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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 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

2D Covalent Organic Frameworks with an Incorporated Manganese Complex for Light Driven Carbon Dioxide Reduction

Covalent organic frameworks (COFs) have emerged as a novel class of crystalline porous photocatalytic materials due to their unique properties such as large surface area, tunable porosity, and rigid structure. Here in this work, we report the direct incorporation of a manganese CO 2 molecular catalyst (MC) into COFs (Mn-TTA-COF) and the evaluation of its capability as photocatalyst for visible light driven CO 2 reduction to form CO. We found that the photocatalytic activity of Mn-TTA-COF is quite low, which mainly results from the elimination of the CO ligand in the Mn MC upon light illumination, rendering its short duration in the catalytic reaction. While this is a central concern for the further use Mn-TTA-COF as a CO 2 reduction catalyst, here we found that the stability and efficiency of Mn MC is largely enhanced after being incorporated into COFs with respect to its homogeneous version, suggesting the capability of COFs as heterogeneous platform to incorporate MC and improve the catalytic performance of MC. Moreover, transient absorption spectroscopic studies show that the intramolecular charge transfer lifetime of the Mn-incorporated COF is longer than that in the parent COF, which suggests that charge separation (CS) may occur from the parent COF to the Mn moiety. These results together suggest that COFs may show promise as a platform for creating next-generation photocatalysts with a built-in photosensitizer and MC, which can facilitate CS and enhance the stability and efficiency of the incorporated MC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

The Significance of the 'Insignificant': Non-covalent Interactions in CO 2 Reduction Reactions with 3C-TM (TM=Sc-Zn) Single-Atom Catalysts

With energy shortages and excessive CO 2 emissions driving climate change, converting CO 2 into high-value-added products offers a promising solution for carbon recycling. We investigate CO 2 reduction reactions (CO2RR) catalyzed by 10 single-atom catalysts (SACs), incorporating weak non-covalent interactions, specifically lone pair-π and H-π interactions. The SACs, consisting of transition metals coordinated by three carbon atoms in a defective graphene substrate (3C-TM, TM=Sc-Zn), leverage these interactions to influence the energy fluctuations of intermediates and the limiting potentials of CO 2 RR, without altering the overall reaction pathway. Further, our findings show that SACs based on early transition metals (Sc, Ti, V, Cr) can serve as catalysts for C 1 products, including HCOOH, HCHO, CH 3 OH, and CH 4 , while those based on Fe and Co are suitable for CO formation. Driving force analysis helps bridge theoretical results with experimental observations and propose a modified approach for assessing hydrogen evolution reactions (HER) competition. SACs based on Ni and Cu exhibit moderate HER tolerance, while early transition metals excel in selective CO 2 reduction. We also identify a linear scaling relationship between the free energies of *COOH and *CO. This study offers valuable insights for future experimental studies and large-scale computational screenings.

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

Dianhydride-Modified Graphitic Carbon Nitride as a Support for Cobalt Single-Atom Photocatalysts

Graphitic carbon nitride (C 3 N 4 ) has been widely explored as a photoactive support for single-atom catalysts (SACs). In this paper, three different π-rich aromatic dianhydrides are employed to introduce molecular quantized trap states into the conduction band of C 3 N 4 to facilitate efficient charge-separation and to promote an enhanced photocatalytic CO 2 reduction response. These modified C 3 N 4 materials have been characterized structurally and spectroscopically for use as the support for Co-based SACs. In photocatalytic CO 2 reduction studies, the Co SAC on naphthalene dianhydride doped C 3 N 4 exhibited the highest activity and selectivity towards CO production among the Co SACs tested in this work. The observed improvement in photocatalytic CO 2 -to-CO conversion activity correlates with trends in photoinduced charge separation, as revealed by photoluminescence spectroscopy.

