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At least 397 records · Page 22

Pyrogenic Organic Matter Laboratory Experiment: Aerobic Respiration and Geochemistry from Variably Inundated Stream Sediments (v3)

This dataset supports a broader study examining the effects of variable inundation and pyrogenic organic matter on ecosystem respiration. The dataset provides data generated from a laboratory batch experiment investigating the interaction between variable inundation conditions (wet and dry sediment) and pyrogenic organic matter (burned and unburned treatments). The contents include time series dissolved oxygen, sediment geochemistry data, and field metadata (including qualitative information on instream and river corridor characteristics). This data package was originally published in November 2025. It was updated in April 2026 (v2; new and modified files) and May 2026 (v3; modified files). See the change history section in the readme for more details For details on how to navigate data packages generated by this project, see https://data.ess-dive.lbl.gov/portals/PNNLRiverCorridorSFA/About. In addition to a readme, this data package also includes a file-level metadata (FLMD) file that describes each file and a data dictionary (DD) that describes all column/row headers and variable definitions. This dataset is comprised of (1) file-level metadata; (2) data dictionary; (3) field metadata; (4) international generic sample number (IGSN) mapping file; (5) readme; (6) field protocol; (7) sample name metadata; (8) an environmental context picture for the dry and inundated sampling locations; and (9) a subfolder with sample data from the sediment incubation experiment. The sample data subfolder contains (1) dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC); (2) total nitrogen (TN); (3) gravimetric moisture; (4) partial pressure and production rates of carbon dioxide, methane, and nitrous oxide; (5) field wet sediment mass, dry sediment mass, water mass, and field wet sediment volume in incubation and sediment NPOC/TN vials; (6) methods codes; (7) respiration rates, pH, and temperature from after the incubation, raw time series dissolved oxygen and temperature, and a subfolder containing associated plots and scripts; (8) ions; (9) FTICR-MS methods; and (10) a subfolder of 12 Tesla (12T) FTICR-MS data. This folder contains the CoreMS processed data and three subfolders, one containing the .xml files, one containing the CoreMS output files, and the other containing instructions and scripts for processing the files in CoreMS (https://github.com/EMSL-Computing/CoreMS). All files are .csv, .pdf, .R, .xml, .html, .Rmd, .py, .cal, .json, or .jpg.

54 ENVIRONMENTAL SCIENCES↗

Laser-Irradiated Holey Graphene-Supported Single-Atom Catalyst towards Hydrogen Evolution and Oxygen Reduction

Single-atom catalysts (SAC) can boost the intrinsic catalytic activity of hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR). However, the challenge remains due to the complex synthesis process and insufficient stability. A sustainable approach is applied to synthesizing SACs through laser irradiation and gaining mesoporous graphene oxide (MGO). The surface dangling bonds of nitrogen-doped MGO (NMGO) extract metal atoms species from Co or Fe metal foams and convert them to SAC via an appropriate synthesis approach. Notably, the Co-NMGO electrocatalyst requires low potentials of 146 mV to convey a current density of 10 mA cm -2 towards HER. Similarly, the Fe-NMGO electrocatalyst offers an onset of 0.79 V towards ORR in acidic solution. The individual metal atoms are confirmed via aberration-corrected scanning transmission electron microscopy, and X-ray absorption near-edge structure and extended X-ray absorption fine structure. Density functional theory calculations by applying the grand canonical potential kinetics model revealed that Co-NMGO shows the optimum free reaction energy of -0.17 eV at -0.1 V for HER, and Fe-NMGO has less limiting potential than that of Co-NMGO for ORR case. Furthermore, this work opens a new approach towards the synthesis of SAC and its mechanistic understandings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

ToF-SIMS Analysis of Chemical Composition of Atmospheric Aerosols in Beijing

Atmospheric aerosols collected from each season in urban Beijing have been studied using time-of-flight secondary ion mass spectrometry (ToF-SIMS). The chemical composition of atmospheric aerosol particles during various atmospheric pollution levels were analyzed and distinguished by principal component analysis (PCA). The differences and sources of the components of the aerosol particles were explored. The results showed that the fine particulate matter from heavily polluted days mainly consists of inorganic salts and organic compounds, such as hydrocarbons, nitrogen- or sulfur-containing hydrocarbons, and their oxides. Samples collected from clean days in the four seasons were also analyzed. Only the samples collected in spring showed a significant difference from the other three seasons. We concluded that the main source of pollution in the Beijing urban area was fossil fuel combustion from motor vehicles.

