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At least 37 records · Page 2

Two Artificial Leaf Architectures for Solar Formate Production From CO 2 and H 2 O

Sunlight-powered artificial leaves for the production of formate from CO 2 are an attractive route to solar fuels, yet existing solar formate devices remain low in performance, and their architecture and material choices are underexplored. Herein, we report the fabrication of two distinct fully integrated, self-standing solar formate device architectures and elucidate the underlying design principles and material selection strategies. The first architecture integrates a Si photocathode with a BiVO 4 photoanode and utilizes a highly active Pd catalyst for CO 2 reduction. It represents the first artificial leaf device comprising two photoelectrodes (excluding photovoltaic [PV]-biased electrodes) for effective formate production under single-beam illumination. The second architecture employs a dark cathode and a dark anode driven by a 4-junction perovskite solar cell and uses a highly stable Bi catalyst for CO 2 reduction. This device delivers a record-high formate production rate of 174 µmol h −1 with a remarkable solar-to-formate energy efficiency of 2% among all artificial leaf devices reported to date. Finally, these results demonstrate the feasibility and outline the design principles of both PV-free and PV-assisted device architectures in solar fuel production.

electrocatalysis

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

Controlling Nb(IV) Defects in SrNbO 2 N Oxygen Evolution Photocatalyst by Ammonolysis With Dinitrogen–Ammonia Mixtures

Strontium niobium oxynitride (SrNbO 2 N) is a promising, corrosion resistant semiconductor for the visible light-driven water splitting reaction, a non-photovoltaic pathway to green hydrogen fuel. However, SrNbO 2 N materials made by ammonolysis usually contain Nb 4+ defect states that cause electron–hole recombination. Here, in this work, we demonstrate that such defects can be minimized by synthesizing SrNbO 2 N from metal oxides in a mixed 13%:87% (vol) NH 3 /N 2 atmosphere. According to electron paramagnetic resonance (EPR), SrNbO 2 N made in pure NH 3 contains paramagnetic impurities with g = 2.002 and 2.195, which can be assigned to lattice and surface Nb 4+ defects. These states also cause broad optical absorptions centered at 800 and 1020 nm, respectively, and the lattice defect produces a 1.55–1.63 eV signal in surface photovoltage spectra. The improved SrNbO 2 N contains five times fewer lattice Nb 4+ defects (8.95 × 10 15 cm −3 ), based on the integrated EPR signal intensity, and supports a water oxidation photocurrent of 1.07 mA cm −2 at 1.23 V versus RHE under simulated sunlight and an apparent quantum efficiency of 5.1% at 400 nm during photocatalytic oxygen evolution. Based on earlier results with LaTiO 2 N and BaTaO 2 N, dilution of NH 3 during synthesis appears generally beneficial to transition metal oxynitrides.

electron paramagnetic resonance

UV-Induced Degradation and Associated Metastability in TOPCon Photovoltaic Modules: Understanding Kinetics and Cell Variance

Tunnel oxide passivated contact (TOPCon) silicon photovoltaic (PV) modules are dominating the PV market, but they may be susceptible to degradation under ultraviolet (UV)-containing light. Quantifying the impacts of UV-induced degradation (UVID) is complicated by an associated metastability causing further degradation under dark storage and rapid recovery under sunlight. Here, we study modules that have -2.3% to -3.2% nonrecoverable UVID loss after 60 kWh/m2 dose of 340 nm light and additional recoverable loss under dark storage. We use in situ electroluminescence (EL) imaging to characterize the post-UVID metastability at the module level. The cell-by-cell dark degradation and recovery kinetics span a wide range from +6% to -70% changes in EL intensity after 520 h of dark storage, which returns to +- 4% of the initial post-UVID EL intensity after illumination. The kinetics follow double exponential rates with dark storage degradation time constants of 345 and 45 h, and UV light recovery time constants of 5 min and 36 s. We propose that this is consistent with prior reports of kinetics for light-soaking metastability in Al2O3 passivation. Finally, we further show that cells having high UVID also have injection-dependent effective carrier lifetimes and significant intra-cell variance, suggesting possible origins of processing inconsistency.

