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At least 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Halide Ion Migration in Perovskite Nanocrystals and Nanostructures

The optical and electronic properties of metal halide perovskites provide insight into the operation of solar cells as well as their long-term operational stability. Halide mobility in perovskite films is an important factor influencing solar cell performance. One can visualize halide ion migration through halide exchange between two nanocrystal suspensions or between physically paired films of two different metal halide perovskites. The ability to tune band gap by varying halide ratios (Cl:Br or Br:I) allows the synthesis of mixed halide perovskites with tailored absorption and emission across the entire visible spectrum. Interestingly, mixed halide (e.g., MAPb(Br 0.5 I 0.5 ) 3 ) films undergo phase segregation to form Br-rich and I-rich sites under steady state illumination. Upon halting illumination, segregated phases mix to restore original mixed halide compositions. Introducing multiple cations (Cs, formamidinium) at the A site or alloying with Cl greatly suppresses halide mobilities. Long-term irradiation of MAPb(Br 0.5 I 0.5 ) 3 films also cause expulsion of iodide leaving behind Br-rich phases. Hole trapping at I-rich sites in MAPb(Br 0.5 I 0.5 ) 3 is considered to be an important step in inducing halide mobility in photoirradiated films. Finally, this Account focuses on halide ion migration in nanocrystals and nanostructured films driven by entropy of mixing in dark and phase segregation under light irradiation.

14 SOLAR ENERGY↗
DOE OSTI2022

Ln 10 S 14 O (Ln = La, Pr, Nd, Sm) Oxysulfides: A Series of Direct n-Type Semiconductors

Lanthanoid oxysulfides are promising materials for technological applications owing to their magnetic, photoluminescent, catalytic, and optoelectronic properties. In this work, we report the solid-state synthesis and structural characterization of Ln 10 S 14 O (Ln = La, Ce, Pr, Nd, Sm) oxysulfides. Then, we present a thorough discussion on their electronic and photophysical properties. Through Tauc plot analysis and the derivation of the absorption spectrum fitting method (DASF), we determine that all oxysulfides have direct band gaps with energies of 2.84 eV (La), 2.02 eV (Ce), 2.56 eV (Pr), 2.64 eV (Nd), and 2.41 eV (Sm). Furthermore, surface photovoltage spectroscopy (SPS) shows photovoltage (ΔCPD) values of –0.4 to –1.1 V for La-, Pr-, Nd-, and Sm-containing compounds when illuminated near the optical band gap, indicating that these oxysulfides are n-type semiconductors, which is consistent with Mott–Schottky analysis. Photovoltages under sub-band gap illumination energy and photovoltage decay data suggest mid-band gap states possibly arising from the lanthanoid 4f orbitals and/or defects within the crystal structure or at the particle surfaces. These photophysical properties suggest possible applications of the oxysulfides in photoelectrochemical and photovoltaic energy conversion.

14 SOLAR ENERGY↗
DOE OSTI2026

Photophysical Properties and Phase Behavior of Ultrawide Photovoltaic Bandgap Cesium–Lead-Based Triple Halide Perovskites