ToF-SIMS, principal component analysis↗

Effects of Remelting Current on Structure, Composition, Microsegregation, and Inclusions in Inconel 718 Electroslag Remelting Ingots

The macro- and microstructures, chemical compositions, microsegregations, and nonmetallic inclusion characteristics at different positions of the as-cast IN718 ingots produced by a laboratory-scale electroslag remelting (ESR) furnace under four remelting currents (150, 200, 250, and 300 A) were compared and investigated comprehensively. The results indicate that the average melting rate increases with the increasing remelting current, and the molten pool tends to be deeper. Thus, at the same position of the ESR ingots, the volume fraction of the segregated phase, the degree of elemental segregation, and the secondary dendrite arm spacing have the same tendency to increase with the increasing remelting current and show an increasing trend from the bottom to the top along the height of each ingot. If the current is set relatively low, the oxygen and nitrogen levels in the ingots increase, the conditions that make the contents and distributions of Al and Ti become unstable. In addition, the major nonmetallic inclusions in the IN718 ESR ingots are MgO·Al{sub 2}O{sub 3} complex oxide inclusions with a three-layer structure and (Nb,Ti)N nitrides. The volume fractions and mean equivalent diameters display a downward trend with the increasing remelting current. The size and quantity of these inclusions are always larger in the upper portions of the ingots than those in the lower portions.

36 MATERIALS SCIENCE↗

Evaluating Ru-RuO 2 @BN as a Bifunctional Electrocatalyst for the Nitrogen Reduction Reaction and the Hydrogen Evolution Reaction

Electrochemical approaches toward clean energy production have been the focus of significant attention. Here, the nitrogen (N 2 ) reduction reaction (NRR) and the hydrogen (H 2 ) evolution reaction (HER) offer a promising method for producing NH 3 and H 2 , respectively. Nevertheless, practical obstacles that must be overcome in creating optimal catalysts are the sluggish kinetics and low selectivity of NRR and HER. Herein, we report on the synthesis of a Ru-RuO 2 -decorated boron nitride (BN) catalyst that shows excellent activity toward NRR. A rate of NH3 formation (V NH3 ) of 16.8 μg h -1 mg -1 and a corresponding Faradaic efficiency (FE) of 52.9% were noted at a potential of −0.5 V in 0.1 M HCl. However, the HER activity of Ru-RuO 2 @BN was found to be highly suppressed in 0.1 M HCl and did not yield a reasonable overpotential value. Thus, the capability of this material toward NRR suggests its viability as a promising catalyst for clean NH 3 production.

30 DIRECT ENERGY CONVERSION↗

Shifts in valence states in bimetallic MXenes revealed by electron energy-loss spectroscopy (EELS)

MXenes are an emergent class of two-dimensional materials with a very wide spectrum of promising applications. The synthesis of multiple MXenes, specifically solid-solution MXenes, allows fine tuning of their properties, expands their range of applications, and leads to enhanced performance. The functionality of solid-solution MXenes is closely related to the valence state of their constituents: transition metals, oxygen, carbon, and nitrogen. However, the impact of changes in the oxidation state of elements in MXenes is not well understood. In this work, three interrelated solid-solution MXene systems (Ti$_{2–y}$Nb$_y$CT$_x$, Nb$_{2–y}$V$_y$CT$_x$, and Ti$_{2–y}$V$_y$CT$_x$) were investigated with scanning transmission electron microscopy and electron energy-loss spectroscopy to determine the localized valence states of metals at the nanoscale. The analysis demonstrates changes in the electronic configuration of V upon modification of the overall composition and within individual MXene flakes. These shifts of oxidation state can explain the nonlinear optical and electronic features of solid-solution MXenes. Vanadium appears to be particularly sensitive to modification of the valence state, while titanium maintains the same oxidation state in Ti–Nb and Ti–V MXenes, regardless of stoichiometry. Here, the study also explains Nb's influential role in the previously observed electronic properties in the Nb–V and Nb–Ti systems.