14 SOLAR ENERGY

Photoelectrochemical materials for solar energy conversion

Research and development on semiconductors for applications in solar energy conversion has witnessed rapid growth over the past several decades. With the aim of producing chemical fuels from sunlight, intense research efforts have focused on the discovery of semiconductors with crystalline structures and chemical compositions that have the potential to satisfy the complex set of required photoelectrochemical properties. This chapter focuses on the foundational structure-property relationships of selected oxide and nitride semiconductors relevant to their uses as n-/p-type photoelectrodes and as photocatalysts. Their solid-state structures and compositions are described, with a special emphasis on strategies proven effective at targeting suitable band gaps with strong visible-light absorption, efficient charge separation and diffusion of charge carriers, and optimal band edge energies for driving surface redox reactions for water splitting.

O’Donnell, Shaun

Feeding from the sun—Successes and prospects in bioengineering photosynthesis for food security

There is an urgent need for increased crop productivity to reduce food insecurity and improve sustainability. Photosynthesis converts sunlight energy into carbohydrates, providing the source of nearly all of humanity’s food. Photosynthesis is a key target for improvement, owing to inherent inefficiencies in the biochemical process. Over the last decade of advancements in bioengineering, strategies to increase the efficiency of photosynthesis were tested with proven enhancements to crop yields in field trials. Simple strategies like increasing the content of photosynthetic proteins have reliably increased photosynthesis and productivity in crops, as have more complex strategies such as bypassing photorespiration. While insertion of carbon-concentrating mechanisms into C3 plants remains an engineering challenge, modeling suggests that achieving that would have the greatest gain for crop improvement. This review discusses the many successes in improving photosynthesis achieved over the past decade and quantifies the potential for future engineering targets to increase crop productivity.

Long, Stephen P. [University of Illinois, Urbana,

Toward solar light-driven photochemical carbon dioxide separation

The feasibility of energy-efficient photochemically driven CO 2 release has been demonstrated in several recent reports, but the regeneration step remains much slower. Recently in Chem, Ahmad et al. reported a fully visible-light-driven CO 2 separation system capable of operating with concentrated sunlight. Here, we discuss this advance and the potential route toward large-scale fully photochemical CO 2 capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

The influence of ambient light spectrum (LED, INC, CFL, Xenon…) on the efficiency of perovskite indoor photovoltaic solar cells for Internet of Things (IoT) applications

This record provides a numerical investigation of a MAGeI₃-based perovskite solar cell with the structure FTO/TiO₂/MAGeI₃/Spiro-OMeTAD, evaluated for both outdoor and indoor light-harvesting applications using the SCAPS-1D simulator. Device performance is analyzed under AM 1.5G sunlight and several artificial light sources, including LED, incandescent, compact fluorescent lamp (CFL), flashlight, and xenon illumination. The study reports initial and optimized power conversion efficiencies and examines the influence of absorber layer thickness and bandgap on device performance under different lighting conditions. The results highlight the potential of MAGeI₃-based perovskite solar cells for indoor energy harvesting and low-power Internet of Things (IoT) applications.

14 SOLAR ENERGY

A proposed high-intensity radiometer calibration method using concentrated solar radiation

Accurate calibration of irradiance measurement devices, or radiometers, is essential for ensuring the reliability of measurements in high heat applications such as concentrating solar power (CSP), aerospace, defense, and pulsed power systems. Despite the critical need, existing calibration standards and service providers are limited to irradiance levels below 100 kW/m 2 and specific radiation sources, which is insufficient for many applications. For instance, CSP technologies, particularly those under the Department of Energy’s Solar Energy Technologies Office (SETO) Gen 3 program, require accurate measurements of broadband irradiance at levels exceeding 2000 kW/m 2 . In even more extreme scenarios, such as re-entry vehicles, heat levels can surpass 10000 kW/m 2 . Current ISO standards, specifically ISO 14934–2 and ISO 14934–3, are constrained to lower irradiance levels and dependent on black body heat sources, limiting their applicability for high-intensity broadband irradiance measurements, particularly in concentrated solar applications. Here, to address this shortfall, the National Solar Thermal Test Facility (NSTTF) at Sandia National Laboratories (SNL) proposes a calibration method and facility capable of characterizing radiometers up to 2750 kW/m 2 using concentrated solar irradiance. Calibrating with concentrated sunlight is important for solar applications as it aligns the calibration process with the solar spectrum. This alignment is crucial for minimizing systematic errors and avoiding the need for additional corrections that may arise when radiometers designed for solar applications are calibrated using black-body or electrical sources. This paper presents the present day NSTTF characterization facility and procedure, detailing the proposed calibration method and uncertainty quantification. The presented method builds upon 1980′s NSTTF methodology and involves both theoretical and empirical methods to establish a robust relationship between gauge voltage output and irradiance intensity, quantifying both measurement and fitting errors. By addressing the limitations of existing standards and extending the characterization range, this work provides an advancement in the field of high-intensity irradiance measurement and instrumentation characterization.

