An official website of the United States government
Abstract Wildfires are a major source of gas‐phase ammonia (NH3) to the atmosphere. Quantifying the evolution and fate of this NH3is important to understanding the formation of secondary aerosol in smoke and its accompanying effects on radiative balance and nitrogen deposition. Here, we use data from the Western Wildfire Experiment for Cloud Chemistry, Aerosol Absorption, and Nitrogen (WE‐CAN) to add new empirical constraints on the e‐folding loss timescale of NH3and its relationship with particulate ammonium (pNH4) within wildfire smoke plumes in the western U.S. during summer 2018. We show that the e‐folding loss timescale of NH3with respect to particle‐phase partitioning ranges from ∼24 to ∼4000 min (median of 55 min). Within these same plumes, oxidation of nitrogen oxides is observed concurrent with increases in the fraction ofpNH4in each plume sampled, suggesting that formation of ammonium nitrate (NH4NO3) is likely. We find wide variability in how close ourin situmeasurements of NH4NO3are to those expected in a dry thermodynamic equilibrium, and find that NH4NO3is most likely to form in fresh, dense smoke plumes injected at higher altitudes and colder temperatures. In chemically older smoke we observe correlations between both the fraction ofpNH4and the fraction of particulate nitrate (pNO3) in the aerosol with temperature, providing additional evidence of the presence of NH4NO3and the influence of injection height on gas‐particle partitioning of NH3.
more »
« less
Electrochemical Cleaning Stability and Oxygen Reduction Reaction Activity of 1‐2 nm Dendrimer‐Encapsulated Au Nanoparticles
Abstract Here we show that just three electrochemical scans to modest positive potentials result in substantial growth of 1–2 nm Au dendrimer‐encapsulated nanoparticles (DENs). We examined two sizes of Au DENs, denoted as G6‐NH2(Au147) and G6‐NH2(Au55), where G6‐NH2represents a sixth‐generation, amine‐terminated, poly(amidoamine) dendrimer and the subscripts, 147 and 55, represent the average number of atoms in each size of DENs.Ex situtransmission electron microscopy (TEM) andin situX‐ray absorption spectroscopy (XAS) results indicate that G6‐NH2(Au55) DENs grow to the same size as the G6‐NH2(Au147) DENs following these scans. Importantly, this growth occurs prior to the onset of detectable faradaic Au oxidation or reduction current. The observed growth in the size of the DENs directly correlates to changes in the electrocatalytic ORR activity. The key point is that after just three positive scans the G6‐NH2(Au147) and G6‐NH2(Au55) DENs are essentially indistinguishable in terms of both physical and electrocatalytic properties.
more »
« less
- Award ID(s):
- 1903576
- PAR ID:
- 10272011
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- ChemElectroChem
- Volume:
- 8
- Issue:
- 13
- ISSN:
- 2196-0216
- Format(s):
- Medium: X Size: p. 2545-2555
- Size(s):
- p. 2545-2555
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Dissecting Critical Factors for Electrochemical CO 2 Reduction on Atomically Precise Au NanoclustersAbstract This work investigates the critical factors impacting electrochemical CO2reduction reaction (CO2RR) using atomically precise Au nanoclusters (NCs) as electrocatalysts. First, the influence of size on CO2RR is studied by precisely controlling NC size in the 1–2.5 nm regime. We find that the electrocatalytic CO partial current density increases for smaller NCs, but the CO Faradaic efficiency (FE) is not directly associated with the NC size. This indicates that the surface‐to‐volume ratio, i.e. the population of active sites, is the dominant factor for determining the catalytic activity, but the selectivity is not directly impacted by size. Second, we compare the CO2RR performance of Au38isomers (Au38Q and Au38T) to reveal that structural rearrangement of identical size NCs can lead to significant changes in both CO2RR activity and selectivity. Au38Q shows higher activity and selectivity towards CO than Au38T, and density functional theory (DFT) calculations reveal that the average formation energy of the key *COOH intermediate on the proposed active sites is significantly lower on Au38Q than Au38T. These results demonstrate how the structural isomerism can impact stabilization of reaction intermediates as well as the overall CO2RR performance of identical size Au NCs. Overall, this work provides important structure–property relationships for tailoring the NCs for CO2RR.more » « less
-
