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Li, Can

Publications and source records attributed to Li, Can.

At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Sequentially prepared Mo-V-Based SCR catalyst for simultaneous Hg 0 oxidation and NO reduction

Molybdenum (Mo)-vanadium (V)-based selective catalytic reduction (SCR) catalyst synthesized by the sequential impregnation of Mo and W followed by V was investigated for simultaneous elemental mercury (Hg 0 ) oxidation and nitrogen oxide (NO) reduction in an existing SCR unit with respect to different TiO 2 phases, calcination temperatures, flue gas constituents, gas velocities, and reaction temperatures. Anatase phase TiO 2 and the calcination temperatures of 400 and 500 degrees C resulted in similar to 69% Hg 0 oxidation at 10 ppmv HCl and 350 degrees C. The high calcination temperature of 700 degrees C resulted in TiO 2 phase transformation from anatase to rutile and agglomeration. The modified SCR catalyst prepared with the impregnation sequence of Mo and W followed by V using anatase TiO 2 and calcination temperature 500 degrees C showed similar to 99% Hg 0 oxidation and 87% NO reduction conversions at an NH 3 /NO molar ratio of 0.9 under 350 degrees C and 5,000 hr -1 space velocity in typical sub-bituminous and lignite coal simulated flue gases. Finally, the effects of these parameters and conditions were further investigated using various characterization techniques including BET, TEM, XRD, NH 3 TPD and XAFS.

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

Unravelling the water oxidation mechanism on NaTaO 3 -based photocatalysts

Understanding the detailed kinetics and mechanisms of water oxidation is crucial because water oxidation is the bottleneck reaction in overall water splitting. In this work, we investigated photocatalytic water oxidation on NaTaO 3 -based photocatalysts. With in situ FT-IR spectroscopy, two new water oxidation intermediates with IR absorption peaks centered at 1058 and 935 cm –1 were observed and assigned to Ta(VI)=O and Ta(O 2 ) peroxo species, respectively. With H 2 18 O as the reactant and NaTa 16 O 3 as the photocatalyst, both 16 O 18 O and 18 O 2 were evolved continuously from overall water splitting as analyzed by mass spectroscopy (MS), demonstrating that the lattice O atoms in NaTaO 3 -based photocatalysts participate in the formation of O 2 during the reaction. DFT results are consistent with the formation of Ta=O, 16 O 18 O and 18 O 18 O intermediates and products, while predicting that several water oxidation pathways are thermodynamically accessible for water oxidation on NaTaO 3 . Based on these observations, we propose a three-step two-site mechanism for photocatalytic water oxidation on NaTaO 3 -based photocatalysts in which lattice oxygen plays a key role. The elucidation of the present mechanism should help in broadly understanding water oxidation on semiconductor-based photocatalysts.

14 SOLAR ENERGY↗
DOE OSTI2019

Photocatalytic Facet Selectivity in BiVO 4 Nanoparticles: Polaron Electronic Structure and Thermodynamic Stability Considerations for Photocatalysis

Selective charge separation among different crystal facets of a semiconductor is an intriguing phenomenon for which there is no firm and full theoretical foundation currently. In this work, we report on a density functional theory + U characterization of band alignment and electron and hole polaron stabilities among the (010), (110), and (011) facets of bismuth vanadate BiVO 4 (BVO). Computation-derived band alignment indicates that the conduction band minima are at nearly the same level among the three facets but that the valence band maxima exhibit a shift. We also modeled electron and hole polarons as localized electrons and holes on vanadium and oxygen, respectively, and determined their relative stabilities from a “bulk” region to a surface region. Calculated stabilities reveal similar stability profiles across the various facets, with electron polarons most stable when localized on subsurface V atoms and hole polarons most stable on surface O atoms. Calculations indicate a small stability preference for electron polarons toward the (011) facet and for hole polarons toward the (110) facet, whereas, experimentally, interfacial reduction is observed to take place selectively on the (010) facet and oxidation on the (110) and (011) facets. Facet selectivity could be occurring on the basis of thermodynamics (electron or holes showing a stronger affinity for some facets over others) or kinetics (electron or hole transport and/or redox processes being more efficient toward/on some facets over others) or a combination of both. This work establishes that thermodynamic stability alone is not responsible for the observed facet selectivity in BVO. Furthermore, we surmise that polaron transport kinetics and interfacial redox kinetics are likely to have a role in facet selectivity in BVO. These issues will be the subject of future publications.