Gardon gauge

Abiotic manganese oxide formation induced by light and copper-driven Fenton chemistry

Redox-active transition metals such as manganese (Mn) and copper (Cu) frequently coexist in surface water systems, where their interactions can significantly influence contaminant fate and water quality. It is widely known that the oxidation of Mn 2+ (aq) to Mn(IV) oxide solids is driven mainly by biotic processes in which Cu 2+ serves as an inhibitor of Mn oxidation. However, Cu 2+ can also trigger Fenton reactions to produce reactive oxygen species (ROS) capable of promoting the abiotic Mn oxidation (i.e., without the involvement of biological organisms), through an alternative natural pathway that remains overlooked in water. In this study, we found that the abiotic oxidation of Mn 2+ can be facilitated by the co-existence of sunlight and Cu 2+ . By contrasting Cu 2+ with other divalent cations, such as Ca 2+ , Mg 2+ , and Zn 2+ , this investigation highlights the distinct role of Cu 2+ in promoting Mn oxidation. Moreover, the study elucidated how light induces ROS to trigger Cu-driven photo-Fenton reactions and identified the roles of ROS in Mn oxidation. Chemical-Fenton reactions (i.e., the interaction between Cu and H 2 O 2 in the absence of light) were also examined for their contribution to the Cu-driven Mn photo-oxidation, supporting the involvement of Fenton chemistry in Mn oxidation. By elucidating the novel photochemical mechanism of Mn oxide formation, our findings advance the understanding of heavy metal interactions in aqueous environments and highlight the intricate roles of Cu 2+ in affecting elemental cycling and the evaluation of heavy metal contamination in water resources. This discovery also underscores the critical contribution of co-existing Fenton-active metals in forming Mn oxide solids.

Abiotic Mn oxidation

Chemistry of Materials Underpinning Photoelectrochemical Solar Fuel Production

Since its inception, photoelectrochemistry has sought to power the generation of fuels, particularly hydrogen, using energy from sunlight. Efficient and durable photoelectrodes, however, remain elusive. Here we review the current state of the art, focusing our discussion on advances in photoelectrodes made in the past decade. We open by briefly discussing fundamental photoelectrochemical concepts and implications for photoelectrode function. We next review a broad range of semiconductor photoelectrodes broken down by material class (oxides, nitrides, chalcogenides, and mature photovoltaic semiconductors), identifying intrinsic properties and discussing their influence on performance. We then identify innovative in situ and operando techniques to directly probe the photoelectrode|electrolyte interface, enabling direct assessment of structure–property relationships for catalytic surfaces in active reaction environments. We close by considering more complex photoelectrochemical fuel-forming reactions (carbon dioxide and nitrogen reduction, as well as alternative oxidation reactions), where product selectivity imposes additional criteria on electrochemical driving force and photoelectrode architecture. By contextualizing recent literature within a fundamental framework, we seek to provide direction for continued progress toward achieving efficient and stable fuel-forming photoelectrodes.

08 HYDROGEN

Ammonolysis Under NH 3 –Limiting Conditions as a Pathway to Improved LaTiO 2 N Water Splitting Photoanodes

LaTiO 2 N is a promising intermediate band gap semiconductor for the water splitting reaction, a pathway to hydrogen fuel from solar energy. However, the photoelectrochemical (PEC) activity of the material is hindered by defects, particularly Ti(III) species, which promote photocarrier recombination. These defects are formed during the high-temperature ammonolysis reaction. Here we show that improved LaTiO 2 N materials can be synthesized under NH 3 -limiting conditions by introducing N 2 to lower the NH 3 partial pressure to0.13atm.This reduces the Ti(III) defect density in the material from 6.06 × 10 16 to ∼4.61 × 10 15 cm −3 , by a factor of 13, based on electron paramagnetic resonance (EPR) spectroscopy. Any remaining Ti(III) defects are localized at the LaTiO 2 N surface, according to X-ray photoelectron spectroscopy (XPS), due to the formation of a depletion layer in the semico. Optical absorption spectra of the improved LaTiO 2 N reveal a blue-shifted band gap absorption edge and a suppressed sub-band gap absorption. Defect removal also reduces a sub-band gap surface photovoltage feature visible in the 1.0 atm reference material. The improved LaTiO 2 N supports a 1.57 mA cm −2 water oxidation photocurrent at 1.23 V RHE under simulated sunlight conditions, and an enhanced quantum efficiency of 4.5% (400 nm) for photocatalytic oxygen evolution from aqueous silver nitrate solution. Stable PEC operation is observed for over 55 min. This confirms that ammonolysis under NH 3 -limiting conditions improves the solar energy conversion properties of LaTiO 2 N. The ability to control metal ion defects in oxynitrides by varying the ammonia partial pressure during ammonolysis might be generally useful for the preparation of metal nitrides and oxynitrides.

