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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

CO 2 Uptake and Stability Enhancement in Vinyltrimethoxysilane‐Treated SBA‐15 Solid Amine‐Based Sorbents

Abstract Silica‐supported amine absorbents, including materials produced by tethering aminosilanes or infusion of poly(ethyleneimine), represent a promising class of materials for CO 2 capture applications, including direct air and point source capture. Various silica surface treatments and functionalization strategies are explored to enhance stability and CO 2 uptake in amine‐based solid sorbent systems. Here, the synthesis and characterization of novel vinyltrimethoxysilane‐treated Santa Barbara Amorphous‐15 (SBA‐15) supports and the corresponding enhancement in CO 2 uptake compared to various SBA‐15‐based control supports are presented. The relationship between CO 2 diffusion and amine efficiency in these systems is explored using a previously reported kinetic model. The synthesized materials are characterized with CO 2 and H 2 O isotherms, diffuse reflectance infrared Fourier transform spectroscopy, 1 H T 1 – T 2 relaxation correlation NMR, and rapid thermal cycling experiments. The novel support materials are shown to enable high amine efficiencies, approaching a fourfold improvement over standard SBA‐15‐supported amines, while simultaneously exhibiting excellent stability when cycled rapidly under humid conditions. As the poly(ethyleneimine) loadings are held constant across the various samples, enhancements in CO 2 uptake are attributed to differences in the way the poly(ethyleneimine) interacts with the support surface.

Vallace, Anthony↗
DOE OSTI2013

Water dissociation on Ni(100) and Ni(111): Effect of surface temperature on reactivity

Water adsorption and dissociation on Ni(100) and Ni(111) surfaces are studied using density functional theory calculations. Water adsorbs on top site on both the surfaces, while H and OH adsorb on four fold hollow and three fold hollow (fcc) sites on Ni(100) and Ni(111), respectively. Transition states (TS) on both surfaces are identified using climbing image-nudged elastic band method. It is found that the barrier to dissociation on Ni(100) surface is slightly lower than that on Ni(111) surface. Dissociation on both the surfaces is exothermic, while the exothermicity on Ni(100) is large. To study the effect of lattice motion on the energy barrier, TS calculations are performed for various values of Q (lattice atom coordinate along the surface normal) and the change in the barrier height and position is determined. Calculations show that the energy barrier to reaction decreases with increasing Q and increases with decreasing Q on both the surfaces. Dissociation probability values at different surface temperatures are computed using semi-classical approximation. Results show that the influence of surface temperature on dissociation probability on the Ni(100) is significantly larger compared to that of Ni(111). Moreover, on Ni(100), a dramatic shift in energy barrier to lower incident energy values is observed with increasing surface temperature, while the shift is smaller in the case of Ni(111)

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

Quantum dot-based microfluidic biosensor for cancer detection

We report results of the studies relating to fabrication of an impedimetric microfluidic–based nucleic acid sensor for quantification of DNA sequences specific to chronic myelogenous leukemia (CML). The sensor chip is prepared by patterning an indium–tin–oxide (ITO) coated glass substrate via wet chemical etching method followed by sealing with polydimethylsiloxane (PDMS) microchannel for fluid control. The fabricated microfluidic chip comprising of a patterned ITO substrate is modified by depositing cadmium selenide quantum dots (QCdSe) via Langmuir–Blodgett technique. Further, the QCdSe surface has been functionalized with specific DNA probe for CML detection. The probe DNA functionalized QCdSe integrated miniaturized system has been used to monitor target complementary DNA concentration by measuring the interfacial charge transfer resistance via hybridization. The presence of complementary DNA in buffer solution significantly results in decreased electro-conductivity of the interface due to presence of a charge barrier for transport of the redox probe ions. The microfluidic DNA biosensor exhibits improved linearity in the concentration range of 10{sup −15} M to 10{sup −11} M.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2023

Superconducting gap symmetry from Bogoliubov quasiparticle interference analysis on Sr 2 RuO 4

