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NASA NTRS1981

Photoassisted carbon dioxide reduction and formation of twoand three-carbon compounds

The photoassisted reduction of aqueous carbon dioxide in the presence of naturally occurring minerals is investigated as a possible abiotic precursor of photosynthesis. Aqueous carbon dioxide saturated suspensions or surfaces of the minerals nontronite, bentonite, anatase, wolframite, molybdenite, minium, cinnabar and hematite were irradiated with high-pressure mercury lamps or sunlight. Chemical analyses reveal the production of formic acid, formaldehyde, methanol and methane, and the two and three-carbon compounds glyoxal (CHOCHO) and malonaldehyde (CH2(CHO)2). It is suggested that such photosynthetic reactions with visible light in the presence of semiconducting minerals may provide models for prebiological carbon and nitrogen fixation in both oxidized and reduced atmospheres.

Halmann, M.↗

NASA NTRS1960

Orbital Thermal Control of the Mercury Capsule

The approach to orbital thermal control of the Project Mercury capsule environment is relatively unsophisticated compared with that for many unmanned satellites. This is made possible by the relatively short orbital flight of about 4 1/2 hours and by the presence of the astronaut who is able to monitor the capsule systems and compensate for undesirable thermal conditions. The general external features of the Mercury configuration as it appears in the orbital phase of flight are shown. The conical afterbody is a double-wall structure. The inner wall serves as a pressure vessel for the manned compartment, and the outer wall, of shingle type construction, acts as a radiating shield during reentry. Surface treatment of the shingles calls for a stably oxidized surface to minimize reentry temperatures. The shingles are supported by insulated stringers attached to the inner skin. Areas between stringers are insulated by blankets of Thermoflex insulation. This insulation is especially effective at high altitude due to the reduction of its thermal conductivity with decreasing pressure. As a result of the design of the afterbody for the severe reentry conditions, the heat balance on the manned compartment indicates the necessity for moderate internal cooling to compensate for the heat generation due to human and electrical sources. This cooling is achieved by the controlled vaporization of water in the cabin and astronaut-suit heat exchangers.

Weston, Kenneth C.↗

DOE OSTI2020

Mercury methylation potential in a sand dune on Lake Michigan's eastern shoreline

Lake Michigan hosts the largest freshwater sand dune system in the world and is economically important for the fishery industry and tourism. Due to industrial pollution and atmospheric mercury (Hg) deposition, toxic levels of methylmercury (MeHg) have been found in the Lake biota, but little information is known regarding MeHg sources and Hg methylation potential in the shoreline sand dunes. In this study, we conducted anaerobic incubation experiments with beach sands collected from Ludington, Michigan, and examined the effects of organic carbon substrate addition, inorganic nitrogen, and mineral magnetite on Hg methylation. Despite nutrient poor and low-organic carbon conditions, appreciable Hg methylation activity coupled with carbon degradation was observed in the sands. Addition of acetate as a carbon source substantially increased MeHg production from 2 to 380 ng/kg sediment while acetate was rapidly degraded in the first 19 days of incubation. Ammonium addition showed little influence on carbon degradation or Hg methylation, whereas iron oxide addition (~1% dry weight) significantly inhibited both carbon degradation and MeHg production (by up to 90%), highlighting strongly coupled interactions between microbes, carbon substrates, and minerals. This research demonstrates the potential of microbial Hg methylation in the sand dunes, which may play a role in MeHg input and bioaccumulation in the Lake Michigan ecosystem.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

Electromagnetic wave absorption of multifunctional cementitious composites incorporating polyvinyl alcohol (PVA) fibers and fly ash: Effects of microstructure and hydration

Highlights: • The cementitious composite shows excellent wide-band electromagnetic wave absorption in a frequency range of 2–18 GHz. • The PVA fibers and the fly ash change the dielectric properties of the cementitious composite by Debye polarization. • The iron oxide of the cementitious binders contributes to the magnetic properties of the composites. • The impacts of the microstructure and the hydration of the cementitious composite on its microwave absorption are analyzed. This paper devises a novel method for the adjustment of the pore structure and the hydration of cement to improve the electromagnetic wave absorption of the cementitious composites incorporating polyvinyl alcohol (PVA) fibers and fly ash in a frequency range of 2–18 GHz. The underlying mechanism of the absorption is investigated to explore the possibility of the structural and functional integration of these composites. The electromagnetic parameters of the prepared cementitious composites and those of the raw materials are analyzed in a frequency range of 0.5–18 GHz. Moreover, the pore structure and the chemical environment of the cementitious composites are examined by mercury intrusion porosimetry (MIP), back-scattered electron detector (BSE), and X-ray photoelectron spectroscopy (XPS). The results indicate that the PVA fibers and the high-volume fly ash have a positive effect on electromagnetic wave absorption of the cementitious composites through the adjustment of their pore structure and hydration.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Deep Eutectic Solvents as Candidates for Lithium Isotope Enrichment

