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At least 1,297 records · Page 72
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Enhancing Acidic Oxygen Evolution Activity by Controlling Oxidation State of Iridium

Iridium oxides with high oxidation states have been reported to be effective in enhancing the acidic oxygen evolution reaction (OER) performance. In this work, we develop ultrasmall IrO x nanoparticles (NPs) over titanium nitride (TiN), which undergoes surface oxidation under oxidative conditions to form oxygen‐modified TiN (oxi‐TiN), enabling the formation of highly oxidized Ir δ+ (δ > 4). This IrO x /oxi‐TiN catalyst delivers higher Ir mass activity than commercial IrO 2 , while comparable stability is maintained. The superior OER activity of IrO x /oxi‐TiN is further demonstrated in a proton exchange membrane water electrolyzer (PEMWE), requiring only 1.88 V to reach 3 A cm −2 , achieving the U.S. Department of Energy 2025 target (1.90 V at 3 A cm −2 ). In situ X‐ray absorption spectroscopy (XAS) confirms that the superior OER activity of IrO x /oxi‐TiN originates from highly oxidized Ir δ+ under OER conditions. Density functional theory (DFT) calculations reveal a general correlation between the oxidation state of Ir and OER overpotential. Specifically, the introduction of interfacial oxygen at the Ir/TiN interface increases the oxidation state of deposited Ir δ+ from δ < 4 to δ > 4, decreasing the OER overpotential. This study highlights the critical role of high oxidation states of Ir δ+ in enhancing OER activity, providing guidance for the development of advanced acidic OER catalysts.

58 GEOSCIENCES↗
DOE OSTI2020

Carbohydrate‐binding domains facilitate efficient oligosaccharides synthesis by enhancing mutant catalytic domain transglycosylation activity

Abstract Chemoenzymatic approaches using carbohydrate‐active enzymes (CAZymes) offer a promising avenue for the synthesis of glycans like oligosaccharides. Here, we report a novel chemoenzymatic route for cellodextrins synthesis employed by chimeric CAZymes, akin to native glycosyltransferases, involving the unprecedented participation of a “non‐catalytic” lectin‐like domain or carbohydrate‐binding modules (CBMs) in the catalytic step for glycosidic bond synthesis using β‐cellobiosyl donor sugars as activated substrates. CBMs are often thought to play a passive substrate targeting role in enzymatic glycosylation reactions mostly via overcoming substrate diffusion limitations for tethered catalytic domains (CDs) but are not known to participate directly in any nucleophilic substitution mechanisms that impact the actual glycosyl transfer step. This study provides evidence for the direct participation of CBMs in the catalytic reaction step for β‐glucan glycosidic bonds synthesis enhancing activity for CBM‐based CAZyme chimeras by >140‐fold over CDs alone. Dynamic intradomain interactions that facilitate this poorly understood reaction mechanism were further revealed by small‐angle X‐ray scattering structural analysis along with detailed mutagenesis studies to shed light on our current limited understanding of similar transglycosylation‐type reaction mechanisms. In summary, our study provides a novel strategy for engineering similar CBM‐based CAZyme chimeras for the synthesis of bespoke oligosaccharides using simple activated sugar monomers.

Bandi, Chandra Kanth↗
DOE OSTI2020

Catalytic Activity of Ti-based MXenes for the Hydrogenation of Furfural

Here, we report on the catalytic activity of Ti-based MXenes (Ti 3 CNT z and Ti 3 C 2 T z ) for biomass transformation. MXenes were found to be active catalysts for the hydrogenation of furfural using either gaseous hydrogen or 2-propanol as solvent and hydrogen source. Both catalysts showed good activity in the conversion of furfural to furfuryl alcohol, with furfuryl ether as the main by-product. Stability tests indicated that Ti 3 CNT z is more stable than Ti 3 C 2 T z against deactivation. Ab initio calculations were used to examine the hydrogenation and etherification reactions pathways and their corresponding reaction energetics on the Ti 3 CNT z MXene. The results indicate that the hydrogenation of the carbonyl bond efficiently proceeds via the heterolytic activation of hydrogen over the metal-oxygen site pair followed by the addition of the proton and hydride to the C and O atoms of the carbonyl. The subsequent hydrogenation of the unsaturated furan ring via metal bound hydrogen, however, is calculated to be much more difficult. Protons bound to the oxygen of the MXene are acidic and can also catalyze the etherification of the resulting alcohols. Finally, the bifunctional acid-metal site pairs also selectively catalyze the hydrogenolysis of the furfuryl alcohol to form 2-methyl furan.

