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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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143 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Quasi-operando quantification of Cu(ii) ions in Cu-SSZ-13 catalyst by an NH 3 temperature-programmed reduction method

In this work, a quasi-operando NH3 temperature-programmed reduction method (NH 3 -TPR), with N 2 :Cu = 1:1, is developed to quantify total Cu(II) ions in Cu-SSZ-13 quenched from SCR-relevant reactions, and its accuracy is confirmed by in situ EPR. [Cu(OH)] + -Z and Cu 2+ -2Z can be further distinguished by NH 3 reduction temperatures, and their different reducibility in SCR is revealed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Photoelectrochemical Proton-Coupled Electron Transfer of TiO 2 Thin Films on Silicon

TiO 2 thin films are often used as protective layers on semiconductors for applications in photovoltaics, molecule–semiconductor hybrid photoelectrodes, and more. Experiments reported here show that TiO 2 thin films on silicon are electrochemically and photoelectrochemically reduced in buffered acetonitrile at potentials relevant to photoelectrocatalysis of CO 2 reduction, N 2 reduction, and H 2 evolution. On both n-type Si and irradiated p-type Si, TiO 2 reduction is proton-coupled with a 1e – :1H + stoichiometry, as demonstrated by the Nernstian dependence of the Ti 4+/3+ E 1/2 on the buffer pK a . Experiments were conducted with and without illumination, and a photovoltage of ∼0.6 V was observed across 20 orders of magnitude in proton activity. The 4 nm films are almost stoichiometrically reduced under mild conditions. The reduced films catalytically transfer protons and electrons to hydrogen atom acceptors, based on cyclic voltammogram, bulk electrolysis, and other mechanistic evidence. TiO 2 /Si thus has the potential to photoelectrochemically generate high-energy H atom carriers. Characterization of the TiO 2 films after reduction reveals restructuring with the formation of islands, rendering TiO 2 films as a potentially poor choice as protecting films or catalyst supports under reducing and protic conditions. Altogether, this work demonstrates that atomic layer deposition TiO 2 films on silicon photoelectrodes undergo both chemical and morphological changes upon application of potentials only modestly negative of RHE in these media. While the results should serve as a cautionary tale for researchers aiming to immobilize molecular monolayers on “protective” metal oxides, the robust proton-coupled electron transfer reactivity of the films introduces opportunities for the photoelectrochemical generation of reactive charge-carrying mediators.

Electrodes↗
DOE OSTI2024

Probing the active sites of oxide encapsulated electrocatalysts with controllable oxygen evolution selectivity

Electrocatalysts encapsulated by nanoscopic overlayers can control the rate of redox reactions at the outer surface of the overlayer or at the buried interface between the overlayer and the active catalyst, leading to complex behavior in the presence of two competing electrochemical reactions. This study investigated oxide encapsulated electrocatalysts (OECs) comprised of iridium (Ir) thin films coated with an ultrathin (2–10 nm thick) silicon oxide (SiO x ) or titanium oxide (TiO x ) overlayer. The performance of SiO x |Ir and TiO x |Ir thin film electrodes towards the oxygen evolution reaction (OER) and Fe(II)/Fe(III) redox reactions were evaluated. An improvement in selectivity towards the OER was observed for all OECs. Overlayer properties, namely ionic and electronic conductivity, were assessed using a combination of electroanalytical methods and molecular dynamics simulations. SiO x and TiO x overlayers were found to be permeable to H 2 O and O 2 such that the OER can occur at the MO x |Ir (M = Ti, Si) buried interface, which was further supported with molecular dynamics simulations of model SiO 2 coatings. In contrast, Fe(II)/Fe(III) redox reactions occur to the same degree with TiO x overlayers having thicknesses less than 4 nm as bare electrocatalyst, while SiO x overlayers inhibit redox reactions at all thicknesses. This observation is attributed to differences in electronic transport between the buried interface and outer overlayer surface, as measured with through-plane conductivity measurements of wetted overlayer materials. These findings reveal the influence of oxide overlayer properties on the activity and selectivity of OECs and suggest opportunities to tune these properties for a wide range of electrochemical reactions.

