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51.
超临界二氧化碳中卟啉与钴(II)、镍(II)、锌(II)配合物反应动力学 总被引:1,自引:0,他引:1
用紫外-可见光谱研究了钴(II)、镍(II)、锌(II)的1, 1, 1, 5, 5, 5-六氟-2, 4-戊二酮-二水配合物[M(hfac)2(H2O)2, M=Co、Ni、Zn]与5, 10, 15, 20-四(五氟苯基)卟啉[H2tpfpp]在超临界二氧化碳中反应生成金属卟啉[M(tpfpp)]的反应动力学. 在金属配合物大大过量时, 反应对卟啉为一级. 其表观一级速率常数随钴(II)、镍(II)配合物的浓度增加先增加、而后趋于稳定, 而表观一级速率常数随锌(II)配合物的浓度增加线形增加. 根据实验事实, 讨论了反应的机理, 得到了相应的热力学和动力学参数. 相似文献
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Dong Xie Xian-hong Wang Xiao-jiang Zhao Fo-song Wang 《高分子科学》2005,(6):671-674
Rare-earth ternary catalysts Y(CCl3COO)3-ZnR2-glycerin were prepared for the copolymerization of carbon dioxide and propylene oxide (PO), where dialkylzincs (ZnR2) were diethylzinc, di(n-propyl)zinc, di(n-butyl)zinc, di(i-propyl)zinc, di(i-butyl)zinc, di(s-butyl)zinc,respectively. The Y(CCl3COO)3-ZnR2-glycerin catalysts displayed the highest catalytic activity at the molar ratio of Y(CCl3COO)3:ZnR2:glycerin = 1:20:10. In the same copolymerization condition, catalysts containing dialkylzincs with branched alkyl group showed lower catalytic activity than that with primary alkyl group. For those catalysts including dialkylzincs with primary alkyl group, their catalytic activity decreases with increasing number of carbon atom in the alkyl group with the following sequence: Y(CCl3COO)3-ZnEt2-glycerin 〉 Y(CCl3COO)3-Zn(n- Pr)2-glycerin〉Y(CCl3COO)3-Zn(n-Bu)2-glycerin. However, the alkyl group in the dialkylzinc does not influence the insertion of PO into the propagation chain end. 相似文献
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Fossil fuels are expected to be the major source of energy for the next few decades. However, combustion of nonrenewable resources leads to the release of large quantities of CO2, the primary greenhouse gas. Notably, the concentration of CO2 in the atmosphere is increasing annually at an astounding rate. Electrochemical CO2 reduction (ECR) to value-added fuels and chemicals using electricity from intermittent renewable energy sources is a carbon-neutral method to alleviate anthropogenic CO2 emissions. Despite the steady progress in the selective generation of C1 products (CO and formic acid), the production of multi-carbon species still suffers from low selectivity and efficiency. As an ECR product, ethylene (C2H4) has a higher energy density than do C1 species and is an important industrial feedstock in high demand. However, the conversion of CO2 to C2H4 is plagued by low productivity and large overpotential, in addition to the severe competing hydrogen evolution reaction (HER) during the ECR. To address these issues, the design and development of advanced electrocatalysts are critical. Here, we demonstrate fine-tuning of ECR to C2H4 by taking advantage of the prominent interaction of Cu with shape-controlled CeO2 nanocrystals, that is, cubes, rods, and octahedra predominantly covered with (100), (110), and (111) surfaces, respectively. We found that the selectivity and activity of the ECR depended strongly on the exposed crystal facets of CeO2. The overall ECR Faradaic efficiency (FE) over Cu/CeO2(110) (FE ≈ 56.7%) surpassed that of both Cu/CeO2(100) (FE ≈ 51.5%) and Cu/CeO2(111) (FE ≈ 48.4%) in 0.1 mol·L-1 KHCO3 solutions with an H-type cell. This was in stark contrast to the exclusive occurrence of the HER over pure carbon paper, CeO2(100), CeO2(110), and CeO2(111). In particular, the FE toward C2H4 formation and the partial current density increased in the sequence Cu/CeO2(111) < Cu/CeO2(100) < Cu/CeO2(110) within applied bias potentials from -1.00 to -1.15 V (vs. the reversible hydrogen electrode), reaching 39.1% over Cu/CeO2(110) at a mild overpotential (1.13 V). The corresponding values for Cu/CeO2(100) and Cu/CeO2(111) were FEC2H4 ≈ 31.8% and FEC2H4 ≈ 29.6%, respectively. The C2H4 selectivity was comparable to that of many reported Cu-based electrocatalysts at similar overpotentials. Furthermore, the FE for C2H4 remained stable even after 6 h of continuous electrolysis. The superior ECR activity of Cu/CeO2(110) to yield C2H4 was attributed to the metastable (110) surface, which not only promoted the effective adsorption of CO2 but also remarkably stabilized Cu+, thereby boosting the ECR to produce C2H4. This work offers an alternative strategy to enhance the ECR efficiency by crystal facet engineering. 相似文献
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中国无烟煤焦气化活性的研究——水蒸气与二氧化碳气化活性的比较 总被引:2,自引:7,他引:2
在常压和920℃~1050℃下,采用热重方法,进行了六种中国典型无烟煤焦水蒸气与二氧化碳气化活性比较的研究。结果表明,无烟煤焦与水蒸气气化反应的活性与无烟煤的煤化程度相对应,无烟煤煤化程度越高,水蒸气气化反应活性越小。无烟煤焦与二氧化碳气化反应的活性与煤中矿物质的催化作用有密切关系,煤中矿物质的催化作用越大,二氧化碳气化反应活性越大。无烟煤焦与二氧化碳气化反应活性明显小于与水蒸气气化反应活性,后者比前者大10倍左右。初步探讨了无烟煤焦与水蒸气和二氧化碳的气化机理。 相似文献
59.
CONVERSION OF METHANE AND CARBON DIOXIDE TO AROMATICS OVER CHROMIUM-BASED CATALYSTS:SELECTIVITY AND YIELD OF MAIN PRODUCTS
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在840℃,0.5MPa,CH4/CO2摩尔比为1.4,接触时间(W/F)为0.79h·g·L-l的条件下,甲烷和二氧化碳在7.5wt%Cr/5.0wt%Na/SiO2催化剂上共活化得到了4.8%的C2选择性,48.7%的芳烃选择性及1.9%的芳烃收率。在钠修饰的铬基催化剂上,成功地一步实现了CH4和CO2转化为乙烯及中间物乙烯聚合为芳烃的过程 相似文献
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