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At least 847 records · Page 47

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DOE OSTI2022

Tunable metal hydroxide–organic frameworks for catalysing oxygen evolution

The oxygen evolution reaction is central to making chemicals and energy carriers using electrons. Combining the great tunability of enzymatic systems with known oxide-based catalysts can create breakthrough opportunities to achieve both high activity and stability. Here we report a series of metal hydroxide–organic frameworks (MHOFs) synthesized by transforming layered hydroxides into two-dimensional sheets crosslinked using aromatic carboxylate linkers. MHOFs act as a tunable catalytic platform for the oxygen evolution reaction, where the π–π interactions between adjacent stacked linkers dictate stability, while the nature of transition metals in the hydroxides modulates catalytic activity. Substituting Ni-based MHOFs with acidic cations or electron-withdrawing linkers enhances oxygen evolution reaction activity by over three orders of magnitude per metal site, with Fe substitution achieving a mass activity of 80A $g^{-1}_{catalyst}$ 1 at 0.3 V overpotential for 20 h. Density functional theory calculations correlate the enhanced oxygen evolution reaction activity with the MHOF-based modulation of Ni redox and the optimized binding of oxygenated intermediates.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Ultra-stable trimetallic phosphide heterostructure with regulated electronic structure for overall water splitting at high current densities

Developing ultra-stable electrocatalysts for highly efficient overall water splitting at high current density (HCD) is critical for renewable hydrogen/oxygen production in the industry. However, the most active electrocatalysts for large current-driven water splitting are seriously handicapped by insufficient electrical contact kinetics due to the intensive bubble overflow. Herein, we demonstrate the ultra-stable trimetallic phosphides of NiFeP/NiCoP catalysts on a hydrophilic Ni foam skeleton via a corrosion-hydrothermal-phosphating strategy. The optimized NiFeP/NiCoP catalyst stabilizes for 600 h at -1 A cm -2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline solution, and it only needs low overpotentials of 237 and 314 mV to drive HER and OER at 1 A cm -2 , respectively. As expected, the optimized NiFeP/NiCoP electrode maintains 1000 h at 0.5 A cm -2 for water splitting, ranking among the top performers among reported catalysts. Such excellent performance could be attributed to the fast electron transfer for electrochemical reactions, the electron-deficient Fe/Ni sites contribute to forming robust metal oxyhydroxide during OER, and electron-rich Co sites facilitate H adsorption during HER. In conclusion, the findings present a highly promising candidate for ultra-stable non-noble metal electrocatalysts, offering a viable option for hydrogen/oxygen supply for fuel cells and metal-air batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Ultrafast Electron Transfer in Au-Cyanobacteria Hybrid for Solar to Chemical Production

The rise of inorganic-biohybrid organisms for solar-to-chemical production has spurred mechanistic investigations into the dynamics of the biotic-abiotic interface to drive the development of next-generation hybrid systems. The model system, cyanobacteria-gold nanoparticle hybrids, combines a light harvester with a photosynthetic bacterium to drive the reduction of CO2 to glycerol with improved efficiency and increased glycerol production by 14.6%, in comparison to cyanobacteria only. In this work, we report insights into this unique photochemical behavior and propose a charge-transfer pathway from Au nanoparticle to cyanobacteria. Transient absorption (TA) spectroscopy revealed that photoexcited electron transfer rates are on the order of a few ps to the potential electron acceptor in photosystem II. This work represents a promising platform to utilize a conventional spectroscopic methodology to extract insights from more complex biotic-abiotic hybrid systems.

charge transfer↗

DOE OSTI2022

Powerful Organic Molecular Oxidants and Reductants Enable Ambipolar Injection in a Large-Gap Organic Homojunction Diode

Doping has proven to be a critical tool for enhancing the performance of organic semiconductors in devices like organic light-emitting diodes. However, the challenge in working with high-ionization-energy (IE) organic semiconductors is to find p-dopants with correspondingly high electron affinity (EA) that will improve the conductivity and charge carrier transport in a film. Here, we use an oxidant that has been recently recognized to be a very strong p-type dopant, hexacyano-1,2,3-trimethylene-cyclopropane (CN6-CP). The EA of CN6-CP has been previously estimated via cyclic voltammetry to be 5.87 eV, almost 300 meV higher than other known high-EA organic molecular oxidants. We measure the frontier orbitals of CN6-CP using ultraviolet and inverse photoemission spectroscopy techniques and confirm a high EA value of 5.88 eV in the condensed phase. The introduction of CN6-CP in a film of large-band-gap, large-IE phenyldi(pyren-1-yl)phosphine oxide (POPy 2 ) leads to a significant shift of the Fermi level toward the highest occupied molecular orbital and a 2 orders of magnitude increase in conductivity. Using CN6-CP and n-dopant (pentamethylcyclopentadienyl)(1,3,5-trimethylbenzene)ruthenium (RuCp*Mes)2, we fabricate a POPy 2 -based rectifying p–i–n homojunction diode with a 2.9 V built-in potential. Blue light emission is achieved under forward bias. Furthermore, this effect demonstrates the dopant-enabled hole injection from the CN6-CP-doped layer and electron injection from the (RuCp*Mes) 2 -doped layer in the diode.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Quinoid-viologen conjugates: Redox properties and host-guest complex with cucurbiturils