Here, the nature of the superconducting order parameter in Sr 2 RuO 4 has generated intense interest in recent years. Since the superconducting gap is very small, high-resolution methods such as scanning tunneling spectroscopy might be the best chance to directly resolve the gap symmetry. Recently, a Bogoliubov quasiparticle interference imaging (BQPI) experiment has suggested that the d x 2 –y 2 gap symmetry is appropriate for Sr 2 RuO 4 . In this work, we use a material-specific theoretical approach based onWannier functions of the surface of Sr 2 RuO 4 to calculate the continuum density of states as detected in scanning tunneling microscopy experiments. We examine several different proposed gap order parameters and calculate the expected BQPI pattern for each case. Comparing to the available experimental data, our results suggest that a s' + id xy gap order parameter is the most probable state, but the measured BQPI patterns still display features unaccounted for by the theory for any of the states currently under discussion.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Two-Step Procedure of Fly Ash Modification as an Alternative Method for Creation of Functional Composite

An appropriate filler is a key component required to achieve an useful composite with expected properties. Not only sophisticated types of filler, like graphene are popular, but also more common ones, like silica flour or fly ash because of their low costs. Besides production costs, adequate size and possibility of functionalization of particles surface to create stable bonds with a matrix are essential in filler selection. To create an useful filler for epoxy resin based composites with use of a waste material, namely fly ash, two-step procedure was proposed. In the first part, raw material was sieved and five different ranges of the filler size were obtained. After mechanical tests with fracture toughness, tensile strength and Young Modulus, as well thermal conductivity, the best size of the fly ash was chosen for further modification. During the second step, filler was modified with coupling agent [3-(2-aminoethylamino)propyl]trimethoxysilane in order to enhance the coupling between particular components of composite. Presence of the silane layer was confirmed with infrared spectroscopy and scanning electron microscopy measurements, whilst prepared epoxy composite filled with silanized fly ash was examined similarly as previous composites. Obtained results have proved the significant influence of size of a filler and bonding to the matrix on mechanical and thermal properties of fly ash-epoxy resin composite. Proposed simple method of fly ash modification is an environmentally friendly way for utilization of the fly ash. Moreover, it creates an alternative material applicable in electrical devices as functional composite.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Plasmon-Assisted Direct Interfacial Charge Transfer Enables Molecular Photodissociation on Metal Surfaces

Plasmonic photocatalysis is promising for driving reactions out of equilibrium, leading to enhanced rates and selectivity, but the energy and charge transfer mechanism at the interface remains to be explored. Here, we revisit visible-light plasmon-assisted photodissociation of dimethyl disulfide molecules (S–S bond cleavage) over single-crystalline silver and copper surfaces, using density functional theory calculations and the delta self-consistent field method. We investigate different excitation mechanisms and show that the direct intramolecular excitations, as suggested earlier to explain the experimental findings, cannot address the observed catalytic bond activation. Instead, the calculated excitations mediated by the metal Fermi level agree well with the threshold energy and maximum-yield energy in experiments and suggest that the reaction follows a direct interfacial charge transfer mechanism. Furthermore, we show that the excitation energy and the charge transfer can be modulated by introducing excess charges in the systems. Here, this study thus provides a fundamental understanding of interfacial charge transfer for driving plasmonic photocatalysis.

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

Surface oxygenation induced strong interaction between Pd catalyst and functional support for zinc–air batteries

Employing the strong metal-support interaction (SMSI) effect for promoting the catalyst's activity toward the oxygen reduction reaction (ORR) is promising due to the electronic structure optimization and high utilization efficiency of platinum group metal (PGM) catalysts. Metal oxides as alternative supports for PGMs facilitate intrinsic activity and improve durability as compared to conventional carbon supports. However, the restricted mass and electron transfer at the metal/support interface need to be addressed. Herein, to strengthen the interaction at the metal/support interfaces and improve the utilization efficiency of PGM, an ultralow loading of Pd was embedded in a surface-oxygenated PdNiMnO porous film. The Mn-doping was designed to promote surface oxygenation using a facile anodization process that created sufficiently exposed interfaces between Pd and the support, strengthening the SMSI effects at the Pd/oxygenated support interface for enhancing ORR performance. Furthermore, the Ni-containing oxygenated catalyst served as both the active component for the oxygen evolution reaction (OER) and the functional support for stabilizing Pd, making PdNiMnO a bifunctional catalyst for zinc–air flow batteries (ZAFB). As a proof-of-concept, the ZAFB (PdNiMnO) shows a maximal power density of 211.6 mW cm –2 and outstanding cycling stability for over 2000 h with a minimal voltage gap of 0.69 V at a current density of 10 mA cm –2 , superior to the state-of-the-art catalysts.