Nuclear fusion is a phenomenon that is well known within the nuclear physics community as a viable option for alternative energy as many natural gases and fossil fuels are phased out of commercial use. Deuterium and tritium fusion reactions are currently the leading candidates for nuclear fusion, with a major limiting factor being a means to produce tritium on an industrial scale. Lithium-6 is a well-known isotope that can produce tritium and helium following a fission reaction with a neutron. Unfortunately, the lithium-6 enrichment methods are limited to the COLEX process, which leaves behind an alarming amount of mercury waste as a potential environmental contaminant. Deep eutectic solvents are believed to be a potential alternative to lithium isotope separations due to the ease of generation, in addition to the minimum environmental waste generated when these solvents are employed. Previous studies have suggested that deep eutectic solvents are capable of separating lithium isotopes by utilizing a 2-thenoyltrifluoroacetone and trioctylphosphine oxide system that can biphasically react with a buffered solution containing lithium chloride. This system displays a separation factor of 1.068, which when compared to the 1.054 separation within the COLEX process, makes it a potential candidate for lithium-6/7 separation. Within this study, we investigate this system in comparison to two newly synthesized deep eutectic solvents and find that within these acetylacetone-based systems, little isotopic separation is observed. We investigate these systems both experimentally and computationally, showing the different lithium cation affinities, in addition to proposing how the electron-donating or -withdrawing nature can influence these systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2009

NASA Tech Briefs, July 2009

Topics covered include: Dual Cryogenic Capacitive Density Sensor; Hail Monitor Sensor; Miniature Six-Axis Load Sensor for Robotic Fingertip; Improved Blackbody Temperature Sensors for a Vacuum Furnace; Wrap-Around Out-the-Window Sensor Fusion System; Wide-Range Temperature Sensors with High-Level Pulse Train Output; Terminal Descent Sensor Simulation; A Robust Mechanical Sensing System for Unmanned Sea Surface Vehicles; Additive for Low-Temperature Operation of Li-(CF)n Cells; Li/CFx Cells Optimized for Low-Temperature Operation; Number Codes Readable by Magnetic-Field-Response Recorders; Determining Locations by Use of Networks of Passive Beacons; Superconducting Hot-Electron Submillimeter-Wave Detector; Large-Aperture Membrane Active Phased-Array Antennas; Optical Injection Locking of a VCSEL in an OEO; Measuring Multiple Resistances Using Single-Point Excitation; Improved-Bandwidth Transimpedance Amplifier; Inter-Symbol Guard Time for Synchronizing Optical PPM; Novel Materials Containing Single-Wall Carbon Nanotubes Wrapped in Polymer Molecules; Light-Curing Adhesive Repair Tapes; Thin-Film Solid Oxide Fuel Cells; Zinc Alloys for the Fabrication of Semiconductor Devices; Small, Lightweight, Collapsible Glove Box; Radial Halbach Magnetic Bearings; Aerial Deployment and Inflation System for Mars Helium Balloons; Steel Primer Chamber Assemblies for Dual Initiated Pyrovalves; Voice Coil Percussive Mechanism Concept for Hammer Drill; Inherently Ducted Propfans and Bi-Props; Silicon Nanowire Growth at Chosen Positions and Orientations; Detecting Airborne Mercury by Use of Gold Nanowires; Detecting Airborne Mercury by Use of Palladium Chloride; Micro Electron MicroProbe and Sample Analyzer; Nanowire Electron Scattering Spectroscopy; Electron-Spin Filters Would Offer Spin Polarization Greater than 1; Subcritical-Water Extraction of Organics from Solid Matrices; A Model for Predicting Thermoelectric Properties of Bi2Te3; Integrated Miniature Arrays of Optical Biomolecule Detectors; A Software Rejuvenation Framework for Distributed Computing; Kurtosis Approach to Solution of a Nonlinear ICA Problem; Robust Software Architecture for Robots; R4SA for Controlling Robots; Bio-Inspired Neural Model for Learning Dynamic Models; Evolutionary Computing Methods for Spectral Retrieval; Monitoring Disasters by Use of Instrumented Robotic Aircraft; Complexity for Survival of Living Systems; Using Drained Spacecraft Propellant Tanks for Habitation; Connecting Node; and Electrolytes for Low-Temperature Operation of Li-CFx Cells.