Viologens are known as an excellent electron acceptor and a versatile supramolecular building block, the physical property of which can be tuned by varying the N-substitution. Here, in this paper, we present a class of unprecedented quinoid-viologen conjugates wherein a quinoidal unit is incorporated as part of an extended π-system of the viologen units through N-substitution. Such class of molecules show intriguing optical and electronic properties inherited from both the viologen and the quinoid constituents, displaying stronger electron accepting characters, visible absorption, reversible redox activity, modulated electrochromism, and characteristic binding towards Cucurbit [n]urils (n = 7 and 8). This molecular design strategy points to a new direction to diversify viologens for functional electroactive materials and complex architectures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Engineering phase-frustration-induced flat bands in an aza-triangulene covalent kagome lattice

π-Conjugated covalent organic frameworks provide a versatile molecular scaffold for the realization of designer quantum nanomaterials. Strong electron–electron correlation within these artificial lattices can give rise to exotic phases of matter. Their experimental realization, however, requires precise control over orbital symmetry, charge localization and band dispersion, all arising from the effective hybridization between molecular linkers and nodes. Here we present a modular strategy for constructing diatomic kagome lattices from aza-[3]triangulene nodes, in which a D 3h -symmetric ground state is stabilized through resonance contributions from a cumulenic linker. First-principles density functional theory and scanning tunnelling spectroscopy reveal that the hybridization of a sixfold-degenerate set of edge-localized Wannier functions in the unit cell gives rise to orbital-phase-frustration-induced non-trivial flat bands. These results establish a general design principle for engineering orbital interactions in organic lattices and open a pathway towards programmable covalent-organic-framework-based quantum materials with correlated electronic ground states.

conjugated polymers↗

DOE OSTI2025

Organic Direct-Bonded-Copper-Based Rapid Prototyping for Silicon Carbide Power Module Packaging

Silicon carbide (SiC) power devices are playing ever- growing roles in high-power-density power electronics converters by offering benefits such as high voltage rating, fast transients, and high thermal performance. Organic direct-bonded copper (ODBC)-based packaging, due to its ductility and ease of han- dling, allows the possibility of a more flexible layout design that may better tap the potential of SiC benefits. In this work, an ODBC-based prototyping routine is developed that accelerates the iterations of packaging layout design with low cost. The properties of ODBC and its handling are briefly introduced, and tools and fabrication steps are explained. Following this routine, a 1.2-kV SiC half-bridge power module is designed and fabricated with the focus on sub-nanohenry ultra-low loop inductance. Simulation and experimental validation are also conducted.

25 ENERGY STORAGE↗

DOE OSTI2026

Heavy Element Spectroscopy in the Gas Phase

Actinides are inherently unstable and undergo nuclear decay processes with a concurrent release of energy. Consequently, they are used for nuclear power generation, nuclear weapons, and nuclear medicine. However, the radioactive decay processes also pose significant technological problems for the safe treatment and storage of spent nuclear materials. Cost-effective extraction of the actinides is the key first step in the remediation of nuclear waste, but the appropriate chemical means have yet to be determined. Our present understanding of the chemistry of actinides is limited, with the role of the 5f electrons posing a set of particularly challenging questions. The work reported here is focused on the use of electronic spectroscopy to probe the bonding of small molecules in the gas phase that contains thorium or uranium. Analyses of these data, carried out within the framework of ligand field theory, reveal clear evidence that the 5f electrons are spectators that retain their atomic metal ion character.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Systems and methods for organic semiconductor devices with sputtered contact layers

Systems and methods for organic semiconductor devices with sputtered contact layers are provided. In one embodiment, an organic semiconductor device comprises: a first contact layer comprising a first sputter-deposited transparent conducting oxide; an electron transport layer interfacing with the first contact layer; a second contact layer comprising a second sputter-deposited transparent conducting oxide; a hole transport layer interfacing with the second contact layer; and an organic semiconductor active layer having a first side facing the electron transport layer and an opposing second side facing the hole transport layer; wherein either the electron transport layer or the hole transport layer comprises a buffering transport layer.