25 ENERGY STORAGE↗
DOE OSTI2017

Biogeochemical cycling at the aquatic–terrestrial interface is linked to parafluvial hyporheic zone inundation history

Abstract. The parafluvial hyporheic zone combines the heightened biogeochemical and microbial interactions indicative of a hyporheic region with direct atmospheric/terrestrial inputs and the effects of wet–dry cycles. Therefore, understanding biogeochemical cycling and microbial interactions in this ecotone is fundamental to understanding biogeochemical cycling at the aquatic–terrestrial interface and to creating robust hydrobiogeochemical models of dynamic river corridors. We aimed to (i) characterize biogeochemical and microbial differences in the parafluvial hyporheic zone across a small spatial domain (6 lateral meters) that spans a breadth of inundation histories and (ii) examine how parafluvial hyporheic sediments respond to laboratory-simulated re-inundation. Surface sediment was collected at four elevations along transects perpendicular to flow of the Columbia River, eastern WA, USA. The sediments were inundated by the river 0, 13, 127, and 398 days prior to sampling. Spatial variation in environmental variables (organic matter, moisture, nitrate, glucose, % C, % N) and microbial communities (16S and internal transcribed spacer (ITS) rRNA gene sequencing, qPCR) were driven by differences in inundation history. Microbial respiration did not differ significantly across inundation histories prior to forced inundation in laboratory incubations. Forced inundation suppressed microbial respiration across all histories, but the degree of suppression was dramatically different between the sediments saturated and unsaturated at the time of sample collection, indicating a binary threshold response to re-inundation. We present a conceptual model in which irregular hydrologic fluctuations facilitate microbial communities adapted to local conditions and a relatively high flux of CO2. Upon rewetting, microbial communities are initially suppressed metabolically, which results in lower CO2 flux rates primarily due to suppression of fungal respiration. Following prolonged inundation, the microbial community adapts to saturation by shifting composition, and the CO2 flux rebounds to prior levels due to the subsequent change in respiration. Our results indicate that the time between inundation events can push the system into alternate states: we suggest (i) that, above some threshold of inundation interval, re-inundation suppresses respiration to a consistent, low rate and (ii) that, below some inundation interval, re-inundation has a minor effect on respiration. Extending reactive transport models to capture processes that govern such dynamics will provide more robust predictions of river corridor biogeochemical function under altered surface water flow regimes in both managed and natural watersheds.

58 GEOSCIENCES↗
DOE OSTI2016

THE ROTATION OF THE SOLAR PHOTOSPHERIC MAGNETIC FIELD

The rotational characteristics of the solar photospheric magnetic field at four flux ranges are investigated together with the total flux of active regions (MF{sub ar}) and quiet regions (MF{sub qr}). The first four ranges (MF{sub 1–4}) are (1.5–2.9) × 10{sup 18}, (2.9–32.0) × 10{sup 18}, (3.20–4.27) × 10{sup 19}, and (4.27–38.01) × 10{sup 19}, respectively (the unit is Mx per element). Daily values of the flux data are extracted from magnetograms of the Michelson Doppler Imager on board the Solar and Heliospheric Observatory . Lomb–Scargle periodograms show that only MF{sub 2}, MF{sub 4}, MF{sub qr}, and MF{sub ar} exhibit rotational periods. The periods of the first three types of flux are very similar, i.e., 26.20, 26.23, and 26.24 days, respectively, while that of MF{sub ar} is longer, 26.66 days. This indicates that active regions rotate more slowly than quiet regions on average, and strong magnetic fields tend to repress the surface rotation. Sinusoidal function fittings and cross-correlation analyses reveal that MF{sub ar} leads MF{sub 2} and MF{sub 4} by 5 and 1 days, respectively. This is speculated to be related with the decaying of active regions. MF{sub 2} and MF{sub ar} are negatively correlated, while both MF{sub 4} and MF{sub qr} are positively correlated with MF{sub ar}. At the timescale of the solar activity cycle, MF{sub ar} leads (negatively) MF{sub 2} by around one year (350 days), and leads MF{sub 4} by about 3 rotation periods (82 days). The relation between MF{sub 2} and MF{sub ar} may be explained by the possibility that the former mainly comes from a higher latitude, or emerges from the subsurface shear layer. We conjecture that MF{sub 4} may partly come from the magnetic flux of active regions; this verifies previous results that were obtained with indirect solar magnetic indices.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1977