14 SOLAR ENERGY↗
DOE OSTI2019

Amino-functionalized graphene quantum dots (aGQDs)-embedded thin film nanocomposites for solvent resistant nanofiltration (SRNF) membranes based on covalence interactions

Solvent resistant nanofiltration (SRNF) membranes are highly demanded in processing organic solutions especially those contain large molecules with molecular weight between 200 to 2000 Da, yet they have some drawbacks such as relatively poor solvent resistance and low solvent permeance. The current work presented an innovative class of amino-functionalized graphene quantum dots (aGQDs) embedded thin film nanocomposites (TFN) for SRNF membranes which were prepared via interfacial polymerization (IP) and subsequent steps (chemical imidization, crosslinking, and solvent activation). The prepared membranes enabled covalent interactions not only between the IP skin layer and the substrate, but also between the IP layer and the embedded aGQDs. The ethanol permeance and surface porosity increased by 44% and 69%, respectively, with the embedment of aGQDs under the optimal conditions, while the Rhodamine B (RDB, 479 Da) rejection maintained essentially stable above 99%. Furthermore, our novel membranes exhibited excellent long-term stability, with a rejection of over 99% for Rose Bengal (RB, 1017 Da) during the continuous filtration of 100 mg L -1 RB/N,N-dimethyl formamide (DMF) solution at room temperature for more than 768 h. They also exhibited good organic solvent resistance and high-temperature tolerance in both DMF and NMP solvents, with a RDB rejection of over 99% and an ethanol permeance of about 38 L m -2 h -1 MPa -1 after being immersed in DMF at 80 °C for 248 h, and a RDB rejection of over 99% and an ethanol permeance of about 41 L m -2 h -1 MPa -1 after being immersed in NMP at 80 °C for 232 h. The results demonstrated that the aGQDs-embedded TFN OSN membrane has vast potential in SRNF applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2018

A New Global Anthropogenic SO2 Emission Inventory for the Last Decade: A Mosaic of Satellite-Derived and Bottom-Up Emissions

Sulfur dioxide (SO2) measurements from the Ozone Monitoring Instrument (OMI) satellite sensor have been used to detect emissions from large point sources. Emissions from over 400 sources have been quantified individually based on OMI observations, accounting for about a half of total reported anthropogenic SO2 emissions. Here we report a newly developed emission inventory, OMI-HTAP, by combining these OMI-based emission estimates and the conventional bottom-up inventory, HTAP, for smaller sources that OMI is not able to detect. OMI-HTAP includes emissions from OMI-detected sources that are not captured in previous leading bottom-up inventories, enabling more accurate emission estimates for regions with such missing sources. In addition, our approach offers the possibility of rapid updates to emissions from large point sources that can be detected by satellites. Our methodology applied to OMI-HTAP can also be used to merge improved satellite-derived estimates with other multi-year bottom-up inventories, which may further improve the accuracy of the emission trends. OMI-HTAP SO2 emissions estimates for Persian Gulf, Mexico, and Russia are 59%, 65%, and 56% larger than HTAP estimates, respectively, in year 2010. We have evaluated the OMI-HTAP inventory by performing simulations with the Goddard Earth Observing System version 5 (GEOS-5) model. The GEOS-5 simulated SO2 concentrations driven by both HTAP and OMI-HTAP were compared against in situ measurements. We focus for the validation on year 2010 for which HTAP is most valid and for which a relatively large number of in situ measurements are available. Results show that the OMI-HTAP inventory improves the agreement between the model and observations, in particular over the US, with the normalized mean bias decreasing from 0.41 (HTAP) to -0.03 (OMI-HTAP) for year 2010. Simulations with the OMI-HTAP inventory capture the worldwide major trends of large anthropogenic SO2 emissions that are observed with OMI. Correlation coefficients of the observed and modelled surface SO2 in 2014 increase from 0.16 (HTAP) to 0.59 (OMI-HTAP) and the normalized mean bias dropped from 0.29 (HTAP) to 0.05 (OMI-HTAP), when we updated 2010 HTAP emissions with 2014 OMI-HTAP emissions in the model.

