RESUMO
Supported metal catalysts have played an important role in optimizing selective semihydrogenation of alkynes for fine chemicals. There into, nitrogen-doped carbons, as a type of promising support materials, have attracted extensive attentions. However, due to the general phenomenon of random doping for nitrogen species in the support, it is still atremendous challenge to finely identify which nitrogen configuration dominates the catalytic property of alkynes' semihydrogenation. Herein, it is reported that uniform mesoporous N-doped carbon spheres derived from mesoporous polypyrrole spheres are used as supports to immobilized subnanometric Pd clusters, which provide a particular platform to research the influence of nitrogen configurations on the alkynes' semihydrogenation. Comprehensive experimental results and density functional theory calculation indicate that pyridinic nitrogen configuration dominates the catalytic behavior of Pd clusters. The high contents of pyridinic nitrogen sites offer abundant coordination sites, which greatly reduces the energy barrier of the rate-determining reaction step and makes Pd clusters own high catalytic activity. The electron effect between pyridinic nitrogen sites and Pd clusters makes the reaction highly selective. Additionally, the good mesostructures also promote the fast transport of substrate. Based on the above, catalyst Pd@PPy-600 exhibits high catalytic activity (99%) and selectivity (96%) for phenylacetylene (C8 H6 ) semihydrogenation.
RESUMO
The ordered mesoporous perovskite oxides with well-defined mesostrcture and versatile metal sites are attractive, but their successful synthesis faces challenges of complicated assembly dynamics and pore collapse in crystalline calcination. Here, we propose an energy balance concept to reveal interplay relationship in assembly process and realize regulation of porous structure for mesoporous perovskite oxides. A series of ordered mesoporous perovskite oxides with unique porous structure were prepared by a modular co-assembly method. Mesoporous La2 Zr2 O7 shows 94 % conversion and 99 % selectivity for hydrogenation of 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydroxymethyl)furan. Experiments reveal that rich Lewis acid sites, active Zr species, and favorable porous structure promote interaction between mesoporous La2 Zr2 O7 and HMF and reduce catalytic energy barrier. This work provides the insight into molecule co-assembly and developing multiple component ordered mesoporous materials.
RESUMO
Monitoring the temporal and spatial variation of soil properties is helpful to understand the evolution of soil properties and adjust the management method in time. Soil fertility evaluation is an urgent need to understand soil fertility level and prevent soil degradation. Here, we conducted an intensive field investigation in Chinese hickory (Carya cathayensis Sarg.) plantation to clarify the spatial and temporal variation of soil properties and its influencing factors, and to evaluate the change of soil fertility. The results showed that the soil pH and soil organic carbon (SOC) significantly increased from 2008 to 2018, while available nitrogen (AN) significantly decreased from 2008 to 2018. The semi-variance revealed that except available phosphorus (AP), the spatial dependencies of soil properties increased from 2008 to 2018. An increasing south-north gradient was found for soil AN, AP, available potassium (AK) and SOC and a decreasing south-north gradient was found for soil pH. The average soil fertility in the whole area was increased from 2008 to 2018. Our findings demonstrated that the changes of the management measures were the reason for the change of soil properties from 2008 to 2018. Therefore, rational fertilization strategies and sod cultivation are recommended to maintain the long-term development of the producing forest.
