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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

A Novel Catalytic Membrane Reactor for DME Synthesis from Renewable Resources

Production of liquid fuels or chemicals from CO 2 (captured from the air or flue gases) and renewable hydrogen presents a new approach to producing clean fuels domestically. While significant progress has been made in the area of renewable electricity generation from solar and wind, a large gap remains with respect to the production of renewable liquid fuels/chemicals. Other processes for producing liquid fuels/chemicals from renewable electricity are constrained by thermodynamic limitations, making them prohibitively expensive and impractical. The team is overcoming these limitations and developing catalytic membrane reactor processes with high yields and low energy penalties. Supported by the Advanced Research Projects Agency-Energy (ARPA-E) of the US Department of Energy (DOE), GTI Energy and partners have been developing a technology for the production of renewable dimethyl ether (DME) from carbon dioxide (CO 2 ) and renewable hydrogen (H 2 ) using a novel catalytic membrane reactor and demonstration of this system at a scale of 1 kg/day. DME is a clean-burning, non-toxic fuel with a high cetane value (55-60), making it an excellent diesel alternative. DME can be stored as a liquid under moderate pressure, eliminating the need for the high-pressure containers used for CNG or cryogenics, as in the case of LNG. DME is also approved as a renewable fuel under the U.S. Environmental Protection Agency’s Renewable Fuels Standard (RFS), making it eligible for Renewable Identification Numbers (RINs) credits. By producing DME through the catalytic conversion of captured CO 2 and renewable H 2 , this process will produce renewable liquid transportation fuel and a means of large-scale utilization of captured CO 2 . In the DME synthesis process, CO 2 and H 2 are fed to a hollow fiber catalytic membrane reactor at 300-600 psig that contains a bi-functional catalyst that combines two reactions, methanol synthesis (CO 2 + 3H 2 → CH 3 OH + H 2 O) and methanol dehydration (2CH 3 OH → CH 3 OCH 3 + H 2 O), into a one-step process to produce DME. The bifunctional catalyst converts methanol to DME, enabling higher overall CO 2 conversion. A Cu/ZnO/ZrO 2 /Al 2 O 3 (CZZA) catalyst is used for methanol synthesis and is coupled with a zeolite catalyst H-ZSM-5 for dehydration. This one-step process intensifies a process that would otherwise require multiple reaction steps. However, combining these two reactions results in increased water production which inhibits catalytic activity. Here, the Na + -gated, water-transport membrane (Science, vol. 367, pp. 667, 2020), removes water in situ, shifting the thermodynamic equilibrium towards product formation while decreasing kinetic inhibition from water adsorption onto the catalyst surface. The Na + gated, water-transport nanochannel membrane showed H 2 O/CO 2 selectivity of 560 at 250 °C and 300 psig for H 2 O/CO 2 /CO/H 2 /MeOH gas mixtures. The selectivities of H 2 O/H 2 , H 2 O/CO, and H 2 O/MeOH were 190, 170, and 80, respectively. In a laboratory-scale membrane reactor, DME synthesis testing using this membrane, a DME production rate of 440 g DME /kg cat /h was achieved at 260 °C and 550 psig. Compared to the packed bed reactor, the CO 2 conversion and DME production rate in the membrane reactor were 80% and three times higher, respectively. A prototype test system (1 kg/day) was designed, constructed, and tested. A DME production rate of 1.31 kg/day and a DME productivity of 360 g/h/kg were achieved in the prototype membrane reactor. Good stability was demonstrated during 150-h continuous operation and multiple startups/shutdowns tests.

