Two new chemically stable metalloporphyrin-bridged metal-catechol frameworks, InTCP-Co and FeTCP-Co, were constructed to achieve artificial photosynthesis without additional sacrificial agents and photosensitizers. The CO2 photoreduction rate over FeTCP-Co considerably exceeds that obtained over InTCP-Co, and the incorporation of uncoordinated hydroxyl groups, associated with catechol, into the network further promotes the photocatalytic activity. The iron-oxo coordination chain assists energy band alignment and provides a redox-active site, and the uncoordinated hydroxyl group contributes to the visible-light absorptance, charge-carrier transfer, and CO2-scaffold affinity. With a formic acid selectivity of 97.8 %, FeTCP-OH-Co affords CO2 photoconversion with a reaction rate 4.3 and 15.7 times higher than those of FeTCP- Co and InTCP-Co, respectively. These findings are also consistent with the spectroscopic study and DFT calculation. 相似文献
Stereocomplex (SC) crystallization has been an effective way to improve the physical performances of stereoregular polymers. However, the competition between homo and SC crystallizations can lead to more complicated crystallization kinetics and polymorphic crystalline structure in stereocomplexable polymers, which influences the physical properties of obtained materials. Herein, we select the medium-molecular-weight (MMW) poly(L-lactic acid)/poly(D-lactic acid) (PLLA/PDLA) asymmetric blends with different PDLA fractions (fD=0.01–0.5) as the model system and investigate the effects of fD and crystallization temperature (Tc) on the crystallization kinetics and polymorphic crystalline structure. We observe the fractionated (i.e., multistep) crystallization kinetics and the formation of peculiar β-form homocrystals (HCs) in the asymmetric blends under quiescent conditions, which are strongly influenced by both fD and Tc. Precisely, crystallization of β-form HCs is favorable in the MMW PLLA/PDLA blends with high fD (≥0.2) at a low Tc (80–100 °C). It is proposed that the formation of metastable β-form HCs is attributed to the conformational matching between β-form HCs and SCs, and the stronger constrain effects of precedingly-formed SCs in the early stage of crystallization. Such effects can also cause the multistep crystallization kinetics of MMW PLLA/PDLA asymmetric blends in the heating process.
Research on Chemical Intermediates - A porous CuO/MnO2 catalyst was synthesized by a gas release-assisted method. Due to the participation of gases (H2O, NH3, CO2) released from ammonia and... 相似文献
Effective receptors for the separation of Li+ from a mixture with other alkali metal ions under mild conditions remains an important challenge that could benefit from new approaches. In this study, it is demonstrated that the 4-phosphoryl pyrazolones, H L 2-H L 4, in the presence of the typical industrial organophosphorus co-ligands tributylphosphine oxide (TBPO), tributylphosphate (TBP) and trioctylphosphine oxide (TOPO), are able to selectively recognise and extract lithium ions from aqueous solution. Structural investigations in solution as well as in the solid state reveal the existence of a series of multinuclear Li+ complexes that include dimers (TBPO, TBP) as well as rarely observed trimers (TOPO) and represent the first clear evidence for the synergistic role of the co-ligands in the extraction process. Our findings are supported by detailed NMR, MS and extraction studies. Liquid-liquid extraction in the presence of TOPO revealed an unprecedented high Li+ extraction efficiency (78 %) for H L 4 compared to the use of the industrially employed acylpyrazolone H L 1 (15 %) and benzoyl-1,1,1-trifluoroacetone (52 %) extractants. In addition, a high selectivity for Li+ over Na+, K+ and Cs+ under mild conditions (pH ∼8.2) confirms that H L 2-H L 4 represent a new class of ligands that are very effective extractants for use in lithium separation. 相似文献
Journal of Solid State Electrochemistry - In order to meet the growing energy demand, it is of great significance to develop high-performance electrochemical energy storage materials. In this... 相似文献
Journal of Solid State Electrochemistry - Jet electrochemical deposition is a relatively new technology for selective electrochemical deposition. Its advantages include high deposition accuracy and... 相似文献