14 SOLAR ENERGY↗
DOE OSTI2026

Exploring the Photogenerated Charge Transfer Mechanism in Cu 2 O@MoS 2 Heterojunction Photocatalyst Using Transient Absorption Spectroscopy

Both heterojunction and core–shell photocatalysts have demonstrated promising performance in photocatalytic CO 2 conversions to fuels. However, fundamental knowledge of heterojunctions in core–shell structures is highly desired to facilitate the design of future photocatalysts. By combining advanced experimental characterizations and density functional theory (DFT) calculations, the role of the Cu 2 O@MoS 2 heterojunction in photocatalytic CO 2 conversions to fuels was investigated. We discovered that the charge dynamics and electron transfer properties of Cu2O@MoS 2 photocatalysts are altered by the heterojunction and Cu 2 O underlayer due to the electron transfer from Cu 2 O to MoS 2 and the change in CO 2 adsorption strength on the hybrid catalyst surface. Consequently, more electrons can travel to the surrounding liquid environment to be consumed by CO 2 reduction. This study provides experimental and theoretical investigations of the fundamental mechanisms of heterojunction core–shell photocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Enabling technologies for the continuous electrically driven conversion of CO 2 and water to multi-carbon products at high current densities

Here, we demonstrate greatly improved conversion of CO 2 using a gas diffusion electrode (GDE) with flowing electrolyte configuration for CO 2 gas delivery in combination with a high surface area nickel phosphide electrocatalyst. This configuration achieves 40–50% selectivity for total carbon products over H 2 formation (HER) at total current densities ranging from 50 to 300 mA cm -2 . We developed a soft-templating method using CTAB detergent micelles for synthesis of phase-pure Ni 2 P, achieving a 260-fold larger surface area (BET) and porous sponge-like morphology that produces stable currents. This catalyst produces mainly one C-product, methylglyoxal (MG, C 3 H 4 O 2 ) with 38–47% overall selectivity, the highest reported selectivity for a 12-electron reduction product. The versatile soft-templating method for electrocatalyst synthesis uses low-temperature (185 °C) that is permissive for incorporation of co-catalysts that are otherwise destroyed by the high temperatures used in traditional solid-state synthesis (SSS). The non-porous Ni 2 P-SSS catalyst produces mainly H 2 at these current densities. Achieving these high currents and C/H selectivity benefits from use of hydrophobic polymers as co-catalyst binders (cationic = Nafion, anionic = PFAEM and neutral = PTFE) to improve CO 2 conversion. PFAEM is the better ionomer for the CO 2 RR at high current density, postulated as due to suppressing CO 2 conversion to inactive bicarbonate. Precipitation of the carbon products as a polycarbonate polymer occurs at high currents.

36 MATERIALS SCIENCE↗
DOE OSTI2023

X-ray Absorption Spectroscopy Studies of a Molecular CO 2 -Reduction Catalyst Deposited on Graphitic Carbon Nitride

Metal-ligand complexes have been extensively explored as well-defined molecular catalysts in small molecule activation reactions such as carbon dioxide (CO 2 ) reduction. Many hybrid photocatalysts have been prepared by coupling such complexes with photoactive surfaces for use in solar CO 2 reduction. In this work, we employ X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies, density functional theory (DFT) and computational XANES modeling to interrogate the structure of a hybrid photocatalyst consisting of a macrocyclic cobalt complex deposited on graphitic carbon nitride (C 3 N 4 ). Results show that the cobalt complex binds on C 3 N 4 through surface OH or NH 2 groups. By refining the local geometry and binding sites of this well-defined molecular cobalt complex on C 3 N 4 , here we established an important benchmark for modeling a large class of molecular catalysts that can be adapted to in situ/operando studies and further enhanced by applying chemometrics-based approaches and machine learning methods of XANES data analysis.