Metal halide perovskite films in the top cell of triple-junction tandems require bandgaps around 2.0 eV to achieve current matching, assuming that the middle absorbing layer is the commonly used FAPbI 3 composition and the bottom cell has a bandgap around 1.1 eV. Unfortunately, mixed organic/inorganic metal halide perovskites that have the necessary Br content to reach a bandgap of 2.0 eV segregate into iodine-rich and bromine-rich phases under illumination, limiting their obtainable voltage. Previous reports have shown improved photostability using either Cs-based inorganic compositions or Cl incorporation on the X-site. Here, we investigate the inorganic triple halide compositional space CsPb­(I 1–x–y Br y Cl x ) 3 where bandgaps near 2.0 eV are expected based on the knowledge that CsPbI2Br has a bandgap of 1.90 eV. Incorporation of Cl occurs readily for x ≤ 0.07–0.10 within perovskites with a Br content of 0.3 ≤ y ≤ 0.42. When x >0.1, X-ray diffraction and photoluminescence (PL) measurements indicate that multiple compositional phases form. We hypothesize that the variable sizes of the three halide ions are not supported within the rigid Cs lattice, resulting in the formation of multiple compositional phases. The photoluminescence quantum yield of the single-phase compositional space–CsPb­(I 1–x–y Br y Cl x ) 3 where x ≤ 0.07was typically 0.001–0.004%, most likely as a result of a high defect density, including mobile iodine species. PL light-soaking measurements of many perovskite compositions with bandgaps in the range of 1.89–2.05 eV demonstrate that phase segregation occurs when initial bandgaps are above 1.95 eV regardless of halide content: indicating further iodide oxidation and corresponding migration under illumination. The conclusion is that further compositional or additive engineering is necessary for the development of inorganic triple halide compositions that accomplish the elusive goal of fabricating high-quality and photostable 2.0 eV films for use in multijunction tandems.

Electrical conductivity↗
DOE OSTI2023

Light- and Chemical-Doping-Induced Magnetic Behavior of Eu Molecular Systems

Variable temperature electron paramagnetic resonance (VT-EPR) was used to investigate the role of the environment and oxidation states of several coordinated Eu compounds. We find that while Eu(III) chelating complexes are diamagnetic, simple chemical reduction results in the formation of paramagnetic species. In agreement with the distorted D 3h symmetry of Eu molecular complexes investigated in this study, the EPR spectrum of reduced complexes showed axially symmetric signals (g ⊥ = 2.001 and g ∥ = 1.994) that were successfully simulated with two Eu isotopes with nuclear spin 5/2 ( 151 Eu and 153 Eu with 48% and 52% natural abundance, respectively) and nuclear g-factors 151 Eu/ 153 Eu = 2.27. Illumination of water-soluble complex Eu(dipic) 3 at 4 K led to the ligand-to-metal charge transfer (LMCT) that resulted in the formation of Eu(II) in a rhombic environment (g x = 2.006, g y = 1.995, g z = 1.988). The existence of LMCT affects the luminescence of Eu(dipic) 3 , and pre-reduction of the complex to Eu(II)(dipic) 3 reversibly reduces red luminescence with the appearance of a weak CT blue luminescence. Furthermore, encapsulation of a large portion of the dipic ligand with Cucurbit[7]uril, a pumpkin-shaped macrocycle, inhibited ligand-to-metal charge transfer, preventing the formation of Eu(II) upon illumination.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Catalight─An Open-Source Automated Photocatalytic Reactor Package Illustrated through Plasmonic Acetylene Hydrogenation

An open-source and modular Python package, Catalight, is developed and demonstrated to automate (photo)catalysis measurements. (Photo)catalysis experiments require studying several parameters to evaluate performance, including the temperature, gas flow rate and composition, illumination power, and spectral profile. Catalight orchestrates measurements over this complicated parameter space and systematically stores, analyzes, and visualizes the results. To showcase the capabilities of Catalight, we perform an automated apparent activation barrier measurement of acetylene hydrogenation over a plasmonic AuPd catalyst on an Al 2 O 3 support, simultaneously varying laser power, wavelength, and temperature in a multiday experiment controlled by a simple Python script. Our chemical results unexpectedly show an increased activation barrier upon light excitation, contrary to previous findings for other plasmonic reactions and catalysts. We show that the reaction rate order with respect to both acetylene and hydrogen remains unchanged upon illumination, suggesting that molecular surface coverage is not changed by light. By analyzing the inhomogeneity of the laser-induced heating, we attribute these results to a partial photothermal effect combined with a photochemical/hot electron-driven mechanism. In conclusion, our findings highlight the capabilities of a new experiment automation tool; explore the photocatalytic mechanism for an industrially relevant reaction; and identify systematic sources of error in canonical photocatalysis experimental procedures.