10 SYNTHETIC FUELS↗
DOE OSTI2021

Design of Efficient Molecular Electrocatalysts for Water and Carbon Dioxide Reduction Using Predictive Models of Thermodynamic Properties

Objectives: 1) To design and synthesize water soluble transition metal complexes that function as electrocatalysts for the reduction of water to hydrogen or carbon dioxide to formate 2) To experimentally measure thermochemical properties, such as hydride donor ability, and use these quantities to optimize catalyst performance in solutions of varying pH 3) To incorporate results from detailed mechanistic and kinetic studies to direct improvements in catalyst design 4) To use thermochemical data from objective 2 to generate predictive models for the properties of new complexes to apply to the development of catalysts for other reductive reactions, with an emphasis on carbon dioxide reduction to methanol Description: Wide-spread implementation of renewable but intermittent energy sources, such as solar, requires the development of efficient methods for energy storage. The high energy density of chemical bonds makes chemical fuels an ideal solution for energy storage. Hydrogen and reduced carbon compounds have been proposed as ideal candidates for chemical fuels. However, the generation of chemical fuels from electricity requires competent electrocatalysts. The proposed research focuses on developing electrocatalysts for the reduction of water to hydrogen, and carbon dioxide to formate. Both products can be used directly as an energy carrier in fuel cells, or as a reductant for more saturated chemical fuels. Hydrogen is the most common fuel used in current commercial fuel cells. Additionally, there is interest in formic acid as a liquid carrier for hydrogen because of its increased storage density and ease of dehydrogenation. Formate is also an intermediate in the sequential reduction of CO 2 to methanol, another potential chemical fuel with high energy storage density. Despite the utility of formate as a chemical fuel or precursor, there are very few examples of electrocatalysts for its production from CO 2 , and even fewer demonstrate high product selectivity. In heterogeneous catalysis, the Sabatier principle is used to generate volcano curves that describe optimal thermochemical properties for key intermediates that result in peak catalytic activity. In most cases, such as hydrogen production and oxidation, the most favorable metals (Pt, Re, Rh, and Ir) are rare and expensive. Molecular inorganic complexes provide an opportunity to use electronic and steric ligand effects to tune the critical thermodynamic parameters of abundant metals to values comparable to key surface intermediates on precious metals. This principle will be applied to the design of aqueous homogeneous catalysts for the reduction of H 2 O and CO 2 optimized to function at specific pH ranges. The critical intermediate in both of these reactions is a metal hydride. The strength of this bond, or hydricity (ΔGH - ) dictates the overall thermodynamics of the reduction of H + to H 2 and the sequential reduction of C1 substrates, such as CO 2 , CO, and H 2 CO (the latter to CH 3 OH). ΔGH - will be systematically measured for a series of first row metal complexes to form predictive models for metal and ligand electronic effects. Benefits and Outcomes: This approach addresses thermodynamic requirements essential for energy-efficient catalyst design and transition state barrier considerations for faster catalysis. The advancements made from this research will include the discovery of efficient, stable, and fast catalysts for hydrogen and formate generation from electricity. The ability to store energy efficiently is critical to the widespread use of renewable energy schemes. This provides a viable solution to produce high energy density fuels for stationary and mobile energy applications. The fundamental research conducted is also directly applicable to the design of catalysts for the generation of further reduced products such as methanol.

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

Tracking the phase changes in micelle-based NiGa nanocatalysts for methanol synthesis under activation and working conditions