36 MATERIALS SCIENCE↗

Magnetic Ni-N-Ni Centers in N-substituted NiO

Here, to explore how anion substitution modifies the existing magnetism in strongly correlated oxides, we investigate local electronic states and magnetic ordering in nickel oxide (NiO) induced by substituting oxygen (O) with nitrogen (N). Each N introduces an additional N 2p hole and modifies the magnetic moment of a neighboring nickel (Ni) cation site, as the exchange interaction between this hole and the Ni $e_{g}$ electrons exceeds the Ni-O-Ni superexchange interaction. This leads to the formation of Ni-N-Ni centers consisting of five spins, without perturbing the antiferromagnetic NiO lattice. These centers are studied using density functional theory and confirmed through high-resolution spectroscopy on N-substituted NiO thin films grown by molecular beam epitaxy. This type of magnetic design may enable future advances in quantum technologies based on strongly correlated materials, such as quantum sensors and spin-based qubits.

Godin, Simon [Univ. of British Columbia, Vancouver↗

Reduced Late Bombardment on Rocky Exoplanets around M Dwarfs

Ocean-vaporizing impacts of chemically reduced planetesimals onto the early Earth have been suggested to catalyze atmospheric production of reduced nitrogen compounds and trigger prebiotic synthesis despite an oxidized lithosphere. While geochemical evidence supports a dry, highly reduced late veneer on Earth, the composition of late-impacting debris around lower-mass stars is subject to variable volatile loss as a result of their hosts' extended pre-main-sequence phase. We perform simulations of late-stage planet formation across the M-dwarf mass spectrum to derive upper limits on reducing bombardment epochs in Hadean-analog environments. We contrast the solar system scenario with varying initial volatile distributions due to extended primordial runaway greenhouse phases on protoplanets and the desiccation of smaller planetesimals by internal radiogenic heating. We find a decreasing rate of late-accreting reducing impacts with decreasing stellar mass. Young planets around stars ≤0.4 M ⊙ experience no impacts of sufficient mass to generate prebiotically relevant concentrations of reduced atmospheric compounds once their stars have reached the main sequence. For M-dwarf planets to not exceed Earth-like concentrations of volatiles, both planetesimals, and larger protoplanets must undergo extensive devolatilization processes and can typically emerge from long-lived magma ocean phases with sufficient atmophile content to outgas secondary atmospheres. Our results suggest that transiently reducing surface conditions on young rocky exoplanets are favored around FGK stellar types relative to M dwarfs.

79 ASTRONOMY AND ASTROPHYSICS↗

Deciphering the Mechanism of Base-Triggered Conversion of Ammonia to Molecular Nitrogen and Methylamine to Cyanide

