Ultrastable Atomic Copper Nanosheets for Selective Electrochemical Reduction of Carbon Dioxide

金属铜表面很容易被空气氧化，因此铜纳米材料在空气中极不稳定，如何制备原子级厚度的二维铜纳米片一直是纳米材料领域的一个挑战性难题。厦门大学化学化工学院郑南峰教授课题组发展了一种制备稳定超薄二维铜基纳米材料的有效方法，并将这类材料应用于二氧化碳的选择性电催化还原。该项研究还发现所合成的复合纳米材料能够将二氧化碳和水选择性地电化学还原为组成可调的合成气（一氧化碳和氢气混合气），在较低的还原电位下可高选择性地将二氧化碳还原成一氧化碳(其法拉第效率高达92%)。铜基纳米材料在二氧化碳电化学还原中具有优异的性能，但产物异常多样，选择性控制的难度很大。该项工作利用简单的表面配位修饰大幅改善电催化选择性的策略为二氧化碳还原电催化剂的设计提供了新思路。 该工作是在郑南峰教授指导下，并与傅钢教授课题组、加拿大Dalhousie大学张鹏教授合作完成，第一作者为化学化工学院博士生代磊，硕士生钦青、博士生汪佩、赵小静等参与了该工作。【Abstract】The electrochemical conversion of CO2 and H2O into syngas using renewably generated electricity is an attractive approach to simultaneously achieve chemical fixation of CO2 and storage of renewable energy. Developing cost-effective catalysts for selective electroreduction of CO2 into CO is essential to the practical applications of the approach. We report a simple synthetic strategy for the preparation of ultrathin Cu/Ni(OH)2 nanosheets as an excellent cost-effective catalyst for the electrochemical conversion of CO2 and H2O into tunable syngas under low overpotentials. These hybrid nanosheets with Cu(0)-enriched surface behave like noble metal nanocatalysts in both air stability and catalysis. Uniquely, Cu(0) within the nanosheets is stable against air oxidation for months because of the presence of formate on their surface. With the presence of atomically thick ultrastable Cu nanosheets, the hybrid Cu/Ni(OH)2 nanosheets display both excellent activity and selectivity in the electroreduction of CO2 to CO. At a low overpotential of 0.39 V, the nanosheets provide a current density of 4.3 mA/cm2 with a CO faradaic efficiency of 92%. No decay in the current is observed for more than 22 hours. The catalysts developed in this work are promising for building low-cost CO2 electrolyzers to produce CO.We thank the beamline BL14W1 (Shanghai Synchrotron Radiation Facility) for providing the beam time. the Ministry of Science and Technology of China (2017YFA0207302 and 2015CB93230)and the National Natural Science Foundation of China (21731005, 21420102001, 21333008). 研究工作得到了科技部和国家自然科学基金委的资助，X-射线吸收光谱测试在上海光源BL14W1线站完成

Photochemical route for synthesizing atomically dispersed palladium catalysts

该工作由校内外多个课题组共同努力，历时三年多完成。我校郑南峰、傅钢等课题组紧密协作负责催化剂的合成、表征、催化测试及机理研究；中科院物理研究所谷林研究员主要负责催化剂的球差校正透射电子显微研究；加拿大达尔豪斯大学的张鹏课题组参与催化剂的同步辐射X-射线吸收谱研究。该研究工作的第一、二作者刘朋昕、赵云均为我校博士生。【Abstract】Atomically dispersed noble metal catalysts often exhibit high catalytic performances, but the metal loading density must be kept low (usually below 0.5%) to avoid the formation of metal nanoparticles through sintering. We report a photochemical strategy to fabricate a stable atomically dispersed palladium–titanium oxide catalyst (Pd 1 /TiO2 ) on ethylene glycolate (EG)–stabilized ultrathin TiO2 nanosheets containing Pd up to 1.5%.The Pd 1 /TiO2 catalyst exhibited high catalytic activity in hydrogenation of C=C bonds, exceeding that of surface Pd atoms on commercial Pd catalysts by a factor of 9.No decay in the activity was observed for 20 cycles. More important, the Pd 1 /TiO2 -EG system could activate H2 in a heterolytic pathway, leading to a catalytic enhancement in hydrogenation of aldehydes by a factor of more than 55.Supported by Ministry of Science and Technology of China grant 2015CB932303; National Natural Science Foundation of China grants 21420102001, 21131005, 21390390, 21133004, 21373167, 21573178, and 21333008; a NSERC CGS Alexander Graham Bell scholarship (D.M.C.); and a NSERC Discovery grant (P.Z.)