The hydrogenation of CO 2 into high energy density fuels such as methanol, where the required H 2 is obtained from renewable sources, is of utmost importance for a sustainable society. In recent years, NiGa alloys have attracted attention as promising catalyst material systems for the hydrogenation of CO 2 into methanol at ambient pressures. They thus represent an energy-saving alternative to the Cu-based catalysts employed in today's catalytic industry that require high pressures for the CO 2 hydrogenation. However, the underlying reaction mechanisms for the NiGa system are still under debate. One of the challenges here is to unravel the evolution and coexistence of the different species in the heterogeneous NiGa catalyst system under activation and reaction conditions. To shed light on their evolution under activation in H 2 and their catalytic roles under CO 2 hydrogenation working conditions on well-defined Ni 3 Ga 1 and Ni 5 Ga 3 nanoparticle (NP) catalysts, we employed a multi-probe approach in this study. It included advanced machine learning-based analysis of operando X-ray absorption spectroscopy data combined with operando powder X-ray diffraction and near ambient pressure X-ray photoelectron spectroscopy measurements, as well as reactivity studies using bed-packed mass flow reactors. In addition, we employed atomic force microscopy and scanning transmission electron microscopy for structural characterization. Under H 2 activation at 1 bar total pressure, we concluded the formation of metallic Ni, starting for Ni 3 Ga 1 at 300 °C, and for Ni 5 Ga 3 at 400 °C. At higher temperatures, the formation of NiGa alloys follows. The α'-Ni 3 Ga 1 alloy phase is predominantly formed for the Ni 3 Ga 1 NPs, while the coexistence of α'-Ni 3 Ga 1 , δ-Ni 5 Ga 3 and Ga 2 O 3 phases is observed for the Ni 5 Ga 3 NPs after the H 2 activation. The formation of the Ga 2 O 3 phase also results in the presence of excess metallic Ni. Under CO 2 hydrogenation reaction conditions, Ga partially oxidizes again to form a Ga 2 O 3 -rich particle shell for both NP compositions, yet, to a larger extent for the Ni 3 Ga 1 NPs, which, in turn, feature a higher amount of excess Ni. We reveal that metallic Ni is responsible for the high selectivity of the Ni 3 Ga 1 NPs towards the production of methane in our catalytic tests. In contrast, the Ni 5 Ga 3 NPs display a strong selectivity toward methanol production (>92%), more than one order of magnitude higher than that for the Ni 3 Ga 1 NPs, which we ascribe to the presence of the δ-Ni 5 Ga 3 phase.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Considerations for Distributed Energy Resource Integration in Puerto Rico: DOE Multi-Lab Grid Modeling Support for Puerto Rico; Analytical Support for Interconnection and IEEE Std 1547-2018 National Renewable Energy Laboratory (Task 3.0)

To ensure the sustainable long-term recovery of Puerto Rico's electric power grid from hurricanes María and Irma and to build capacity to manage future potential natural disasters in the most secure and resilient way, the U.S. Department of Energy (DOE) convened experts from multiple national laboratories to develop a comprehensive set of data, models, analytic tools, and studies, considering inputs from a wide variety of stakeholder groups, to support technically sound recommendations for Puerto Rico's energy investment decisions. A resilient electric grid is vital to Puerto Rico's security, economy, and way of life, and it will provide the foundation for essential services that people and businesses on the island rely on every day. This report shows progress for a grid modeling task under the DOE-sponsored project that is a collaboration among the National Renewable Energy Laboratory (NREL) and other national laboratories. In Phase 1 of the multilab effort to support Puerto Rico's recovery, NREL provided the utility company Puerto Rico Electric Power Authority (PREPA) recommendations for a new framework of interconnection standards to accelerate the integration of utility-scale, transmission-connected renewable electrical generation and energy storage that ensure cross-technology compatibility and enable high deployment levels without compromising grid reliably, safety, or security. This Phase 2 report focuses on the interconnection of distributed energy resources (DERs) to the electric distribution system in Puerto Rico. This report is intended to familiarize the reader with Puerto Rico's distribution infrastructure and operational practices and procedures that are relevant to DER interconnection. The report also provides considerations for streamlining the interconnection process given the expected increase in deployments resulting from Puerto Rico's renewable portfolio standard (RPS) goal of 100% renewables by 2050. Accordingly, the report identifies considerations and concerns associated with the increase in intermittent generation, strategies for DER interconnection best practices, and the potential use of the latest technological solutions identified in the latest revision of the Institute of Electrical and Electronics Engineers (IEEE) 1547-2018 interconnection standard.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2023

Modeling of a Networked Community Microgrid with High Solar Penetration Considering Control Dynamics of Inverter-Based Resources

Microgrids help facilitate the integration of renewable energy in distribution-level grids and increase the resilience of the electric grid to extreme weather, especially in rural areas. Compared to traditional microgrids, a networked microgrid leverages multiple grid-forming sources to form a potential meshed grid and is more flexible in operation. This paper demonstrates the simulation modeling of an actual networked microgrid located in Adjuntas, Puerto Rico. The model contains representations of power inverters that connect the battery energy storage systems and photovoltaic generation systems to the networked microgrid and is capable of simulating fast grid transients as well as long-term operation of the networked microgrid. The modeling technique for power inverters allows the time-efficient simulation of the microgrid with a minimal penalty on model accuracy.