08 HYDROGEN↗
DOE OSTI2020

Beyond Ammonia: Nitrogen–Element Bond Forming Reactions with Coordinated Dinitrogen

The functionalization of coordinated dinitrogen to form nitrogen-element bonds en route to nitrogen-containing molecules is a long-standing challenge in chemical synthesis. The strong triple bond and the non-polarity of the N 2 molecule pose thermodynamic and kinetic challenges for promoting reactivity. Although heterogeneous, homogeneous and biological catalysts are all known for catalytic nitrogen fixation to ammonia, the catalytic synthesis of more complicated nitrogen-containing organic molecules has far less precedent. Examples of silyl radical additions to coordinated nitrogen to form silylamines stands as the lone example of a catalytic reaction involving N 2 to form a product other than ammonia. Our review surveys the field of molecular transition metal complexes, as well as recent boron examples for the formation of nitrogen-element bonds. Emphasis is placed on the coordination and activation modes of N 2 in the various metal compounds from across the transition series and how these structures can rationally inform reactivity studies. Over the past few decades, the field has evolved from the addition of carbon electrophiles in a manner similar to protonation reactions to more organometallic-inspired reactivity including insertions, 1,2-additions and cycloadditions. Various N–C, N–Si and N–B bond-forming reactions have been discovered highlighting that the challenge for catalytic chemistry is not in the reactivity of coordinated dinitrogen but rather removal of the functionalized ligand from the coordination sphere of the metal.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Disordered TiO x –SiO x Nanocatalysts Using Bioinspired Synthetic Routes

Metal oxide nanomaterials have increasing significance and broad applications in catalysis, ranging from support materials to active catalysts. Here, we have demonstrated a facile synthetic strategy to create disordered, high-surface-area metal oxide nanomaterials using biomineralization-inspired methods. Using protamine as a protein template, a range of TiO x –SiO x nanomaterials were synthesized and implemented for catalytic CO 2 thermal reduction reactions. The modularity of synthetic options afforded via biomineralization enables increases in surface area, which are ideally suited for subsequent modification to regulate catalytic performance. All materials were thoroughly characterized using a suite of synchrotron scattering and spectroscopic methods. Through these techniques, we have demonstrated that protamine-induced biomineralization results in largely disordered materials with changes in the local atomic structure dependent on the applied synthetic conditions. Protamine removal with treatment under acidic conditions greatly increased material surface area while causing measurable changes in the structure as revealed by X-ray absorption spectroscopy. Upon subsequent hydrogenation, Ti- and Si-based defects were induced in the materials while the disordered nature of the material was still largely retained. Furthermore, we found that the incorporation of Si into TiO x was able to mitigate the known anatase to rutile phase change during the reaction while stabilizing the defect sites. The synthetic strategies described in this work are expected to be translatable to other metal oxide nanomaterial chemical structures, providing a means to control catalytic properties using benign synthetic strategies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

From Serendipity to Exploration: Synthesis and Properties of PtSiSb

PtSiSb is a compound with covalent Si–Sb bonds, which are relatively rare instances in solid-state materials. The original report on PtSiSb indicates synthetic challenges for the isolation of single-phase samples, as well as potential discrepancies in the predicted electronic structure and experimental transport properties. In this work, we considered PtSiSb as a case study with the objective of demonstrating the importance of synthesis as a bridge between theoretical predictions and experimental properties. Using guidance from in situ powder X-ray diffraction, the synthesis of single-phase polycrystalline samples was developed, allowing further experimental characterization of transport and catalytic properties. Thermal conductivity and heat capacity demonstrated anomalous behavior, indicating an unconventional phonon scattering mechanism in PtSiSb. Charge transport measurements indicated semimetallic behavior. Hydrogen evolution reaction (HER) tests in acidic electrolyte revealed that the PtSiSb cathode needs an overpotential η 10 = 120 mV to achieve a current density j = −10 mA/cm 2 . This is lower activity than elemental Pt but comparable to known and active transition-metal phosphide HER catalysts, such as CoP, with η 10 = 93 mV when measured at identical conditions.