VOC Characteristics and Their Source Apportionment in the Yangtze River Delta Region during the G20 Summit

To evaluate the effectiveness of measures to reduce the levels of volatile organic compounds (VOCs), which are important precursors of ground-level ozone formation, the real-time monitoring data of VOCs at the urban Zhaohui supersite (ZH), the Dianshan Lake regional supersite (DSL) and the urban Yixing station (YX) in the Yangtze River Delta region were analyzed from 23 August to 15 September 2016 during the G20 Hangzhou Summit. The average mole ratios of VOCs at the three sites were 6.56, 21.33 and 19.62 ppb, respectively, which were lower than those (13.65, 27.72 and 21.38 ppb) after deregulation. The characteristics of the VOCs varied during the different control periods. Synoptic conditions and airmass transport played an important role in the transport and accumulation of VOCs and other pollutants, which affected the control effects. Using the positive matrix factorization (PMF) method in source apportionment, five factors were identified, namely, vehicle exhaust (19.66–31.47%), plants (5.59–17.07%), industrial emissions (13.14–33.82%), fuel vaporization (12.83–26.34%) and solvent usage (17.84–28.95%) for the ZH and YX sites. Factor 4 was identified as fuel vaporization + incomplete combustion (21.69–25.35%) at the DSL site. The Non-parametric Wind Regression (NWR) method showed that regional transport was the main factor influencing the VOC distribution

Additional file 1 of Maternal and neonatal complications after IVF/ICSI-fresh embryo transfer in low-prognosis women under the POSEIDON criteria: a retrospective cohort study

Additional file 1

Electrochemical Partial Reforming of Ethanol into Ethyl Acetate Using Ultrathin Co3O4 Nanosheets as a Highly Selective Anode Catalyst

[Image: see text] Electrochemical partial reforming of organics provides an alternative strategy to produce valuable organic compounds while generating H(2) under mild conditions. In this work, highly selective electrochemical reforming of ethanol into ethyl acetate is successfully achieved by using ultrathin Co(3)O(4) nanosheets with exposed (111) facets as an anode catalyst. Those nanosheets were synthesized by a one-pot, templateless hydrothermal method with the use of ammonia. NH(3) was demonstrated critical to the overall formation of ultrathin Co(3)O(4) nanosheets. With abundant active sites on Co(3)O(4) (111), the as-synthesized ultrathin Co(3)O(4) nanosheets exhibited enhanced electrocatalytic activities toward water and ethanol oxidations in alkaline media. More importantly, over the Co(3)O(4) nanosheets, the electrooxidation from ethanol to ethyl acetate was so selective that no other oxidation products were yielded. With such a high selectivity, an electrolyzer cell using Co(3)O(4) nanosheets as the anode electrocatalyst and Ni–Mo nanopowders as the cathode electrocatalyst has been successfully built for ethanol reforming. The electrolyzer cell was readily driven by a 1.5 V battery to achieve the effective production of both H(2) and ethyl acetate. After the bulk electrolysis, about 95% of ethanol was electrochemically reformed into ethyl acetate. This work opens up new opportunities in designing a material system for building unique devices to generate both hydrogen and high-value organics at room temperature by utilizing electric energy from renewable sources

Carbon Monoxide Promotes the Catalytic Hydrogenation on Metal Cluster Catalysts

Size effect plays a crucial role in catalytic hydrogenation. The highly dispersed ultrasmall clusters with a limited number of metal atoms are one candidate of the next generation catalysts that bridge the single-atom metal catalysts and metal nanoparticles. However, for the unfavorable electronic property and their interaction with the substrates, they usually exhibit sluggish activity. Taking advantage of the small size, their catalytic property would be mediated by surface binding species. The combination of metal cluster coordination chemistry brings new opportunity. CO poisoning is notorious for Pt group metal catalysts as the strong adsorption of CO would block the active centers. In this work, we will demonstrate that CO could serve as a promoter for the catalytic hydrogenation when ultrasmall Pd clusters are employed. By means of DFT calculations, we show that Pdn n=2‐147 clusters display sluggish activity for hydrogenation due to the too strong binding of hydrogen atom and reaction intermediates thereon, whereas introducing CO would reduce the binding energies of vicinal sites, thus enhancing the hydrogenation reaction. Experimentally, supported Pd2CO catalysts are fabricated by depositing preestablished [Pd2(μ-CO)2Cl4]2- clusters on oxides and demonstrated as an outstanding catalyst for the hydrogenation of styrene. The promoting effect of CO is further verified experimentally by removing and reintroducing a proper amount of CO on the Pd cluster catalysts

Temporal changes in genetic diversity of msp-1, msp-2, and msp-3 in Plasmodium falciparum isolates from Grande Comore Island after introduction of ACT