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

Fluxionality of Subnano Clusters Reshapes the Activity Volcano of Electrocatalysis

The Sabatier activity volcano provides intuitive guide for catalyst design, but also imposes fundamental limitations on the composition and maximal activity of catalysts. Here we show that the ORR activity volcano is shifted and reshaped by the potential-dependent fluxionality of subnano cluster catalysts. Fluxionality causes the typically under-binding Ag/Au to gain optimal activity in the cluster form, and surpass Pt/Pd. Furthermore, isomerization of clusters as a function of the potential breaks linear scaling relationships, enabling surpassing the volcano “apex” relative to the bulk. The effect is likely general for fluxional cluster catalysts.

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

Bio‐Inspired In Situ Tuning of the Hydrophobic Environment Around Catalytically Active Organic Ligand‐Stabilized Ruthenium Nanoparticles

Abstract The organic ligand environment surrounding enzymatic and homogeneous catalytic active sites often determines catalytic activity. Ruthenium nanoparticles, ≤1 nm in diameter, are synthesized using monodentate thiol, monodentate phosphine, and bidentate bisphosphine ligands. Even though some of the ruthenium surface is blocked by the ligands, catalytic activity is still observed for CO oxidation and H 2 O 2 decomposition. All three ligand‐stabilized ruthenium nanoparticles have similar CO oxidation rates; however, the bisphosphine‐stabilized Ru nanoparticles are approximately 2.5 times less active than the monothiol‐stabilized and monophosphine‐stabilized ruthenium nanoparticles for H 2 O 2 decomposition. It is observed that the organic ligand environment is modulated in situ during nanoparticle synthesis via partial oxidation of the bisphosphine as confirmed by 31 P NMR measurements. We hypothesize that bisphosphine‐bound Ru nanoparticles consist of a Ru core with some of the ligands bound in a monodentate manner where the other P atom is oxidized and not bound to the Ru surface leading to a thicker hydrophobic layer around the Ru nanoparticles. The increase in hydrophobicity is confirmed via contact angle and zeta potential measurements. H 2 O 2 decomposition rates are known to decrease with increasing hydrophobicity, and this work illustrates a pathway for increasing hydrophobicity in situ using ligand‐bound metallic nanoparticles.

Sufyan, Sayed Abu [Department of Chemical Engineer↗
DOE OSTI2020

In Situ Structural Determination of a Homogeneous Ruthenium Racemization Catalyst and Its Activated Intermediates Using X-Ray Absorption Spectroscopy

The activation process of a known Ru-catalyst, dicarbonyl(pentaphenylcyclopentadienyl)ruthenium chloride, has been studied in detail using time resolved in situ X-ray absorption spectroscopy. The data provide bond lengths of the species involved in the process as well as information about bond formation and bond breaking. On addition of potassium tert-butoxide, the catalyst is activated and an alkoxide complex is formed. The catalyst activation proceeds via a key acyl intermediate, which gives rise to a complete structural change in the coordination environment around the Ru atom. The rate of activation for the different catalysts was found to be highly dependent on the electronic properties of the cyclopentadienyl ligand. During catalytic racemization of 1-phenylethanol a fast-dynamic equilibrium was observed.

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

Bioinspired Activation of N 2 on Asymmetrical Coordinated Fe Grafted 1T MoS 2 at Room Temperature

Inspired by the nitrogen fixation process on MoFe nitrogenase, asymmetrical coordinated Fe grafted onto 1T MoS 2 were successfully synthesized. The unique electron -rich structure with asymmetrical coordination made the 1T Fe 0.1 Mo 0.9 S 2 layered material actively react with water and dinitrogen at room temperature and atmosphere pressure. Subsequently, ammonia can be produced with a yield of 800 pmol (NH 4 + ) g -1 (12.5% yield in mole). The activation, fixation and reduction of dinitrogen were confirmed by isotopically labeled experiments. The location and the specific coordination environment of grafted Fe in Fe-Mo-S were further determined by X-ray absorption spectroscopy analysis. Our work demonstrates that the nitrogen fixation and reduction for ammonia at room temperature without any chemical and electrochemical assistance is distinctly different from traditional bionic -inspired nitrogen fixation process. The mechanism of the activation and reduction of N 2 was further investigated by density functional theory calculation and Raman spectra. Compared with 1T MoS 2 , the enriched electron nature and asymmetrical coordination of Fe in Fe-Mo-S materials play a critical role in the bioinspired activation of N 2 at ambient condition.