defects

Aircraft Measurements from a U.S. Western Wildfire Demonstrating Day and Night Differences in the Chemical Composition and Optical Properties of Biomass Burning Aerosols and Their Atmospheric Evolution

The composition and transformations of biomass burning aerosols (BBA) have been measured onboard the NOAA Twin Otter research aircraft during the Fire Influence on Regional to Global Environments and Air Quality field study. Here, we analyze real-time aerosol mass spectrometry measurements across three flights during the afternoon, late afternoon, and night of August 28, 2019, for one midsized wildfire. Analysis of several metrics showed that the aerosol composition and optical properties varied depending on the burning conditions at the fire zone and the time of day the BBA was emitted, with substantial variations in the available sunlight. The total aerosol mass loadings were dominated by organic components with a much smaller contribution from inorganic species. A gradual buildup of organic material was observed during the afternoon as the plume aged, indicating the condensation of photochemically formed low-volatility oxidized organic compounds. Highly hygroscopic ammonium nitrate was the main inorganic component, suggesting potential water content in BBA particles and the likelihood of their aqueous-phase reactivity. Depletions of particle-phase NO 3 – and Cl – relative to carbon monoxide were observed in the late afternoon and nighttime plumes, respectively, aligning with known gas-particle partitioning thermodynamics and the heterogeneous chemistry of dissolved nitrate and chloride. The wavelength-dependent light absorption by aerosol species was higher for the plume sampled at night and showed no significant changes with plume age, despite observed trends in composition and mass downwind. These differences in particle composition and optical properties demonstrate that the processes involved in BBA aging are not uniform for the same wildfire over the course of the day and depend highly on when the BBA was emitted, as well as the burning phase at the emissions source.

54 ENVIRONMENTAL SCIENCES

Chemical Composition and Mixing State of Wintertime Aerosol from the European Arctic Site of Ny-Ålesund, Svalbard

The Arctic is rapidly warming, and aerosols play an increasingly important role by scattering and absorbing sunlight and by participating in cloud formation. Their optical and cloud-forming properties depend on the mixing state and chemical composition, but observations of these features remain limited. This study comprehensively characterizes 25,254 individual particles collected at Ny-Ålesund, Svalbard (November −December 2020), using microspectroscopy techniques to investigate their size, morphology, mixing state, and chemical composition. Fresh sea salt aerosols (SSA) were identified as the most abundant (∼85%), of the total observed aerosol population, with potential sources from sea spray and blowing snow. Air masses originating from the Arctic Ocean surrounding Svalbard likely contribute to increased concentrations of sub-micrometer “Fresh SSA” particles. “Aged SSA” particles (7.4%) are enriched in sulfur and nitrogen, compared to “Fresh SSA”. These elevated ratios may result from various atmospheric aging processes including the uptake of sulfuric and nitric acids. Here, our results suggest that aged SSA, with sizes larger than 300 nm, likely underwent chlorine depletion by sulfuric and nitric acids during transport. Additionally, elemental analysis reveals that both fresh and aged SSA can mix with dust particles, regardless of the SSA size (49.9% in sub-micrometer size and 50.1% in super-micrometer size, respectively). Dust particles are efficient ice-nucleating particles (INPs), and SSA is known to act as cloud condensation nuclei (CCN), and therefore, their mixtures may inherit both properties. The non-negligible number (4.4%) of SSA-dust mixtures underscores the importance of these particles as potential sources of CCN and INP in the Arctic atmosphere.

