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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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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Effect of iodides on thermal behavior and phase partitioning in LiCl-KCl

Liquid-fueled molten salt reactors (MSRs) are designed to operate with fissile materials and, ultimately, fission products dissolved in the primary molten salt coolant. Understanding the speciation and transport of iodine—a high-yield fission product—is essential because this element’s accidental release poses significant environmental concerns due to its capacity to be readily absorbed by the human thyroid gland. Here, we report the impact of iodide species (LiI and KI) on phase transitions, phase distribution, and phase stability in LiCl–KCl-eutectic salt mixtures. The study employed a combination of computational and experimental techniques, including thermodynamic FactSage calculations, differential scanning calorimetry, and high-temperature X-ray diffraction. The results indicate that the presence of iodide (10–25 wt%) significantly alters the melting behavior of the LiCl–KCleutectic system. Adding 10 wt% LiI has a more-pronounced effect than 10 wt% KI, as LiI converts to KI, leading to formation of LiCl, thereby, altering the LiCl-KCl ratio which significantly affects the melting temperature of the mixture. Furthermore, the evolution of crystalline structure, solid-fraction composition, and the dynamics of mixed-halide solid–liquid partitioning as a function of temperature indicate the potential for selective iodide separation from chloride-salt mixtures via solid–liquid separation techniques. Overall, the presented findings provide valuable insights that are beneficial for the design and operation of MSRs, as well as for the safe handling and effective processing of used nuclear fuel using advanced pyrochemical techniques.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Life-Cycle Emissions and Human Health Implications of Multi-Input, Multi-Output Biorefineries

To meaningfully broaden the supply of fuels for the transportation sector, biofuel production must be scaled up and this requires a wider array of biomass feedstocks, including agricultural residues and organic waste. Rather than pursuing conversion of lignocellulosic biomass to fuels and anaerobic digestion of wastes as separate pathways, there are economic and environmental advantages associated with integrating these processes in a single facility. However, existing research rarely goes beyond carbon footprints in quantifying the effects of such a shift in bioenergy production. In addition to CO2, CH4, and N2O, this study explores the life-cycle air pollution (NH3, volatile organic compounds, NOx, SO2, and PM2.5), marine eutrophication, acidification, and local external cost implications of biorefineries capable of taking in crop residues, food waste, and manure to produce liquid fuel, electricity, and/or other options such as renewable natural gas (RNG), hydrogen, bioplastics, and protein-rich livestock feed. Relative to a single-input, single-output baseline, biorefineries integrated with organic waste codigestion to coproduce electricity or RNG can reduce life-cycle CO2-equivalent emissions by 84-149%, and the monetized external impacts across all scenarios range from $1.07/gallon to -$0.75/gallon ethanol.

Air pollution↗
DOE OSTI2024

Integration of Concentrating Solar Power with High Temperature Electrolysis for Hydrogen Production: Preprint

Hydrogen (H2) has been identified as a leading sustainable contender to replace fossil fuels in transportation and electricity generation. H2 production can be achieved by concentrating solar thermal power (CSP) systems collecting thermal energy from the sun to various chemical processes for fuel production. Fuel production via solar thermal chemical processes integrated with CSP uses the full spectrum of sunlight compared with photovoltaic power conversion and stores solar energy directly and efficiently [1]. The solar fuel production can be realized by thermochemical processes (e.g., water splitting for H2 production, carbon dioxide reduction, or methane reforming) or thermal electrochemical methods (e.g., integration with solid oxide electrolysis cell). Technology development for CSP-integrated solar fuel production requires broad technological bases from solar energy collection to chemical energy conversion. H2 generated from renewable sources can be an energy carrier for a carbon-free economy. Integrating CSP with high temperature electrolysis (HTE) using solid oxide electrolysis cells (SOEC) provides a renewable path for H2 generation. The CSP-HTE integration approach provides the benefit of thermal energy storage (TES) for continuous operation, improved capacity, and SOEC life. H2 gas has low energy density for transportation, pipeline networks are expensive, and H2 liquefaction is energy intensive. However, an alternative method for H2 distribution is to use carbon dioxide (CO2) capture and liquid hydrocarbon synthesis to convert solar energy into liquid fuels that are compatible with the existing fossil fuel infrastructure.