Li, Dingrui↗
DOE OSTI2021

Power System Modeling for the Study of High Penetration of Distributed Photovoltaic Energy

Many conventional power systems are evolving due to the growth of renewable energy and distributed energy resources (DERs). Modeling the interplay of transmission and distribution systems is critical to analyze how DERs impact a system’s conventional operation and which electric infrastructure improvements are needed to achieve a balance between centralized generation and DERs. This article describes the process, tools, and resources used to model electric power systems with a centralized infrastructure in an isolated context and limited access to actual utility data. Photovoltaic systems installed on residential rooftops were the main design option. This work broadened the typical power system modeling to include planning and social considerations. This integrative engineering-social method allows for interdisciplinary teams to work in the development of a model as part of broader design goals for a renewable-dominant energy system. The Puerto Rico electric power system was used as a case study to demonstrate the process. The integrative engineering-social perspective in developing the model and the actions to manage data limitations are aspects that could be followed in other locations with aggressive renewable energy goals and where utility data are not readily available.

Cuello-Polo, Gustavo↗
DOE OSTI2024

Optimal Droop Setting for Congestion Reduction in a 100% Grid-Forming Inverter-based Power System

he high penetration of inverter-based resources (IBRs) introduces new challenges to power systems due to the complex inverter control. However, IBRs can be configured to maximize their benefits to improve system resilience and reliability. This paper proposes a steady-state optimization model that aims to mitigate transmission congestion in a 100% grid- forming (GFM) IBR-based power system. This goal is achieved by determining the optimal droop settings for the GFM IBRs under different congestion conditions due to renewable energy and load variations. The numerical solution is rigorously verified by a high-fidelity model of the IEEE 39-bus test system with detailed GFM IBR control in the time-domain electromagnetic transient (EMT) simulation tool PSCAD. The numerical solution and simulation results show a significant congestion reduction while meeting all other operating requirements. It is also observed that the numerical solving time is substantially less compared to the EMT simulation time.

Nguyen, Quan H.↗
DOE OSTI2023

Hierarchical Cellulose Superinsulation Membrane

The environment-friendly components coupled with the ability to mimic the simplicity and originality of nature necessitate advanced sustainable materials with structural capabilities for energy-efficient applications. The use of feedstock deriving from plant-based, renewable organic material to produce nanofibril that embodies enhanced insulating properties and high mechanical strength constitutes an efficient development strategy. In this work, a free-standing, hierarchical superinsulation membrane by leveraging the principle of the bottom-up method is reported. The electrospun cellulose nanofibrils/aerogel-based core layer provides exceptional thermal properties with its thermal conductivity of 10.2 mW m –1 K –1 . The lightweight, flexible, and durable paper-like membrane features a tensile strength of 11.3 MPa and a bending rigidity in the order of 4.6 cN mm –1 . The hydrophobic superinsulation membrane material also exhibits a ΔT of ≈25 °C under continuous sunlight illumination and allows thermal runaway mitigation of rechargeable lithium-ion batteries. All the aforementioned properties position this hybrid superinsulation membrane as a promising material for energy-saving thermal management applications.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Rationalizing Acidic Oxygen Evolution Reaction over IrO 2 : Essential Role of Hydronium Cation

Abstract The development of active, stable, and more affordable electrocatalysts for acidic oxygen evolution reaction (OER) is of great importance for the practical application of electrolyzers and the advancement of renewable energy conversion technologies. Currently, IrO 2 is the only catalyst with high stability and activity, but a high cost. Further optimization of the catalyst is limited by the lack of understanding of catalytic behaviors at the acid‐IrO 2 interface. Here, in strong interaction with the experiment, we develop an explicit model based on grand‐canonical density function theory (GC‐DFT) calculations to describe acidic OER over IrO 2 . Compared to the explicit models reported previously, hydronium cations (H 3 O + ) are introduced at the electrochemical interface in the current model. As a result, a variation in stable IrO 2 surface configuration under the OER operating condition from previously proposed complete *O‐coverage to a mixture coverage of *OH and *O is revealed, which is well supported by in situ Raman measurements. In addition, the accuracy of predicted overpotential is increased in comparison with the experimentally measured. More importantly, an alteration of the potential limiting step from previously identified *O→*OOH to *OH→*O is observed, which opens new opportunities to advance the IrO 2 ‐based catalysts for acidic OER.

