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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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52 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Scalable bottom-up synthesis of Co-Ni–doped graphene

Introducing heteroatoms into graphene is a powerful strategy to modulate its catalytic, electronic, and magnetic properties. At variance with the cases of nitrogen (N)– and boron (B)–doped graphene, a scalable method for incorporating transition metal atoms in the carbon (C) mesh is currently lacking, limiting the applicative interest of model system studies. This work presents a during-growth synthesis enabling the incorporation of cobalt (Co) alongside nickel (Ni) atoms in graphene on a Ni(111) substrate. Single atoms are covalently stabilized within graphene double vacancies, with a Co load ranging from 0.07 to 0.22% relative to C atoms, controllable by synthesis parameters. Structural characterization involves variable-temperature scanning tunneling microscopy and ab initio calculations. The Co- and Ni-codoped layer is transferred onto a transmission electron microscopy grid, confirming stability through scanning transmission electron microscopy and electron energy loss spectroscopy. This method holds promise for applications in spintronics, gas sensing, electrochemistry and catalysis, and potential extension to graphene incorporation of similar metals.

Science & Technology - Other Topics↗
DOE OSTI2020

Supported and coordinated single metal site electrocatalysts

The ever-increasing global environmental and energy crisis issues necessitates technological innovation, especially in the development of renewable energy-related devices, such as electrochemical energy conversion and storage technologies, including fuel cells, water electrolyzers, and CO 2 electrolyzers. Reliable and sustainable energy conversion devices are highly dependent on engineering of electrocatalysts. Furthermore, state-of-the-art electrocatalysts for these electrochemical conversion systems are usually platinum group metal (PGM)-based nanoparticles with high cost, which has sparked intensive research on atomically dispersed single metal site electrocatalysts for decreasing metal loadings and boosting catalytic efficiencies by taking advantage of their inherent electronic effects, quantum size effects, and metal-support interactions. In this review, we first introduced the intrinsic active site identification and stabilization, followed by addressing the mutual metal-support interactions, and most important, their correlations with catalytic properties. Next, the advances in synthetic strategies and characterization techniques for single metal site electrocatalysts are highlighted. Additionally, recent advances in single metal site electrocatalysts designs for applications in electrochemical conversion reactions are also presented. Finally, remaining challenges and a forward-looking perspective on this field of research are provided.

25 ENERGY STORAGE↗
DOE OSTI2025

Elucidating the Interfacial Effects of Nonmetallic Elements on the Dehydrogenation Behavior of Nanoconfined NaAlH 4 in Zeolite-Templated Carbon

Confining materials within nanoscale volumes alters their physical and chemical properties, with positive consequences for energy storage, conversion, and catalysis. The pore structure and composition of scaffolds are essential variables for optimizing these properties, with carbon-based materials being preferred due to their tunable porous structures and chemical versatility. This study investigates the influence of surface functional groups on the dehydrogenation kinetics of nanoconfined NaAlH4 using zeolite-templated carbons (ZTCs). Here we focus on oxygen functional groups commonly present as intrinsic impurities on carbon scaffolds, analyzing three ZTC scaffolds to determine how their concentrations and configurations affect dehydrogenation behavior. Our findings reveal that carbonyl groups enhance charge transfer and destabilize Al–H bonds more effectively than ether or phenol groups. This indicates that the type of oxygen functional group is more critical than the quantity, highlighting the importance of properly tailoring oxygen defects to improve hydrogen storage performance in nanoconfined systems.

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

Beam-driven dynamics of aluminium dopants in graphene

Abstract Substituting heteroatoms into graphene can tune its properties for applications ranging from catalysis to spintronics. The further recent discovery that covalent impurities in graphene can be manipulated at atomic precision using a focused electron beam may open avenues towards sub-nanometer device architectures. However, the preparation of clean samples with a high density of dopants is still very challenging. Here, we report vacancy-mediated substitution of aluminium into laser-cleaned graphene, and without removal from our ultra-high vacuum apparatus, study their dynamics under 60 keV electron irradiation using aberration-corrected scanning transmission electron microscopy and spectroscopy. Three- and four-coordinated Al sites are identified, showing excellent agreement with ab initio predictions including binding energies and electron energy loss spectrum simulations. We show that the direct exchange of carbon and aluminium atoms predicted earlier occurs under electron irradiation, although unexpectedly it is less probable than the same process for silicon. We also observe a previously unknown nitrogen–aluminium exchange that occurs at Al–N double-dopant sites at graphene divacancies created by our plasma treatment.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Insights into activators on biomass-derived carbon-based composites for electrochemical energy storage