Here we report an in-depth investigation into the ammonia oxidation mechanism by the catalyst [Ru III (tpy)(dmabpy)NH 3 ] 3 + ([Ru(NH 3 )] 3 + ). Stoichiometric reactions of [Ru(NH 3 )] 3 + were carried out with exogenous noncoordinating bases to trigger a proposed redox disproportionation reaction, which was followed using variable-temperature NMR spectroscopy. An intermediate species was identified as a dinitrogen-bridged complex using 15 N NMR and Raman spectroscopy on isotopically labeled complexes. This intermediate is proposed to derive from coupling of nitridyl species formed upon sequential redox disproportion reactions. Acetonitrile displaces the dinitrogen bridge to yield free N 2 . DFT calculations support this lower-energy pathway versus that previously reported for ammonia oxidation by the parent [Ru III (tpy)(bpy)NH 3 ] 3 + complex. These experimental and computational results are consistent with the interpretation of redox disproportionation involving sequential hydrogen atom transfer reactions by an amide/aminyl intermediate, [Ru(NH 2 ) – ] + $\Leftrightarrow$ [Ru(NH 2 ) • ] + , formed upon deprotonation of the parent complex. Control experiments employing a large excess of ammonia as a base indicate this new proposed lower-energy pathway contributes to the oxidation of ammonia to dinitrogen in conditions relevant to electrocatalysis. In addition, analogous methylamine complexes, [Ru(NH 2 CH 3 )] 2 + /3 + , were prepared to further test the proposed mechanism. Treating [Ru(NH 2 CH 3 )] 3 + with a base cleanly yields two products [Ru(NH 2 CH 3 )] 2 + and [Ru(CN)] + in an ~3:1 ratio, fully consistent with the proposed cascade of hydrogen atom transfer reactions by an intermediate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ferrous and Ferric Ion-Facilitated Dilute Acid Pretreatment of Lignocellulosic Biomass under Anaerobic or Aerobic Conditions: Observations of Fe Valence Interchange and the Role of Fenton Reaction

Ferrous ion co-catalyst enhancement of dilute-acid (DA) pretreatment of biomass is a promising technology for increasing the release of sugars from recalcitrant lignocellulosic biomass. However, due to the reductive status of ferrous ion and its susceptibility to oxidation with exposure to atmosphere, its effective application presumably requires anaerobic aqueous conditions created by nitrogen gas-purging, which adds extra costs. The objective of this study was to assess the effectiveness of oxidative iron ion, (i.e., ferric ion) as a co-catalyst in DA pretreatment of biomass, using an anaerobic chamber to strictly control exposure to oxygen during setup and post-pretreatment analyses. Remarkably, the ferric ions were found to be as efficient as ferrous ions in enhancing sugar release during DA pretreatment of biomass, which may be attributed to the observation that a major portion of the initial ferric ions were converted to ferrous during pretreatment. Furthermore, the detection of hydrogen peroxide in the liquors after DA/Fe ion pretreatment suggests that Fenton reaction chemistry was likely involved in DA/Fe ion pretreatments of biomass, contributing to the observed ferric and ferrous interchanges during pretreatment. These results help define the extent and specification requirements for applying iron ions as co-catalysts in DA pretreatments of biomass.

09 BIOMASS FUELS↗

Electron donation of non-oxide supports boosts O 2 activation on nano-platinum catalysts

Activation of O 2 is a critical step in heterogeneous catalytic oxidation. Here, the concept of increased electron donors induced by nitrogen vacancy is adopted to propose an efficient strategy to develop highly active and stable catalysts for molecular O 2 activation. Carbon nitride with nitrogen vacancies is prepared to serve as a support as well as electron sink to construct a synergistic catalyst with Pt nanoparticles. Extensive characterizations combined with the first-principles calculations reveal that nitrogen vacancies with excess electrons could effectively stabilize metallic Pt nanoparticles by strong p-d coupling. The Pt atoms and the dangling carbon atoms surround the vacancy can synergistically donate electrons to the antibonding orbital of the adsorbed O 2 . This synergistic catalyst shows great enhancement of catalytic performance and durability in toluene oxidation. The introduction of electron-rich non-oxide substrate is an innovative strategy to develop active Pt-based oxidation catalysts, which could be conceivably extended to a variety of metal-based catalysts for catalytic oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Flux Synthesis of Lattice‐Engineered Rutile Solid Solutions for Acidic Oxygen Evolution