36 MATERIALS SCIENCE↗
DOE OSTI2021

3D-Printable Fluoropolymer Gas Diffusion Layers for CO 2 Electroreduction

The electrosynthesis of value-added multicarbon products from CO 2 is a promising strategy to shift chemical production away from fossil fuels. Particularly important is the rational design of gas diffusion electrode (GDE) assemblies to react selectively, at scale, and at high rates. However, the understanding of the gas diffusion layer (GDL) in these assemblies is limited for the CO 2 reduction reaction (CO 2 RR): particularly important, but incompletely understood, is how the GDL modulates product distributions of catalysts operating in high current density regimes > 300 mA cm -2 . Here, 3D-printable fluoropolymer GDLs with tunable microporosity and structure are reported and probe the effects of permeance, microstructural porosity, macrostructure, and surface morphology. Under a given choice of applied electrochemical potential and electrolyte, a 100× increase in the C 2 H 4 :CO ratio due to GDL surface morphology design over a homogeneously porous equivalent and a 1.8× increase in the C 2 H 4 partial current density due to a pyramidal macrostructure are observed. Overall, these findings offer routes to improve CO 2 RR GDEs as a platform for 3D catalyst design.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Selective Ligand Modification of Cobalt Porphyrins for Carbon Dioxide Electrolysis: Generation of a Renewable H2/CO Feedstock for Downstream Catalytic Hydrogenation

Catalytic hydrogenation is an attractive approach to produce green fuels and chemicals. The building blocks for these processes may be effectively produced from renewable power via direct electrochemical reduction of carbon dioxide in an aqueous media. For the first time, the impact of increasing the local proton concentration of cobalt porphyrin was examined by synthesizing new cobalt porphyrins 2, Co(o-OCH3)TPP and cobalt porphyrin 3, Co(o-OH)TPP. Cobalt porphyrins coated on carbon paper converted carbon dioxide and water into a mixture of hydrogen and carbon monoxide in an aqueous electrolyte at near neutral pH. Increasing the local proton availability of the commercial cobalt porphyrin 1, accelerates hydrogen generation under heterogeneous conditions across the range of potentials tested (-0.85 to -1.5 V vs. Ag/AgCl) and demonstrates high Faradaic efficiencies (ca. 90%) at low over-potentials (ca. 540 mV). The culmination of this work can help identify key parameters that facilitate generation of sustainable reagents for catalytic hydrogenation under practical and scalable conditions.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗
DOE OSTI2021

Monolithic Photoelectrochemical CO 2 Reduction Producing Syngas at 10% Efficiency

We report increasing anthropogenic carbon dioxide emissions have prompted the search for photoelectrochemical (PEC) methods of converting CO 2 to useful commodity products, including fuels. Ideally, such PEC approaches will be sustained using only sunlight, water, and CO 2 as energetic and reactant inputs. However, low peak conversion efficiencies (< 5%) have made commercialization of fully-integrated PEC devices prohibitive. Here, a 4 cm 2 monolithic PEC device exceeding 10% solar-to-fuel efficiency with principal fuel products of carbon monoxide and hydrogen is reported. The corresponding solar-to-CO and solar-to-H 2 efficiencies are 7% and 3.5%, respectively. Screening of a range of operating conditions reveals a tunable product mixture of H 2 and CO using a gold electrocatalyst. Accordingly, it is shown that device optimization yields a H 2 -to-CO ratio of 1:2 commonly present in synthesis gas (syngas). Notably, the modularity and facile fabrication of this device permit the incorporation of a broad array of materials for various applications. For example, the electrocatalyst may easily be swapped to target a different set of products.

36 MATERIALS SCIENCE↗
DOE OSTI2023

A Bifunctional Ionic Liquid for Capture and Electrochemical Conversion of CO 2 to CO over Silver