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

Hot-Carrier Transfer at Photocatalytic Silicon/Platinum Interfaces

Interfacial charge transfer from silicon to heterogeneous catalysts plays a key role in silicon-based photoelectrochemical systems. In general, prior to interfacial charge transfer, carriers that are generated by photons with energies above the bandgap dissipate the excess kinetic energy via hot-carrier cooling, and such energy loss limits the maximum power conversion efficiency. The excess energy of hot-carriers, however, could be utilized through hot-carrier transfer from silicon to the catalysts, but such hot-carrier extraction has not yet been demonstrated. In this work, we exploit transient reflection spectroscopy to interrogate charge transfer at the interface between silicon and platinum. Additionally, quantitative modeling of the surface carrier kinetics indicates that the velocity of charge transfer from silicon to platinum exceeds 2.6 x 10 7 cm s -1 , corresponding to an average carrier temperature of extracted carriers of ~600 K, two times higher than the lattice temperature. The charge transfer velocity can be controllably reduced by inserting silica spacing layers between silicon and platinum.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2010

Fabrication of Single, Vertically Aligned Carbon Nanotubes in 3D Nanoscale Architectures

Plasma-enhanced chemical vapor deposition (PECVD) and high-throughput manufacturing techniques for integrating single, aligned carbon nanotubes (CNTs) into novel 3D nanoscale architectures have been developed. First, the PECVD growth technique ensures excellent alignment of the tubes, since the tubes align in the direction of the electric field in the plasma as they are growing. Second, the tubes generated with this technique are all metallic, so their chirality is predetermined, which is important for electronic applications. Third, a wafer-scale manufacturing process was developed that is high-throughput and low-cost, and yet enables the integration of just single, aligned tubes with nanoscale 3D architectures with unprecedented placement accuracy and does not rely on e-beam lithography. Such techniques should lend themselves to the integration of PECVD grown tubes for applications ranging from interconnects, nanoelectromechanical systems (NEMS), sensors, bioprobes, or other 3D electronic devices. Chemically amplified polyhydroxystyrene-resin-based deep UV resists were used in conjunction with excimer laser-based (lambda = 248 nm) step-and-repeat lithography to form Ni catalyst dots = 300 nm in diameter that nucleated single, vertically aligned tubes with high yield using dc PECVD growth. This is the first time such chemically amplified resists have been used, resulting in the nucleation of single, vertically aligned tubes. In addition, novel 3D nanoscale architectures have been created using topdown techniques that integrate single, vertically aligned tubes. These were enabled by implementing techniques that use deep-UV chemically amplified resists for small-feature-size resolution; optical lithography units that allow unprecedented control over layer-to-layer registration; and ICP (inductively coupled plasma) etching techniques that result in near-vertical, high-aspect-ratio, 3D nanoscale architectures, in conjunction with the use of materials that are structurally and chemically compatible with the high-temperature synthesis of the PECVD-grown tubes. The techniques offer a wafer-scale process solution for integrating single PECVD-grown nanotubes into novel architectures that should accelerate their integration in 3D electronics in general. NASA can directly benefit from this technology for its extreme-environment planetary missions. Current Si transistors are inherently more susceptible to high radiation, and do not tolerate extremes in temperature. These novel 3D nanoscale architectures can form the basis for NEMS switches that are inherently less susceptible to radiation or to thermal extremes.