Radar backscattering from a sea having an anisotropic large-scale surface, part 2

A two scale scattering model was derived that combines specular reflections from sea waves and Bragg scattering in a manner consistent with energy conservation. The effect of the tilting of the small scale roughness by the large scale roughness was included, which accounted for the reduction of reflected power. The special case of backscattering for which the transmitted polarization equaled the received polarization was considered. An anisotropic large scale surface was used to specify the probability density function of the large scale surface normal. In order to isolate the azimuthal variation of the normalized radar cross section produced by the anisotropic probability density function, an isotropical small scale spectrum was assumed.

Wentz, F. J.↗
DOE OSTI2017

Fine-tuning the release of molecular guests from mesoporous silicas by controlling the orientation and mobility of surface phenyl substituents

Phenyl-functionalized mesoporous silica materials were used to explore the effect of non-covalent interactions on the release of Ibuprofen into simulated body fluid. Variations in orientation and conformational mobility of the surface phenyl groups were introduced by selecting different structural precursors: a rigid upright orientation was obtained using phenyl groups directly bound to surface Si atoms (Ph-MSN), mobile groups were produced by using ethylene linkers to connect phenyl groups to the surface (PhEt-MSN), and groups co-planar to the surface were obtained by synthesizing a phenylene-bridged periodic mesoporous organosilica (Ph-PMO). The Ibuprofen release profiles from these materials and non-functionalized mesoporous silica nanoparticles (MSN) were analyzed using an adsorption-diffusion model. The model provided kinetic and thermodynamic parameters that evidenced fundamental differences in drug-surface interactions between the materials. All phenyl-bearing materials show lower Ibuprofen initial release rates than bare MSN. The conformationally locked Ph-MSN and Ph-PMO have stronger interactions with the drug (negative ΔG of adsorption) than the flexible PhEt-MSN and bare MSN (positive ΔG of adsorption). These differences in strength of adsorption are consistent with differences between interaction geometries obtained from DFT calculations. B3LYP-D3-optimized models show that π-π interactions contribute more to drug adsorption than H-bonding with silanol groups. Here, the results suggest that the type and geometry of interactions control the kinetics and extent of drug release, and should therefore serve as a guide to design new drug delivery systems with precise release behaviors customized to any desired target.

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

Oxygen Deficiency and Reactivity of Spinel NiCo 2 O 4 (001) Surfaces

We carried out density functional theory (DFT) calculations with on-site Hubbard U corrections to investigate the structure, defects, and reactivity of (001) surfaces of spinel NiCo 2 O 4 (NCO), a promising catalyst for CO and methane oxidation. By examining surfaces with different Co/Ni compositions, we find that the formation of surface oxygen vacancies (VOs) on NCO(001) is strongly affected by the neighboring cation in the third layer, the computed formation energy being largest (~1.2 eV) for O vacancies coordinated to third layer Co and smallest (~0.5 eV) for VOs coordinated to a Ni neighboring another Ni ion. As a result, VO formation is generally much easier on NCO (001) than on Co 3 O 4 (001) surfaces, suggesting that NCO may be a better catalyst than Co 3 O 4 for oxidation reactions based on the Mars–Van Krevelen mechanism. Surface oxygen vacancies on reduced NCO surfaces can be healed through dissociative water adsorption at room temperature. In contrast, adsorption of molecular oxygen at VOs is energetically unfavorable under ambient conditions, suggesting that O 2 adsorption may represent the thermodynamic limiting step for oxidation reactions on NCO(001) surfaces.