Developing efficient and stable electrocatalysts for the acidic oxygen evolution reaction (OER) is vital for advancing proton exchange membrane water electrolysis (PEMWE) technologies. Here, in this study, we report a flux synthesis of nitrogen-doped Ti–Ru rutile-type solid-solution oxides (M-TiRu 4 ) using molten NaNO 3 as the flux medium. The flux medium promotes the low-temperature conversion of TiN to rutile TiO 2 , while in situ-formed RuO 2 nanoparticles facilitate lattice templating and couple with interfacial ion migration, enabling the formation of homogeneous solid solutions with abundant lattice heterogeneity. Simultaneously, nitrogen atoms are stably incorporated into the lattice of solid solutions, inducing bandgap narrowing, which enhances electronic conductivity. The developed M-TiRu 4 catalyst exhibits exceptional acidic OER performance, delivering a low overpotential of 194 mV at 10 mA cm −2 , superior durability over 600 h, and a Ru mass activity 7.8 times that of commercial RuO 2 . At the device level, M-TiRu 4 enables PEMWE operation at 1.64 V @ 2 A cm −2 and maintains stable performance at 500 mA cm −2 for 200 h with a minimal degradation rate of 20 µV h −1 . This work demonstrates a robust approach for designing high-performance, durable acidic OER catalysts via synergistic lattice and electronic structure engineering, paving the way for next-generation water-splitting technologies.

Wang, Fan [Univ. of Tennessee, Knoxville, TN (Unit↗

Oxidative Dehydrogenation of N ‐Heteroaromatic Alkyl Alcohols and Amines Facilitated by Dearomative Tautomerization

The oxidation of alcohols, amines, and halides is a fundamental transformation in organic chemistry with significant applications in the synthesis of fine chemicals, pharmaceuticals, and natural products. Here we show that a broad variety of N-heteroarenes bearing hydroxymethyl, aminomethyl, or halomethyl groups are oxidatively dehydrogenated to their respective aldehydes by simply heating them in acidic or basic aqueous solution under ambient atmosphere. The quantitative oxidation of 9-acridinemethanol to 9-acridinecarboxaldehyde serves as an illustrative example, proceeding to completion within 3 hours in refluxing 5% aqueous acetic acid or even household vinegar. Quinoline derivatives may be similarly oxidized but require higher temperatures and longer reaction times, while indole derivatives are oxidized under basic conditions. Based on comprehensive regioselectivity screens, internal kinetic isotope competition, and density functional theory (DFT) calculations, we propose a mechanism in which migration of a methylene hydrogen to the pyridinic nitrogen by acid-catalyzed dearomative tautomerization yields an unstable enol or enamine intermediate that then irreversibly loses two hydrogen atoms to atmospheric oxygen. In addition to the simplicity and environmentally benign nature of our method, we observe no indication of any over-oxidation to carboxylic acids. Finally, we demonstrate the synthetic utility of this reaction through two different one-pot formylations of acridine.

Chemistry↗

Spontaneous N 2 formation by a diruthenium complex enables electrocatalytic and aerobic oxidation of ammonia

The electrochemical conversion of ammonia to dinitrogen in a direct ammonia fuel cell (DAFC) is a necessary technology for the realization of a Nitrogen Economy. Previous efforts to catalyze this reaction with molecular complexes require the addition of exogenous oxidizing reagents or application of potentials greater than the thermodynamic potential for the oxygen reduction reaction (ORR) – the cathodic process of a DAFC. We report a stable metal–metal bonded diruthenium complex that spontaneously produces dinitrogen from ammonia under ambient conditions. The resulting reduced diruthenium material can be re-oxidized with oxygen for subsequent reactions with ammonia, demonstrating its ability to spontaneously promote both half reactions necessary for a DAFC. Here, the diruthenium complex also acts as a redox mediator for the electrocatalytic oxidation of ammonia to dinitrogen at potentials as low as –255 mV vs Fc 0/+ and operates below the ORR potential in alkaline conditions, thus achieving a thermodynamic viability relevant for the future development of DAFCs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Computational analysis of metal–metal bonded dimetal tetrabenzoate redox potentials in the context of ammonia oxidation electrocatalysis

