu- and Zr-based metal organic frameworks and their composites with graphene oxide for capture of acid gases at ambient temperature

Highlights: • Incorporation of GO in Cu- and Zr-based MOFs resulted in additional porosity at the interstitial MOF/GO spaces. • The UiO-66-NH{sub 2}/GO composite exhibited enhanced CO{sub 2} capacity at higher pressures. • CO{sub 2}/N{sub 2} selectivity of HKUST-1/GO was higher compared to pure HKUST-1. • The HKUST-1 crystallites in the presence of GO exhibited enhanced H{sub 2}S sorption kinetics. • The UiO-66 based adsorbents were more stable in humidity conditions than the HKUST-1 based ones. - Abstract: Capture of acid gases (CO{sub 2} and H{sub 2}S) by liquid solvent absorption is the common industrial practice, yet capture relying on solid adsorbents is increasingly gaining interest as potential alternative towards less energy-demanding operations. Herein, we developed and examined various metal organic frameworks (MOFs) bearing Cu- and Zr- metal clusters and their composites with graphene oxide (GO), and evaluated their performance for CO{sub 2} and H{sub 2}S adsorption. Specifically, UiO-66, UiO-66-NH{sub 2}, HKUST-1, and their GO composites were grown, subjected to structural, morphological, and textural characterization, and subsequently evaluated for their adsorption capacity and selectivity at ambient temperature. The crystallinity of the parent MOFs was preserved upon in-situ growth of the MOF/GO composites, while incorporation of GO yielded uniformly-shaped and well-dispersed MOF crystals resulting in enhanced sorption kinetics, and increased the pore volume compared to pure MOFs due to additional porosity formed in the interstitial spaces between the MOF crystallites and the GO flakes. To this extent, the interplay between additional porosity and pore functionalities in the competitive CO{sub 2} and N{sub 2} adsorption was investigated. UiO-66-NH{sub 2} exhibited enhanced CO{sub 2} capacity (3.07 mmol/g at 25 °C and 4 bar) and the highest CO{sub 2}/N{sub 2} selectivity (167 at 1 bar) among the tested MOFs, due to the presence of the amine functional groups in the organic linker that enhanced affinity with CO{sub 2}. At increased pressures, the UiO-66-NH{sub 2}/GO composite exhibited higher CO{sub 2} capacity compared to pure UiO-66-NH{sub 2}, which is attributed to activation of the additional porosity between the MOF crystallites and the GO layers. HKUST-1/GO selectivity was also enhanced compared to HKUST-1 in all pressures tested. Under humid environment, the UiO-66 based structures were relatively stable in contrast to the HKUST-1 ones that underwent gradual degradation. These composites offer functionalization tunability due to the presence of both MOF and GO counterparts for targeted gas capture applications.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Influence of porous aluminosilicate grain size materials in experimental and modelling Cs + adsorption kinetics and wastewater column process

This paper focuses on the influence of the grain size of a geopolymer based adsorbent on its Cs + adsorption performances both in batch and fixed-bed process. The geopolymer phase was used as a binder to support NaY zeolite particle in a 20 wt% charged porous composite with 160 m 2 .g –1 of porous surface area. These samples were shaped with three grain sizes (50 /100/500 µm) to remove 80–90 mg/g of Cs + in batch and column operations. After their microstructural and porous characterizations, their efficiency and adsorption characteristics were investigated through adsorption isotherms and kinetic in the two processes. While the grain size has no influence on the maximal extraction capacity of the adsorbent, it strongly affects the sorption kinetic. By coupling experimental data and a modelling approach, the complex sorption mechanism was highlighted, suggesting a new insight of the contaminant sorption kinetic. Then, comparison of batch and column adsorption experiments illustrates the detailed explanation of various process parameters for column study. The results show challenges for fixed-bed column utilization by the choice of the appropriate grain size as a compromise between the material sorption kinetic and hydrodynamic considerations. Furthermore, this is of high importance to more accurately optimize the design of column adsorption to assess the transport of Cs+ in multi-porous tailored grain size materials.

36 MATERIALS SCIENCE↗