Kaul, Anupama B.↗
DOE OSTI2020

Knock Mitigation Effectiveness of EGR across the Pressure-Temperature Domain

Exhaust gas recirculation (EGR) has been shown to enable efficiency improvements in SI engines through multiple different mechanisms, including decreasing the knock propensity at high load, which allows higher compression ratio. While many of the benefits of EGR are applicable to both low and high power density engines, including reductions in pumping work and improved specific heat ratio, the knock benefits and corresponding compression ratio increases have been limited to low power density naturally aspirated engines primarily intended for hybrid vehicle architectures. An earlier study [1] indicated that there may be a kinetic limitation for the ability of EGR to mitigate knock under these conditions, but that study only considered a small number of conditions. In this investigation, we expand on that study while also providing data for model validation for the new light-duty combustion consortium from the U.S. Department of Energy: Partnership for Advancing Combustion Engines (PACE). In this investigation, the effectiveness of EGR to mitigate knock is studied with regards to the effect of engine speed (1,500 and 3,000 rpm), changing trajectory in the pressure-temperature domain by varying the intake manifold temperature (35, 60, and 90 deg C), and by considering the effect of minor species by studying the effect of untreated EGR vs. EGR that has been treated by an automotive three-way catalyst. Additionally, to increase the relevance of these data for future modeling studies, the performance of the full boiling range gasoline was compared relative to a surrogate formulation. The study found that the fuel surrogate performs well, confirmed the kinetic limitations of EGR to mitigate knock under boost, and showed improvements in EGR performance with catalyzed EGR.

42 ENGINEERING↗
DOE OSTI2020

The superior hydrothermal stability of Pd/SSZ-39 in low temperature passive NOx adsorption (PNA) and methane combustion

We successfully synthesized uniform SSZ-39 with an average crystal size of about a micron. Pd (0.7 - 3 wt%) was supported on SSZ-39 with Si/Al ratio ~12. The as-synthesized materials were characterized by FTIR, XRD, Helium Ion Microscopy, HAADF-STEM imaging, 27 Al, 29 Si and H solid state NMR spectroscopic techniques. FTIR studies with CO and NO probe molecules reveal that the 0.7 wt% Pd/SSZ-39 material with Si/Al ~12 has the majority of Pd dispersed atomically as isolated Pd(II) and Pd(II)-OH centers, and thus can be used as a low-temperature passive NOx adsorber. Pd(II)-NO, Pd(II)(OH)(NO) and Pd(II)(CO)(NO) complexes form during PNA in this material. We compare this PNA material directly with the Pd/SSZ-13 system (with Si/Al ratio ~12) and show its superior hydrothermal stability. Remarkably, Pd/SSZ-39 with Si/Al ratio ~12 survives hydrothermal aging up to 815 ºC in 10% H 2 O/Air vapor for 16 hours without significant loss in activity. The SSZ-39 crystal structure remains intact during hydrothermal aging up to 1,000 ºC as we elucidate it with XRD and HAADF-STEM imaging/EDS mapping. However, changes to the framework during such harsh hydrothermal treatment significantly change the NOx release profiles during PNA as evidenced by high-field 27 Al NMR on fresh and aged Pd/SSZ-39 samples as well as PNA performance measurements. Besides PNA application, these hydrothermally very stable materials (3 wt% Pd on SSZ-39 with Si/Al ratio ~12) can be used as a robust methane combustion catalyst under industrially relevant conditions (GHSV~600,000hr -1 ). This catalyst shows minimal deactivation after both harsh hydrothermal aging at 750 and 800 ºC, and prolonged time on stream (105 hrs) at 425 °C. In contrast, both 3wt% Pd/alumina and 3wt% SSZ-13 supported samples lose a significant portion of their activity. Our study opens new avenues to prepare the most hydrothermally stable known Pd/zeolite materials with applications for adsorption and catalytic hydrocarbon combustion under industrially relevant conditions.

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

Surface Immobilization of a Re(I) Tricarbonyl Phenanthroline Complex to Si(111) through Sonochemical Hydrosilylation

A sonochemical-based hydrosilylation method was employed to covalently attach a rhenium tricarbonyl phenanthroline complex to silicon(111). fac-Re(5-(p-Styrene)-phen)(CO) 3 Cl (5-(p-styrene)-phen = 5-(4-vinylphenyl)-1,10-phenanthroline) was reacted with hydrogen-terminated silicon(111) in an ultrasonic bath to generate a hybrid photoelectrode. Subsequent reaction with 1-hexene enabled functionalization of remaining atop Si sites. Attenuated total reflectance–Fourier transform infrared spectroscopy confirms attachment of the organometallic complex to silicon without degradation of the organometallic core, supporting hydrosilylation as a strategy for installing coordination complexes that retain their molecular integrity. Detection of Re(I) and nitrogen by X-ray photoelectron spectroscopy (XPS) further support immobilization of fac-Re(5-(p-styrene)-phen)(CO) 3 Cl. Cyclic voltammetry and electrochemical impedance spectroscopy under white light illumination indicate that fac-Re(5-(p-styrene)-phen)(CO) 3 Cl undergoes two electron reductions. Mott–Schottky analysis indicates that the flat band potential is 239 mV more positive for p-Si(111) co-functionalized with both fac-Re(5-(p-styrene)-phen)(CO) 3 Cl and 1-hexene than when functionalized with 1-hexene alone. XPS, ultraviolet photoelectron spectroscopy, and Mott–Schottky analysis show that functionalization with fac-Re(5-(p-styrene)-phen)(CO) 3 Cl and 1-hexene introduces a negative interfacial dipole, facilitating reductive photoelectrochemistry.