Source record↗

NASA NTRS1972

Study of mechanism which causes film formation on mercury surfaces

The mechanism by which small quantities of dissolved tin, sodium, and lithium lower the rate of evaporation of mercury in vacuum is determined. An apparatus was built in which dilute amalgams could be prepared and studied in an oxygen-free environment before being exposed to oxygen under controlled conditions. The apparatus was able to maintain a pressure of less than 1.3 x 0.000001 N/sqm (10 to the minus 8th power torr) of gases and vapors other than mercury and less than 1.3 x 10 to the minus 8th N/sq m (10 to the minus 10th power torr) partial pressure of oxygen; also, it provided for mechanical sweeping of the liquid metal surfaces in the vacuum environment. The rates of evaporation of pure mercury and of dilute amalgams of tin (52 ppm), sodium (229 ppm), and lithium (165 ppm) were determined at temperature between 25 and 55 C both before and after 70 minute exposures to an approximately 270 N/sq m (2 torr) pressure of oxygen. The rates of evaporation of the pure mercury and the amalgams as first prepared were similar but the rates for the amalgams were reduced by at least 80% at 25 C as a result of the exposure to oxygen. The effect of the oxygen treatment could be completely removed by sweeping the amalgam surfaces. It was concluded that the reduced rates of evaporation resulted from the formation of transparent, insoluble, oxide films on the amalgam surfaces.

Frohnsdorff, G.↗

DOE OSTI2021

Biological Treatment of Flue Gas Desulfurization Wastewater

In order to limit and mitigate the environmental impacts associated with coal combustion, flue gas desulfurization (FGD) systems have been put into place to reduce the release of contaminates. The main constituent targeted by FGD systems is sulfur oxide gasses (SOx). While FGD systems have been able to achieve high removal rates of SOx gasses, the wastewater effluent requires treatment before release back into the environment. The release of wastewater is heavily regulated by the U.S. Environmental Protection Agency (EPA) and their effluent guideline limitations rule (ELG). The ELG rule set new limits on discharges containing constituents such as selenium, nitrogenous species, mercury, and arsenic in the effluent. This report seeks to give background on abiotic removal methods as well as highlight the most important issues when utilizing biological treatment to treat the FGD wastewater for the constituents of interest mentioned. This report also seeks to discuss the issues of foaming which can occur during biological treatment.

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2022

Genome-Wide Association Study Reveals Complex Genetic Architecture of Cadmium and Mercury Accumulation and Tolerance Traits in Medicago truncatula

Heavy metals are an increasing problem due to contamination from human sources that and can enter the food chain by being taken up by plants. Understanding the genetic basis of accumulation and tolerance in plants is important for reducing the uptake of toxic metals in crops and crop relatives, as well as for removing heavy metals from soils by means of phytoremediation. Following exposure of Medicago truncatula seedlings to cadmium (Cd) and mercury (Hg), we conducted a genome-wide association study using relative root growth (RRG) and leaf accumulation measurements. Cd and Hg accumulation and RRG had heritability ranging 0.44 – 0.72 indicating high genetic diversity for these traits. The Cd and Hg trait associations were broadly distributed throughout the genome, indicated the traits are polygenic and involve several quantitative loci. For all traits, candidate genes included several membrane associated ATP-binding cassette transporters, P-type ATPase transporters, oxidative stress response genes, and stress related UDP-glycosyltransferases. The P-type ATPase transporters and ATP-binding cassette protein-families have roles in vacuole transport of heavy metals, and our findings support their wide use in physiological plant responses to heavy metals and abiotic stresses. We also found associations between Cd RRG with the genes CAX3 and PDR3, two linked adjacent genes, and leaf accumulation of Hg associated with the genes NRAMP6 and CAX9. When plant genotypes with the most extreme phenotypes were compared, we found significant divergence in genomic regions using population genomics methods that contained metal transport and stress response gene ontologies. Several of these genomic regions show high linkage disequilibrium (LD) among candidate genes suggesting they have evolved together. Minor allele frequency (MAF) and effect size of the most significant SNPs was negatively correlated with large effect alleles being most rare. This is consistent with purifying selection against alleles that increase toxicity and abiotic stress. Conversely, the alleles with large affect that had higher frequencies that were associated with the exclusion of Cd and Hg. Overall, macroevolutionary conservation of heavy metal and stress response genes is important for improvement of forage crops by harnessing wild genetic variants in gene banks such as the Medicago HapMap collection.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2021

