Coordination Synergy between Iridium Photosensitizers and Metal Nanoclusters Leading to Enhanced CO₂ Cycloaddition under Mild Conditions

The achievement of photocatalytic CO2 and epoxide cycloaddition under mild conditions such as room temperature and atmospheric pressure is important for green chemistry, which can be achieved by developing coordination synergies between catalysts and photosensitizers. In this context, we exploit the use of coordinate bonds to connect pyridine-appended iridium photosensitizers and catalysts for CO2 cycloaddition, which is systematically demonstrated by 1H nuclear magnetic resonance titration and X-ray photoelectron spectroscopic measurements. It is shown that the hybrid Ir(Cltpy)2/Mn2Cd4 photocatalytic system with coordination synergy exhibits excellent catalytic performance (yield ≈ 98.2%), which is 3.75 times higher than that of the comparative Ir(Cltpy-Ph)2/Mn2Cd4 system without coordination synergy (yield ≈ 26.2%), under mild conditions. The coordination between the Mn2Cd4 catalyst and the Ir(Cltpy)2 photosensitizer enhances the light absorption and photoresponse properties of the Mn2Cd4 catalyst. This has been confirmed through transient photocurrent, electrochemical impedance, and electron paramagnetic tests. Consequently, the efficiency of cycloaddition was enhanced by utilizing mild conditions

Long term effect of nitrogen addition on understory community in a Chinese boreal forest

Increasing atmospheric nitrogen (N) deposition is an important driver of biodiversity change. By conducting an eight-year N addition experiment (0, 20, 50 and 100 kg N ha(-1) yr(-1)), we investigated the long-term effect of simulated N deposition on understory species composition and richness in a boreal forest, northeast China. We found that moss cover decreased significantly with increasing N addition. N addition had no significant effect on vascular plants species richness but changed the plant community composition. The relative coverage of evergreen shrubs decreased, while that of graminoids increased under high-level N addition (100 kg N ha(-1) yr(-1)). Under the high-level N treatment, Deyeuxia angustifolia cover increased significantly after 4 years, while that of Vaccinium vitis-idaea decreased significantly after 3 years and almost disappeared after 5 years. The negative effect of N addition on mosses and evergreen shrubs accumulated over time, while the positive effect on graminoids increased during the first 4 years and did not change significantly thereafter. Our results suggest that the effect of N deposition varies across functional groups and shifts over time. (C) 2018 Elsevier B.V. All rights reserved

Nonlinear responses of ecosystem carbon fluxes to nitrogen deposition in an old-growth boreal forest

Nitrogen (N) deposition is known to increase carbon (C) sequestration in N-limited boreal forests. However, the long-term effects of N deposition on ecosystem carbon fluxes have been rarely investigated in old-growth boreal forests. Here we show that decade-long experimental N additions significantly stimulated net primary production (NPP) but the effect decreased with increasing N loads. The effect on soil heterotrophic respiration (Rh) shifted from a stimulation at low-level N additions to an inhibition at higher levels of N additions. Consequently, low-level N additions resulted in a neutral effect on net ecosystem productivity (NEP), due to a comparable stimulating effect on NPP and Rh, while NEP was increased by high-level N additions. Moreover, we found nonlinear temporal responses of NPP, Rh and NEP to low-level N additions. Our findings imply that actual N deposition in boreal forests likely exerts a minor contribution to their soil C storage

Effects of nitrogen addition on leaf nutrient stoichiometry in an old-growth boreal forest

Boreal forests have been evidenced to be highly sensitive to enhanced nitrogen (N) deposition due to prevailing N limitations, and external N inputs from atmospheric deposition are expected to alter plant nutrient stoichiometry. Previous studies have mostly focused on the dominant tree species while neglecting understory plants that often play important role in the nutrient cycles in forest ecosystems. By conducting a six-year N-addition experiment with four treatments of 0 (control), 20 (low N), 50 (medium N), and 100 (high N) kg N.ha(-1).yr(-1) in a boreal forest in Northeast China, we assessed the responses of leaf nutrient stoichiometry (N, phosphorus [P], potassium [K], calcium [Ca], and magnesium [Mg]) for tree, shrubs, and grass. Although the responses of different species to N addition varied, six-year N addition, especially the medium and high N treatments, generally increased the leaf N concentration and decreased the leaf P and Ca concentrations. As a result, the foliar N:P, N:K, N:Ca, and N:Mg ratios increased consistently across plant functional groups under the high N addition compared with the control, and the grass Deyeuxia angustifolia showed a larger increase in its foliar N:P, N:Ca, and N:Mg than the shrubs. The leaf N concentration increased consistently with soil inorganic N in a nonlinear saturating form, while the other leaf nutrients either decreased (P, Ca) or were not affected (Mg, K) by the soil N availability. Consequently, the foliar N:P, N:K, N:Ca, and N:Mg ratios increased linearly with increasing soil N availability. In spite of this alteration of the leaf nutrient stoichiometry with increasing soil N availability, foliar nutrients and their stoichiometry were less affected under the low N treatment in both trees and understory plants, suggesting minor effects of current N deposition rates on the foliar nutrient balance in boreal forests

Responses of forest ecosystems to increasing N deposition in China: A critical review

China has been experiencing a rapid increase in nitrogen (N) deposition due to intensified anthropogenic N emissions since the late 1970s. By synthesizing experimental and observational data taken from literature, we reviewed the responses of China's forests to increasing N deposition over time, with a focus on soil biogeochemical properties and acidification, plant nutrient stoichiometry, understory biodiversity, forest growth, and carbon (C) sequestration. Nitrogen deposition generally increased soil N availability and soil N leaching and decreased soil pH in China's forests. Consequently, microbial biomass C and microbial biomass N were both decreased, especially in subtropical forests. Nitrogen deposition increased the leaf N concentration and phosphorus resorption efficiency, which might induce nutrient imbalances in the forest ecosystems. Although experimental N addition might not affect plant species richness in the overstorey, it did significantly alter species composition of understory plants. Increased N stimulated tree growth in temperate forests, but this effect was weak in subtropical and tropical forests. Soil respiration in temperate forests was non-linearly responsive to N additions, with an increase at dosages of 60 kg N ha(-1) yr(-1). However, it was consistently decreased by increased N inputs in subtropical and tropical forests. In light of future trends in the composition (e.g., reduced N vs. oxidized N) and the loads of N deposition in China, further research on the effects of N deposition on forest ecosystems will have critical implications for the management strategies of China's forests. (C) 2018 Elsevier Ltd. All rights reserved