X-ray photoelectron spectroscopy↗
DOE OSTI2023

Theory and Simulation of Metal–Insulator–Semiconductor (MIS) Photoelectrodes

A metal–insulator–semiconductor (MIS) structure is an attractive photoelectrode-catalyst architecture for promoting photoelectrochemical reactions, such as the formation of H 2 by proton reduction. The metal catalyzes the generation of H 2 using electrons generated by photon absorption and charge separation in the semiconductor. The insulator layer between the metal and the semiconductor protects the latter element from photo-corrosion and, also, significantly impacts the photovoltage at the metal surface. Understanding how the insulator layer determines the photovoltage and what properties lead to high photovoltages is critical to the development of MIS structures for solar-to-chemical energy conversion. Herein, we present a continuum model for charge-carrier transport from the semiconductor to the metal with an emphasis on mechanisms of charge transport across the insulator. The polarization curves and photovoltages predicted by this model for a Pt/HfO 2 /p-Si MIS structure at different HfO 2 thicknesses agree well with experimentally measured data. The simulations reveal how insulator properties (i.e., thickness and band structure) affect band bending near the semiconductor/insulator interface and how tuning them can lead to operation closer to the maximally attainable photovoltage, the flat-band potential. This phenomenon is understood by considering the change in tunneling resistance with insulator properties. The model shows that the best MIS performance is attained with highly symmetric semiconductor/insulator band offsets (e.g., BeO, MgO, SiO 2 , HfO 2 , or ZrO 2 deposited on Si) and a low to moderate insulator thickness (e.g., between 0.8 and 1.5 nm). Beyond 1.5 nm, the density of filled interfacial trap sites is high and significantly limits the photovoltage and the solar-to-chemical conversion rate. These conclusions are true for photocathodes and photoanodes. This understanding provides critical insight into the phenomena enhancing and limiting photoelectrode performance and how this phenomenon is influenced by insulator properties. The study gives guidance toward the development of next-generation insulators for MIS structures that achieve high performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2005

Growing Aligned Carbon Nanotubes for Interconnections in ICs

A process for growing multiwalled carbon nanotubes anchored at specified locations and aligned along specified directions has been invented. Typically, one would grow a number of the nanotubes oriented perpendicularly to a silicon integrated-circuit (IC) substrate, starting from (and anchored on) patterned catalytic spots on the substrate. Such arrays of perpendicular carbon nanotubes could be used as electrical interconnections between levels of multilevel ICs. The process (see Figure 1) begins with the formation of a layer, a few hundred nanometers thick, of a compatible electrically insulating material (e.g., SiO(x) or Si(y)N(z) on the silicon substrate. A patterned film of a suitable electrical conductor (Al, Mo, Cr, Ti, Ta, Pt, Ir, or doped Si), having a thickness between 1 nm and 2 m, is deposited on the insulating layer to form the IC conductor pattern. Next, a catalytic material (usually, Ni, Fe, or Co) is deposited to a thickness between 1 and 30 nm on the spots from which it is desired to grow carbon nanotubes. The carbon nanotubes are grown by plasma-enhanced chemical vapor deposition (PECVD). Unlike the matted and tangled carbon nanotubes grown by thermal CVD, the carbon nanotubes grown by PECVD are perpendicular and freestanding because an electric field perpendicular to the substrate is used in PECVD. Next, the free space between the carbon nanotubes is filled with SiO2 by means of CVD from tetraethylorthosilicate (TEOS), thereby forming an array of carbon nanotubes embedded in SiO2. Chemical mechanical polishing (CMP) is then performed to remove excess SiO2 and form a flat-top surface in which the outer ends of the carbon nanotubes are exposed. Optionally, depending on the application, metal lines to connect selected ends of carbon nanotubes may be deposited on the top surface. The top part of Figure 2 is a scanning electron micrograph (SEM) of carbon nanotubes grown, as described above, on catalytic spots of about 100 nm diameter patterned by electron-beam lithography. These and other nanotubes were found to have lengths ranging from 2 to 10 m and diameters ranging from 30 to 200 nm, the exact values of length depending on growth times and conditions and the exact values of diameter depending on the diameters and thicknesses of the catalyst spots. The bottom part of Figure 2 is an SEM of an embedded array of carbon nanotubes after CMP.