Metal–metal bonded complexes are promising candidates for catalyzing redox transformations. Of particular interest is the oxidation of ammonia to dinitrogen, an important half reaction for the potential utilization of ammonia as a fuel or hydrogen carrier. This work computationally explores 30 different metal–metal bonded dimers (5 different metal centers and 6 different benzoate ligand derivatives) to explore the tunability of the redox potential when ammonia is bound to the complexes as an axial ligand, modeling the first step in ammonia oxidation electrocatalysis. We calculate the redox potentials of these compounds, making reference to experimental data when appropriate, identifying two degrees of tunability: a coarse adjustment, changing the metal center, allows for a wide range of redox potentials to be accessed (from +1.0 to –2.0 V vs. ferrocene/ferrocenium in acetonitrile solution) and a fine adjustment, the para-substituent of the benzoate derivative, which affects the redox potential in a smaller range based on the electron donating/withdrawing effects of the substituent. Ruthenium and osmium tetrabenzoate catalysts are prime candidates for next generation ammonia oxidation catalysts because their redox potentials fall within the direct ammonia fuel cell “viability zone” bracketed by the thermodynamic potentials of oxygen reduction (ORR) and nitrogen reduction (NRR). Rhodium tetrabenzoate species fall above the ORR potential, suggesting ammonia oxidation promoted by Rh 2 catalysts could instead be used to facilitate hydrogen production through coupling to hydrogen evolution at a cathode. The redox potentials of rhenium and iridium tetrabenzoate catalysts fall below the NRR potential suggesting that these compounds could be further investigated in the context of electrochemical ammonia synthesis. Each redox event studied involves electron transfer from the M–M δ* orbital regardless of choice of metal or benzoate ligand derivative; this leads us to believe that the chemical reactivity of the various studied compounds will be similar in the context of ammonia oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Simultaneous occupancy of Cu C and Cu D in the ammonia monooxygenase active site

Ammonia monooxygenase (AMO), a copper-dependent membrane enzyme, catalyzes the first and rate-limiting step of nitrification: the oxidation of ammonia to hydroxylamine. Despite its central role in the global nitrogen cycle and its biotechnological relevance, structural characterization of AMO has lagged behind that of its homolog, particulate methane monooxygenase (pMMO), due to the slow growth rates of ammonia-oxidizing bacteria and the instability of AMO upon purification. Recent cryoEM studies of Nitrosomonas europaea AMO and Methylococcus capsulatus (Bath) pMMO in native membranes revealed new structural features, including two adjacent copper-binding sites in the transmembrane region, Cu C and Cu D , believed to constitute the active site. Although multiple structures were determined under various conditions, simultaneous occupancy of Cu C and Cu D was never observed, leaving their potential functional interplay unresolved. Here we report the 2.6 Å resolution cryoEM structure of AMO from Nitrosospira briensis C-128 in isolated native membranes. This structure reveals the first instance of simultaneous copper occupancy of the Cu C and Cu D sites, along with occupancy of the periplasmic Cu B site. Electron paramagnetic resonance (EPR) spectroscopic data indicate that the Cu B site is primarily occupied by Cu(II), while Cu C and Cu D are primarily occupied by diamagnetic ions, presumably Cu(I). Notably, a lipid molecule is bound between the Cu C and Cu D sites, separating them by ∼8.0 Å. The results underscore the importance of studying these enzymes in their native environments across species to resolve conserved and divergent molecular features.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Baltimore Ecosystem Study: Soil atmosphere fluxes of carbon dioxide, nitrous oxide and methane, 1998 - ongoing