Hammond, Scott R.↗

DOE OSTI2024

Systems and methods for organic semiconductor devices with sputtered contact layers

Hammond, Scott R.↗

DOE OSTI2021

Blade-Coated Electron Transport Layers to Enable Scalable Perovskite Photovoltaics

With substantial improvements in efficiency of organic-inorganic halide perovskite solar cells (PSCs), attention has shifted to scale and commercial viability. While deposition of the perovskite absorber layer has been demonstrated using high throughput blade coating and even roll-to-roll printing, associated transport layers are often deposited using energy- and cost-intensive methods such as thermal evaporation. Here, we present an ambient process to blade coat mixed fullerene and bathocuproine (BCP) electron transport layers (ETLs) in inverted PSCs for low-cost, high throughput, scalable devices demonstrating efficiencies matching evaporated methods and >15% for device areas of 1 cm2.

bathocuproine↗

DOE OSTI2025

Improving Surface Quality of Titanium Electrodeposition from a Deep Eutectic Solvent with Organic and Inorganic Additives

Titanium electroreduction is desired for a variety of medical, electronic, and bonding applications but has not been possible until recently. Titanium electrodeposition with leveler and brightener additives in the deep eutectic solvent ethaline has been studied for effects on spectroscopic reflectance. Polymeric leveling agents and several small‐molecule brighteners produce level/bright films (respectively) with high values for both specular and diffuse reflectance. The application of these leveling and brightening agents can produce films with appearances and surface roughnesses that may be suitable for application in medical implants such as stents, corrosion protection of electronics for wearable technology, and as interlayers between dissimilar metals.

deep eutectic solvents↗

DOE OSTI2020

Exploring the Limits of Dative Boratrane Bonding: Iron as a Strong Lewis Base in Low-Valent Non-Heme Iron-Nitrosyl Complexes

We previously reported the synthesis and preliminary characterization of a unique series of low-spin (ls) {FeNO} 8–10 complexes supported by an ambiphilic trisphosphineborane ligand, [Fe(TPB)(NO)] +/0/– . In this study, we use advanced spectroscopic techniques and density functional theory (DFT) calculations to extract detailed information as to how the bonding changes across the redox series. We find that, in spite of the highly reduced nature of these complexes, they feature an NO + ligand throughout with strong Fe–NO π-backbonding and essentially closed-shell electronic structures of their FeNO units. This is enabled by an Fe–B interaction that is present throughout the series. In particular, the most reduced [Fe(TPB)(NO)] – complex, an example of a ls-{FeNO} 10 species, features a true reverse dative Fe → B bond where the Fe center acts as a strong Lewis-base. Hence, this complex is in fact electronically similar to the ls-{FeNO} 8 system, with two additional electrons “stored” on site in an Fe–B single bond. The outlier in this series is the ls-{FeNO} 9 complex, due to spin polarization (quantified by pulse EPR spectroscopy), which weakens the Fe–NO bond. These data are further contextualized by comparison with a related N 2 complex, [Fe(TPB)(N 2 )] – , which is a key intermediate in Fe(TPB)-catalyzed N 2 fixation. Our present study finds that the Fe → B interaction is key for storing the electrons needed to achieve a highly reduced state in these systems, and highlights the pitfalls associated with using geometric parameters to try to evaluate reverse dative interactions, a finding with broader implications to the study of transition metal complexes with boratrane and related ligands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

EELS Studies of Cerium Electrolyte Reveal Substantial Solute Concentration Effects in Graphene Liquid Cells

Graphene liquid cell transmission electron microscopy is a powerful technique to visualize nanoscale dynamics and transformations at atomic resolution. However, the solution in liquid cells is known to be affected by radiolysis, and the stochastic formation of graphene liquid cells raises questions about the solution chemistry in individual pockets. In this study, electron energy loss spectroscopy (EELS) was used to evaluate a model encapsulated solution, aqueous CeCl 3 . First, the ratio between the O K-edge and Ce M-edge was used to approximate the concentration of cerium salt in the graphene liquid cell. It was determined that the ratio between oxygen and cerium was orders of magnitude lower than what is expected for a dilute solution, indicating that the encapsulated solution is highly concentrated. To probe how this affects the chemistry within graphene liquid cells, the oxidation of Ce 3+ was measured using time-resolved parallel EELS. Here, it was determined that Ce 3+ oxidizes faster under high electron fluxes, but reaches the same steady-state Ce 4+ concentration regardless of flux. The time-resolved concentration profiles enabled direct comparison to radiolysis models, which indicate rate constants and g-values of certain molecular species are substantially different in the highly concentrated environment. Finally, electron flux-dependent gold nanocrystal etching trajectories showed that gold nanocrystals etch faster at higher electron fluxes, correlating well with the Ce 3+ oxidation kinetics. Understanding the effects of the highly concentrated solution in graphene liquid cells will provide new insight on previous studies and may open up opportunities to systematically study systems in highly concentrated solutions at high resolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Toroidal polar topology in strained ferroelectric polymer