Abstract Background Malaria is still one of the serious public health problems in Grande Comore Island, although the number of annual cases has been greatly reduced in recent years. A better understanding of malaria parasite population diversity and transmission dynamics is critical for assessing the effectiveness of malaria control measures. The objective of this study is to investigate temporal changes in genetic diversity of Plasmodium falciparum populations and multiplicity of infection (MOI) in Grande Comore 10 years after introduction of ACT. Methods A total of 232 P. falciparum clinical isolates were collected from the Grande Comore Island during two sampling periods (118 for 2006‒2007 group, and 114 for 2013‒2016 group). Parasite isolates were characterized for genetic diversity and complexity of infection by genotyping polymorphic regions in merozoite surface protein gene 1 (msp-1), msp-2, and msp-3 using nested PCR and DNA sequencing. Results Three msp-1 alleles (K1, MAD20, and RO33), two msp-2 alleles (FC27 and 3D7), and two msp-3 alleles (K1 and 3D7) were detected in parasites of both sampling periods. The RO33 allele of msp-1 (84.8%), 3D7 allele of msp-2 (90.8%), and K1 allele of msp-3 (66.7%) were the predominant allelic types in isolates from 2006–2007 group. In contrast, the RO33 allele of msp-1 (63.4%), FC27 allele of msp-2 (91.1%), and 3D7 allele of msp-3 (53.5%) were the most prevalent among isolates from the 2013–2016 group. Compared with the 2006‒2007 group, polyclonal infection rates of msp-1 (from 76.7 to 29.1%, P < 0.01) and msp-2 (from 62.4 to 28.3%, P < 0.01) allelic types were significantly decreased in those from 2013‒2016 group. Similarly, the MOIs for both msp-1 and msp-2 were higher in P. falciparum isolates in the 2006–2007 group than those in 2013–2016 group (MOI = 3.11 vs 1.63 for msp-1; MOI = 2.75 vs 1.35 for msp-2). DNA sequencing analyses also revealed reduced numbers of distinct sequence variants in the three genes from 2006‒2007 to 2013‒2016: msp-1, from 32 to 23 (about 28% decline); msp-2 from 29 to 21 (about 28% decline), and msp-3 from 11 to 3 (about 72% decline). Conclusions The present data showed dramatic reduction in genetic diversity and MOI among Grande Comore P. falciparum populations over the course of the study, suggesting a trend of decreasing malaria transmission intensity and genetic diversity in Grande Comore Island. These data provide valuable information for surveillance of P. falciparum infection and for assessing the appropriateness of the current malarial control strategies in the endemic area

Arabinose substitution degree in xylan positively affects lignocellulose enzymatic digestibility after various NaOH/H2SO4 pretreatments in Miscanthus

Xylans are the major hemicelluloses in grasses, but their effects on biomass saccharification remain unclear. In this study, we examined the 79 representative Miscanthus accessions that displayed a diverse cell wall composition and varied biomass digestibility. Correlation analysis showed that hemicelluloses level has a strong positive effect on lignocellulose enzymatic digestion after NaOH or H2SO4 pretreatment. Characterization of the monosaccharide compositions in the KOH-extractable and non-KOH-extractable hemicelluloses indicated that arabinose substitution degree of xylan is the key factor that positively affects biomass saccharification. The xylose/arabinose ratio after individual enzyme digestion revealed that the arabinose in xylan is partially associated with cellulose in the amorphous regions, which negatively affects cellulose crystallinity for high biomass digestibility. The results provide insights into the mechanism of lignocellulose enzymatic digestion upon pretreatment, and also suggest a goal for the genetic modification of hemicelluloses towards the bioenergy crop breeding of Miscanthus and grasses. (C) 2012 Elsevier Ltd. All rights reserved

Polymorphisms of the artemisinin resistant marker (K13) in Plasmodium falciparum parasite populations of Grande Comore Island 10 years after artemisinin combination therapy

Abstract Background Plasmodium falciparum malaria is a significant public health problem in Comoros, and artemisinin combination therapy (ACT) remains the first choice for treating acute uncomplicated P. falciparum. The emergence and spread of artemisinin-resistant P. falciparum in Southeast Asia, associated with mutations in K13-propeller gene, poses a potential threat to ACT efficacy. Detection of mutations in the P. falciparum K13-propeller gene may provide the first-hand information on changes in parasite susceptibility to artemisinin. The objective of this study is to determinate the prevalence of mutant K13-propeller gene among the P. falciparum isolates collected from Grande Comore Island, Union of Comoros, where ACT has been in use since 2004. Methods A total of 207 P. falciparum clinical isolates were collected from the island during March 2006 and October 2007 (n = 118) and March 2013 and December 2014 (n = 89). All isolates were analysed for single nucleotide polymorphisms (SNPs) and haplotypes in the K13-propeller gene using nested PCR and DNA sequencing. Results Only three 2006–2007 samples carried SNPs in the K13-propeller gene, one having a synonymous (G538G) and the other having two non-synonymous (S477Y and D584E) substitutions leading to two mutated haplotypes (2.2 %, 2/95). Three synonymous mutations (R471R, Y500Y, and G538G) (5.9 %, 5/85) and 7 non-synonymous substitutions (21.2 %, 18/85) with nine mutated haplotypes (18.8 %, 16/85) were found in isolates from 2013 to 2014. However, none of the polymorphisms associated with artemisinin-resistance in Southeast Asia was detected from any of the parasites examined. Conclusion This study showed increased K13-propeller gene diversity among P. falciparum populations on the Island over the course of 8 years (2006–2014). Nevertheless, none of the polymorphisms known to be associated with artemisinin resistance in Asia was detected in the parasite populations examined. Our data suggest that P. falciparum populations in Grande Comore are still effectively susceptible to artemisinin. Our results provide insights into P. falciparum populations regarding mutations in the gene associated with artemisinin resistance and will be useful for developing and updating anti-malarial guidance in Comoros