Electrochemical conversion of CO 2 requires selective catalysts and high solubility of CO 2 in the electrolyte to reduce the energy requirement and increase the current efficiency. In this study, the CO 2 reduction reaction (CO 2 RR) over Ag electrodes in acetonitrile-based electrolytes containing 0.1 M [EMIM][2-CNpyr] (1-ethyl-3-methylimidazolium 2-cyanopyrolide), a reactive ionic liquid (IL), is shown to selectively (>94%) convert CO 2 to CO with a stable current density (6 mA·cm –2 ) for at least 12 h. The linear sweep voltammetry experiments show the onset potential of CO 2 reduction in acetonitrile shifts positively by 240 mV when [EMIM][2-CNpyr] is added. This is attributed to the pre-activation of CO 2 through the carboxylate formation via the carbene intermediate of the [EMIM] + cation and the carbamate formation via binding to the nucleophilic [2-CNpyr] – anion. The analysis of the electrode–electrolyte interface by surface-enhanced Raman spectroscopy (SERS) confirms the catalytic role of the functionalized IL where the accumulation of the IL-CO 2 adduct between –1.7 and –2.3 V vs Ag/Ag + and the simultaneous CO formation are captured. Furthermore, this study reveals the electrode surface species and the role of the functionalized ions in lowering the energy requirement of CO 2 RR for the design of multifunctional electrolytes for the integrated capture and conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Covalent Organic Framework (COF) Derived Ni–N–C Catalysts for Electrochemical CO 2 Reduction: Unraveling Fundamental Kinetic and Structural Parameters of the Active Sites

Electrochemical CO 2 reduction is a potential approach to convert CO 2 into valuable chemicals using electricity as feedstock. Abundant and affordable catalyst materials are needed to upscale this process in a sustainable manner. Nickel-nitrogen-doped carbon (Ni-N-C) is an efficient catalyst for CO 2 reduction to CO, and the single-site Ni-N x motif is believed to be the active site. However, critical metrics for its catalytic activity, such as active site density and intrinsic turnover frequency, so far lack systematic discussion. In this work, we prepared a set of covalent organic framework (COF)-derived Ni-N-C catalysts, for which the Ni-N x content could be adjusted by the pyrolysis temperature. The combination of high-angle annular dark-field scanning transmission electron microscopy and extended X-ray absorption fine structure evidenced the presence of Ni single-sites, and quantitative X-ray photoemission addressed the relation between active site density and turnover frequency.

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

TaO x electron transport layers for CO 2 reduction Si photocathodes

Electron transport layers (ETLs) used as components of photocathodes for light-driven CO 2 reduction (CO 2 R) in aqueous media should have good electronic transport, be stable under CO 2 R conditions, and, ideally, be catalytically inert for the competing hydrogen evolution reaction (HER). Here, using planar p-Si (100) as the absorbing material, we show that TaO x satisfies all three of the above criteria. TaO x films were synthesized by both pulsed laser deposition (PLD) and radio-frequency (RF) sputtering. In both cases, careful control of the oxygen partial pressure during growth was required to produce ETLs with acceptable electron conductivity. p-Si/TaO x photocathodes were interfaced with ca. 10 nm of a CO 2 R catalyst: Cu or Au. Under front illumination with simulated AM 1.5G in CO 2 -saturated bicarbonate buffer, we observed, for both metals, faradaic efficiencies for CO 2 R products of ~50% and ~30% for PLD TaO x and RF sputtered TaO x , respectively, at photocurrent densities up to 8 mA cm -2 . p-Si/TiO 2 /Cu photocathodes were also evaluated but produced mostly H 2 (>97%) due to reduction of the TiO 2 to Ti metal under CO 2 R conditions. In contrast, a dual ETL photocathode (p-Si/TiO 2 /TaO x /Cu) was selective for CO 2 R, which suggests a strategy for separately optimizing selective charge collection and the stability of the ETL/water interface. The maximum photovoltage obtained with p-Si/TaO x /Cu devices was 300 mV which was increased to 430–460 mV by employing ion implantation to make pn + -Si/TaO x /Cu structures. Photocathodes with RF sputtered TaO x ETLs are stable for CO 2 R for at least 300 min. In conclusion, techno-economic analysis shows that the reported system, if scaled, could allow for an economically viable production of feedstocks for chemical synthesis under the adoption of specific CO 2 credit schemes, thus becoming a significant component of carbon-neutral manufacturing.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Covalent Organic Framework Photocatalysts for Water Oxidation and Overall Artificial Photosynthesis