1T MoS2↗
DOE OSTI2024

Hydrogen Peroxide‐Induced Overoxidation of Fe−N−C Catalysts: Implications for ORR Activity

Fe−N−C (iron-nitrogen-carbon) electrocatalysts have emerged as promising alternatives to precious metals for the oxygen reduction reaction (ORR), but they remain insufficiently stable for widespread adoption in fuel cell technologies. One plausible mechanism to explain this lack of stability, and the associated catalyst degradation, is oxidative attack on the catalyst surface by hydrogen peroxide, a non-selective byproduct of the ORR. In this work, we perform a detailed analysis of this degradation mechanism, using a combination of periodic Density Functional Theory (DFT) calculations and ab-initio molecular dynamics (AIMD) simulations to probe the thermodynamics and kinetics of hydrogen peroxide activation on a series of candidate active sites for the Fe−N−C catalyst. The results demonstrate that carbon atoms neighbouring FeN 4 active sites can be strongly over-oxidized via formation of hydroxyl or epoxy groups when hydrogen peroxide is present in the electrolyte. In most cases, the interaction between the over-oxidizing groups and the ORR reaction intermediates reduces the ORR activity, and we further propose that the over-oxidized sites are likely precursors to irreversible carbon corrosion and further catalyst deactivation.

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

Hierarchical Porous Activated Carbon from Wheat Bran Agro-Waste: Applications in Carbon Dioxide Capture, Dye Removal, Oxygen and Hydrogen Evolution Reactions

Here this work reports an efficient method for facile synthesis of hierarchically porous carbon (WB-AC) utilizing wheat bran waste. Obtained carbon showed 2.47 mmol g -1 CO 2 capture capacity with good CO 2 /N 2 selectivity and 27.35 to 29.90 kJ mol -1 isosteric heat of adsorption. Rapid removal of MO dye was observed with a capacity of ~555 mg g -1 . Moreover, WB-AC demonstrated a good OER activity with 0.35 V low overpotential at 5 mA cm -2 and a Tafel slope of 115 mV dec -1 . It also exhibited high electrocatalytic HER activity with 57 mV overpotential at 10 mA cm -2 and a Tafel slope of 82.6 mV dec -1 . The large SSA (757 m 2 g -1 ) and total pore volume (0.3696 cm 3 g -1 ) result from N 2 activation contributing to selective CO 2 uptake, high and rapid dye removal capacity and superior electrochemical activity (OER/HER), suggesting the use of WB-AC as cost effective adsorbent and metal free electrocatalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Engineering Active Fe Sites on Nickel–Iron Layered Double Hydroxide through Component Segregation for Oxygen Evolution Reaction

Nickel-iron layered double hydroxide (NiFe LDH) is a promising oxygen evolution reaction (OER) electrocatalyst under alkaline conditions. Much research has been performed to understand the structure-activity relationship of NiFe LDH under OER conditions. However, the specific role of the Fe species remains unclear and under debate. Herein, based on DFT calculations, it was discovered that the edge Fe sites show higher activity towards OER than either the edge Ni sites or lattice sites. Therefore, a facile acid-etching method was proposed to controllably induce the formation of edge Fe sites in NiFe LDH, and the obtained sample exhibited higher OER activity. X-ray absorption near edge structure and extended X-ray absorption fine structure analyses further revealed that the interaction of the edge Fe species with Ni is believed to contribute to the enhancement of the OER performance. This work provides a new understanding of the structure-activity relationship in NiFe LDH and offers a facile method for the design of efficient electrocatalysts in an alkaline environment.

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

Active and Stable PtPd Diesel Oxidation Catalysts under Industry‐Defined Test Protocols

Nanoparticle-supported Pt and Pd catalysts are employed industrially to convert CO and hydrocarbon residue from incomplete diesel fuel combustion into more environmentally-benign products. However, these catalysts deactivate over time due to sintering, especially for Pt nanoparticles which readily generate volatile species under high operating temperatures. Here, we turned the detrimental vapor-mediated sintering of Pt into an advantage by using a physical mixture of Pt and Pd catalysts prepared using a raspberry-colloid-templating (RCT) method. The RCT method produced Pt/Al 2 O 3 and Pd/Al 2 O 3 catalysts with partially embedded NPs to inhibit surface-mediated sintering pathways. As validated using an industry-defined emission control test protocol, aging a physical mixture of Pt/Al 2 O 3 and Pd/Al 2 O 3 at high temperature produced an alloyed PtPd/Al 2 O 3 catalyst that outperformed the fresh catalyst mixture and both individual catalysts for hydrocarbon conversion, while exhibiting high catalytic stability and resistance to sintering and to SO 2 poisoning. X-ray photoelectron spectroscopy revealed that in the aged catalyst mixture, half of the Pd content existed in the more active metallic state, compared to the less active oxide forms in the fresh mixture and both individual catalysts, explaining the unusual activity enhancement. Our results represent a practical approach to producing active and stable PtPd/Al 2 O 3 diesel oxidation catalysts for emission control applications.

