Soot formation is quantified in detail (volume fraction, particle size, number concentration, and light emissivity dispersion exponent) in a series of partially premixed counterflow flames of ethylene at equivalence ratios equal to 6.5, 5.0, and 4.0, and with maximum temperature spanning approximately 200 K. The focus is to investigate the effect of peak temperature and equivalence ratio on soot formation while maintaining constant global strain and stoichiometric mixture fraction. Oxygen is progressively displaced from the oxidizer to the fuel stream of a diffusion flame to stabilize partially premixed flames of decreasing, showing a double-flame structure consisting of a rich premixed flame component stabilized on the fuel side of the stagnation plane and a diffusion flame component stabilized on the oxidizer side. Soot is detected in the region sandwiched between the two flame components, is formed in both
of them, and is convected away radially at the Particle Stagnation Plane (PSP). At fixed , raising the peak temperature invariably raises the soot volume fraction throughout the probed region. Vice versa, at fixed peak temperature, lowering the equivalence ratio causes the premixed flame component to shift away from the diffusion flame component, with the consequent broadening of the soot forming region and an increase in both soot volume fraction as well as soot particle sizes through an enhancement of surface growth. Detailed probing of the region in the vicinity of the PSP offers evidence of soot oxidation from molecular oxygen. Furthermore, when the maximum temperature is sufficiently low, the net soot production rate turns negative because surface oxidation overwhelms surface growth. Comparing the soot number production rate inferred from experiments to the dimerization rate of benzene, naphthalene, and pyrene reveals that only the smallest aromatics are present in flames at sufficiently large concentrations to account for soot nucleation. This observation applies to both the diffusion flame and the premixed flame components and confirms previous findings in strictly diffusion flames.
more »
« less
Formation of nanocrystalline manganese oxide in flames: oxide phase governed by classical nucleation and size-dependent equilibria
Particle nucleation and growth of crystalline manganese oxide nanoparticles was examined in a complementary experimental and modelling study. Gas-to-particle conversion occurred in a flame-assisted chemical vapor deposition process whereby a premixed stagnation flame drove the high-temperature synthesis. The structure of the stagnation flame was computed using pseudo one-dimensional and axisymmetric two-dimensional methods to assess the accuracy of using a faster similarity-based calculation for flame-deposition design. The pseudo one-dimensional computation performs reasonably well for the narrow aspect ratio stagnation flow currently studied as evidenced by reasonable agreement between the measured flame position and both computational methods. Manganese oxide nanoparticles having II, II–III, III or IV oxidation states were observed depending on the flame conditions. These observations may be explained by size-dependent equilibria between nano-scale manganese oxide and surrounding gas-phase oxygen. Local equilibrium was assessed during the particle temperature–oxygen–time history to gain insight into oxide formation in the flame. Analysis of the saturation ratio for formation of condensed MnO in the flame indicates that nucleation may be limited by a thermodynamic barrier. This nucleation mechanism is supported by measured particle sizes smaller than what would be expected from a coagulation limited growth process. Nanocrystalline MnO, reported here for the first time by flame synthesis, was obtained in oxygen lean flames. MnO 2 is the phase predicted to be thermally stable as the particles approach the deposition surface, yet other metastable oxide phases were produced in many of the flames examined. In fact, MnO 2 was only observed in the smallest particle size conditions which may indicate that high cooling rates limit phase equilibrium to less massive particles.
more »
« less
- Award ID(s):
- 1841357
- NSF-PAR ID:
- 10207765
- Date Published:
- Journal Name:
- CrystEngComm
- Volume:
- 22
- Issue:
- 33
- ISSN:
- 1466-8033
- Page Range / eLocation ID:
- 5509 to 5521
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
more » « less
Abstract Water oxidation and concomitant dioxygen formation by the manganese-calcium cluster of oxygenic photosynthesis has shaped the biosphere, atmosphere, and geosphere. It has been hypothesized that at an early stage of evolution, before photosynthetic water oxidation became prominent, light-driven formation of manganese oxides from dissolved Mn(2+) ions may have played a key role in bioenergetics and possibly facilitated early geological manganese deposits. Here we report the biochemical evidence for the ability of photosystems to form extended manganese oxide particles. The photochemical redox processes in spinach photosystem-II particles devoid of the manganese-calcium cluster are tracked by visible-light and X-ray spectroscopy. Oxidation of dissolved manganese ions results in high-valent Mn(III,IV)-oxide nanoparticles of the birnessite type bound to photosystem II, with 50-100 manganese ions per photosystem. Having shown that even today’s photosystem II can form birnessite-type oxide particles efficiently, we propose an evolutionary scenario, which involves manganese-oxide production by ancestral photosystems, later followed by down-sizing of protein-bound manganese-oxide nanoparticles to finally yield today’s catalyst of photosynthetic water oxidation.