concentrating solar thermal power↗
DOE OSTI2025

Comprehensive Life Cycle Analysis of Methanol Production and Methanol-to-Diesel Conversion

Methanol is a strategic chemical and intermediate in the manufacture of synthetic diesel, due to its versatility, diesel’s compatibility with existing infrastructure, and their role in industrial and transport applications. Conventional production methods for methanol, primarily steam methane reforming (SMR), rely on natural gas and are subject to the price variability due to market conditions and geopolitical events. They are also associated with greenhouse gas (GHG) emissions. Methanol and synthetic diesel production could be integrated with nuclear energy to stabilize fuel prices and insulate pricing from outside geopolitical events due to the relative stability of nuclear fuel as compared to natural gas. This could lead to increased transportation fuel security, reliability and resilience. An added benefit is the abatement of emissions when substituting nuclear energy for conventional energy from natural gas. This report presents a comprehensive life cycle analysis(LCA) framework which was developed to evaluate the GHG emissions reduction potential associated with nuclear integrated methanol production, methanol-to-diesel upgrading, and end-use combustion. Gate-to-gate methanol production and cradle-to-grave emissions were evaluated in, starting with a business-as-usual (BAU) SMR-based methanol plant, and then considering stepwise nuclear integration. Methanol-to-diesel (MTD) conversion was evaluated accounting for nuclear energy integration and hydrogen production via high-temperature steam electrolysis (HTSE) using electricity either from the grid or from a dedicated nuclear power system. This multi-step process diverts stable and reliable nuclear energy into the transportation sector by upgrading low energy dense natural gas into liquid fuels fully compatible with existing infrastructure.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2024

Nonthermal hydrogen plasma-enabled ambient, fast lignin hydrogenolysis to valuable chemicals and bio-oils

The reduction of fossil fuel resources and the ongoing surge in global energy demand have captured the interest of researchers worldwide, prompting a focus on developing renewable energy sources. For this reason, biomass conversion has emerged as a crucial pathway for renewable fuel production. Lignin, constituting 10–35% of woody biomass, represents a significant and largely untapped sustainable feedstock. Despite the potential of lignin, a substantial portion of this lignocellulosic residue remains unused, with approximately 60% considered waste. This study addresses the challenge of underutilized lignin by introducing an innovative approach to its hydrogenolysis. Despite their potential, existing hydrogenolysis methods face obstacles such as complexity, high cost, and the need for high temperatures or pressures. Herein we report a noncatalytic nonthermal hydrogen plasma method for lignin hydrogenolysis, conducted under ambient temperature and pressure conditions. Our method proves to be highly effective in breaking lignin bonds, achieving complete conversion, and generating valuable gaseous and bio-oil products including methane and aromatic dimers and monomers obtained from guaiacyl and syringyl units within the lignin structure. Our results showed an increase in gaseous products, especially methane, and aromatic monomer yields, as well as a reduction in total bio-oil and biochar yields and lignin functional groups by increasing reaction time, input power, and H2 partial pressure. This research confirms the considerable promise of utilizing noncatalytic nonthermal hydrogen plasma-assisted hydrogenolysis as an effective technique for producing gaseous and liquid fuels from lignin.

Pishva, Parsa↗
DOE OSTI2025

Polyethylene Upcycling to Liquid Alkanes in Molten Salts under Neat and External Hydrogen Source-Free Conditions

Development of facile approaches to convert plastic waste into liquid fuels under neat conditions is highly desired but challenging, particularly without noble metal catalysts and an external hydrogen source. Herein, highly efficient and selective polyethylene-to-gasoline oil (branched C 6 –C 12 alkanes) conversion was achieved under mild conditions (<170 °C) using commercially available AlCl 3 -containing molten salts as reaction media and to provide catalytic sites (no extra solvents, additives, or hydrogen feeding). The high catalytic efficiency and selectivity was ensured by the abundant active Al sites with strong Lewis acidity (comparable to the Al type in acidic zeolite) and highly ionic nature of the molten salts to stabilize the carbenium intermediates. Dynamic genesis of the Al sites was elucidated via time-resolved Al K-edge soft X-ray and 27 Al NMR, confirming the tricoordinated Al 3+ as active sites and its coordination with the as-generated alkene/aromatic intermediates. Further, the carbenium formation and polyethylene chain variation was illustrated by inelastic neutron scattering (INS) and an isotope-labeling experiment. Theoretical simulations further demonstrated the successive hydride abstraction, β-scission, isomerization, and internal hydrogen transfer reaction pathway with AlCl 3 as active sites. This facile catalytic system can further achieve the conversion of robust, densely assembled, and high molecular weight plastic model compounds to liquid alkane products in the diesel range.