Shi, Xiao↗
NASA NTRS1994

Spectroscopy of the young cluster Blanco 1

We present spectroscopic observations of some 115 stars of the cluster Blanco 1, extending from the Ca II(H,K) region to the Ca II(I-R) triplet, supporting an age similar to that of the young cluster alpha Persei. The H-alpha absorption equivalent with vs (B - V) diagram forms a well-defined locus, with decreasing absorption equivalent width for decreasing effective temperature, akin to solar neighborhood dwarfs. A large spread in the Ca II surface flux, as a function of (B - V), also indicates the presence of a high degree of surface inhomogeneity, synonymous with high magnetic activity in young stars. A drop-off in the Ca II flux at (B - V) = 1.0 is also similar to the solar neighborhood stars, and shows that the primary chromospheric cooling changes from the Ca II and Mg II lines to the Balmer lines. The mean chromospheric temperature for stars at 4800 K lies between 8000 K and 10,000 K, based on theoretical models, which is somewhat higher than the older solar neighborhood dwarfs. The high mean Ca II surface flux of the sample is also consistent with that of other young clusters. We were able to measure the equivalent width of the Li(6708) line, whose strength as a function of (B - V) indicates an age similar to the young cluster alpha Persei. The lithium abundance decreases with decreasing effective temperature, consistent with the premise of lithium depletion in stars with larger convection zones. Using published photometry and a recent Zero Age Main Sequence (ZAMS) fitting method, we also re-define the distance to the cluster to be 246 pc.

Panagi, P. M.↗
DOE OSTI2018

Influence of surface pattern on the biological properties of Ti grade 2

Highlights: • Laser modification causes changes in chemical composition of the surface. • Laser treatment creates roughness in a range from nano- to micrometers. • The surface modification presented results in a multimodal topography. • A hierarchical topography promotes protein adsorption. - Abstract: This paper presents a detailed characterization of Ti surface geometries as produced by non-contact laser functionalization and its impact on the process of protein adsorption. The proposed surface modification is designed for the local treatment of implantable devices with original roughness. In this work, titanium plates were initially modified by the two most common mechano-chemical treatments, shot peening and acid etching. The material under study was next functionalized DLIL (Direct Laser Interference Lithography) in order to obtained two different surface patterns: grooves and islands. The modified surfaces were characterized in terms of their shape, roughness, wettability, surface energy and chemical composition. For this purpose, the following methods were used: scanning electron microscopy, optical profilometry, atomic force microscopy, contact angle measurements, and X-ray photoelectron spectroscopy. Protein adsorption tests were conducted to consider the potential of the proposed methodology in biomedical applications and to compare the influence of the two different surface patterns on the initial state of ossointegration. To this end, XPS and FTIR studies were conducted. The systematic analysis presented will be useful when selecting an appropriate surface geometry for the local surface functionalization of implantable devices.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Adsorption of Rare Earth Elements onto DNA-Functionalized Mesoporous Carbon

The recovery and separation of rare earth elements (REEs) are of national importance owing to the specific usages, high demand, and low supply of these elements. In this research, we have investigated the adsorption of rare earth elements onto DNA-functionalized mesoporous carbons with a BET surface area of 605 m2/g and a median mesopore width of 48 Å. Additionally, three types of single-stranded DNA, one with 100 base units of thymine, another with 20 units of thymine, and the third, a 2000 unit long DNA from salmon milt were grafted on the carboxylated mesoporous carbon surface. All of the DNA-functionalized mesoporous carbons demonstrated higher adsorption of REEs compared to pristine mesoporous carbon and DNA grafted with 100 units of thymine demonstrated slightly higher adsorbed amounts compared to others. Pure neodymium (Nd(III)) adsorption in the aqueous phase demonstrated an adsorbed amount of 110.4 mg/g with respect to the initial concentration of 500 mg/g. A pH variation study with pure Nd(III) demonstrated that the adsorbed amount is higher at elevated pH compared to that at lower pH, thereby suggesting possible recovery at lower pH. Adsorption of a mixture of 16 REEs, including Sc, Lu, Tm, Yb, Er, Ho, Tb, Dy, Y, Eu, Gd, Sm, Ce, Nd, Pr, and La revealed that the adsorbed amount increased with an increase in the atomic weight and metallic radii of elements within the lanthanides. The calculation of the distribution coefficients for all of the equilibrium adsorption amounts suggested that adsorption is more effective in the lower concentration region. The Nd L3-edge X-ray absorption near edge structure (XANES) confirmed a 3+ oxidation state of Nd in the adsorbed phase. The extended X-ray absorption fine structure (EXAFS) confirmed the local atomic structure relaxation of Nd complexes in the adsorbed phase and shortening of the Nd–O bond distance by about 0.03–0.04 Å, which may be associated with their local complexation at the carbon surface.