Sulfur dioxide (SO2)↗
DOE OSTI2018

Covalent organic frameworks (COFs)-incorporated thin film nanocomposite (TFN) membranes for high-flux organic solvent nanofiltration (OSN)

This paper reports a new class of thin film nanocomposite (TFN) membranes incorporated with covalent organic frameworks (COFs) nanoparticles in the polyamide skin layer and having enhanced solvent (ethanol) permeation flux and high solute rejection for organic solvent nanofiltration (OSN). These OSN membranes were prepared via interfacial polymerization of m-phenylenediamine (MPD) and trimesoyl chloride with the presence of COFs nanoparticles in the MPD aqueous solution, followed by chemical crosslinking and solvent activation. The prepared TFN membranes exhibited an improved surface hydrophilicity and a decreased skin layer thickness, which leading to a 46.7% increment in the ethanol permeance (up to 79.8 L m –2 h –1 MPa –1 ) compared to those COFs-free membranes, as well as an increased Rhodamine B (479 Da) rejection (up to 99.4%). Moreover, our prepared TFN OSN membranes exhibited an excellent solvent resistance after being statically immersed in N, N-dimethylformamide (DMF) at ambient temperature over 100 days, and after being consecutively cross-flow filtrated using Rose Bengal/DMF solution at ambient temperature over 7 days, both with no significant changes in the separation performance. Moreover, they showed only minor decrease in flux and rejection after being statically immersed in DMF at 80 °C over 14 days, which provides a strong potential in OSN applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Dose-response relationship between blood lead levels and hematological parameters in children from central China

Highlights: • A cross-sectional study conducted in children of 5–8 years from two counties of central China. • BLLs were associated with hematological parameters (i.e. Hb, RBC, PLT and MCH) negatively. • BLLs associated with Hb level, RBC count, and PLT count in a non-linear dose-response pattern. Lead is a heavy metal that can affect the human hematological system. However, reports are limited on the dose-response relationship between blood lead levels (BLLs) and hematological parameters in children. This study aimed to explore the dose-response relationship between BLLs and hematological measurements among children in China.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

High solvent-resistant and integrally crosslinked polyimide-based composite membranes for organic solvent nanofiltration

This study reports a new class of integral polyimide (PI)-based thin film composite (TFC) membranes (with improved solvent resistance in both the skin layer and the substrate) for organic solvent nanofiltration (OSN). The OSN membrane was prepared via interfacial polymerization (IP) onto a PI ultrafiltration (UF) substrate, followed by an imidization, a chemical crosslinking, and a solvent activation process. During the IP process, m-phenylenediamine (MPD), dopamine (DA), and 1,2,4,5-benzene tetracarboxylic acyl chloride (BTAC) were respectively used as an aqueous monomer, an aqueous additive, and an organic monomer. We proved that amide bonding formed between MPD and the PI substrate during the immersion of the substrate in the aqueous MPD solution, thus providing a strong binding between the substrate and the subsequently formed skin layer of polyamide acid (PAA), which was formed due to reaction between MPD and BTAC during the IP process. DA contains amine group and could also help build a strong binding between the substrate and the skin layer during the same IP process. The subsequent imidization step converted the PAA molecules of the skin layer into PI polymers, which was quite similar to that of the substrate. The final crosslinking step crosslinked not only the inner molecules of the skin layer, and the inner molecules of the substrate, but also the interface molecules between the skin and substrate so as to form an integral composite membrane with improving solvent resistance. Finally, the fabricated OSN membranes under optimal preparation conditions exhibited an ethanol permeance of 2.03 L m -2 h -1 bar -1 with a rejection of 98% for Rhodamine B (479 Da) and exhibited an outstanding organic solvent resistance without compromising separation performance during the persistent immersion in DMF at 80 °C for two weeks, indicating a promising prospective in OSN applications.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Source apportionments of aerosols and their direct radiative forcing and long-term trends over continental United States