Abstract Freshwater snails of the genusBiomphalariaserve as intermediate hosts for the digenetic trematodeSchistosoma mansoni, the etiological agent for the most widespread form of intestinal schistosomiasis. As neuropeptide signaling in host snails can be altered by trematode infection, a neural transcriptomics approach was undertaken to identify peptide precursors inBiomphalaria glabrata, the major intermediate host forS.mansoniin the Western Hemisphere. Three transcripts that encode peptides belonging to the FMRF‐NH2‐related peptide (FaRP) family were identified inB.glabrata. One transcript encoded a precursor polypeptide (Bgl‐FaRP1; 292 amino acids) that included eight copies of the tetrapeptide FMRF‐NH2and single copies of FIRF‐NH2, FLRF‐NH2, and pQFYRI‐NH2. The second transcript encoded a precursor (Bgl‐FaRP2;347amino acids) that comprised 14 copies of the heptapeptide GDPFLRF‐NH2and 1 copy of SKPYMRF‐NH2. The precursor encoded by the third transcript (Bgl‐FaRP3; 287 amino acids) recapitulatedBgl‐FaRP2but lacked the full SKPYMRF‐NH2peptide. The three precursors shared a common signal peptide, suggesting a genomic organization described previously in gastropods. Immunohistochemical studies were performed on the nervous systems ofB.glabrataandB.alexandrina, a major intermediate host forS.mansoniin Egypt. FMRF‐NH2‐like immunoreactive (FMRF‐NH2‐li) neurons were located in regions of the central nervous system associated with reproduction, feeding, and cardiorespiration. Antisera raised against non‐FMRF‐NH2peptides present in the tetrapeptide and heptapeptide precursors labeled independent subsets of the FMRF‐NH2‐li neurons. This study supports the participation of FMRF‐NH2‐related neuropeptides in the regulation of vital physiological and behavioral systems that are altered by parasitism inBiomphalaria.more » « less
-
Abstract We present new Atacama Large Millimeter/submillimeter Array (ALMA) continuum and NH2D, N2D+, and H2D+line emission at matched, ∼100 au resolution toward the dense star-forming cores SM1N and N6 within the Ophiuchus molecular cloud. We determine the density and temperature structure of SM1N based on radiative transfer modeling and simulated observations of the multiwavelength continuum emission at 0.8, 2, and 3 mm. We show that SM1N is best fit by either a broken power-law or Plummer-like density profile with high central densities (n∼ 108cm−3), and an inner transition radius of only ∼80–300 au. The free-fall time of the inner region is only a few ×103yr. The continuum modeling rules out the presence of an embedded first hydrostatic core (FHSC) or protostar. SM1N is therefore a dynamically unstable but still starless core. We find that NH2D is likely depleted at high densities within SM1N. The nonthermal velocity dispersions increase from NH2D to N2H+and H2D+, possibly tracing increasing (but still subsonic) infall speeds at higher densities as predicted by some models of starless core contraction. Toward N6, we confirm the previous ALMA detection of a faint, embedded point source (N6-mm) in 0.8 mm continuum emission. NH2D and N2D+avoid N6-mm within ∼100 au, while H2D+is not strongly detected toward N6. The distribution of these tracers is consistent with heating by a young, warm object. N6-mm thus remains one of the best candidate FHSCs detected so far, although its observed (sub)millimeter luminosity remains below predictions for FHSCs.more » « less
-
Abstract The electrocatalytic reduction of molecular nitrogen to ammonia—the nitrogen reduction reaction (NRR)—is of broad interest as an environmentally- and energy-friendly alternative to the Haber–Bosch process for agricultural and emerging energy applications. Herein, we review our recent findings from collaborative electrochemistry/surface science/theoretical studies that counter several commonly held assumptions regarding transition metal oxynitrides and oxides as NRR catalysts. Specifically, we find that for the vanadium oxide, vanadium oxynitride, and cobalt oxynitride systems, (a) there is no Mars–van Krevelen mechanism and that the reduction of lattice nitrogen and N2to NH3occurs by parallel reaction mechanisms at O-ligated metal sites without incorporation of N into the oxide lattice; and (b) that NRR and the hydrogen evolution reaction do occur in concert under the conditions studied for Co oxynitride, but not for V oxynitride. Additionally, these results highlight the importance of both O-ligation of the V or Co center for metal-binding of dinitrogen, and the importance of N in stabilizing the transition metal cation in an intermediate oxidation state, for effective N≡N bond activation. This review also highlights the importance and limitations ofex situandin situphotoemission—involving controlled transfer between ultra-high vacuum and electrochemistry environments, and ofoperandonear ambient pressure photoemission coupled within situstudies, in elucidating the complex chemistry relevant to the electrolyte/solid interface.more » « less