Biomass-derived carbon materials are now an essential source of carbon electrodes for high-performance supercapacitors due to their cost-effectiveness and abundant heteroatom self-doping properties. When preparing porous carbon materials from biomass for supercapacitor use, the use of activators can significantly increase the specific surface area of carbon materials, enhance pore structures, introduce more heteroatoms, promote the generation of various functional groups, and play a crucial role in the capacitance performance of biomass-derived carbon materials. However, the role of activators during the activation process has been overlooked in previous work focused on improving supercapacitor capacitance performance. In addition, there is a lack of comprehensive reviews summarizing the role of activators. Therefore, this work classifies the types of activators, discusses their activation mechanisms, operability, economy, and environmental friendliness, and proposes future development directions for activators. The main mixing methods of activators and carbon materials are also demonstrated, highlighting the advantages and disadvantages of each method. In conclusion, this work could provide valuable insights for the development of activators for high-performance supercapacitors.

25 ENERGY STORAGE↗
DOE OSTI2023

Conducting Polymers Meet Lithium–Sulfur Batteries: Progress, Challenges, and Perspectives

Lithium–sulfur (Li–S) batteries have attracted increased interest because of the high theoretical energy density, low cost, and environmental friendliness. Conducting polymers (CPs), as one of the most promising materials used in Li–S batteries, can not only facilitate electron transfer and buffer the large volumetric change of sulfur benefiting from their porous structure and excellent flexibility, but also enable stronger physical/chemical adsorption capacity toward polysulfides (LiPSs) when doped with abundant heteroatoms to promote the sulfur redox kinetics and achieve the high sulfur loading. This review firstly introduces the properties of various CPs including structural CPs (polypyrrole (PPy), polyaniline (PANi), polyethylene dioxothiophene [PEDOT]) and compound CPs (polyethylene oxide (PEO), polyvinyl alcohol (PVA) and poly(acrylic acid) [PAA]), and their application potential in Li–S batteries. Furthermore, the research progress of various CPs in different components (cathode, separator, and interlayer) of Li–S batteries is systematically summarized. Finally, the application perspective of the CPs in Li–S batteries as a potential guidance is comprehensively discussed.

Chen, Xin↗
DOE OSTI2020

Universal Approach to Fabricating Graphene-Supported Single-Atom Catalysts from Doped ZnO Solid Solutions

Single-atom catalysts (SACs) have attracted widespread interest for many catalytic applications because of their distinguishing properties. However, general and scalable synthesis of efficient SACs remains significantly challenging, which limits their applications. Here we report an efficient and universal approach to fabricating a series of high-content metal atoms anchored into hollow nitrogen-doped graphene frameworks (M-N-Grs; M represents Fe, Co, Ni, Cu, etc.) at gram-scale. The highly compatible doped ZnO templates, acting as the dispersants of targeted metal heteroatoms, can react with the incoming gaseous organic ligands to form doped metal-organic framework thin shells, whose composition determines the heteroatom species and contents in M-N-Grs. We achieved over 1.2 atom % (5.85 wt %) metal loading content, superior oxygen reduction activity over commercial Pt/C catalyst, and a very high diffusion-limiting current (6.82 mA cm -2 ). Both experimental analyses and theoretical calculations reveal the oxygen reduction activity sequence of M-N-Grs. Additionally, the superior performance in Fe-N-Gr is mainly attributed to its unique electron structure, rich exposed active sites, and robust hollow framework: This synthesis strategy will stimulate the rapid development of SACs for diverse energy-related fields.

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

Heteroatom anchoring to enhance electrochemical reversibility for high-voltage P2-type oxide cathodes of sodium-ion batteries

P2-type cathode has received extensive attention due to its faster Na+ diffusion and a high theoretical capacity in sodium-ion batteries (SIBs). However, undesirable phase transformations have induced dramatic capacity decay of SIBs during the cycling process. In this study, heteroatom anchoring through Cu/Mg dual doping is introduced into P2-type Na 0.67 Ni 0.33 Mn 0.67 O 2 cathode to enhance high-voltage electrochemical reversibility and modulate interfacial Na + kinetics. Further, the as-prepared Na 0.67 Ni 0.23 Mg 0.05 Cu 0.05 Mn 0.67 O 2 exhibits an outstanding capacity retention (83.4% after 2000 cycles at 10C) and rate performance (73 mAh g -1 at 10C, accounting for 58.7% of that at 0.1 C) over the voltage range of 2.5–4.4 V. Intensive explorations further manifest that the modified mechanism of dual-ion doping strategy is attributed to the synergistic coupling effect of a substantial change in Na occupancy distribution and an increase in oxygen vacancy buffer. Thus, the optimized cathode expedites Na + diffusion and reduces detrimental phase transformation, which favors high-rate performance and long-term cycling stability. This study develops a route to rationally design high-voltage cathode materials for SIBs.