Catalysts↗
DOE OSTI2021

Exploring Responses of Contact Kelvin Probe Force Microscopy in Triple-Cation Double-Halide Perovskites

Hybrid organic–inorganic perovskite (HOIP) solar cells have undergone unprecedentedly rapid improvement in power conversion efficiencies during the last decade, but controversy remains regarding the role of local phenomena and heterogeneity in grain by grain. These challenges in turn necessitate understanding the fundamental mechanisms operating at individual grains and exploring how these mechanisms give rise to the collective behaviors of the films. Although numerous efforts have targeted local phenomena in these materials using classical scanning probe microscopy modalities, the measurements remain difficult to interpret due to intrinsic coupling between possible ferroelectric, ion migration, bulk and surface electrochemical phenomena, and the effects of light on these behaviors. Here, we explore the electromechanical responses in (Cs 0.05 FA 0.85 MA 0.15 )Pb(I 0.85 Br 0.15 ) 3 perovskite thin film in the dark and under illumination using band excitation-piezoresponse force microscopy (BE-PFM). To identify and separate ferroic, electrostatic, and electrochemical responses, we utilize contact-Kelvin probe force microscopy (cKPFM). The cKPFM responses show weak variability with morphological features in the dark, while such variability significantly increases under illumination. Deconvolution of the cKPFM responses via principal component analysis (PCA) shows heterogeneity in grain to grain possibly due to variation in migration and segregation of halide ions in mixed perovskites at specific grains. Further, we propose an electrostatic mechanism based on the physics of semiconductors, which can directly link the observed cKPFM behaviors with the ionic and electronic density of states (DOS) and their time dynamics. Here, these findings suggest that cKPFM is a powerful probe of local ionic behaviors on the nanoscale, both in HOIPs and other materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Interfacial Properties of Gold and Cobalt Oxyhydroxide in Plasmon-Mediated Oxygen Evolution Reaction

Water electrolysis is one green approach of storing electrical energy within chemical bonds of the high-energy hydrogen gas (H2). The anodic reaction involved in the oxygen evolution reaction (OER) requires high kinetic overpotential on the overall rate of the process. Recently, plasmonic gold nanoparticles (Au NPs) have been added to enhance the charge transfer at the interface of the OER electrocatalysts and electrolyte under light illumination. However, mechanistic understanding of how Au NPs on the photo-assisted electrochemical process is still lacking. We applied a model system of plasmonic Au electrode and a cobalt (Co)-based OER electrocatalyst in alkaline electrolytes to investigate the plasmon-mediated OER process with (photo)electrochemical and spectroscopic studies. Our results demonstrated that the electrodeposited and surfactant-free plasmonic Au electrode could enhance the electrocatalytic performances of the Co-based electrocatalysts in the OER process with continuous visible and near infrared light illumination. Both the photothermal and energetic charge carriers were found to contribute to the enhanced OER performance based on the transient photocurrent studies, and the interfaces of Au and the Co-based electrocatalysts determined the enhancement mechanisms. The active phase of the cobalt based OER electrocatalyst at operating potentials was identified with electrochemical Raman measurements.

OER↗
DOE OSTI2025

Redox Couples Control Band Bending, Photovoltage, and Quasi-Fermi Levels in Tungsten Oxide (WO 3 ) Photoanodes

