Oxygen-Bridged Cu Binuclear Sites for Efficient Electrocatalytic CO2 Reduction to Ethanol at Ultralow Overpotential.

Electrocatalytic CO2 reduction (CO2RR) to alcohols offers a promising strategy for converting waste CO2 into valuable fuels/chemicals but usually requires large overpotentials. Herein, we report a catalyst comprising unique oxygen-bridged Cu binuclear sites (CuOCu-N4) with a Cu···Cu distance of 3.0-3.1 Å and concomitant conventional Cu-N4 mononuclear sites on hierarchical nitrogen-doped carbon nanocages (hNCNCs). The catalyst exhibits a state-of-the-art low overpotential of 0.19 V (versus reversible hydrogen electrode) for ethanol and an outstanding ethanol Faradaic efficiency of 56.3% at an ultralow potential of -0.30 V, with high-stable Cu active-site structures during the CO2RR as confirmed by operando X-ray adsorption fine structure characterization. Theoretical simulations reveal that CuOCu-N4 binuclear sites greatly enhance the C-C coupling at low potentials, while Cu-N4 mononuclear sites and the hNCNC support increase the local CO concentration and ethanol production on CuOCu-N4. This study provides a convenient approach to advanced Cu binuclear site catalysts for CO2RR to ethanol with a deep understanding of the mechanism.

Constructing Gold Single-Atom Catalysts on Hierarchical Nitrogen-Doped Carbon Nanocages for Carbon Dioxide Electroreduction to Syngas.

Precious-metal single-atom catalysts (SACs), featured by high metal utilization and unique coordination structure for catalysis, demonstrate distinctive performances in the fields of heterogeneous and electrochemical catalysis. Herein, gold SACs are constructed on hierarchical nitrogen-doped carbon nanocages (hNCNC) via a simple impregnation-drying process and first exploited for electrocatalytic carbon dioxide reduction reaction (CO2RR) to produce syngas. The as-constructed Au SAC exhibits the high mass activity of 3319 A g-1 Au at -1.0 V (vs reversible hydrogen electrode, RHE), much superior to the Au nanoparticles supported on hNCNC. The ratio of H2/CO can be conveniently regulated in the range of 0.4-2.2 by changing the applied potential. Theoretical study indicates such a potential-dependent H2/CO ratio is attributed to the different responses of HER and CO2RR on Au single-atom sites coordinating with one N atom at the edges of micropores across the nanocage shells. The catalytic mechanism of the Au active sites is associated with the smooth switch between twofold and fourfold coordination during CO2RR, which much decreases the free energy changes of the rate-determining steps and promotes the reaction activity.

Risk assessment of nitrate and petroleum-derived hydrocarbon addition on Contricriba weissflogii biomass, lifetime, and nutritional value.

Coastal diatoms are often exposed to both petroleum-derived hydrocarbon pollution and eutrophication. How these exposures influence on algal biomass, lifetime, and nutritional value are unknown. To examine a more accurate risk assessment of the pollutants on the role of diatoms in coastal ecosystem functions, Conticribra weissflogii was maintained at different concentrations of nitrate (N) and/or water-soluble fractions of No.0 diesel oil (WSF). Algal density, cell growth cycle, protein, chlorophyll a, superoxide dismutase (SOD) activity, and malonaldehyde (MDA) were determined for the assessment of algal biomass, lifetime, nutritional value, photosynthesis and respiration, antioxidant capacity, and lipid peroxidation, respectively.When N addition was combined with WSF pollution, the cell growth cycles were shortened by 27-44%; SOD activities were decreased by 1-64%; algal density, the concentrations of chlorophyll a, protein, and MDA were varied between 38 and 310%, 62 and 712%, 4 and 124%, and 19 and 233% of the values observed in N addition experiments, respectively. Coastal ecosystem functions were severely weakened by N and WSF additions, and the influence was increased in the order: N

Risk assessment of nitrate and oxytetracycline addition on coastal ecosystem functions.