36 MATERIALS SCIENCE↗
DOE OSTI2014

The effects of surface chemistry of mesoporous silica materials and solution pH on kinetics of molsidomine adsorption

Adsorption kinetics of molsidomine on mesoporous silica material (UMS), the phenyl- (PhMS) and mercaptopropyl-functionalized (MMS) derivatives from solution with different pH and 298 K was studied. The adsorption kinetics was found to follow the pseudo-second-order kinetic model for all studied silica materials and pH. Effects of surface functional groups and pH on adsorption efficiency and kinetic adsorption parameters were investigated. At all studied pH, the highest molsidomine amount is adsorbed on PhMS due to π–π interactions and hydrogen bonding between surface groups of PhMS and molsidomine molecules. An increase of pH results in a decrease of the amounts of adsorbed molsidomine onto the silica materials. Furthermore, the highest adsorption rate kinetically evaluated using a pseudo-second-order model, is observed onto UMS and it strongly depends on pH. The mechanism of the adsorption process was determined from the intraparticle diffusion and Boyd kinetic film–diffusion models. The results showed that the molsidomine adsorption on the silica materials is controlled by film diffusion. Effect of pH on the diffusion parameters is discussed. - Graphical abstract: The kinetic study showed that the k{sub 2} value, the rate constant of pseudo-second order kinetic model, is the highest for molsidomine adsorption on UMS and strongly depends on pH because it is determined by availability and accessibility of the reaction sites of the adsorbents molsidomine binding. Display Omitted - Highlights: • The adsorption capacities of UMS, PhMS and MMS were dependent on the pH. • At all studied pH, the highest molsidomine amount is adsorbed on PhMS. • The highest adsorption rate, k{sub 2}, is observed onto UMS and strongly depends on pH. • Film diffusion was the likely rate-limiting step in the adsorption process.

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

Adsorptive separation of CO 2 in sulfur-doped nanoporous carbons: Selectivity and breakthrough simulation

In this research, we have synthesized two sulfur functionalized nanoporous carbons by post-synthesis modifications with sulfur bearing activating agents that simultaneously enhanced the surface area and introduced sulfur functionalities on the carbon surface. The Brunauer–Emmett–Teller (BET) surface areas of these materials were 2865 and 837 m 2 /g with total sulfur contents of 8.2 and 12.9 %, respectively. The sulfur-functionalized carbons were characterized with pore textural properties, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA) and electron microscopy (SEM and TEM). In both the carbons, CO 2 adsorption isotherms and kinetics were measured in three different temperatures of 298, 288 and 278 K and pressures up to 760 torr. The gravimetric CO 2 uptake followed the trend with BET surface area but the surface area-based uptake was reversed and it followed the trend of sulfur content. The heat of adsorption of CO 2 in low uptake was 60-65 kJ/mol, which is the highest for CO 2 adsorption in porous carbons. In order to investigate the adsorptive separation of CO 2 , N 2 and CH 4 adsorption isotherms were also measured at 298 K and 760 torr. The selectivity of separation for CO 2 /N 2 and CO 2 /CH 4 was calculated based on the Ideal Adsorbed Solution Theory (IAST) and all the results demonstrated the high CO 2 selectivity for the carbon with higher sulfur content. The adsorption isotherms were combined with mass balances to calculate the breakthrough behavior of the binary mixtures of CO 2 /N 2 and CO 2 /CH 4 . The simulation results demonstrated that the dimensionless breakthrough time is a decreasing function of the mole fraction of CO 2 in the feed stream. The overall results suggest that the sulfurfunctionalized carbons can be employed as potential adsorbents for CO 2 separation.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Band Bending Engineering at Organic/Inorganic Interfaces Using Organic Self‐Assembled Monolayers

Adsorbing strong electron donors or acceptors on semiconducting surfaces induces band bending, whose extent and magnitude are strongly dependent on the doping concentration of the semiconductor. This study applies hybrid density‐functional theory calculations together with the recently developed charge reservoir electrostatic sheet technique to account for charge transfer from the bulk of the semiconductor to the interface. This study further investigates the impact of surface‐functionalization with specifically tailored self‐assembled monolayers (SAMs). For the example of three chemically‐similar SAMs, that all bond to the ZnO surface via pyridine docking groups, it is shown that the SAMs introduce shallow or deep donor levels that pin the band bending at the position of the SAM's highest occupied molecular orbital. In this way, the magnitude of the induced band bending can be controlled by the type of SAM, to a point where the doping‐concentration dependence is completely eliminated.

Hofmann, Oliver T.↗