Li, Jun↗
DOE OSTI2026

Lignin to adipic acid in a high-yield chemical and biological redox process

Viable manufacturing pathways to produce bio-based chemicals from renewable feedstocks, such as lignin derived from plant biomass, are needed to decarbonize the chemicals manufacturing sector. Converting the recalcitrant lignin polymer to valuable bioproducts remains a longstanding challenge in biorefining, with the highest reported single-product yield from lignin currently around 20 wt%. Most existing lignin depolymerization strategies target aryl–ether bond cleavage, which can produce aromatic monomers in yields of only about 30 wt%, and still as complex mixtures with C–C-linked dimers and oligomers. The recalcitrance of these C–C linkages between aromatic moieties fundamentally limits single-product yields from lignin, prompting the development of strategies to efficiently cleave these C–C bonds. Here, in this study, we show how reductive processing of lignin from poplar accesses a hydrocarbon mixture of alkyl-aromatic monomers and oligomers that is privileged for oxidative conversion to monomeric aromatic carboxylic acids, comprising mostly benzoic acid and phthalic acid isomers in up to 73 wt% monomer yields, using a Co/Mn/Br catalyst. The soil bacterium Pseudomonas putida KT2440 was engineered to convert this mixture of aromatic carboxylic acids to muconolactone, a precursor to bio-based nylons, enabling final adipic acid yields up to 26 wt% (gram adipic acid per gram lignin) with a maximum theoretical yield of 57 wt%. This pairing of reductive and oxidative steps with lignin resembles processes in petrochemical refining and shows how lignin may be converted into a single, valuable bioproduct in high yields.

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

Critical roles of Cu(OH)2 in low-temperature moisture-induced degradation of Cu-SAPO-34 SCR catalyst: Correlating reversible and irreversible deactivation

Cu-SAPO-34 selective catalytic reduction (SCR) catalyst deactivates upon exposure to water vapor at temperatures lower than 100 °C, which deteriorates its application prospects. The deactivation under cycled aging-regeneration conditions can be categorized into two stages, namely reversible and irreversible deactivation. Based on SCR reaction tests, and characterizations with diffuse reflection infrared Fourier transform spectroscopy (DRIFTS), NH3 temperature-programmed desorption (NH3-TPD) and H2 temperature-programmed reduction (H2-TPR), it is concluded that the transformation of SCR active isolated Cu(II) ions to Cu(OH)2 is critical to both types of deactivation. Within the frame of reversible deactivation, Cu(OH)2 is converted back to SCR active Cu(II) ions by interacting with Brønsted acid sites during high-temperature regeneration. However, interactions between Cu(OH)2 and hydrolyzed framework Al lead to the formation of CuAl2O4-like species, causing permanent loss of active Cu(II) ions and thus, irreversible deactivation. The authors from Tsinghua University would like to acknowledge the financial support from projects of China Science and Technology Exchange Centre (No. 2016YFE0126600) and the National Key R&D Program of China (No. 2017YFC0211102). YM also acknowledges Tsinghua Scholarship for Overseas Graduate Studies for a visit to the Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the US Department of Energy (DOE) under contract DE-AC05-76RL01830. FG is supported by DOE, Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office.

