2019, Yang, W., Velkos, G., Liu, F., Sudarkova, S.M., Wang, Y., Zhuang, J., Zhang, H., Li, X., Zhang, X., Büchner, B., Avdoshenko, S.M., Popov, A.A., Chen, N.

A new class of single-molecule magnets (SMMs) based on Dy-oxide clusterfullerenes is synthesized. Three isomers of Dy2O@C82 with Cs(6), C3v(8), and C2v(9) cage symmetries are characterized by single-crystal X-ray diffraction, which shows that the endohedral Dy−(µ2-O)−Dy cluster has bent shape with very short Dy−O bonds. Dy2O@C82 isomers show SMM behavior with broad magnetic hysteresis, but the temperature and magnetization relaxation depend strongly on the fullerene cage. The short Dy−O distances and the large negative charge of the oxide ion in Dy2O@C82 result in the very strong magnetic anisotropy of Dy ions. Their magnetic moments are aligned along the Dy−O bonds and are antiferromagnetically (AFM) coupled. At low temperatures, relaxation of magnetization in Dy2O@C82 proceeds via the ferromagnetically (FM)-coupled excited state, giving Arrhenius behavior with the effective barriers equal to the AFM-FM energy difference. The AFM-FM energy differences of 5.4–12.9 cm−1 in Dy2O@C82 are considerably larger than in SMMs with {Dy2O2} bridges, and the Dy∙∙∙Dy exchange coupling in Dy2O@C82 is the strongest among all dinuclear Dy SMMs with diamagnetic bridges. Dy-oxide clusterfullerenes provide a playground for the further tuning of molecular magnetism via variation of the size and shape of the fullerene cage.

2014, Wagner, B., Wilke, T., Krastel, S., Zanchetta, G., Sulpizio, R., Reicherter, K., Leng, M.J., Grazhdani, A., Trajanovski, S., Francke, A., Lindhorst, K., Levkov, Z., Cvetkoska, A., Reed, J.M., Zhang, X., Lacey, J.H., Wonik, T., Baumgarten, H., Vogel, H.

The Scientific Collaboration on Past Speciation Conditions in Lake Ohrid (SCOPSCO) project is an international research initiative to study the influence of major geological and environmental events on the biological evolution of lake taxa. SCOPSCO drilling campaigns were carried out in 2011 and 2013. In 2011 we used gravity and piston coring at one of the five proposed drill sites, and in 2013 we undertook deep drilling with the Deep Lake Drilling System (DLDS) of Drilling, Observation and Sampling of the Earth's Continental Crust (DOSECC). In April and May 2013, a total of 2100 m sediments were recovered from four drill sites with water depths ranging from 125 to 260 m. The maximum drill depth was 569 m below the lake floor in the centre of the lake. By retrieving overlapping sediment sequences, 95% of the sediment succession was recovered. Initial data from borehole logging, core logging and geochemical measurements indicate that the sediment succession covers >1.2 million years (Ma) in a quasi-continuous sequence. These early findings suggest that the record from Lake Ohrid will substantially improve the knowledge of long-term environmental change and short-term geological events in the northeastern Mediterranean region, which forms the basis for improving understanding of the influence of major geological and environmental events on the biological evolution of endemic species.

2015, Rumbaur, C., Thevs, N., Disse, M., Ahlheim, M., Brieden, A., Cyffka, B., Duethmann, D., Feike, T., Frör, O., Gärtner, P., Halik, Ü., Hill, J., Hinnenthal, M., Keilholz, P., Kleinschmit, B., Krysanova, V., Kuba, M., Mader, S., Menz, C., Othmanli, H., Pelz, S., Schroeder, M., Siew, T.F., Stender, V., Stahr, K., Thomas, F.M., Welp, M., Wortmann, M., Zhao, X., Chen, X., Jiang, T., Luo, J., Yimit, H., Yu, R., Zhang, X., Zhao, C.