Mou, Tianyou↗
DOE OSTI2025

Fe‐Triazolate Metal–Organic Frameworks as Water Oxidation Catalysts with Dual Photoanode Functionality

Artificial photosynthesis is an emerging technology that achieves renewable fuels, such as hydrogen, from sunlight. Its realization depends on finding highly active and stable catalysts of water splitting and photoactive materials for light absorption. To be scalable, these should contain only abundant elements. Here, for the first time, Fe-triazolate (Fe(ta) 2 ) and its metal substituted derivatives (Fe-Metal(ta) 2 ) Metal-organic frameworks (MOFs) are characterized as new dual-function materials for photo-absorption and water oxidation catalysis in acidic media. The materials were studied by a range of structural, spectroscopic, and computational density functional theory (DFT) techniques. Fe(ta) 2 and Fe-Mn(ta) 2 were found to be highly active and stable in chemical and photochemical water oxidation, and in addition function as photoanodes, with photo-electrocatalytic currents (∼2.00 x 10 −3 Acm −2 at + 1.4 V vs. Ag/AgCl) at pH = 1. The possibility of a unique catalytic mechanism where O─O bond formation is possible from the coupling of two adjacent Fe IV = O fragments was demonstrated by DFT analysis. Thus, Fe-triazolate MOF has been established as a new, stable, scalable, versatile, and efficient platform for sustainable energy conversion in the realm of artificial photosynthesis.

Artificial photosynthesis↗
DOE OSTI2024

Rationalizing Acidic Oxygen Evolution Reaction over IrO 2 : Essential Role of Hydronium Cation

The development of active, stable, and more affordable electrocatalysts for acidic oxygen evolution reaction (OER) is of great importance for the practical application of electrolyzers and the advancement of renewable energy conversion technologies. Currently, IrO 2 is the only catalyst with high stability and activity, but a high cost. Further optimization of the catalyst is limited by the lack of understanding of catalytic behaviors at the acid-IrO 2 interface. Here, in strong interaction with the experiment, we develop an explicit model based on grand-canonical density function theory (GC-DFT) calculations to describe acidic OER over IrO 2 . Compared to the explicit models reported previously, hydronium cations (H 3 O + ) are introduced at the electrochemical interface in the current model. As a result, a variation in stable IrO 2 surface configuration under the OER operating condition from previously proposed complete *O-coverage to a mixture coverage of *OH and *O is revealed, which is well supported by in situ Raman measurements. In addition, the accuracy of predicted overpotential is increased in comparison with the experimentally measured. More importantly, in this study, an alteration of the potential limiting step from previously identified *O→*OOH to *OH→*O is observed, which opens new opportunities to advance the IrO 2 -based catalysts for acidic OER.

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

Low-Cost, Screen-Printed Silver Metal Complex Inks for Silicon Heterojunction Solar Cells

Screen printing using metal particle pastes, the current photovoltaic industry metallization standard, provides fast and reliable metal grids for silicon solar cells. Recently, metal complex or reactive metal inks are attracting research interest due to their significantly low cost and higher performance compared to traditional nanoparticle silver pastes. In this work, we demonstrate, for the first time, screen-printed high-efficiency silicon heterojunction solar cells metallized by silver metal complex inks on industrial G1-size (158.75 x 158.75 mm2) wafers. We demonstrate screen-printed Ag metal complex ink grid patterns with continuous fingers ~100-120 ..mu..m wide. The printed Ag grid is very thin (~1 ..mu..m), which is an order of magnitude thinner than the current ~20-30 ..mu..m fingers printed with low-temperature nanoparticle-based pastes. Double printing allows silicon heterojunction devices with efficiencies >20%. This is the highest efficiency so far, to our knowledge, of industrial solar cell precursors using this metallization technology. Simulation results suggested that increasing the thickness of the metal film does not significantly improve efficiency due to the dense, highly conductive films. So, a single print of ~1 ..mu..m finger would be enough to produce cells that perform similarly to a ~20 ..mu..m thick nanoparticle paste printed cells. Additionally, solar cells printed on G1 wafers with silver metal complex ink required more than 10 times less silver (~0.03 g) compared to those using silver/copper nanoparticle paste (~0.4 g of Ag). These results indicate that metal complex inks are a very promising replacement for silver nanoparticle pastes for industrial-scale metallization in an age of resource scarcity and high costs of noble metals.