Polar topological texture has become an emerging research field for exotic phenomena and potential applications in reconfigurable electronic devices. Here, we report toroidal topological texture self-organized in a ferroelectric polymer, poly(vinylidene fluoride-ran-trifluoroethylene) [P(VDF-TrFE)], that exhibits concentric topology with anticoupled chiral domains. The interplay among the elastic, electric, and gradient energies results in continuous rotation and toroidal assembly of the polarization perpendicular to polymer chains, whereas relaxor behavior is induced along polymer chains. Such toroidal polar topology gives rise to periodic absorption of polarized far-infrared (FIR) waves, enabling the manipulation of the terahertz wave on a mesoscopic scale. Our observations should inform design principles for flexible ferroic materials toward complex topologies and provide opportunities for multistimuli conversions in flexible electronics.

36 MATERIALS SCIENCE↗

DOE OSTI2023

A p -orbital honeycomb-Kagome lattice realized in a two-dimensional metal-organic framework

The experimental realization of p-orbital systems is desirable because p-orbital lattices have been proposed theoretically to host strongly correlated electrons that exhibit exotic quantum phases. Here, we synthesize a two-dimensional Fe-coordinated bimolecular metal-organic framework which constitutes a honeycomb lattice of 1,4,5,8,9,12-hexaazatriphenylene molecules and a Kagome lattice of 5,15-di(4-pyridyl)-10,20-diphenylporphyrin molecules on a Au(111) substrate. Density-functional theory calculations show that the framework features multiple well-separated spin-polarized Kagome bands, namely Dirac cone bands and Chern flat bands, near the Fermi level. Using tight-binding modelling, we reveal that these bands are originated from two effects: the low-lying molecular orbitals that exhibit p-orbital characteristics and the honeycomb-Kagome lattice. This study demonstrates that p-orbital Kagome bands can be realized in metal-organic frameworks by using molecules with molecular orbitals of p-orbital like symmetry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1992

Ion produced cometary organic crust

For several years many experimental results have been obtained on the chemical and physical changes induced by ion and electron irradiation of materials with a view to their Astrophysical relevance. Among the studied effects, one of particular interest is the formation of an organic refractory residue left over after ion irradiation and warming-up at room temperature. We call this residue IPHAC (ion produced hydrogenated amorphous carbon). Although 'in situ' infrared spectroscopy points out the formation of new molecular species during bombardment at low temperature, it is not clear if IPHAC is already formed or if its formation is triggered by temperature increase during warming-up of the irradiated target. Since Raman Spectroscopy is a technique particularly suitable for the analysis of carbonaceous materials, we have thought and build-up an experimental apparatus to obtain Raman Spectra of frozen hydrocarbons during ion irradiation. The present experimental results point out clearly to the formation of IPHAC already at low T and low energy deposition (approximately equal to a few eV/C-atom).

Baratta, G. Antonio↗

DOE OSTI2021

Gas phase protonated nicotine is a mixture of pyridine- and pyrrolidine-protonated conformers: implications for its native structure in the nicotinic acetylcholine receptor

The infrared (IR) spectra of gas phase protonated nicotine has been measured in the never-before probed N–H “fingerprint region” (3200–3500 cm -1 ). The protonated molecules generated by an electrospray source are thermalized in the first ion trap with water vapor and He gas at a pre-determined temperature prior to being probed by IR spectroscopy in the second ion trap at 4 K. The IR spectra exhibit two N–H stretching bands which are assigned to the pyridine and pyrrolidine protomers with the aid of high-level electronic structure calculations. This finding is in sharp contrast to previous spectroscopic studies that suggested a single population of the pyridine protomer. The relative populations of the two protomers vary by changing the temperature of the thermalizing trap from 180-300 K. The relative conformer populations at 240 K and 300 K are well reproduced by the theoretical calculations, unequivocally determining that gas phase nicotine is a 3 : 2 mixture of both pyridine and pyrrolidine protomers at room temperature. The thermalizing anhydrous vapor does not result in any population change. It rather demonstrates the catalytic role of water in achieving equilibrium between the two protomers. The combination of IR spectroscopy and electronic structure calculations establish the small energy difference between the pyridine and pyrrolidine protomers in nicotine. Finally, one of the gas phase nicotine pyrrolidine protomers has the closest conformational resemblance among all low-lying energy isomers with the X-ray structure of nicotine in the nicotinic acetylcholine receptor (nAChR).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