The Tarim River basin, located in Xinjiang, NW China, is the largest endorheic river basin in China and one of the largest in all of Central Asia. Due to the extremely arid climate, with an annual precipitation of less than 100 mm, the water supply along the Aksu and Tarim rivers solely depends on river water. This is linked to anthropogenic activities (e.g., agriculture) and natural and semi-natural ecosystems as both compete for water. The ongoing increase in water consumption by agriculture and other human activities in this region has been enhancing the competition for water between human needs and nature. Against this background, 11 German and 6 Chinese universities and research institutes have formed the consortium SuMaRiO (Sustainable Management of River Oases along the Tarim River; http://www.sumario.de), which aims to create a holistic picture of the availability of water resources in the Tarim River basin and the impacts on anthropogenic activities and natural ecosystems caused by the water distribution within the Tarim River basin. On the basis of the results from field studies and modeling approaches as well as from suggestions by the relevant regional stakeholders, a decision support tool (DST) will be implemented that will then assist stakeholders in balancing the competition for water, acknowledging the major external effects of water allocation to agriculture and to natural ecosystems. This consortium was formed in 2011 and is funded by the German Federal Ministry of Education and Research. As the data collection phase was finished this year, the paper presented here brings together the results from the fields from the disciplines of climate modeling, cryology, hydrology, agricultural sciences, ecology, geoinformatics, and social sciences in order to present a comprehensive picture of the effects of different water availability schemes on anthropogenic activities and natural ecosystems along the Tarim River. The second objective is to present the project structure of the whole consortium, the current status of work (i.e., major new results and findings), explain the foundation of the decision support tool as a key product of this project, and conclude with application recommendations for the region. The discharge of the Aksu River, which is the major tributary of the Tarim, has been increasing over the past 6 decades. From 1989 to 2011, agricultural area more than doubled: cotton became the major crop and there was a shift from small-scale to large-scale intensive farming. The ongoing increase in irrigated agricultural land leads to the increased threat of salinization and soil degradation caused by increased evapotranspiration. Aside from agricultural land, the major natural and semi-natural ecosystems are riparian (Tugai) forests, shrub vegetation, reed beds, and other grassland, as well as urban and peri-urban vegetation. Within the SuMaRiO cluster, focus has been set on the Tugai forests, with Populus euphratica as the dominant tree species, because these forests belong to the most productive and species-rich natural ecosystems of the Tarim River basin. At sites close to the groundwater, the annual stem diameter increments of Populus euphratica correlated with the river runoffs of the previous year. However, the natural river dynamics cease along the downstream course and thus hamper the recruitment of Populus euphratica. A study on the willingness to pay for the conservation of the natural ecosystems was conducted to estimate the concern of the people in the region and in China's capital. These household surveys revealed that there is a considerable willingness to pay for conservation of the natural ecosystems, with mitigation of dust and sandstorms considered the most important ecosystem service. Stakeholder dialogues contributed to creating a scientific basis for a sustainable management in the future.

2022, Thiel, T.A., Zhang, X., Radhakrishnan, B., van de Krol, R., Abdi, F.F., Schroeter, M., Schomäcker, R., Schwarze, M.

Photodeposition is a specific method for depositing metallic co-catalysts onto photocatalysts and was applied for immobilizing platinum nanoparticles onto cellulose, a photocatalytically inactive biopolymer. The obtained Pt@cellulose catalysts show narrow and well-dispersed nanoparticles with average sizes between 2 and 5 nm, whereby loading, size and distribution depend on the preparation conditions. The catalysts were investigated for the hydrogenation of para-nitrophenol via transfer hydrogenation using sodium borohydride as the hydrogen source, and the reaction rate constant was determined using the pseudo-first-order reaction rate law. The Pt@cellulose catalysts are catalytically active with rate constant values k from 0.09 × 10−3 to 0.43 × 10−3 min−1, which were higher than the rate constant of a commercial Pt@Al2O3 catalyst (k = 0.09 × 10−3 min−1). Additionally, the Pt@cellulose catalyst can be used for electrochemical hydrogenation of para-nitrophenol where the hydrogen is electrocatalytically formed. The electrochemical hydrogenation is faster compared to the transfer hydrogenation (k = 0.11 min−1).

2018, Zhang, X., Li, W., Feng, L., Chen, X., Hansen, A., Grimme, S., Fortier, S., Sergentu, D.-C., Duignan, T.J., Autschbach, J., Wang, S., Wang, Y., Velkos, G., Popov, A.A., Aghdassi, N., Duhm, S., Li, X., Li, J., Echegoyen, L., Schwarz, W.H.E., Chen, N.

Unsupported non-bridged uranium-carbon double bonds have long been sought after in actinide chemistry as fundamental synthetic targets in the study of actinide-ligand multiple bonding. Here we report that, utilizing I h(7)-C80 fullerenes as nanocontainers, a diuranium carbide cluster, U=C=U, has been encapsulated and stabilized in the form of UCU@I h(7)-C80. This endohedral fullerene was prepared utilizing the Krätschmer-Huffman arc discharge method, and was then co-crystallized with nickel(II) octaethylporphyrin (NiII-OEP) to produce UCU@I h(7)-C80·[NiII-OEP] as single crystals. X-ray diffraction analysis reveals a cage-stabilized, carbide-bridged, bent UCU cluster with unexpectedly short uranium-carbon distances (2.03 Å) indicative of covalent U=C double-bond character. The quantum-chemical results suggest that both U atoms in the UCU unit have formal oxidation state of +5. The structural features of UCU@I h(7)-C80 and the covalent nature of the U(f1)=C double bonds were further affirmed through various spectroscopic and theoretical analyses.

2014, Zhang, X., Wang, P., Zhang, Z., Fang, Y., Sun, M.

Plasmon-driven sequential chemical reactions were successfully realized in an aqueous environment. In an electrochemical environment, sequential chemical reactions were driven by an applied potential and laser irradiation. Furthermore, the rate of the chemical reaction was controlled via pH, which provides indirect evidence that the hot electrons generated from plasmon decay play an important role in plasmon-driven chemical reactions. In acidic conditions, the hot electrons were captured by the abundant H + in the aqueous environment, which prevented the chemical reaction. The developed plasmon-driven chemical reactions in an aqueous environment will significantly expand the applications of plasmon chemistry and may provide a promising avenue for green chemistry using plasmon catalysis in aqueous environments under irradiation by sunlight.