25 ENERGY STORAGE↗
DOE OSTI2024

Tailoring Pore Architecture and Heteroatom Functionality of Polymeric Waste-Derived Nanoporous Carbon for CO 2 Capture Applications

This study proposes upcycling polymeric waste, i.e., waste floral foam, into high-performance nanoporous carbon that efficiently captures CO 2 . This paper presents strategies for improving the properties of nanoporous carbon, which aid in a superior CO 2 capture performance. Initially, pristine nanoporous carbon was produced from waste floral foam using various KOH impregnation ratios. The nanoporous carbon with a 1:2 (waste floral foam:KOH) ratio exhibiting optimal CO 2 capture capability was further advanced through single and dual atom doping. The doping of N and codoping of N,S atoms into the nanoporous carbon altered its textural and surface chemical properties, making them efficient for CO 2 capture. Comparative CO 2 capture studies of pristine nanoporous carbon (NC-x), N-doped nanoporous carbon (N-NC2), and N,S-codoped nanoporous carbon (N,S-NC2) demonstrate the superiority of N-doping. N-doped nanoporous carbon exhibited the largest ultramicroporosity (0.3100 cm3/g, 63.43%) and highest heteroatom content (34.94 atomic %), contributing to its enhanced CO 2 capture capability (4.54 mmol/g). Finally, implementing the “waste-to-depollution” approach, this research lays the groundwork for producing low-cost, environmentally friendly nanoporous carbon with remarkable CO 2 capture attributes.

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

Doped-carbon composites, synthesizing methods and applications of the same

A composite synthesized by the steps of preparing a solution having a carbon source material and a heteroatom containing additive; evaporating the solution to yield a plurality of powders; and subjecting the plurality of powders to a heat treatment for a duration of time effective to produce a doped carbon composite.

Viswanathan, Tito↗
DOE OSTI2019

Enhancing Chemical Interaction of Polysulfide and Carbon through Synergetic Nitrogen and Phosphorus Doping

The shuttling effect of the polysulfide (PS) is the most detrimental factor that causes capacity fading of Li–S batteries. By substituting carbon atoms with heteroatoms, the host materials can provide a chemical interaction with PS to trap it within the electrochemically active range of the cathode. In this study, first-principles-based calculations identify the most stable nitrogen (N) and phosphorus (P) codoped atomic structures and their corresponding adsorption energy toward different PS species. Based on the simulated predictions, we introduce a glucosamine-derived carbon nanotube aerogel (CNA) with a secondary dopant of P during the synergetic polymerization and carbonization process. The N–P codoped CNA and S composite (NPCNA-S) renders a highly stable performance even at a sulfur loading of 3.5 mg cm –2 . In conclusion, the specific capacity is >900 mAh g –1 and the stabilized capacity retention is >70% over 450 cycles at 0.2 C rate (1 C = 1675 mA g –1 ).

25 ENERGY STORAGE↗
DOE OSTI2023

Effect of Phosphorus Modulation in Iron Single‐Atom Catalysts for Peroxidase Mimicking

Abstract Fe–N–C single‐atom catalysts (SACs) exhibit excellent peroxidase (POD)‐like catalytic activity, owing to their well‐defined isolated iron active sites on the carbon substrate, which effectively mimic the structure of natural peroxidase's active center. To further meet the requirements of diverse biosensing applications, SAC POD‐like activity still needs to be continuously enhanced. Herein, a phosphorus (P) heteroatom is introduced to boost the POD‐like activity of Fe–N–C SACs. A 1D carbon nanowire (FeNCP/NW) catalyst with enriched Fe–N 4 active sites is designed and synthesized, and P atoms are doped in the carbon matrix to affect the Fe center through long‐range interaction. The experimental results show that the P‐doping process can boost the POD‐like activity more than the non‐P‐doped one, with excellent selectivity and stability. The mechanism analysis results show that the introduction of P into SAC can greatly enhance POD‐like activity initially, but its effect becomes insignificant with increasing amount of P. As a proof of concept, FeNCP/NW is employed in an enzyme cascade platform for highly sensitive colorimetric detection of the neurotransmitter acetylcholine.

