Wettability Engineering of Solar Methanol Synthesis.

Engineering the wettability of surfaces with hydrophobic organics has myriad applications in heterogeneous catalysis and the large-scale chemical industry; however, the mechanisms behind may surpass the proverbial hydrophobic kinetic benefits. Herein, the well-studied In2O3 methanol synthesis photocatalyst has been used as an archetype platform for a hydrophobic treatment to enhance its performance. With this strategy, the modified samples facilitated the tuning of a wide range of methanol production rates and selectivity, which were optimized at 1436 µmol gcat-1 h-1 and 61%, respectively. Based on in situ DRIFTS and temperature-programmed desorption-mass spectrometry, the surface-decorated alkylsilane coating on In2O3 not only kinetically enhanced the methanol synthesis by repelling the produced polar molecules but also donated surface active H to facilitate the subsequent hydrogenation reaction. Such a wettability design strategy seems to have universal applicability, judged by its success with other CO2 hydrogenation catalysts, including Fe2O3, CeO2, ZrO2, and Co3O4. Based on the discovered kinetic and mechanistic benefits, the enhanced hydrogenation ability enabled by hydrophobic alkyl groups unleashes the potential of the surface organic chemistry modification strategy for other important catalytic hydrogenation reactions.

Distribution, behavior and budget of Pb in suspended particles in the Changjiang Estuary and adjacent east China sea.

Content, isotopes and budget of Pb in suspended particulate matter (SPM) in the Changjiang Estuary and adjacent East China Sea (ECS) were determined to investigate the biogeochemical cycling of particulate Pb in coastal sea. The content of particulate Pb ranged from 11.3 to 669.4 µg/g in February (winter) and from 20.1 to 79.4 µg/g in August (summer). Except in surface water, particulate Pb content in August is higher than that in February. In lower water, particulate Pb and Th and SPM all decreased gradually from the estuary towards the sea, indicating their lithogenic origin from the Changjiang River. Particulate Pb displayed abnormally high concentration in February surface water, resulting from the atmospheric deposition of anthropogenic Pb in winter. 208Pb/206Pb and 207Pb/206Pb in surface water north to the estuary were higher than background values, suggesting anthropogenic disturbance of Pb. Particulate Pb content in the Changjiang River and the estuary had increased by 77-78% from the 1980s to 2016 due to pollution. Pb was also scavenged by organic matter, leading to higher Pb content in waters with high productivity. Budget of particulate Pb in the northern ECS was established. The Changjiang River contributed 97.0% and 58.1% of particulate Pb input in summer and winter half year, respectively. 88.8% of particulate Pb was deposited in the estuary and adjacent coastal sea in summer but 88.7% was exported with southward coastal currents in winter.

New black indium oxide-tandem photothermal CO2-H2 methanol selective catalyst.

It has long been known that the thermal catalyst Cu/ZnO/Al2O3(CZA) can enable remarkable catalytic performance towards CO2 hydrogenation for the reverse water-gas shift (RWGS) and methanol synthesis reactions. However, owing to the direct competition between these reactions, high pressure and high hydrogen concentration (≥75%) are required to shift the thermodynamic equilibrium towards methanol synthesis. Herein, a new black indium oxide with photothermal catalytic activity is successfully prepared, and it facilitates a tandem synthesis of methanol at a low hydrogen concentration (50%) and ambient pressure by directly using by-product CO as feedstock. The methanol selectivities achieve 33.24% and 49.23% at low and high hydrogen concentrations, respectively.

A numerical study of the Ulva prolifera biomass during the green tides in China - toward a cleaner Porphyra mariculture.

The green tides caused by Ulva prolifera have become a recurrent phenomenon in Yellow Sea, China. Investigating the factors governing the biomass of green tides is important for developing management strategies. In this study, an U. prolifera growth model was combined with a hydrodynamic model. This biophysical model can reasonably reproduce the spatiotemporal variation of the green tides in 2012. Among three zones (northern, central, and southern-zones) of Porphyra mariculture region, the northern and central zones were more important in controlling the bloom intensity, and the central zone was the key area in controlling the amount of biomass landed on beaches. Due to the limitation of temperature and nutrients, an earlier or postponed facility recycling might effectively reduce the magnitude of green tides in 2012. This study provides useful information for mitigation of green tides and management of Porphyra mariculture.

Spatiotemporal variations in the summer hypoxia in the Bohai Sea (China) and controlling mechanisms.

Based on field observations in the summer of 2006 and long-term series data, this paper investigates the spatiotemporal variations of hypoxia and associated physical-biogeochemical driving mechanisms in the Bohai Sea (BS), China. Results show that the benthic hypoxic zone is mainly distributed in the "V"-shaped trough region in the western BS, and it tends to form two hypoxic centers which generally correspond to the bottom cold-water core. The regional difference in the intensity of stratification has a significant impact on the spatial distribution of hypoxia. The relatively weak stratification and the mesoscale anticyclonic eddy in the central shoal of the BS weaken the connectivity between the southern and northern hypoxic zones. Organic matter decomposition contributes to hypoxia and results in corresponding nutrient pool with a "dual (southern and northern)-core" structure. Intensified eutrophication is the main drive for decreasing in bottom dissolved oxygen and expansion of hypoxic zone in the BS.

Hydro-biogeochemical processes and their implications for Ulva prolifera blooms and expansion in the world's largest green tide occurrence region (Yellow Sea, China).

The hydro-biogeochemical processes in the world's largest area of green tide occurrence, off the Jiangsu coast in the Yellow Sea, are investigated in the summer, and their implications for Ulva prolifera blooms are discussed. The results show that the offshore transport of coastal water and the inshore upwelling of offshore bottom water both occur off the Jiangsu coast, and the upwelling position is consistent with the 20- to 30-m isobath off the Subei Shoal. The upwelling results in nutrient supplementation off the shoal, where a rapid decrease in the suspended particulate matter content contributes to good light conditions. As a result, a high-value area of phytoplankton is formed within the 20- to 30-m isobath. Eutrophication in the shoal has provided nutrients for the frequent occurrence of Ulva prolifera in recent years, whereas the upwelling area off the shoal has served as a "service station" or "courier station" for floating Ulva prolifera and promoted the species' propagation. The propagation of Ulva prolifera in the upwelling area and its blooms within the Subei Shoal can have a spatially synergistic effect, leading to its large-scale development. Our findings reveal the mechanisms that trigger the world's largest green tides from the perspective of physical-biogeochemical interactions.