The Baltimore Ecosystem Study (BES) established a network of long-term permanent biogeochemical study plots in 1998. These plots provide long-term data on vegetation, soil and hydrologic processes in the key ecosystem types within the urban ecosystem. The network of study plots includes forest plots (upland and riparian), chosen to represent the range of forest conditions in the area and grass plots (to represent home lawns). Plots are instrumented with lysimeters (drainage and tension) to sample soil solution chemistry, time domain reflectometry probes to measure soil moisture, dataloggers to measure and record soil temperature, and trace gas flux chambers to measure the flux of carbon dioxide, nitrous oxide and methane from soil to the atmosphere. Measurements of in situ nitrogen mineralization, nitrification and denitrification were made at approximately monthly intervals from Fall 1998 - Fall 2000. Detailed vegetation characterization (all layers) was done in summer 1998 and 2015. Data from these plots has been published in Groffman et al. (2006, 2009), Groffman and Pouyat (2009), Savva et al. (2010), Costa and Groffman (2013), Duncan et al. (2013), Waters et al. (2014), Ni and Groffman (2018), Templeton et al. (2019). Literature Cited Costa, K.H. and P.M. Groffman. 2013. Factors regulating net methane flux in urban forests and grasslands. Soil Science Society of America Journal 77:850 - 855. Duncan, J. M., L. E. Band, and P. M. Groffman. 2013. Towards closing the watershed nitrogen budget: Spatial and temporal scaling of denitrification. Journal of Geophysical Research Biogeosciences 118:1-5; DOI: 10.1002/jgrg.20090 Groffman PM, Pouyat RV, Cadenasso ML, Zipperer WC, Szlavecz K, Yesilonis IC,. Band LE and Brush GS. 2006. Land use context and natural soil controls on plant community composition and soil nitrogen and carbon dynamics in urban and rural forests. Forest Ecology and Management 236:177-192. Groffman, P.M., C.O. Williams, R.V. Pouyat, L.E. Band and I.C. Yesilonis. 2009. Nitrate leaching and nitrous oxide flux in urban forests and grasslands. Journal of Environmental Quality 38:1848-1860. Groffman, P.M. and R.V. Pouyat. 2009. Methane uptake in urban forests and lawns. Environmental Science and Technology 43:5229-5235. DOI: 10.1021/es803720h. Ni, X. and P.M. Groffman. 2018. Declines in methane uptake in forest soils. Proceedings of the National Academies of Science of the United States of America 115:8587-8590. Savva, Y., K. Szlavecz, R. V. Pouyat, P. M. Groffman, and G. Heisler. 2010. Effects of land use and vegetation cover on soil temperature in an urban ecosystem. Soil Science Society of America Journal 74:469-480. Templeton, L., M.L. Cadenasso, J. Sullivan, M. Neel and P.M. Groffman. 2019. Changes in vegetation structure and composition of urban and rural forest patches in Baltimore from 1998 to 2015. Forest Ecology and Management. In press. Waters, E.R., J.L. Morse, N.D. Bettez and P.M. Groffman. 2014. Differential carbon and nitrogen controls of denitrification in riparian zones and streams along an urban to exurban gradient. Journal of Environmental Quality 43:955–963.

Groffman, Peter M↗

Stabilization of Ultrasmall Platinum Nanoparticles by Nitrogen-Doped Carbon: Implications for Catalysis and Electrocatalysis

Heterogeneous materials comprising platinum nanoparticles on carbon supports have numerous applications including fuel cell electrodes and heterogeneous catalysts. The effective application of these materials for fuel cells and catalysis will be greatly advanced by the ability to control the oxidation and sintering of the nanoparticles by modifications of the carbon support. One attempt of such control has been doping carbon supports with nitrogen. Here, in this work, a cutting-edge, high-sensitivity, in situ XRD instrument, which allows observation of ultrasmall Pt nanoparticles, has been combined with in situ XPS to provide unprecedented clarity in the characterization of supported Pt nanoparticles in oxidizing and high-temperature environments. On a nitrogen-doped carbon support derived from poly-phenylporphyrin, Pt nanoparticles show increased stability to oxidation and thermal sintering. The enhanced Pt–support interaction arising from the N dopant versus the N-free carbon is manifested by (1) decreased initial Pt particle sizes, (2) small particle size at higher surface densities, (3) increased resistance of Pt nanoparticles to oxidation, (4) increased electron binding energy of Pt0, and (5) increased resistance of Pt nanoparticles to sintering. It is expected that the higher stability of Pt on NC will be manifested in higher activity in fuel cells and high-temperature catalytic reactions.

catalytic reactions↗