Ding, Shichao↗
DOE OSTI2024

Enhancing the Reaction Kinetics and Stability of Co‐Free Li‐Rich Cathode Materials via a Multifunctional Strategy

Co-free Li-rich layered oxides (CFLLOs) with anionic redox activity are among the most promising cathode materials for high-energy-density and low-cost lithium-ion batteries (LIBs). However, irreversible oxygen release often causes severe structural deterioration, electrolyte decomposition, and the formation of unstable cathode-electrolyte interface (CEI) film with high impedance. Additionally, the elimination of cobalt elements further deteriorates the reaction kinetics, leading to reduced capacity and poor rate performance. Here, in this study, a multifunctional strategy is proposed, incorporating Li 2 MnO 3 phase content regulation, micro-nano structure design, and heteroatom substitution. The increased content of Li 2 MnO 3 phase enhances the capacity through oxygen redox. The smaller nanoscale primary particles induce greater tensile strain and introduce more grain boundaries, thereby improving the reaction kinetics and reactivity, while the larger micron-sized secondary particles help to reduce interfacial side reactions. Furthermore, Na⁺ doping modulates the local coordination environment of oxygen, stabilizing both the anion framework and the crystal structure. As a result, the designed cathode exhibits enhanced rate performance, delivering a capacity of 158 mAh g⁻¹ at 5.0 C and improved cyclic stability, with a high capacity retention of 99% after 400 cycles at 1.0 C. This multifunctional strategy holds great promise for advancing the practical application of CFLLOs in next-generation LIBs.

Co-free Li-rich layered oxide↗
DOE OSTI2022

Construction of Nitrogen-abundant Graphyne Scaffolds via Mechanochemistry-Promoted Cross-Linking of Aromatic Nitriles with Carbide Toward Enhanced Energy Storage

The 2D graphyne-related scaffolds linked by carbon–carbon triple bonds have demonstrated promising applications in the field of catalysis and energy storage due to their unique features including high conductivity, permanent porosity, and electron-rich properties. However, the construction of related scaffolds is still mainly limited to the cross-linking of CaC 2 with multiple substituted aromatic halogens and there is still a lack of efficient methodology capable of introducing high-concentration heteroatoms within the architectures. The development of alternative and facile synthesis procedures to afford nitrogen-abundant graphyne materials is highly desirable yet challenging in the field of energy storage, particularly via the facile mechanochemical procedure under neat and ambient conditions. Here, in this study, graphyne materials with abundant nitrogen-containing species (nitrogen content of 6.9–29.3 wt.%), tunable surface areas (43–865 m 2 g -1 ), and hierarchical porosity are produced via the mechanochemistry-driven pathway by deploying highly electron-deficient multiple substituted aromatic nitriles as the precursors, which can undergo cross-linking reaction with CaC 2 to afford the desired nitrogen-doped graphyne scaffolds efficiently. Unique structural features of the as-synthesized materials contributed to promising performance in supercapacitor-related applications, delivering high capacitance of 254.5 F g -1 at 5 mV s -1 , attractive rate performance, and good long-term stability.

25 ENERGY STORAGE↗
DOE OSTI2022

Does boron or nitrogen substitution affect hydrogen physisorption on open carbon surfaces?

Incorporation of heteroatoms in carbon materials is commonly expected to influence their physical or chemical properties. Furthermore, contrary to previous results for methane adsorption, no technologically significant effect was identified for the hydrogen physisorption energies (measured 4.1–4.6 kJ mol –1 and calculated q st = –ΔH ads = 4.1 ± 0.7 kJ mol –1 using a comprehensive set of levels of theory) as a function of B- and N-substitution of a mid-plane C-site on open carbon surfaces.

08 HYDROGEN↗
DOE OSTI2026

Vapor-Phase Heteroatom Incorporation into Semiconductive Molecular-Scale Magic-Size Clusters

Magic-size metal chalcogenide clusters of molecular size exhibit well-defined structure and unique properties that might be further expanded with the incorporation or substitution of a second metal. Here, we report the postmodification of magic-size clusters synthesized in polymer thin films via exposure to volatile metal organic precursors commonly utilized for atomic layer deposition. Exposure of In 6 S 6 (CH 3 ) 6 clusters to dimethylcadmium results in exposure-dependent incorporation of Cd 2+ , which extends the optical absorbance of the clusters into the visible spectrum. The mechanism for Cd 2+ incorporation is consistent with Cd 2+ replacement of In 3+ that includes methyl ligand removal to maintain charge neutrality. Even for clusters embedded in a polymer matrix, ligand loss leads to sintering and transformation into larger nanoscale aggregates with zinc blende-type structure. The extent of Cd incorporation can be modulated by varying the process temperature and volatile metal organic exposure as well as the choice of volatile metal organic precursor. A computational thermodynamic analysis of heteroatom incorporation for several metals and chemistries reveals that both the stability of the substituted cluster and the favorability of reaction byproducts jointly determine the favorability of cation incorporation.

atomic layer deposition↗