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

SAM Code Enhancements for Fission Product Tracking of Noble Gases and Metals in MSRs

This report documents fiscal year 2026 enhancements to the System Analysis Module (SAM) for modeling fission product transport in liquid-fueled molten salt reactors (MSRs). The work advances three principal areas: noble gas transport, noble metal deposition, and user interface improvements. The noble gas transport capability integrates drift-flux gas transport, Henry’s law two-film interphase mass transfer with pressure-based nucleation suppression, Knudsen-regime pore diffusion into porous graphite with a conjugate salt-graphite interface constraint, built-in material properties, five Sherwood-number mass transfer correlations including three derived from high-fidelity NekRS simulations, and xenon-135 reactivity feedback through SAM’s point-kinetics model. This work also presents a comprehensive verification test suite, including new analytically verified cases for pressure-dependent onset of interphase gas transfer in a stagnant vertical pipe, a postulated FLiBe-graphite Xe extraction permeator, a gravity riser with a fission-product source, and a descending pipe with gas redissolution driven by hydrostatic pressure. A machine learning framework for bubble rise velocity prediction in molten salt systems is developed and benchmarked on molten-salt and diverse aqueous bubble datasets. The best-performing fine-tuned transfer-learning networks achieve an 82% reduction in RMSE relative to the Clift correlation, and is implemented directly in SAM. The noble metal transport capability is developed, including a liquid-wall deposition model and a gas-surface flotation mechanism that transfers insoluble particles entrained by sparging gas to wetted structures. Verification tests and demonstration cases cover the surface deposition, flotation efflux, and flotation shedding. Finally, a new [SpeciesTransport] input structure replaces positional global vectors with selfcontained, order-independent, named species blocks, simplifies the specification of multiphase species and decay chains, and remains fully compatible with existing SAM input files. Together, these developments improve the physical fidelity, verification basis, and usability of SAM for system-level analyses of fissionproduct behavior in MSRs.

Mui, Travis (ORCID:0000000303736470)↗
DOE OSTI2024

Catalytic Reduction of Esters over Zirconia-Supported Metal Catalysts

Esters are often produced as unwanted byproducts during the catalytic upgrading of ethanol to diesel fuel precursors through Guerbet coupling. Removal of esters from the product stream is important to prevent the loss of downstream catalyst activity from ester-derived carboxylic acids. In this work, we studied ester hydrogenolysis to the parent alcohols as a viable route for enhanced diesel fuel production. Specifically, we investigated the reduction of hexyl acetate in butanol over ZrO 2 -supported Ni, Co, Cu, Rh, Pd, and Pt catalysts, where Cu/ZrO 2 was the most selective catalyst for the hydrogenolysis of hexyl acetate into hexanol and ethanol. Thermodynamic analysis reveals that a 90% alcohol yield can be obtained at 200 °C, 30 bar, and a relatively high H 2 :hexyl acetate molar ratio of 480:1. Experimentally, an alcohol yield of 88% yield was obtained with a 10 wt % Cu/ZrO 2 catalyst at these conditions with a residence time of 5.4 h kg cat kmol gas –1 . Catalytic tests on the support revealed that ZrO 2 catalyzes the transesterification reaction between hexyl acetate and butanol. However, only the Cu sites can catalyze the hydrogenolysis of the esters into the final alcohols. We developed a kinetic model for our experimental results, which shows that the transesterification and hydrogenolysis reactions run at two different timescales, the former being 10 times faster than the latter. Data regression has been used to develop a model to predict the mole fraction distribution of ester hydrogenolysis products over a wide range of contact times. Cu/ZrO 2 loses half its catalytic activity after 80 h of time on stream. Modeling of deactivation data reveals that the ZrO 2 support conserves a residual activity due to external active sites, while active sites over the Cu surface deactivate at different rates. Furthermore, the catalytic conversion of esters into their parent alcohols is relevant to the production of surrogate liquid fuels since alcohols can be bimolecularly dehydrated to produce a blend of ethers with diesel fuel-like properties.