Diatoms dominate phytoplankton communities in the well-mixed coastal and upwelling regions. Coastal diatoms are often exposed to both aquaculture pollution and eutrophication. But how these exposures influence on coastal ecosystem functions are unknown. To examine these influences, a coastal centric diatom, Conticribra weissflogii was maintained at different concentrations of nitrate (N) and/or oxytetracycline (OTC). Algal density, cell growth cycle, protein, chlorophyll a, superoxide dismutase (SOD) activity, and malonaldehyde (MDA) were determined for the assessment of algal biomass, lifetime, nutritional value, photosynthesis and respiration, antioxidant capacity, and lipid peroxidation, respectively. When N addition was combined with OTC pollution, the cell growth cycles were shortened by 56-73%; algal density, SOD activities, the concentrations of chlorophyll a, protein, and MDA varied between 73 and 121%, 19 and 397%, 52 and 693%, 19 and 875%, and 66 and 2733% of the values observed in N addition experiments, respectively. According to P-value analysis, the influence of OTC on algal density and SOD activity was not significant, but the effect on cell growth cycle, protein, chlorophyll a, and MDA were significant (P<0.05). The influence of N addition with simultaneous OTC pollution on the above six end points was significant. Algal biomass, lifetime, nutrition, antioxidant capacity, lipid peroxidation, photosynthesis, and respiration were all affected by the addition of OTC and N. Coastal ecosystem functions were severely affected by N and OTC additions, and the influence was increased in the order: N

Study of the distributed thermal lens of LD end pumped rectangular gain.

In the LD end pumped rectangular laser gain medium, the thermal induced refractive index is not only non-uniformly transversely, but also non-uniformly and distributed along the pumping beam propagation, the effect of thermal lens is a distributed not a lumped lens effect as previously considered. In this paper, the effect of a distributed thermal lens is analyzed.

[Effects of different accumulated temperature on photosynthetic performances of spring maize varieties during grain-filling period].

Taking cold-resistant maize variety Fengdan 3 and cold-sensitive maize variety Zhengdan 958 as test materials, field experiments were conducted in I, II, and III accumulated temperature zones in Heilongjiang Province of Northeast China to study the effects of different accumulated temperature on the photosynthetic performances of different types of cold-resistant spring maize varieties during their grain-filling period. In the three accumulated temperature zones, the tasseling and maturing periods of Fengdan 3 and Zhengdan 958 were prolonged in the order of I > II > and III, and the grain bulk density decreased in the same order. The RuBPCase and PEPCase activities of Fengdan 3 and Zhengdan 958 leaves had different temperature sensitivity. For Fengdan 3, its leaf RuBPCase and PEPCase activities were high in early grain filling period (0-20 days after anthesis), and the variety could ripen in temperature-limited region. For Zhengdan 958, its leaf RuBPCase and PEPCase activities were high within 0-10 days and 40-60 days after anthesis but not sensitive to the active accumulated temperature during 10-40 days after anthesis, and the variety could not ripen in temperature-limited region. The photosynthetic rates of the two varieties were significantly positively correlated with the active accumulated temperature during 0-10 days and 30-40 days after anthesis. The effects of the accumulated temperature in the three zones on the photosynthetic performances were significant at both early and later grain filling stages. For the same varieties, the higher the active accumulated temperature in grain filling period, the higher the grain yield. Zhengdan 958 had higher yield than Fengdan 3.

[Effects of PASP-KT-NAA on the grain-filling of maize in different accumulated temperature zones of Hilongjiang Province, Norheast China].

Taking the two maize varieties Zhengdan 958 and Fengdan 3 grown on the three accumulated temperature zones (I, II and III) in Heilongjiang Provice as test materials, a field investigation was made in 2010 and 2011 to study the effects of PASP-KT-NAA (PKN), a compound of exogenous plant growth regulators, on the grain filling and yield of the varieties under different environmental temperatures. From zone I to III, the air temperature at the grain filling stage had a decreasing trend, with the average minimum temperature being 12.16, 11.40, and 9.56, respectively. The effective accumulated temperature at the mid-ate amt sae stage of grain filling was too low to be sufficient for grain filling, which severely affected the grain filling process. Applying N, P and K promoted the dry matter accumulation of maize grain and the grain filling rate in the three zones, delayed the peak time (Tmax) of the grain filling rate of Fengdan 3 but advanced that of Zhengdan 958, promoted the growth capacity at peak time of grain filling rate and the maximum grain filling rate of the two varieties, and shortened their active grain filling period. Applying N, P, and K increased the grain yield of the two varieties in the three zones obviously, and, as compared with those in zones I and II , the grain yields of Zhengdan 958 and Fengdan 3 in zone III were increased by 8.2% and 5.1% , and 3.4% and 0.8% , respectively. Therefore, applying N, P and K could help maize utilizing the limited accumulation temperature, improve the grain filling rate, decrease the grain water content, and ultimately, increase the maize yield.