Tungsten oxide (WO 3 ) is a well-known photoanode and photocatalyst for photoelectrochemical (PEC) water oxidation. Because the compound has a deep valence band, it can facilitate the oxygen evolution reaction without added cocatalysts, and it can drive the oxidation of species with much higher electrochemical potentials, including the conversion of water to hydrogen peroxide, sulfate to persulfate, and iodate to meta-periodate. Here, we use the liquid vibrating Kelvin probe surface photovoltage (liquid VK-SPV) technique in combination with open circuit potential (OCP) and photoelectrochemical (PEC) scans to assess the possibility of reaching such oxidizing potentials in aqueous electrolytes and at open circuit. Here, this is done by mapping the quasi-Fermi levels of electrons and holes at the interfaces as a function of the light intensity. Nanostructured WO 3 photoelectrodes for this purpose were fabricated by thermal annealing of a tungstic acid solution on fluorine-doped tin oxide. Electrochemical measurements are conducted at open circuit and 400 nm LED light illumination in electrolytes containing fast (O 2 /H 2 O 2 ), slow (O 2 /H 2 O), and very oxidizing (NaIO 4 /NaIO 3 ) redox couples. Photovoltage values scale with the light intensity and with the built-in potential for each redox couple and reach values up to 0.61 V under 20 mW cm –2 illumination for the NaIO 4 electrolyte. This shows that the photoelectrodes behave like Schottky-type diodes whose maximum possible energy output is determined mainly by the built-in voltage of each junction. For slow redox couples, the quasi-Fermi level of the holes increases with light intensity due to hole accumulation at the WO 3 –liquid interface. For example, for the O 2 /H 2 O electrolyte, interfacial hole accumulation and removal occur on the 90–300 s time scale. For the fast hole acceptor H 2 O 2 , on the other hand, the quasi-Fermi level of the photoholes is pinned to the electrochemical potential of the O 2 /H 2 O 2 couple. This limits the energy conversion efficiency of the electrode. Overall, these results reveal the influence of charge transfer thermodynamics and kinetics on the photovoltage of WO 3 . Furthermore, the work further establishes VK-SPV as a contactless method to observe the photovoltage, carrier dynamics, and quasi-Fermi levels of semiconductor-liquid junctions.

Electrodes↗
DOE OSTI2026

Light-Driven Iodine Loss and Photoluminescence Homogenization in Mixed-Halide Perovskite Semiconductors

Carrier-induced instabilities in lead halide perovskites are often investigated as either transient phenomena, e.g., photoinduced halide segregation or permanent performance changes, e.g., photodegradation, while the mechanistic links between them remain unclear. Here, we aim to connect these observations by studying a model mixed-halide system, MAPb(Br x I 1–x ) 3 . By combining grazing-incidence X-ray diffraction, photothermal deflection spectroscopy, and photoluminescence measurements with hyperspectral microscopy, we investigate the role of mobile halide defects and local chemistry on reversible and long-term instabilities in these materials. Our results show that mixed-halide perovskites are uniquely susceptible to photoinduced changes with illumination driving initial iodide redistribution (i.e., halide segregation), eventual selective iodine expulsion, and subsequent changes in photoinduced halide segregation behavior. By quantifying structural and compositional changes, we estimate an approximately 3–5% iodine loss in our mixed-halide samples after only 24 h of illumination. Further, using microscale measurements, we identify pre-existing iodide-rich domains as key contributors to both the observed transient photostability and permanent iodine loss in MAPbBrI 2 , and see evidence that extended light soaking results in iodide redistribution that improves optoelectronic homogeneity. Overall, our results emphasize the importance of carrier-induced halide oxidation in creating a dynamic defect landscape in mixed-halide perovskites and provide a framework for interpreting apparent light-driven changes in optoelectronic behavior through the lens of permanent compositional changes.

electrical conductivity↗
DOE OSTI2021

Probing Charge Dynamics in Diamond with an Individual Color Center

Control over the charge states of color centers in solids is necessary to fully utilize them in quantum technologies. However, the microscopic charge dynamics of deep defects in wide-band-gap semiconductors are complex, and much remains unknown. We utilize a single-shot charge-state readout of an individual nitrogen-vacancy (NV) center to probe the charge dynamics of the surrounding defects in diamond. We show that the NV center charge state can be converted through the capture of holes produced by optical illumination of defects many micrometers away. With this method, we study the optical charge conversion of silicon-vacancy (SiV) centers and provide evidence that the dark state of the SiV center under optical illumination is SiV 2– . These measurements illustrate that charge carrier generation, transport, and capture are important considerations in the design and implementation of quantum devices with color centers and provide a novel way to probe and control charge dynamics in diamond.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2023