Incorporating concentration-dependent sediment microbial activity into methylmercury production kinetics modeling

We report in anoxic environments, anaerobic microorganisms carrying the hgcAB gene cluster can mediate the transformation of inorganic mercury (Hg(II)) to monomethylmercury (MMHg). The kinetics of Hg(II) transformation to MMHg in periphyton from East Fork Poplar Creek (EFPC) in Oak Ridge, TN have previously been modeled using a transient availability model (TAM). The TAM for Hg(II) methylation combines methylation/demethylation kinetics with kinetic expressions for processes that decrease Hg(II) and MMHg availability for methylation and demethylation (multisite sorption of Hg(II) and MMHg, Hg(II) reduction/Hg(0) oxidation). In this study, the TAM is used for the first time to describe MMHg production in sediment. We assessed MMHg production in sediment microcosms using two different sediment types from EFPC: a relatively anoxic, carbon-rich sediment with higher microbial activity (higher CO 2 production from sediment) and a relatively oxic, sandy, carbon-poor sediment with lower microbial activity (lower CO 2 production from sediment). Based on 16s rRNA sequencing, the overall microbial community structure in the two sediments was retained during the incubations. However, the hgcA containing methanogenic Euryarchaeota communities differed between sediment types and their growth followed different trajectories over the course of incubations, potentially contributing to the distinct patterns of MMHg production observed. The general TAM paradigm performed well in describing MMHg production in the sediments. However, the MMHg production and ancillary data suggested the need to revise the model structure to incorporate terms for concentration-dependent microbial activity over the course of the incubations. We modified the TAM to include Monod-type kinetics for methylation and demethylation and observed an improved fit for the carbon-rich, microbially active sediment. Overall our work shows that the TAM can be applied to describe Hg(II) methylation in sediments and that including expressions accounting for concentration-dependent microbial activity can improve the accuracy of the model description of the data in some cases.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2026

Preparation and Photocatalytic Hydrogen Production of TiO 2 /(AlMnCoNiZn) 3 O 4 Nanocomposites

Photocatalytic water splitting is a promising strategy for addressing the global energy crisis and environmental pollution. In this study, spinel-type high-entropy oxide (HEO) nanoparticles, (AlMnCoNiZn) 3 O 4 , were successfully synthesized via a solution combustion method. TiO 2 /(AlMnCoNiZn) 3 O 4 nanocomposites with varying molar ratios were subsequently fabricated through solid-state sintering, and their photocatalytic water-splitting performance was systematically investigated. The hydrogen production rate initially increased and then decreased with increasing TiO 2 content. The optimal nanocomposite achieved a hydrogen evolution rate of 1450 μmol·h −1 ·g −1 under simulated sunlight irradiation, which is 2.2 times higher than that of pure TiO 2 nanoparticles. In addition, the TiO 2 /(AlMnCoNiZn) 3 O 4 nanocomposites exhibited significantly improved photocorrosion resistance compared with TiO 2 nanoparticles. After 12 h irradiation under a 500-W high-pressure mercury lamp, the hydrogen production rates of the nanocomposites and pure TiO 2 retained 79.3% and 5.47% of their initial values, respectively. These results demonstrate the important role of (AlMnCoNiZn) 3 O 4 and other HEOs in enhancing the photocatalytic performance of nanoheterojunction catalysts. Lastly, this work broadens the potential applications of (AlMnCoNiZn) 3 O 4 and related HEO materials in the field of photocatalysis.