14 SOLAR ENERGY↗
DOE OSTI2025

Amorphous electrocatalysts for oxygen and hydrogen evolution reactions: Advances in hydrogen production

The electrochemical splitting of water into oxygen and hydrogen is fundamental for renewable energy storage and conversion. The development of cost-effective and highly efficient electrocatalysts remains essential for industrial-scale implementation of this technology. Recent advances have highlighted the superior activity, stability and structural adaptability of amorphous electrocatalysts compared to their crystalline counterparts. This review critically examines synthesis strategies, characterisation techniques, and the electrochemical performance of amorphous materials for both oxygen evolution (OER) and hydrogen evolution (HER) reactions. Key factors influencing catalytic efficiency, including electronic structure and surface chemistry, are discussed in detail and contextualised with established literature. The review also highlights the critical role of enthalpic contributions in governing reaction energetics and catalyst performance, which aids in understanding and optimising electrocatalytic efficiency. Notably, ongoing research continues to reveal that amorphous catalysts consistently deliver improved performance in water-splitting applications, highlighting their growing relevance in electrocatalysis. The rationale for employing amorphous catalysts in water splitting is articulated, emphasising their unique advantages. By integrating recent findings and outlining future research directions, this review underscores the pivotal role of amorphous materials in advancing sustainable hydrogen production and identifies promising avenues for catalyst innovation.

Amorphous catalysts↗
DOE OSTI2020

Calculations of Astrophysical Reaction Rates Using ENDF/B-VIII.0 Library

Recent observations of neutron stars merger (GW170817) renewed interest in stellar nucleosynthesis. Stellar nucleosynthesis modeling requires fully traceable, unbiased, high fidelity nuclear data. The Evaluated Nuclear Data File (ENDF) libraries contain complete collections of reaction data sets over the nuclear industry standard 10 -5 eV - 20 MeV energy span. For the first time, the (n,γ), (n,fission), (n,p), and (n,α) astrophysical reaction rates were computed within the 0.01-10 GK range of temperatures using the ENDF/B-VIII.0 library, and nuclear Reaction rate Library for astrophysics (REACLIB) fit parameters were deduced. The present results were used to estimate the slow neutron capture timescale. These findings demonstrate the potential astrophysical applications of the ENDF libraries and the complementary relations between the nuclear industry and astrophysics data developments.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

A review of Sb 2 Se 3 photovoltaic absorber materials and thin-film solar cells

Energy generated from environmentally friendly, cost-effective solar cells is a key aspect for developing a clean renewable-energy economy. Non-toxic and Earth-abundant materials with high absorption coefficient (>10 5 cm -1 ) and optimal bandgap (1-1.5 eV) have received great attention as photovoltaic (PV) absorber layers during the last few decades. Among them, antimony selenide (Sb 2 Se 3 ) has been a promising PV absorber, with steadily increasing power-conversion efficiency (PCE) compared to other emerging compounds. Very recent studies showed that high-quality ZnO:Al/ZnO/CdS/TiO 2 /Sb 2 Se 3 /MoSe 2 /Mo devices with PCE of 9.2% can be fabricated using cost-effective novel compounds. Considering these recent advances, this article provides an overview of the material properties of Sb2Se3 thin films and the recent progress made with Sb 2 Se 3 -based solar cells. Furthermore, analysis of Sb 2 Se 3 -based thin-film solar cells has also shown that the devices have relatively good light management due to their suitable bandgap and high absorption coefficient, whereas carrier management, i.e. collection efficiency of photo-generated carriers, needs significant improvement. Overall, this study provides background knowledge on material properties and device performance and suggests main research directions to overcome the limiting factors of solar cell performance.