Spin Solar Cell Phenomenon on a Single-Molecule Magnet (SMM) Impacted CoFeB-Based Magnetic Tunnel Junctions

The single-molecule magnet (SMM) is demonstrated here to transform conventional magnetic tunnel junctions (MTJs), a memory device used in present-day computers, into solar cells. For the first time, we demonstrated an electronic spin-dependent solar cell effect on an SMM-transformed MTJ under illumination from unpolarized white light. We patterned cross-junction-shaped devices to form a CoFeB/MgO/CoFeB-based MTJ. The MgO barrier thickness at the intersection between the two exposed junction edges was less than the SMM extent, which enabled the SMM molecules to serve as channels to conduct spin-dependent transport. The SMM channels yielded a region of long-range magnetic ordering around these engineered molecular junctions. Our SMM possessed a hexanuclear [Mn 6 (μ 3 -O) 2 (H 2 N-sao) 6 (6-atha) 2 (EtOH) 6 ] [H 2 N-saoH = salicylamidoxime, 6-atha = 6-acetylthiohexanoate] complex and thioesters end groups to form bonds with metal films. SMM-doped MTJs were shown to exhibit a solar cell effect and yielded ≈80 mV open-circuit voltage and ≈10 mA/cm 2 saturation current density under illumination from one sun equivalent radiation dose. A room-temperature Kelvin Probe AFM (KPAFM) study provided direct evidence that the SMM transformed the electronic properties of the MTJ’s electrodes over a lateral area in excess of several thousand times larger in extent than the area spanned by the molecular junctions themselves. As a result, the decisive factor in observing this spin-photovoltaic effect is the formation of SMM spin channels between the two different ferromagnetic electrodes, which in turn is able to catalyze the long-range transformation in each electrode around the junction area.

14 SOLAR ENERGY↗
DOE OSTI2022

Understanding Mass Transport in Copper Electrolyte-Based Dye-Sensitized Solar Cells

Copper redox shuttles, particularly [Cu(tmby) 2 ] 2+/1+ (tmby = bis(4,4',6,6'-tetramethyl-2,2'-bipyridine)), proved to be among the best electrolytes for dye-sensitized solar cells (DSCs), realizing higher power conversion efficiencies both under full sun and indoor illumination than conventional iodide/triiodide and cobalt electrolytes. Even though [Cu(tmby) 2 ] 2+/1+ renders a relatively higher performance, this metal complex is bulky and is limited by mass transport. Since the regeneration of the dye ground state by Cu I and the reaction of Cu II at the counter electrode are comparatively faster processes, the efficiency of DSC involving Cu I /Cu II electrolytes under relatively high light intensities is largely governed by the diffusion of Cu I /Cu II species. Understanding mass transport in these solar cells will enable further improvements in the performance of such copper-based DSCs. Here in the present study, the role of illumination intensity on the photogenerated current and its relationship to mass transport is evaluated using the best cosensitized dye (D35:XY1) and copper electrolyte ([Cu(tmby) 2 ] 2+/1+ ) combination.