Lim, Kang Rui Garrick [Harvard University, Cambrid↗
DOE OSTI2020

Single vs double atom catalyst for N 2 activation in nitrogen reduction reaction: A DFT perspective

Abstract Ammonia synthesis through electrochemical reduction of nitrogen molecules is a promising strategy to significantly reduce the energy consumption in traditional industrial process. Detailed mechanism study of multistep complex nitrogen reduction reaction is prerequisite for the design of highly efficient catalyst. Stable atomically dispersed catalyst with unique geometric and electronic structure is suitable for the mechanism clarification of such a complex reaction. In this study, d ‐block transition‐metal (TM) anchored C 2 N single layer catalyst is investigated by the density functional theory (DFT) calculation. Both single TM‐anchored single atom catalyst (SAC) and double TM‐anchored double atom catalyst (DAC) exhibit good thermodynamic stability in atomically dispersed catalyst. In the case of SACs, IVB metals (Ti, Zr, Hf) exhibit the highest reactivity and lowest overpotential. While in the case of DACs, Cr─Cr system leads to the NH 3 formation, but V─V system leads to the N 2 H 4 formation. The SACs show much lower overpotential and stronger activation of N 2 molecule than the DACs due to the different activation mechanisms: traditional σ ‐donation/ π ‐backdonation N 2 activation mechanism is found in SACs, while a new π ‐donation/π‐backdonation N 2 activation mechanism is found in the DACs. The present work demonstrates that the different catalytic effect for NRR between SAC and DAC and their corresponding electronic structure origin, which gives more insight into the single atom catalyst. image

Qian, Yumin↗
DOE OSTI2024

Water aging and the quality of organic carbon sources drive niche partitioning of the active bathypelagic prokaryotic microbiome

Abstract Due to the scarcity of organic matter (OM) sources in the bathypelagic (1000–4000 m depth), prokaryotic metabolism is believed to be concentrated on particles originating from the surface. However, the structure of active bathypelagic prokaryotic communities and how it changes across environmental gradients remains unexplored. Using a combination of 16S rRNA gene and transcripts sequencing, metagenomics, and substrate uptake potential measurements, here we aimed to explore how water masses aging and the quality of OM influence the structure of the active microbiome, and the potential implications for community function. We found that the relative contribution of taxa with a free‐living lifestyle to the active microbiome increased in older water masses that were enriched in recalcitrant OM, suggesting that these prokaryotes may also play a substantial role in the bathypelagic metabolism of vast areas of the ocean. In comparison to particle‐associated prokaryotes, free‐living prokaryotes exhibited lower potential metabolic rates, and harbored a limited number of two‐component sensory systems, suggesting they have less ability to sense and respond to environmental cues. In contrast, particle‐associated prokaryotes carried genes for particle colonization and carbohydrate utilization that were absent in prokaryotes with a free‐living lifestyle. Consistently, we observed that prokaryotic communities inhabiting older waters displayed reduced abilities to colonize particles, and higher capabilities to use complex carbon sources, compared to communities in waters with a higher proportion of labile OM. Our results provide evidence of regionalization of the bathypelagic active prokaryotic microbiome, unveiling a niche partitioning based on the quality of OM.

Marine & Freshwater Biology↗
DOE OSTI2021

Photodepositing CdS on the Active Cyano Groups Decorated g‐C 3 N 4 in Z‐Scheme Manner Promotes Visible‐Light‐Driven Hydrogen Evolution