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

Mechanical and Light Activation of Materials for Chemical Production

Abstract Mechanical expansion and contraction of pores within photosynthetic organisms regulate a series of processes that are necessary to manage light absorption, control gas exchange, and regulate water loss. These pores, known as stoma, allow the plant to maximize photosynthetic output depending on environmental conditions such as light intensity, humidity, and temperature by actively changing the size of the stomal opening. Despite advances in artificial photosynthetic systems, little is known about the effect of such mechanical actuation in synthetic materials where chemical reactions occur. It is reported here on a hybrid hydrogel that combines light‐activated supramolecular polymers for superoxide production with thermal mechanical actuation of a covalent polymer. Superoxide production is important in organic synthesis and environmental remediation, and is a potential precursor to hydrogen peroxide liquid fuel. It is shown that the closing of pores in the hybrid hydrogel results in a substantial decrease in photocatalysis, but cycles of swollen and contracted states enhance photocatalysis. The observations motivate the development of biomimetic photosynthetic materials that integrate large scale motion and chemical reactions.

Đorđević, Luka [Department of Chemical Sciences Un↗
DOE OSTI2024

Cobalt‐Doped Bismuth Nanosheet Catalyst for Enhanced Electrochemical CO 2 Reduction to Electrolyte‐Free Formic Acid

Electrochemical carbon dioxide (CO 2 ) reduction reaction (CO 2 RR) to valuable liquid fuels, such as formic acid/formate (HCOOH/HCOO − ) is a promising strategy for carbon neutrality. Enhancing CO 2 RR activity while retaining high selectivity is critical for commercialization. To address this, we developed metal-doped bismuth (Bi) nanosheets via a facile hydrolysis method. These doped nanosheets efficiently generated high-purity HCOOH using a porous solid electrolyte (PSE) layer. Among the evaluated metal-doped Bi catalysts, Co-doped Bi demonstrated improved CO 2 RR performance compared to pristine Bi, achieving ~90 % HCOO − selectivity and boosted activity with a low overpotential of ~1.0 V at a current density of 200 mA cm −2 . In a solid electrolyte reactor, Co-doped Bi maintained HCOOH Faradaic efficiency of ~72 % after a 100-hour operation under a current density of 100 mA cm −2 , generating 0.1 M HCOOH at 3.2 V. Density functional theory (DFT) results revealed that Co-doped Bi required a lower applied potential for HCOOH generation from CO 2 , due to stronger binding energy to the key intermediates OCHO* compared to pure Bi. In conclusion, this study shows that metal doping in Bi nanosheets modifies the chemical composition, element distribution, and morphology, improving CO 2 RR catalytic activity performance by tuning surface adsorption affinity and reactivity.

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

X‐Ray Absorption Studies of Local Structure of Dilute Ionic Species in Molten Salts

Molten salts are crucial materials with exceptional properties that make them suitable for applications such as heat transfer media, coolants, and liquid fuels in molten salt nuclear reactors and the concentrated solar power industry. Understanding their properties requires unraveling the intricate mysteries of their structure. To achieve this, advanced characterization tools are essential. Among various techniques, X‐ray absorption fine structure (XAFS) stands out as a versatile method capable of studying the structure of molten salts under in situ conditions. This review highlights recent advancements in the application of XAFS for investigating the local structure of molten salts, discusses its limitations and potential improvements, and explores complementary approaches such as simulations, machine learning, and correlative experimental methods.

22 - GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2025

Rheology of lignin and lignin-based solutions, dispersions, gels, polymer blends, and melts

Lignin is an abundant resource that finds application in energy and sustainable materials development. In addition to the utilization of lignin in three-dimensional (3D) printing and hydrogel production, recent studies have reported the use of lignin as a liquid fuel additive. The characterization of the rheological properties of lignin and its derivatives is a dynamic and evolving field, underpinned by advances in experimental, analytical, and modeling techniques. Here, this review provides a comprehensive overview of the recent progress in the study of lignin rheology, highlighting the interplay between structure, modification, and flow behavior in lignin-based solutions, dispersions, gels, polymer blends, and melts. A specific highlight of this review is how lignin concentration affects the rheological properties of lignin-based solutions and dispersions. Furthermore, the effect of lignin type on the properties of 3D-printed lignin-based composites is discussed. For polymer systems, this review discussed lignin-in-polymer solutions separately from lignin-filled polymer systems. Finally, challenges and perspectives on lignin rheology are presented.