Heterojunction↗

NASA NTRS1961

Effect of Surface Preparation and Gas Flow on Nitrogen Atom Surface Recombination

The effects of surface preparation and gas flow on the recombination of nitrogen atoms at copper and platinum surfaces were determined. Atoms were generated by an electrodeless 2450-megacycle-per-second discharge, and their concentration was measured by gas-phase titration with nitric oxide. Test surfaces were either vacuum-evaporated films or spheres machined from bulk metal and cemented around small glass-bead thermistors. Heat released by recombination was measured as the difference in electrical energy required to maintain a given thermistor temperature with and without a catalytic surface exposed. Recombination coefficients measured at flow velocities of 1120, 1790, 2250, and 3460 centimeters per second and at pressures of 0.42 and 0.59 millimeter of mercury showed that flow conditions had no effect. The results were also independent of atom concentration. A rough indication of the temperature dependence was obtained; it was greater for copper than for platinum. Platinum films deposited on platinum or on glass had the same activity - about 3 percent of the atoms impinging recombined. With copper, however, the glass substrate greatly reduced the percent of atoms recombining over that of a bulk copper substrate where 4 percent of the impinging atoms recombined. This effect could be overcome by depositing a second film on top of the first. Bulk metal samples were subjected to various surface treatments including polishing, degreasing with a chlorinated hydrocarbon, washing with nitric acid, and rinsing with water. Polished, degreased platinum had low activity compared to an evaporated film, but nitric acid treatment made it equivalent. Polished, degreased copper was only slightly less active than a copper film; nitric acid etching decreased the activity still further, probably by preferentially exposing facets of low catalytic efficiency.

Prok, George M.↗

NASA NTRS1973

Investigation of mercury thruster isolators

Mercury ion thruster isolator lifetime tests were performed using different isolator materials and geometries. Tests were performed with and without the flow of mercury through the isolators in an oil diffusion pumped vacuum facility and cryogenically pumped bell jar. The onset of leakage current in isolators occurred in time intervals ranging from a few hours to many hundreds of hours. In all cases, surface contamination was responsible for the onset of leakage current and subsequent isolator failure. Rate of increase of leakage current and the leakage current level increased approximately exponentially with isolator temperature. Careful attention to shielding techniques and the elimination of sources of metal oxides appear to have eliminated isolator failures as a thruster life limiting mechanism.

Mantenieks, M. A.↗

NASA NTRS1973

Investigation of mercury thruster isolators

Mercury ion thruster isolator lifetime tests were performed using different isolator materials and geometries. Tests were performed with and without the flow of mercury through the isolators in an oil diffusion pumped vacuum facility and cryogenically pumped bell jar. The onset of leakage current in isolators tested occurred in time intervals ranging from a few hours to many hundreds of hours. In all cases, surface contamination was responsible for the onset of leakage current and subsequent isolator failure. Rate of increase of leakage current and the leakage current level increased approximately exponentially with isolator temperature. Careful attention to shielding techniques and the elimination of sources of metal oxides appear to have eliminated isolator failures as a thruster life limiting mechanism.

Mantenieks, M. A.↗

NASA NTRS2014

Visible-Light-Responsive Catalysts Using Quantum Dot-Modified TiO2 for Air and Water Purification

Photocatalysis, the oxidation or reduction of contaminants by light-activated catalysts, utilizing titanium dioxide (TiO2) as the catalytic substrate has been widely studied for trace contaminant control in both air and water applications. The interest in this process is due primarily to its low energy consumption and capacity for catalyst regeneration. Titanium dioxide requires ultraviolet light for activation due to its relatively large band gap energy of 3.2 eV. Traditionally, Hg-vapor fluorescent light sources are used in PCO reactors; however, the use of mercury precludes the use of this PCO technology in a spaceflight environment due to concerns over crew Hg exposure. The development of a visible-light responsive (VLR) TiO2-based catalyst would eliminate the concerns over mercury contamination. Further, VLR development would allow for the use of ambient visible solar radiation or highly efficient LEDs, both of which would make PCO approaches more efficient, flexible, economical, and safe. Though VLR catalyst development has been an active area of research for the past two decades, there are few commercially available VLR catalysts. Those VLR catalysts that are commercially available do not have adequate catalytic activity, in the visible region, to make them competitive with those operating under UV irradiation. This study was initiated to develop more effective VLR catalysts through a novel method in which quantum dots (QD) consisting of narrow band gap semiconductors (e.g., CdS, CdSe, PbS, ZnSe, etc.) are coupled to TiO2 via two preparation methods: 1) photodeposition and 2) mechanical alloying using a high-speed ball mill. A library of catalysts was developed and screened for gas and aqueous phase applications using ethanol and 4-chlorophenol as the target contaminants, respectively. Both target compounds are well studied in photocatalytic systems and served as model contaminants for this research. Synthesized catalysts were compared in terms of preparation method, nature of the quantum dots, and dosage of quantum dots.