Abstract g‐C 3 N 4 /CdS heterojunctions are potential photocatalysts for hydrogen production but their traditional type‐II configuration generally leads to weak oxidative and reductive activity. How to construct the novel Z‐scheme g‐C 3 N 4 /CdS counterparts to address this issue remains a great challenge in this field. In this work, a new direct Z‐scheme heterojunction of defective g‐C 3 N 4 /CdS is designed by introducing cyano groups (NC‐) as the active bridge sites. Experimental observations in combination with density functional theory (DFT) calculations reveal that the unique electron‐withdrawing feature of cyano groups in the defective g‐C 3 N 4 /CdS heterostructure can endow this photocatalyst with numerous advantageous properties including high light absorption ability, strong redox performance, satisfactory charge separation efficiency, and long lifetime of charge carriers. Consequently, the resultant photocatalytic system exhibits more active performance than CdS and g‐C 3 N 4 under visible light and reaches an excellent hydrogen evolution rate of 1809.07 µmol h −1 g −1 , which is 6.09 times higher than pristine g‐C 3 N 4 . Moreover, the defective g‐C 3 N 4 /CdS photocatalyst maintains good stability after 40 h continuous test. This work provides new insights into design and construction of Z‐scheme heterojunctions for regulating the visible‐light‐induced photocatalytic activity for H 2 evolution.

Wang, Zhipeng↗
DOE OSTI2023

Genesis of Active Pt/CeO 2 Catalyst for Dry Reforming of Methane by Reduction and Aggregation of Isolated Platinum Atoms into Clusters

Atomically dispersed metal catalysts offer the advantages of efficient metal utilization and high selectivities for reactions of technological importance. Such catalysts have been suggested to be strong candidates for dry reforming of methane (DRM), offering prospects of high selectivity for synthesis gas without coke formation, which requires ensembles of metal sites and is a challenge to overcome in DRM catalysis. However, investigations of the structures of isolated metal sites on metal oxide supports under DRM conditions are lacking, and the catalytically active sites remain undetermined. Data characterizing the DRM reaction-driven structural evolution of a cerium oxide- supported catalyst, initially incorporating atomically dispersed platinum, and the corresponding changes in catalyst performance are reported. X-ray absorption and infrared spectra show that the reduction and agglomeration of isolated cationic platinum atoms to form small platinum clusters/nanoparticles are necessary for DRM activity. Density functional theory calculations of the energy barriers for methane dissociation on atomically dispersed platinum and on platinum clusters support these observations. Here the results emphasize the need for in-operando experiments to assess the active sites in such catalysts. The inferences about the catalytically active species are suggested to pertain to a broad class of catalytic conversions involving the rate-limiting dissociation of light alkanes.

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

Structural characterization and biological activity of an α-glucan from the mollusk Marcia hiantina (Lamarck, 1818)

Marcia hiantina (Mollusca, Bivalvia) (Lamarck, 1818), is an edible clam mainly distributed along the tropical coastal regions. Recent researches have demonstrated that clams can possess compounds, including polysaccharides, with a wide range of biological actions including antioxidant, immunomodulatory and antitumor activities. Here an α-glucan was isolated from M. hiantina by hot water, purified by anion exchange chromatography, and its structure was characterized by a combination of multiple nuclear magnetic resonance (NMR) methods (1D 1 H, 1 H- 1 H COSY, 1 H- 1 H TOCSY, 1 H- 1 H NOESY, 1 H- 13 C HSQC and 1 H- 13 C HSQC-NOESY spectra), gas chromatography-mass spectrometry, and high performance size exclusion chromatography (HPSEC). The analysis from NMR, monosaccharide composition, methylation analyses and HPSEC combined with multi angle light scattering (MALS) of M. hiantina-derived α-glycan confirmed a branched polysaccharide exclusively composed of glucose (Glc), mostly 4-linked in its backbone, branched occasionally at 6-positions, and having a molecular weight of ~ 570 kDa. The mollusk α-glucan was subjected to four cell-based assays: (i) viability of three cell lines (RAW264.7, HaCaT, and HT-29), (ii) activity on lipopolysaccharide (LPS)-induced prostaglandin production in RAW264.7 cells, (iii) inhibitory activities of in H 2 O 2 - and LPS-induced reactive oxygen species (ROS) production in HMC3 cells, and (iv) HaCaT cell proliferation. Furthermore, results have indicated no cytotoxicity, potent inhibition of both H 2 O 2 - and LPS-induced ROS, and potent cell proliferative activity.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Radiochronometric analysis of an historic Cs-137 activity standard

In this work, a 137 Cs activity standard discovered during routine inventory was analyzed to determine its model age using radiochronometry. The aqueous activity standard was separated using an established separation method that employs commercially available Sr resin. The method was also tested against a nuclear forensics reference material developed specifically for benchmarking 137 Cs radiochronometry methods. Results of the analyses showed good agreement between the results and the certified values of the reference material. Analysis of the discovered activity standard were also in good agreement with the activity certification date, though uncertainty was higher due to natural Ba contaminating the sample and the stable 133 Cs used as a carrier during the standard’s production.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