Artificial photosynthesis through proton reduction or CO 2 reduction to generate chemical fuels has gained increasing attention as an attractive strategy for solar-to-fuel conversion. In these systems, the oxygen evolution reaction (OER) provides the necessary electrons and protons for driving the overall reaction but represents the rate-limiting step due to its inherently sluggish kinetics. Therefore, efficient overall artificial photosynthesis requires photocatalysts that can drive both the oxidation and reduction half-reactions, which impose stringent demands on catalyst design. Covalent organic frameworks (COFs) offer a versatile platform for designing such photocatalysts, owing to their strong light-harvesting capabilities , periodic architectures, and highly tunable frameworks that allow programmable catalytic sites and adjustable electronic band structures. While notable progress has been made in developing COF photocatalysts for the OER and overall artificial photosynthesis, these advances remain scattered across the literature and existing reviews, and a dedicated, systematic overview of the OER and its central role in integrated artificial photosynthetic processes is still lacking. This Review systematically summarizes recent advances in COF-based photocatalysts for the OER half-reaction and overall artificial photosynthesis. Our aim is to offer a comprehensive roadmap that establishes fundamental design principles for next-generation COF-based photocatalysts toward efficient and sustainable artificial photosynthesis.

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

Bioadaptive Ni single atoms unlock high rate microbial electrosynthesis of isopropanol from CO 2

Hybrid systems that integrate electrochemical CO 2 reduction with microbial upgrading offer a viable route to high value organic compounds from CO 2 at ambient conditions. However, electrocatalyst deactivation in microbial growth media remains a key barrier, limiting efficiency and increasing cost. Here we show that a bioadaptive single-atom nickel catalyst (Ni SAC), coupled with genetically engineered Clostridium ljungdahlii, enables robust electrosynthesis of isopropanol (IPA) from CO 2 via a CO-mediated pathway. Instead of relying on H 2 as an electron carrier, the system applies high-rate CO formation in complex growth media, maintaining a tunable CO Faradaic efficiency up to 92%, which is 9.4 to 52.7 times greater than conventional Ag catalysts. This performance supports stable IPA production at current density of 10.8 A/m 2 and production rate of 161.3 mg/L/day. In situ Raman and X-ray absorption spectroscopy, together with theoretical calculations, indicate that the Ni SAC can resist competing organic adsorption and retain its coordination structure during CO 2 reduction in bioelectrolytes, providing a mechanistic basis for the catalyst stability and integrated process performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Accessing and Photo-Accelerating Low-Overpotential Pathways for CO 2 Reduction: A Bis-Carbene Ruthenium Terpyridine Catalyst

A ruthenium catalyst bearing a bidentate bis(carbene) ligand is prepared and studied as a catalyst for CO 2 electroreduction. The catalyst [Ru(tpy)(bis-mim)(MeCN)][PF 6 ] 2 (tpy) is 2,2′,:6′,2″-terpyridine; bis-mim is (methylenebis(N-methylimidazol-2-ylidene)) mediates reduction of CO 2 into CO with a turnover frequency of 630 s –1 and Faradaic efficiency (FE) of 30% at an overpotential of 730 mV. The strongly donating bis(carbene) ligand also enables access to a pathway operating at a lower overpotential of ca. 310 mV. While low-overpotential catalysis is slow in the dark (TOF = 0.01 s –1 ), visible light illumination increases the rate 10-fold (TOF = 0.11 s –1 ). Here, a full mechanistic picture is developed using kinetic analysis from cyclic voltammetry, spectroelectrochemistry, and computational methods, with the bis-mim ligand facilitating rapid CO 2 activation at low overpotentials. Comparisons with other ruthenium catalysts yield insight into the ability to tune the rate of chemical steps (e.g., ligand dissociation and CO 2 nucleophilic attack) and the overpotential by tailoring the primary coordination sphere while retaining the “redox-active” tpy ligand.