14 SOLAR ENERGY↗
DOE OSTI2021

Understanding the Stability of Etched or Platinized p-GaInP Photocathodes for Solar-Driven H 2 Evolution

The long-term stability in acidic or alkaline aqueous electrolytes of p-Ga 0.52 In 0.48 P photocathodes, with a band gap of ~1.8 eV, for the solar-driven hydrogen-evolution reaction (HER) has been evaluated from a thermodynamic, kinetic, and mechanistic perspective. At either pH 0 or pH 14, etched p-GaInP electrodes corroded cathodically under illumination and formed metallic In 0 on the photoelectrode surface. In contrast, under the same conditions, electrodeposition of Pt facilitated the HER kinetics and stabilized p-GaInP/Pt photoelectrodes against such cathodic decomposition. When held at 0 V versus the reversible hydrogen electrode, p-GaInP/Pt electrodes in either pH = 0 or pH = 14 exhibited stable current densities (J) of ~-9 mA cm -2 for hundreds of hours under simulated 1 sun illumination. During the stability tests, the current density-potential (J-E) characteristics of the p-GaInP/Pt photoelectrodes degraded due to pH-dependent changes in the surface chemistry of the photocathode. This work provides a fundamental understanding of the stability and corrosion mechanisms of p-GaInP photocathodes that constitute a promising top light absorber for tandem solar-fuel generators.

14 SOLAR ENERGY↗
DOE OSTI2026

Syngas Production at Si Hybrid Photoelectrodes Modified with Re(I) and Mn(I) Tricarbonyl Phenanthroline Complexes Containing Reactive Aryl Azide Groups

We installed molecular CO 2 reduction (CO 2 R) catalysts directly onto Si (photo)electrodes. The highly reactive M(5-azido-1,10-phenanthroline)(CO) 3 X (where M = Mn or Re, X = Br or Cl) complexes readily bubbled when dissolved in polar organic solvents, in both the presence and absence of an ultraviolet light source. When placed on hydrogen-terminated Si (H-Si) and native silicon oxide (SiOx), similar amounts of the complex were attached to the surface under illumination (367 nm, 50–200 mW/cm 2 ) or in the dark. Surprisingly, these films revealed submonolayer coverages instead of the multilayered structures we expected. DFT analyses support monolayer formation, showing that the triplet-state nitrene of the complex is more energetically favorable than the singlet state. Using controlled-potential electrolysis experiments, we showed that Re- and Mn-containing films on pSi photoelectrodes generated small amounts of CO when exposed to 1 atm of CO 2 and 1 sun illumination. These amounts of CO were an order of magnitude greater than control surfaces, producing 5.59 × 10 –7 mol CO/h for Re(az-phen) and 7.83 × 10 –7 mol CO/h for Mn(az-phen) films. Much of the charge passed at the pSi electrodes was consumed by the competing hydrogen evolution reaction, which we attribute to the low molecular coverage and the presence of native oxide on the electrode surface after attachment. Finally, this work demonstrates the feasibility of reacting azide-containing ligands with Si surfaces. Still, it highlights the need for alternative ligand structures and reaction conditions to form multilayer films.

azides↗
DOE OSTI2025

ZnTiN 2 as an Electron-Selective, Protective Layer on Si Photocathodes

Photoelectrochemical production of fuels requires photoelectrodes that efficiently convert sunlight to electrochemical energy by producing photovoltage and photocurrent and maintain this ability over time under a variety of pH, illumination, and applied bias conditions. Work in the photovoltaic community has demonstrated that interfaces with high charge carrier selectivity provide high photovoltages. This offers a co-design opportunity to create semiconductor photoelectrodes with contact layers that are both carrier-selective and offer protection from degradation in aqueous solutions. In this work, we explored the ternary nitride ZnTiN 2 as an electronselective, protective layer for Si-based photocathodes. We demonstrated that ZnTiN 2 formed a heterojunction with p-type Si that facilitated electron movement toward the ZnTiN 2 surface for light-driven reduction reactions. Across a variety of electrolyte conditions, ZnTiN 2 /Si produced an open circuit voltage of ca. 400 mV vs the solution potential, while bare Si produced 220−480 mV vs the solution potential depending on conditions. ZnTiN 2 was also shown to protect Si over 72 h at open circuit in the dark in 0.1 M KHCO 3 aqueous solution at pH 10.5, with a 2.4% loss in open circuit voltage compared to a 17% loss for unprotected Si. A protective effect was also observed under illumination during methyl viologen reduction at pH 3.5 for 21 h, with a 2.5% loss in open circuit voltage observed for ZnTiN 2 /Si compared to a 25% loss in open circuit voltage for unprotected Si under the same conditions. Elemental characterization revealed the presence of oxides on the surface of ZnTiN 2 that are consistent with the Pourbaix diagram after photoelectrochemical operation; these oxides appeared to support durability without hindering charge carrier extraction to drive electrochemical work. This work highlights the promise of ZnTiN 2 for durable photoelectrochemical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