Cu-SAPO-34, low-temperature deactivation, reversib↗
NASA NTRS2011

Carbon Nanofibers Synthesized on Selective Substrates for Nonvolatile Memory and 3D Electronics

A plasma-enhanced chemical vapor deposition (PECVD) growth technique has been developed where the choice of starting substrate was found to influence the electrical characteristics of the resulting carbon nanofiber (CNF) tubes. It has been determined that, if the tubes are grown on refractory metallic nitride substrates, then the resulting tubes formed with dc PECVD are also electrically conducting. Individual CNFs were formed by first patterning Ni catalyst islands using ebeam evaporation and liftoff. The CNFs were then synthesized using dc PECVD with C2H2:NH3 = [1:4] at 5 Torr and 700 C, and approximately equal to 200-W plasma power. Tubes were grown directly on degenerately doped silicon <100> substrates with resistivity rho approximately equal to 1-5 meterohm-centimeter, as well as NbTiN. The approximately equal to 200-nanometer thick refractory NbTiN deposited using magnetron sputtering had rho approximately equal to 113 microohm-centimeter and was also chemically compatible with CNF synthesis. The sample was then mounted on a 45 beveled Al holder, and placed inside a SEM (scanning electron microscope). A nanomanipulator probe stage was placed inside the SEM equipped with an electrical feed-through, where tungsten probes were used to make two-terminal electrical measurements with an HP 4156C parameter analyzer. The positive terminal nanoprobe was mechanically manipulated to physically contact an individual CNF grown directly on NbTiN as shown by the SEM image in the inset of figure (a), while the negative terminal was grounded to the substrate. This revealed the tube was electrically conductive, although measureable currents could not be detected until approximately equal to 6 V, after which point current increased sharply until compliance (approximately equal to 50 nA) was reached at approximately equal to 9.5 V. A native oxide on the tungsten probe tips may contribute to a tunnel barrier, which could be the reason for the suppressed transport at low biases. Currents up to approximately 100 nA could be cycled, which are likely to propagate via the tube surface, or sidewalls, rather than the body, which is shown by the I-V in figure (a). Electrical conduction via the sidewalls is a necessity for dc NEMS (nanoelectromechanical system) applications, more so than for the field emission applications of such tubes. During the tests, high conductivity was expected, because both probes were shorted to the substrate, as shown by curve 1 in the I-V characteristic in figure (b). When a tube grown on NbTiN was probed, the response was similar to the approximately equal to 100 nA and is represented by curve 2 in figure (b), which could be cycled and propagated via the tube surface or the sidewalls. However, no measureable currents for the tube grown directly on Si were observed as shown by curve 3 in figure (b), even after testing over a range of samples. This could arise from a dielectric coating on the sidewalls for tubes on Si. As a result of the directional nature of ion bombardment during dc PECVD, Si from the substrate is likely re-sputtered and possibly coats the sidewalls.

Kaul, Anupama B.↗
DOE OSTI2025

Red-Light-Driven Biophotochemical Diode Based on a Microorganism–Silicon Nanowire Interface for Stable and Efficient Bias-Free CO 2 Reduction

Artificial photosynthesis offers a promising route for sustainable liquid fuel and feedstock production, yet integrating efficient CO 2 reduction catalysts with light-harvesting systems remains challenging. Here, in this study, we present a biophotochemical diode that couples microorganism-driven CO 2 reduction with glycerol oxidation, enabled by silicon nanowire photoelectrodes under varying red-light intensities. Tuning the biotic-abiotic interface─by increasing biocatalyst loading and adjusting the catholyte pH to mitigate local alkalization─significantly improves performance and stability. The enhanced-loading biocathode maintains a high faradaic efficiency across a wide potential range, even under elevated light intensities. At 60 mW/cm 2 , the system achieves a bias-free current density of 3.5 mA/cm 2 . Long-term stability testing at 40 mW/cm 2 demonstrates stable operation for over 100 h. The photoanode generates valuable C 3 products, primarily glycerate and lactate, enhancing the economic viability. This work showcases the importance of microenvironmental control at the biotic-abiotic interface and establishes a scalable platform for light-driven CO 2 reduction using earth-abundant silicon.

Artificial Photosynthesis↗