Dispersions↗
DOE OSTI2025

Molecular simulation and artificial intelligence for the circular economy of bioenergy and bioproducts

The concept of the circular bioeconomy is a carbon neutral, sustainable system with zero waste. One vision for such an economy is based upon lignocellulosic biomass. This lignocellulosic circular bioeconomy requires CO 2 absorption from biomass growth and the efficient deconstruction of recalcitrant biomass into solubilized and fractionated biopolymers, which are then used as precursors for the sustainable production of high-quality liquid fuels, chemical bioproducts, and bio-based materials. Here, in this study, we summarize the roles that molecular dynamics (MD) simulations and machine learning (ML) are playing in overcoming several fundamental challenges hindering the adoption of a circular bioeconomy. Specifically, we discuss the role of MD and ML/AI in overcoming lignocellulose recalcitrance by designing biomass pretreatment methods to efficiently produce solubilized cellulose/lignin/hemicellulose and of that in improving energy-intensive manufacturing of biomass-based materials and their structural and mechanical properties. Quantum mechanical methods and MD simulations, in addition to offering a mechanistic understanding of biomass deconstruction and biomaterials design, can provide meaningful structural, energetics, and physiochemical properties as inputs to train AI/ML models. The ML models can guide the experimental prioritization of materials/solvents and process parameters that significantly accelerate the development of biofuel and biomaterial components of the circular bioeconomy.

Smith, Jeremy C. [Oak Ridge National Laboratory (O↗
DOE OSTI2025

Experimental and modeling study of the autoignition behavior of a saturated heterocycle: Pyrrolidine

Experiments are conducted in both rapid compression machine (RCM) and shock tube (ST) to better quantify autoignition behavior (e.g., ignition delay, heat release) and understand heteroatomic effects in heterocyclic compounds, which are important reference components for the combustion of biomass-derived liquid fuels. These tests focus on the nitrogen-containing, five-membered saturated ring, pyrrolidine, at diluted conditions covering pressures of 20 and 50 bar, temperatures of 720–1450 K and a range of stoichiometries (ϕ = 0.5–2). A chemical kinetic model is developed and coupled to an existing combustion kinetics framework describing key nitrogen containing intermediates (e.g. pyrrole, ammonia and NOx). H-abstraction reactions by OH, H, CH 3 and HO 2 , are determined using ab-initio transition state theory methods, while analogies to cyclopentane are adopted for many other reactions, such as ring-opening. Here, the autoignition measurements reveal the lack of negative temperature coefficient (NTC) behavior and low-temperature chemistry for pyrrolidine, as opposed to its saturated hydrocarbon analogue, cyclopentane. Interestingly, at the lowest temperatures (T < 750 K), the reactivity of cyclopentane is greater than pyrrolidine, while at higher temperatures, pyrrolidine becomes more reactive. Agreement between the experimental measurements and the model is good, and it is found that H-abstraction reactions by HO 2 and ensuing chemistry play key roles in controlling the reactivity of this cyclic amine. Most of the fluxes, i.e., >70 %, are predicted to move through 1- or 2-pyrroline (C 4 H 7 N) and then the cyclic C 4 H 6 N radical, at both lower and higher temperatures, to form either CH 2 CHCHCHNH via ring-opening or pyrrole via β-scission. It appears that the ring opens more easily at lower temperature whereas the C–H β-scission dominates at higher temperature and lower pressure, such that the reaction of the fuel radical intermediate carrying an unpaired electron on the nitrogen atom with HO 2 is the next most notable in promoting oxidation. When comparing pyrrolidine and cyclopentane, which exhibits distinct pathways in different temperature regimes, the pyrrolidine pathways and sensitivity analysis align more closely to the high temperature case of cyclopentane where the important role of HO 2 radicals is seen to provide chain branching through HO 2 reaction with the fuel, accompanied by H 2 O 2 formation and decomposition to OH. The formation of 5-membered diene rings and ring opening reactions are also found to be highly relevant. Of particular note, it is found that there is little influence of small molecule nitrogen-chemistry, e.g., NH 2 , HCN, NO/NO 2 on the reactivity of the pyrrolidine mixtures investigated here where no recirculated combustion gases are included.