visible light↗

NASA NTRS2014

Visible-Light Responsive Catalysts Using Quantum Dot-Modified TiO2 for Air and Water Purification

visible light↗

NASA NTRS2011

NASA Tech Briefs, February 2011

Topics covered include: Multi-Segment Radius Measurement Using an Absolute Distance Meter Through a Null Assembly; Fiber-Optic Magnetic-Field-Strength Measurement System for Lightning Detection; Photocatalytic Active Radiation Measurements and Use; Computer Generated Hologram System for Wavefront Measurement System Calibration; Non-Contact Thermal Properties Measurement with Low-Power Laser and IR Camera System; SpaceCube 2.0: An Advanced Hybrid Onboard Data Processor; CMOS Imager Has Better Cross-Talk and Full-Well Performance; High-Performance Wireless Telemetry; Telemetry-Based Ranging; JWST Wavefront Control Toolbox; Java Image I/O for VICAR, PDS, and ISIS; X-Band Acquisition Aid Software; Antimicrobial-Coated Granules for Disinfecting Water; Range 7 Scanner Integration with PaR Robot Scanning System; Methods of Antimicrobial Coating of Diverse Materials; High-Operating-Temperature Barrier Infrared Detector with Tailorable Cutoff Wavelength; A Model of Reduced Kinetics for Alkane Oxidation Using Constituents and Species for N-Heptane; Thermally Conductive Tape Based on Carbon Nanotube Arrays; Two Catalysts for Selective Oxidation of Contaminant Gases; Nanoscale Metal Oxide Semiconductors for Gas Sensing; Lightweight, Ultra-High-Temperature, CMC-Lined Carbon/Carbon Structures; Sample Acquisition and Handling System from a Remote Platform; Improved Rare-Earth Emitter Hollow Cathode; High-Temperature Smart Structures for Engine Noise Reduction and Performance Enhancement; Cryogenic Scan Mechanism for Fourier Transform Spectrometer; Piezoelectric Rotary Tube Motor; Thermoelectric Energy Conversion Technology for High-Altitude Airships; Combustor Computations for CO2-Neutral Aviation; Use of Dynamic Distortion to Predict and Alleviate Loss of Control; Cycle Time Reduction in Trapped Mercury Ion Atomic Frequency Standards; and A (201)Hg+ Comagnetometer for (199)Hg+ Trapped Ion Space Atomic Clocks.

Source record↗

DOE OSTI2025

Tetracene Functionalized Si(111) Achieves Enhanced Solar-to-Chemical Energy Conversion via Molecular Acceptor States

The properties of semiconductor|liquid interfaces play a critical role in determining the efficiency of solar-to-hydrogen (STH) conversion. Here, we investigate how molecular functionalization of Si(111) and Si(111)|TiO 2 surfaces impacts photoelectrochemical (PEC) hydrogen production efficiency. We find that functionalization of ∼3% of the atop sites of Si(111) with either 9-anthracene (Anth) or 5-tetracene (Tet), with the remaining sites passivated by methyl groups, provides substrates with high electronic quality and low surface oxide densities, as determined by X-ray photoelectron spectroscopy (XPS) measurements. Surface photovoltage (SPV) spectroscopy shows that surfaces modified with Anth or Tet exhibit an increased photovoltage, with Tet-functionalized surfaces yielding an additional 192 meV relative to methyl-terminated Si(111), indicating improved charge separation for Si-Tet. Further improvement in onset potential was achieved by replacing a nitrogen-containing TiO 2 atomic layer deposition (ALD) precursor (TDMAT) with a precursor lacking nitrogen (TTIP), which eliminates the parasitic defect band in the TiO 2 overlayer (p-Si(111)-Tet|TTIP-TiO 2 |Pt: V OC = +0.283 ± 0.041 V vs RHE). Density functional theory (DFT) analysis demonstrates that compared with Anth-modified Si(111), the Tet-modified surface exhibits more hybridized Si(111)-Tet states closer to the silicon band edges. Mercury contact current–voltage (I–V, dark) measurements quantified the relative interfacial density of states of Si-Tet, Si-Anth and Si-Me surfaces─revealing that the interfacial state density was highest for Si-Tet. This suggests that such hybridized interfaces serve to capture better photoexcited charge, which enables facile electron transfer to molecular acceptors in solution. Altogether, the data indicate that beneficial hybrid molecular LUMO surface states interacting with the Si conduction band edge results in improved hydrogen evolution (HER) performance for p-Si devices.

Group theory↗