-
We investigate the effect of pressure on both flame structure and soot formation in nitrogen diluted counterflow diffusion flames of ethylene in the 8–32atm pressure range. Capillary-probe gas sampling is performed to resolve spatially the profiles of gaseous species up to three-ring aromatics by GC/MS analysis and multi-color pyrometry is used to quantify the soot volume fraction and dispersion exponent. Self-similarity of flames is preserved by keeping constant mixture fraction and strain rate, so that profiles of concentrations and temperature, normalized with respect to their peak values, are unaffected by changes in pressure, once the axial coordinate is nondimensionalized with respect to the pressure-dependent diffusion length scale. When conditions are chosen so that the overall soot loading is approximately constant and compatible with the diagnostics, it is found that both the soot volume fraction and the profiles of key aromatics in the high-temperature nucleation region are virtually invariant. For it to happen, a twofold increase in pressure must be compensated by a ∼100 K decrease in peak flame temperature and, therefore, in the temperature across the soot forming region. The implication is that from the perspective of the chemical kinetics of soot formation these two actions counterbalance each other. As pressure increases (and temperature decreases) the peak production rate of the high-temperature soot mechanism decreases and, further downstream, towards the particle stagnation plane, a low-temperature soot mechanism sets in, yielding an increase in soot H/C content. This mechanism is enhanced as the pressure is raised, causing a higher overall soot volume production rate in the 16atm flame and, especially, in the 32atm one. The role of C4/C2 species in the formation of C6H6 increases with increasing pressure and dominates over the recombination of propargyl radical at sufficiently high pressures. A comprehensive database is established for soot models at high pressures of relevance to applications.more » « less
-
Iron oxide nanomaterials participate in redox processes that give them ideal properties for their use as earth-abundant catalysts. Fabricating nanocatalysts for such applications requires detailed knowledge of the deposition and growth. We report the spontaneous deposition of iron oxide nanoparticles on HOPG in defect areas and on step edges from a metal precursor solution. To study the nucleation and growth of iron oxide nanoparticles, tailored defects were created on the surface of HOPG using various ion sources that serve as the target sites for iron oxide nucleation. After solution deposition and annealing, the iron oxide nanoparticles were found to nucleate and coalesce at 400 °C. AFM revealed that the particles on the sp 3 carbon sites enabled the nanoparticles to aggregate into larger particles. The iron oxide nanoparticles were characterized as having an Fe 3+ oxidation state and two different oxygen species, Fe–O and Fe–OH/Fe–OOH, as determined by XPS. STEM imaging and EDS mapping confirmed that the majority of the nanoparticles grown were converted to hematite after annealing at 400 °C. A mechanism of spontaneous and selective deposition on the HOPG surface and transformation of the iron oxide nanoparticles is proposed. These results suggest a simple method for growing nanoparticles as a model catalyst.more » « less
-
more » « less
Abstract Comprehensive treatment of indoor contaminants such as volatile organic compounds (VOCs) and fine particulate matter (PM2.5) using transition metal oxide catalysts or functional fibrous filters has gained substantial attention recently. However, coupling VOC oxidation catalysts into high‐performance filter systems remains a challenge. Herein, an overall solution to strongly bind manganese dioxide (MnO2) nanocrystals onto polypropylene (PP) nonwoven fabrics is provided. For the first time, uniform heterogeneous nucleation and growth of MnO2onto PP nonwoven fabrics using intermediate inorganic nucleation films, including Al2O3, TiO2, and ZnO, formed conformally on the fabrics via atomic layer deposition (ALD) are demonstrated. How different ALD thin films influence the crystallinity, morphology, surface area, and surface oxygen species of the MnO2grown ALD‐coated PP fibers is further investigated. In addition to uniformity and integrity, ZnO thin films give rise to MnO2crystals with the largest fraction of available surface oxygen, enabling 99.5% catalytic oxidation of formaldehyde within 60 min. Moreover, the metal oxide filters provide excellent PM removal efficiencies (
e PM), achievinge PM2.590% ande PM1098%, respectively, making the approach an outstanding method to produce fully dual‐functional filtration media.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d0ce00734j