Autoignition↗
DOE OSTI2025

A control-inspired approach for energy transition planning under uncertainty

As the global carbon footprint continues to grow, many countries are implementing carbon emission reduction policies which have incentivized the expansion of low-carbon and renewable technologies. However, the speed and scale of deployment falls short of that needed to meet climate goals. Energy system models serve as key tools for guiding investment decisions and helping policymakers evaluate the effects of various policies on the development of an energy system. This study focuses on the energy system of the United States and builds upon prior work by incorporating more geographic granularity to account for the trade of commodities and addresses transmission congestion through electricity price adjustments. Furthermore, real-world characteristics, such as delays in constructing new liquid fuel production and electricity generation facilities, are integrated using a sequential decision-making approach that better reflects how decisions can be updated as uncertainties unfold. Results demonstrate that stochastic programming combined with sequential decision-making produces energy transition pathways that are robust to multiple uncertain futures. Additionally, considering real-world characteristics significantly impacts the deployment of renewable technologies and the ability to meet carbon emission reduction goals while also reliably meeting demand. These findings highlight the importance of accounting for uncertainty and real-world characteristics to avoid overly optimistic projections in energy system planning.

energy systems↗
DOE OSTI2024

Properties and Autoignition Reactivity of Diesel Boiling Range Ethers Produced from Guerbet Alcohols

We examine the properties of diesel boiling range ethers made from coupling of alcohols produced by oligomerization of ethanol (Guerbet alcohols) for their utility as low-carbon liquid fuel blendstocks. Basic properties of boiling point, flash point, freezing point, density and viscosity are well suited for blending into diesel fuels. For the mixture of ethers the lightest component, di-n-butyl ether, can be present at up to 20 vol% while still having adequately high flashpoint for safe handling. Soot formation tendency (as yield sooting index) is well below that of conventional diesel. The ethers have similar compatibility with elastomers as conventional diesel, based on Hansen solubility parameter analysis. Oxidation stability was assessed for 30 vol% blends of individual ethers in a conventional diesel fuel using a long-term storage test. Over 6 weeks we observed no formation of peroxides or degradation. n-alkyl ethers with carbon number of 8 or higher have cetane number over 100, which is outside the defined range of cetane number, while branched ethers are over 70. The ethers also blend antagonistically into conventional diesel for cetane number, meaning that the blend cetane value is lower than predicted based on a linear by volume, mass, or mole model. We show that aromatics and naphthenes likely act as radical scavengers to slow or shut down autoignition of the highly reactive ethers at low to medium blend levels. Overall, diesel boiling range ethers show significant promise as high quality low-net carbon diesel blendstocks.

09 BIOMASS FUELS↗
DOE OSTI2025

Fullerene Promotes CO 2 Reduction to Methanol by a Cobalt(II) Phthalocyanine Electrocatalyst

Heterogenization of molecular electrocatalysts offers an attractive way to improve the catalytic selectivity and efficiency of CO 2 conversion to liquid fuels. Herein, we employ density functional theory to compare the mechanism of CO 2 RR by a cobalt(II) tetra(amino)phthalocyanine (Co(II)Pc(NH 2 ) 4 ) electrocatalyst with and without the presence of fullerene support. Our DFT calculations suggest that the CO 2 reduction mechanism is initiated by a metal-based electron reduction followed by subsequent CO 2 nucleophilic addition, electron transfer, proton transfer, water dissociation, and proton-coupled electron transfer steps that lead to CO and methanol formation. We show that graphitic interactions between the Co(II)Pc(NH 2 ) 4 electrocatalyst and C 60 support selectively improve the CO 2 RR to methanol at mild potentials. The undesirable hydrogen evolution reaction (HER) was also investigated for both electrocatalysts and proceeds via the protonation of the cobalt metal center over the nitrogen atom in the inner ring. The competition between the HER and the CO 2 RR was improved in favor of CO and methanol formation using the Co(II)Pc(NH 2 ) 4 @C 60 electrocatalyst. Overall, our results suggest C 60 as a promising graphitic support for molecular electrocatalysts integration for CO 2 catalysis.

Alcohols↗
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↗