Due to US air pollution regulations, aerosol and precursor emissions have decreased during recent decades, while changes in emissions in other regions of the world also influence US aerosol trends through long-range transport. We examine here the relative roles of these domestic and foreign emission changes on aerosol concentrations and direct radiative forcing (DRF) at the top of the atmosphere over the continental US. Long-term (1980-2014) trends and aerosol source apportionment are quantified in this study using a global aerosol-climate model equipped with an explicit aerosol source tagging technique. Due to US emission control policies, the annual mean near-surface concentration of particles, consisting of sulfate, black carbon, and primary organic aerosol, decreases by about –1.1 (±0.1) / –1.4 (±0.1) μg m -3 in western US and –3.3 (±0.2) / –2.9 (±0.2) μg m -3 in eastern US during 2010–2014, as compared to those in 1980–1984. Meanwhile, decreases in US emissions lead to a warming of +0.48 (±0.03) / –0.46 (±0.03) W m -2 in western US and +1.41 (±0.07) /+1.32 (±0.09) W m -2 in eastern US through changes in aerosol DRF. Increases in emissions from East Asia generally have a modest impact on US air quality, but mitigated the warming effect induced by reductions in US emissions by 25% in western US and 7% in eastern US. Thus, as US domestic aerosol and precursor emissions continue to decrease, foreign emissions may become increasingly important to radiative forcing over the US.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2018

The Ozone Monitoring Instrument: Overview of 14 Years in Space

This overview paper highlights the successes of the Ozone Monitoring Instrument (OMI) on board the Aura satellite spanning a period of nearly 14 years. Data from OMI has been used in a wide range of applications and research resulting in many new findings. Due to its unprecedented spatial resolution, in combination with daily global coverage, OMI plays a unique role in measuring trace gases important for the ozone layer, air quality, and climate change. With the operational very fast delivery (VFD; direct readout) and near real-time (NRT) availability of the data, OMI also plays an important role in the development of operational services in the atmospheric chemistry domain.

KNMI↗
DOE OSTI2018

Bimodal hole transport in bulk BiVO 4 from computation

We report first principles and mesoscale kinetic simulations of intrinsic electron and hole transport in stoichiometric monoclinic BiVO 4 (BVO). A main finding is that hole transport is bimodal: there are fast hole hops within VO 4 tetrahedra that are not ‘transport-efficient’ and slower hole hops across VO 4 tetrahedra that are ‘transport-efficient’. This bimodality in hole transport may explain the slow transport/high recombination characteristics of BVO. In this work, polaron hops were described via the two-state Marcus/Holstein model of V V –V IV and O I –O II interchanges for electron and hole polarons respectively. The relevant parameters in the theory were obtained using the density functional theory DFT+U method. Hopping activation energies were combined with Einstein diffusion theory to yield mobility as well as with kinetic Monte Carlo (KMC) modeling. All unique nearest neighbor electron and hole hopping processes were characterized. For V-to-V hops of electron polarons, we obtained activation energies of ~0.37 eV that compare well with the experimental activation energy of ~0.30 eV for drift mobility. Electron polarons remain localized on single sites along the hopping pathways before hopping via tunneling, suggestive of small non-adiabatic coupling and a diabatic character consistent with V-to-V electron transfer through space (no bridge linkers). These simulations yield a small electron transport anisotropy, with transport in the (a,b) plane being faster than along the c direction by a factor of ~2. For hole polarons our calculations support the character of small polarons localized on O atoms as well. Some nearest neighbor hole hops have a diabatic character, while other nearest neighbor hops are adiabatic and phonon-assisted with an Arrhenius thermal dependence. Hops through O–V–O bridges and through space have low activation barriers (~0.17 eV and ~0.25 eV) while hops through O–Bi–O bridges have higher activation barriers (~0.37 eV and higher). The mobility is gated by the slower transport across VO 4 tetrahedra through O–Bi–O bridges owing to the underlying BVO lattice network. Hole mobility is determined to be about one order of magnitude larger than electron mobility consistent with THz spectroscopy measurements. Here, this work sets the foundation to address facet selectivity of charge carriers in shape and size-tailored crystals.

36 MATERIALS SCIENCE↗