All-Perovskite Tandem Photoelectrodes for Unassisted Solar Hydrogen Production

Unassisted solar water splitting by multi-junction tandem photoelectrodes is a sustainable approach to generating green hydrogen fuels. Here, we report on the fabrication of monolithically integrated all-perovskite tandem photocathodes for efficient unassisted solar water splitting. All-perovskite tandem photocathodes wired to an iridium oxide anode deliver a high photovoltage of more than 2 V with an operating photocurrent density of 12.5 mA cm -2 at zero applied bias under simulated AM1.5G one sun illumination, yielding a solar-to-hydrogen (STH) conversion efficiency of 15%. The tandem photoelectrode demonstrates continuous operation for more than 120 hours in water under simulated one-sun illumination with less than 5% efficiency loss. A technoeconomic analysis shows the projected production cost of all-perovskite tandem photoelectrodes is $\$30$ m -2 , promising a levelized cost of hydrogen of less than $\$1$/kg if sufficient device longevity is realized. Finally, this work provides a path toward achieving cost-effective unassisted solar hydrogen fuel production.

08 HYDROGEN↗
DOE OSTI2024

CO 2 Conversion to Butene via a Tandem Photovoltaic–Electrochemical/Photothermocatalytic Process: A Co-design Approach to Coupled Microenvironments

Here, we developed a tandem, unassisted, solar-driven electrochemical and photothermocatalytic process for the single-pass conversion of CO 2 to butene using only simulated solar irradiation as the energetic input. The two-step process involves electrochemical CO 2 reduction (CO 2 R) to ethylene followed by ethylene dimerization to butene. We assessed two unassisted electrochemical setups to concentrate ethylene in the CO 2 R reactor, achieving concentrations up to 5.4 vol.% with 1.8% average solar-to-ethylene conversion and 5.6% average CO 2 -to-ethylene single-pass conversion under 1-sun illumination. When passed through the photothermocatalytic ethylene oligomerization reactor, we generated 600 ppm of butene under 3-sun illumination. Through analysis of this process, we identified that the presence of H 2 , CO, and H 2 O leads to rapid deactivation of the Ni-based ethylene oligomerization catalyst.

14 SOLAR ENERGY↗
DOE OSTI2025

Red Light-Powered Nanowire Photochemical Diodes for Unassisted Hydrogen Evolution and Glycerol Valorization

Artificial photosynthesis via unassisted photochemical diodes is a promising approach for generating solar fuels. However, photoelectrochemical systems often degrade under solar diurnal cycling, and reliance on solar insolation exacerbates land use. Narrow-band LED illumination offers continuous and constant operation, enabling the vertical integration of stable photochemical diodes. In this study, 740 nm red light was investigated as the illumination source for silicon-based photochemical diodes integrating the hydrogen evolution reaction with the glycerol oxidation reaction (GOR), where replacing the oxygen evolution reaction with GOR increases attainable bias-free photocurrents. Increasing photovoltages, saturation current densities, and power conversion efficiencies were observed with increasing incident red light intensity. Under a red light intensity of 60 mW cm –2 , these systems are stable above 7.5 mA cm –2 for 6 days with periodic electrolyte refreshing. In conclusion, these results offer a promising prospect for red light-powered photochemical diodes that integrate other significant reduction reactions, such as CO 2 reduction.

Alcohols↗