14 SOLAR ENERGY↗
DOE OSTI2021

Crabtree/Warburg-like aerobic xylose fermentation by engineered Saccharomyces cerevisiae

Bottlenecks in the efficient conversion of xylose into cost-effective biofuels have limited the widespread use of plant lignocellulose as a renewable feedstock. The yeast Saccharomyces cerevisiae ferments glucose into ethanol with such high metabolic flux that it ferments high concentrations of glucose aerobically, a trait called the Crabtree/Warburg Effect. In contrast to glucose, most engineered S. cerevisiae strains do not ferment xylose at economically viable rates and yields, and they require respiration to achieve sufficient xylose metabolic flux and energy return for growth aerobically. Here, we evolved respiration-deficient S. cerevisiae strains that can grow on and ferment xylose to ethanol aerobically, a trait analogous to the Crabtree/Warburg Effect for glucose. Through genome sequence comparisons and directed engineering, we determined that duplications of genes encoding engineered xylose metabolism enzymes, as well as TKL1, a gene encoding a transketolase in the pentose phosphate pathway, were the causative genetic changes for the evolved phenotype. Reengineered duplications of these enzymes, in combination with deletion mutations in HOG1, ISU1, GRE3, and IRA2, increased the rates of aerobic and anaerobic xylose fermentation. Importantly, we found that these genetic modifications function in another genetic background and increase the rate and yield of xylose-to-ethanol conversion in industrially relevant switchgrass hydrolysate, indicating that these specific genetic modifications may enable the sustainable production of industrial biofuels from yeast. We propose a model for how key regulatory mutations prime yeast for aerobic xylose fermentation by lowering the threshold for overflow metabolism, allowing mutations to increase xylose flux and to redirect it into fermentation products.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Hydrogenation of CO 2 to Methanol on a Au δ+ –In 2 O 3–x Catalyst

CO 2 hydrogenation to methanol has attracted increasing attention with the development of renewable hydrogen. A big challenge is to identify catalysts able to achieve high conversion and selectivity. In this work, we report an In 2 O 3 -supported Au catalyst that exhibits excellent performance for hydrogenation of CO 2 selectively to methanol. In situ characterizations using time-resolved X-ray diffraction, ambient-pressure X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy confirm that a strong metal–support interaction leads to a reactive Au δ+ –In 2 O 3– x interface for activation and hydrogenation of CO 2 to methanol. An effective gold-indium oxide bonding favors the dispersion of the noble metal and prevents its sintering under reaction conditions. The methanol selectivity reaches 100% at temperatures below 225 °C and is more than 70% at 275 °C over the Au δ+ –In 2 O 3– x catalyst. It is even 67.8% with a space time yield of methanol of 0.47 g MeOH /(h·g cat ) at 300 °C, 5 MPa, and 21,000 cm 3 h –1 g cat –1 . The results obtained here represent the highest selectivity and activity ever reported for CO 2 hydrogenation over supported gold catalysts. Our study shows that the strong Au/In 2 O 3 interaction and the intrinsic chemical activity of In 2 O 3 can be used to significantly improve the catalytic performance of Au catalysts, providing promising routes for the rational design and application of Au catalysts beyond CO 2 hydrogenation.

36 MATERIALS SCIENCE↗
DOE OSTI2019

High-temperature, spectrally-selective, scalable, and flexible thin-film Si absorber and emitter

Solar thermal technologies have great potential to provide low-cost storage for solar energy. However, their efficiencies are limited by a lack of scalable, mechanically flexible, durable, yet highly-efficient spectrally-selective solar absorbers suitable for high temperatures at low solar concentrations. Here, we overcome these challenges by fabricating a scalable free-standing spectrally-selective thin-film Si absorber and emitter (SSTFS) composite. Its high-temperature emittance shows strong spectral selectivity, even at 595 °C. Thermal stability is proven by measuring optical properties before and after thermal cycling equivalent to one day of concentrated sunlight. Despite the use of crystalline Si, the fabricated SSTFS composite exhibits exceptional mechanical flexibility to cover most surface geometries. The SSTFS composite demonstrates the potential of high-temperature, efficient and flexible solar absorbers and thermal emitters to advance renewable solar energy with storage.

36 MATERIALS SCIENCE↗