CO2 reduction↗
DOE OSTI2023

Shape-persistent phthalocyanine cages

Phthalocyanine (Pc), an electro-redox active moiety, has many attractive properties stemming from its large aromatic system and ability to act as a catalyst in electrochemical reactions, such as the CO 2 reduction reaction (CO 2 RR). However, due to the synthetic challenge related to geometric requirements and poor solubility (strong aggregation), discrete shape-persistent cages consisting of site-isolated, readily accessible Pc moieties have not been available. Here, we report the synthesis of Zn- and Ni-metallated Pc-based molecular cages via one-step dynamic spiroborate linkage formation in high yields. The ZnPc cage structure is unambiguously elucidated at the atomic level by single-crystal X-ray diffraction. Moreover, owing to the site-isolated redox-active metal centers, readily accessible intrinsic cavity, and shape-persistent backbone, the Ni-metallated Pc (NiPc) cage exhibits high catalytic efficiency, selectivity, and stability, superior to the non-caged control molecules in electrocatalytic CO 2 RR.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Electrochemical Control of the Morphology and Functional Properties of Hierarchically Structured, Dendritic Cu Surfaces

Electrodeposited dendritic copper foams have been extensively studied as an electrocatalyst for CO 2 reduction reaction (CO 2 RR). Many parameters, such as dendrite size, porosity, pore size, and crystal faceting, define the hierarchical properties of these structures and their subsequent bubble evolution and CO 2 RR capabilities. Herein, the effects the electrodeposition conditions (potential, pH) have on the resulting crystallinity, microstructure, and macroporosity of the copper foam are studied. These morphological differences and the corresponding effects on electrocatalytic activity are characterized. It is shown that the composition of the electrodeposition bath can have significant effects on the mechanics of bubble formation and detachment at the surface during hydrogen evolution reaction in acidic solutions. Similarly, the electrodeposition conditions for the synthesis of the foam affect the product selectivity during CO 2 RR electrocatalysis. As a result, foams deposited in alkaline electrodeposition solutions show high faradaic efficiency and specificity toward C 2 H 6 , an uncommon product of CO 2 RR, at modest applied potentials (−0.8 V versus reversible hydrogen electrode.

14 SOLAR ENERGY↗
DOE OSTI2021

Water and Solute Activities Regulate CO 2 Reduction in Gas-Diffusion Electrodes

Electrolysis of CO 2 at gas-diffusion electrodes (GDEs) has typically been limited by the supply of gas to the electrocatalyst, overshadowing the importance of the supply of water. However, at high current densities that approach 1 A cm –2 , where the electrolyte becomes highly concentrated in the catalyst layer of a GDE, the activity of water and solutes deviate from their bulk dilute solution values, potentially slowing reaction rates and changing reaction equilibrium potentials. In addition, as flow plates for the gas stream are introduced to enable larger electrodes and high single pass conversion of CO 2 to product, variations in the gas composition will become important. By drawing upon literature for the oxygen reduction reaction (ORR), here we explain how to account for these effects in future modeling and experimental work, with particular attention to accurate use of the Nernst equation for electrode potentials and the Arrhenius equation for reaction rates. Specifically, using measurements of KOH solvent and solute activity reported in literature, and assuming the second protonation of CO 2 by water as the rate-determining step, we show the Nernst equation dilute-solution approximation of the CO 2 to CO equilibrium potential to be accurate below 5 M KOH, but it has a 74 mV error when increasing the concentration up to 10 M KOH. Finally, a simple one-dimensional model of a serpentine flow-field on a GDE demonstrated that a reactor with constant pressure of 1 bar and 1 A cm –2 at the inlet had only ~0.3 A cm –2 at the outlet for a conversion in CO 2 partial pressure from 0.90 to 0.48 bar, showing the significant practical implications of this work.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