Arctic

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

Investigation of Solid Particle Reactors for Nonoxidative Dehydrogenation of Ethane: Toward Solar Thermal Ethylene Production

Concentrating solar power plants can generate renewable heat at temperatures well above those of most industrial processes. Ceramic particles irradiated with concentrated sunlight can store high-quality sensible heat and transfer this to power generation systems. These concepts and materials hold great potential to also enable thermal processes in the chemical industry, but effective strategies for transferring heat from thermal energy storage media into chemical reactors are still under development. This present work evaluated the thermal and chemical compatibility of various solid particle media (including quartz, bauxite, and alumina particles) integrated directly into tube reactors and the subsequent effects on reactor performance for the nonoxidative dehydrogenation of ethane reaction. Empty tube reactors without loaded particles (representing conventional ethane cracking coils) showed significant heat transfer limitations as the tube diameter was scaled. The incorporation of media into the reactor significantly aided heat transfer to the gaseous ethane reactant and increased its conversion by as much as 10% at similar space velocities. Despite direct contact with hydrocarbon gases, alumina and quartz media showed negligible coke formation. Even during reaction in 100% ethane feed gas at 825 °C, the average selectivity of the coke product was only 0.57% when using the quartz media. These materials further demonstrated excellent thermal stability during subsequent reoxidation in air at 800 °C, which simulated the reheating of particles in a circulating particle solar receiver. Conversely, high rates of coke formation, with a product selectivity of 27.5%, were observed on sintered bauxite particles during the reaction, likely promoted by transition metal constituents. These particles fractured upon reoxidation due to exotherms generated from coke combustion. In conclusion, while the use of cofed steam could mitigate attrition of redox-active particles, the ability of inert metal oxide particles to efficiently transfer heat to concentrated ethane reactant gas while suppressing side reactions or degradation suggests that these media could effectively couple solar thermal plants to reactors for next-generation production of ethylene and other critical chemicals.

Hydrocarbons

Anionic Lipids Regulate the Light-Harvesting Complex 1-Reaction Center Photocycle in Purple Bacteria

Photosynthetic purple bacteria can capture and convert sunlight with a remarkable, nearly 100% quantum efficiency. The light-harvesting complex 1-reaction center (LH1-RC) core complex is the membrane complex fundamentally responsible for solar energy conversion. LH1-RC has a highly conserved surrounding lipid composition known to favor anionic lipids for an unknown function. Here, in this work, we compared experimentally the rate of LH1-to-RC energy transfer in detergent, membrane nanodiscs with varying lipid compositions, purified membrane fragments, and live cells. The energy transfer rate indicated that RC turnover decreased in neutral lipids, yet was partially restored in anionic lipids, revealing an unexpected lipid dependence. In complementary molecular dynamics simulations, the anionic lipid cardiolipin showed electrostatic interactions with LH1-RC that may mediate quinone exchange, providing a mechanism for the observed lipid dependence. Overall, these results revealed that anionic lipids facilitate LH1-RC redox cycling, identifying a functional role for membrane composition in photosynthetic solar energy conversion.

bacteria

pH-Dependent Vibrational Dynamics Drives Excited-State Quenching in the Phycobiliprotein Complex PC645

Phycocyanin 645 (PC645) is a closed-form lightharvesting complex found in the lumen of the photosynthetic membrane of cryptophyte algae. These peripheral antenna complexes contain bilin chromophores that absorb sunlight and transfer excitation energy to the core antenna complexes embedded in the thylakoid membrane. The location of cryptophyte antenna complex on the luminal side of the membrane is unusual. During photosynthetic activity, the pH of the lumen drops, by up to two pH units. There is little known about how this pH-change affects the light-harvesting complexes. In this study, we report multiscale simulations using a computationally efficient density functional tight-binding framework to investigate the spectroscopy and excitation energy transfer in the PC645 complex. Complementary experiments were conducted using both steady-state and time-resolved spectroscopic measurements at low, neutral, and high pH values. Our study shows that (de)protonation of specific bilin pigments, namely, the mesobiliverdins (MBVs), modulates the excitation energies, excitonic couplings, and spectral densities. These changes cause excitation transfer rates to increase by up to a factor of two to three, leading to pH-dependent energy transfer pathways in the complex. Using this model, we calculated the pH-dependent fluorescence quantum yield of the system, obtaining quantitative agreement with the experimental results. These computational simulations, supported by experiments, identify MBVs as a more prominent excitation sink than previously realized, and that this role is tuned by pH.

Maity, Sayan [Constructor Univ., Bremen (Germany);