Substrate co-doping modulates electronic metal-support interactions and significantly enhances single-atom catalysis

Transitional metal nanoparticles or atoms deposited on appropriate substrates can lead to highly economical, efficient, and selective catalysis. One of the greatest challenges is to control the electronic metal–support interactions (EMSI) between the supported metal atoms and the substrate so as to optimize their catalytic performance. Here, from first-principles calculations, we show that an otherwise inactive Pd single adatom on TiO2(110) can be tuned into a highly effective catalyst, e.g. for O2 adsorption and CO oxidation, by purposefully selected metal–nonmetal co-dopant pairs in the substrate. Such an effect is proved here to result unambiguously from a significantly enhanced EMSI. A nearly linear correlation is noted between the strength of the EMSI and the activation of the adsorbed O2 molecule, as well as the energy barrier for CO oxidation. Particularly, the enhanced EMSI shifts the frontier orbital of the deposited Pd atom upward and largely enhances the hybridization and charge transfer between the O2 molecule and the Pd atom. Upon co-doping, the activation barrier for CO oxidation on the Pd monomer is also reduced to a level comparable to that on the Pd dimer which was experimentally reported to be highly efficient for CO oxidation. The present findings provide new insights into the understanding of the EMSI in heterogeneous catalysis and can open new avenues to design and fabricate cost-effective single-atom-sized and/or nanometer-sized catalysts

Desorption characteristics of H₂O and CO₂ from alumina F200 under different feed/purge pressure ratios and regeneration temperatures

Air pre-purification is an important process for industrial air separation with cryogenic distillation method. This process is typically realized by pressure swing adsorption or temperature swing adsorption. H₂O and CO₂ are the two major components to be removed among the contaminants. In this paper, we establish a mathematical model describing the mass and heat balances in the adsorption bed, and the double-component adsorption/desorption equilibriums of H₂O/CO₂ on alumina F200. To conduct desorption performance analysis, a one-cycle process consisting of feed, blowdown, and purge step under different operating conditions, such as feed/purge pressure ratio and regeneration temperature, is numerically studied. The effect of heat on the desorption performance of H₂O and CO₂ is investigated by changing the purge gas temperature within 30–200 °C under feed/purge pressure ratios of 6:1.1 and 10:1.1, respectively. Detailed results of the H₂O and CO₂ adsorption/desorption behaviors in the bed are demonstrated. The mass and heat transfer characteristics during desorption are also analyzed. Suggestions on the optimization of the heating temperature and duration of purge gas are also proposed

Assessing impacts of climate change and human activities on streamflow and sediment discharge in the Ganjiang River basin (1964-2013)

© 2019 by the authors. National large-scale soil and water conservation controls on the Gangjiang River basin have been documented, but the effect of governance on regional watershed hydrology and how the main driving factors act have not been systematically studied yet. To do this, this study evaluated changing trends and detected transition years for both streamflow and sediment discharge using long-term historical records at seven hydrological stations in the Ganjiang River basin over the past 50 years. The double mass curve (DMC) method was used to quantify the effects of both climate change and human activities on hydrological regime shifts. The results showed that the distributions of precipitation, streamflow, and sediment discharge within a year are extremely uneven and mainly concentrated in the flood season of Jiangxi Province. None of the stations showed significant trends over time for either annual precipitation or streamflow, while the annual sediment discharge at most stations decreased significantly over time. The estimation of sediment discharge via DMC indicated that after the transition years, there were rapid reductions in sediment discharge at all hydrological stations, and the average decline degree of midstream and downstream were much larger than that of upstream. Human activities, especially the increase of vegetation cover and construction of large and medium-sized reservoirs, provided a significantly greater contribution to the reduction of sediment discharge than did precipitation changes. As a case study of river evolution under global change environment, this study could provide scientific basis for the control of soil erosion and the management of water resources in Ganjiang River, as well as for the related research of Poyang Lake and the Yangtze River basin of China

Broadband gradient impedance matching using an acoustic metamaterial for ultrasonic transducers

2016-2017 > Academic research: refereed > Publication in refereed journal201804_a bcmaVersion of RecordPublishe

An oxidized magnetic Au single atom on doped TiO2(110) becomes a high performance CO oxidation catalyst due to the charge effect

Catalysis using gold nanoparticles supported on oxides has been under extensive investigation for many important application processes. However, how to tune the charge state of a given Au species to perform a specific chemical reaction, e.g. CO oxidation, remains elusive. Here, using first-principles calculations, we show clearly that an intrinsically inert Au anion deposited on oxygen-deficient TiO2(110) (Au@TiO2(110)) can be tuned and optimized into a highly effective single atom catalyst (SAC), due to the depletion of the d-orbital by substrate doping. Particularly, Ni- and Cu-doped Au@TiO2 complexes undergo a reconstruction driven by one of the two dissociated O atoms upon CO oxidation. The remaining O atom heals the surface oxygen vacancy and results in a stable bow-shaped surface “O–Au–O” species; thereby the highly oxidized Au single atom now exhibits magnetism and dramatically enhanced activity and stability for O2 activation and CO oxidation, due to the emergence of high density of states near the Fermi level. Based on further extensive calculations, we establish the “charge selection rule” for O2 activation and CO oxidation on Au: the positively charged Au SAC is more active than its negatively charged counterpart for O2 activation, and the more positively charged the Au, the more active it is

Addition of multiple rare SNPs to known common variants improves the association between disease and gene in the Genetic Analysis Workshop 17 data

The upcoming release of new whole-genome genotyping technologies will shed new light on whether there is an associative effect of previously immeasurable rare variants on incidence of disease. For Genetic Analysis Workshop 17, our team focused on a statistical method to detect associations between gene-based multiple rare variants and disease status. We added a combination of rare SNPs to a common variant shown to have an influence on disease status. This method provides us with an enhanced ability to detect the effect of these rare variants, which, modeled alone, would normally be undetectable. Adjusting for significant clinical parameters, several genes were found to have multiple rare variants that were significantly associated with disease outcome

Resonances in J/ψ→ϕπ+π−J/\psi \to \phi \pi ^+\pi ^- and ϕK+K−\phi K^+K^-

A partial wave analysis is presented of $J/\psi \to \phi \pi ^+\pi ^-$ and $\phi K^+K^-$ from a sample of 58M $J/\psi$ events in the BES II detector. The $f_0(980)$ is observed clearly in both sets of data, and parameters of the Flatt\' e formula are determined accurately: $M = 965 \pm 8$ (stat) $\pm 6$ (syst) MeV/c$^2$, $g_1 = 165 \pm 10 \pm 15$ MeV/c$^2$, $g_2/g_1 = 4.21 \pm 0.25 \pm 0.21$. The $\phi \pi \pi$ data also exhibit a strong $\pi \pi$ peak centred at $M = 1335$ MeV/c$^2$. It may be fitted with $f_2(1270)$ and a dominant $0^+$ signal made from $f_0(1370)$ interfering with a smaller $f_0(1500)$ component. There is evidence that the $f_0(1370)$ signal is resonant, from interference with $f_2(1270)$. There is also a state in $\pi \pi$ with $M = 1790 ^{+40}_{-30}$ MeV/c$^2$ and $\Gamma = 270 ^{+60}_{-30}$ MeV/c$^2$; spin 0 is preferred over spin 2. This state, $f_0(1790)$, is distinct from $f_0(1710)$. The $\phi K\bar K$ data contain a strong peak due to $f_2'(1525)$. A shoulder on its upper side may be fitted by interference between $f_0(1500)$ and $f_0(1710)$.Comment: 17 pages, 6 figures, 1 table. Submitted to Phys. Lett.

Measurement of the Branching Fraction of J/psi --> pi+ pi- pi0

Using 58 million J/psi and 14 million psi' decays obtained by the BESII experiment, the branching fraction of J/psi --> pi+ pi- pi0 is determined. The result is (2.10+/-0.12)X10^{-2}, which is significantly higher than previous measurements.Comment: 9 pages, 8 figures, RevTex

First Measurements of eta_c Decaying into K^+K^-2(pi^+pi^-) and 3(pi^+pi^-)

The decays of eta_c to K^+K^-2(pi^+pi^-) and 3(pi^+pi^-) are observed for the first time using a sample of 5.8X10^7 J/\psi events collected by the BESII detector. The product branching fractions are determined to be B(J/\psi-->gamma eta_c)*B(eta_c-->K^+K^-pi^+pi^-pi^+pi^-)=(1.21+-0.32+- 0.23)X10^{-4}$,B(J/\psi-->gamma eta_c)*B(eta_c-->K^{*0}\bar{K}^{*0}pi^+pi^-)= (1.29+-0.43+-0.32)X10^{-4}$, and (J/\psi-->gamma eta_c)* B(eta_c-->pi^+pi^-pi^+pi^-pi^+pi^-)= (2.59+-0.32+-0.48)X10^{-4}. The upper limit for eta_c-->phi pi^+pi^-pi^+pi^- is also obtained as B(J/\psi-->gamma eta_c)*B(eta_c--> phi pi^+pi^-pi^+pi^-)< 6.03 X10^{-5} at the 90% confidence level.Comment: 11 pages, 4 figure

Organochlorine Pesticides in Consumer Fish and Mollusks of Liaoning Province, China: Distribution and Human Exposure Implications

Fish and mollusk samples were collected from markets located in 12 cities in Liaoning province, China, during August and September 2007, and 22 organochlorine pesticides (OCPs) were detected. DDT, HCH, endosulfan, chlordane, and HCB were the dominating OCPs, with mean concentrations and ranges of, respectively, 15.41 and 0.57 to 177.56 ng/g, 0.84 and below detection limit (BDL) to 22.99 ng/g, 1.31 and BDL to 13.1 ng/g, 1.05 and BDL to 15.68 ng/g, and 0.63 and BDL to 9.21 ng/g in all fish and mollusk samples. The concentrations of other OCPs generally were low and were detectable in a minority of samples, reflecting the low levels of these OCPs in the study region. In general, OCP concentrations were obviously higher in fish than in mollusks, and higher in freshwater fish than in marine fish, which indicated, first, that freshwater fish are more easily influenced than seawater fish and mollusks by OCP residues in agricultural areas and, second, that there are different biota accumulation factors for OCPs between fish and mollusk. To learn the consumption of fish and mollusk, 256 questionnaires were sent to families in 12 cities of Liaoning province. Using the contamination data, average estimated daily intakes of OCPs via fish and mollusk consumption were calculated, which were used for exposure assessment. The public health risks caused by exposure to OCPs in the course of fish and mollusk consumption were compared to noncancer benchmarks and cancer benchmarks