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31.
利用IR,EXAFS, ~(13)CO同位素交换反应及与NO作用等手段研究了Pt羰基簇合物[Pt_3(CO)_6]~(2-)_n(n=3,4)在NaY分子筛超笼内的合成机理.在氧化样品Pt~(2+)/NaY上300-373 K的还愿羰基化过程中,首先Pt~(2+)与CO反应生成PtO(CO)物种(波数σ_(CO)=2110 cm~(-1)),然后聚集成“Pt_3(CO)_6”(σ_(CO)=2112,1896和1841 cm~(-1)),最后生成深绿色的Pt羰基簇合物Pt_(12)(CO)_(24)]~(2-)/NaY(σ_(CO)=2080,1824 cm~(-1)).“Pt_3(CO)_6”的羰基在室温下能迅速地与~(13)CO发生交换,而[Pt_3(CO)_6]~(2-)_n(n=3,4)的羰基与~(13)CO的同位素交换即使在343 K也进行得很慢,室温下,NO能逐步破坏Pt羰基簇合物的层间和层内Pt-Pt键,得到中间物种“Pt_3(CO)_6”和PtO(CO),同时在气相产生CO_2和N_2O.而由上述两中间物种出发,300-353 K温度下,在CO气氛中的还原羰基化又能可逆地得到原羰基簇合物. 相似文献
32.
由XPS研究CO2在低压甲醇合成中的作用 总被引:4,自引:1,他引:4
本文应用XPS,在模拟工业催化剂和实际操作条件下,对低压甲醇合成铜基催化剂的表面形态进行了研究.结果表明,在还原及反应状态下,催化剂表面没有稳定的Cu~(2+)、Cu~+离子存在,仅Cu~0能被检测到;ZnO被还原,形成缺氧结构ZnOx(X≤1),表面出现氧空位.认为高度分散的Cu~0与其紧密接触的部分还原的ZnOx联合组成了甲醇合成的表面活性中心,也即表面上的Cu-Zn-O(“口”为氧空位)构成了最佳合成活性单元.提出反应原料气中适量CO_2的加入有助于金属Cu微晶的分散,认为CO_2的作用主要是使反应气氛中含有一定的氧化势,它与原料气中的CO+H_2一起,对金属Cu微晶起氧化还原作用.CO_2可将Cu~0氧化成Cu~(?+)(甚至Cu~+).但Cu~(?+)会马上被CO+H_2还原成Cu~0.通过这样的氧化还原循环,阻止了Cu微晶的聚集长大,延长了催化剂的使用寿命. 相似文献
33.
34.
1 INTRODUCTION In 1984, thiolate ligand was successfully introduced into molybdenum carbonyl compound by the reaction of Mo(CO)6 with [Et4N]SR( R = C6H5, But) in a moderate condition[1]. From then on, a series of dinuclear molybdenum(0) carbonyl thiolate compounds have been synthesized and characterized by using a variety of thiolate ligands in our research group. It was found that a planar Mo2S2 unit is in the compound [Et4N]2[Mo2(CO)8(SC6H4-CH_3-p)2][2] (2) and a "butterfly" t… 相似文献
35.
Using renewable green hydrogen and carbon dioxide (CO2) to produce methanol is one of the fundamental ways to reduce CO2 emissions in the future, and research and development related to catalysts for efficient and stable methanol synthesis is one of the key factors in determining the entire synthesis process. Metal nanoparticles stabilized on a support are frequently employed to catalyze the methanol synthesis reaction. Metal-support interactions (MSIs) in these supported catalysts can play a significant role in catalysis. Tuning the MSI is an effective strategy to modulate the activity, selectivity, and stability of heterogeneous catalysts. Numerous studies have been conducted on this topic; however, a systematic understanding of the role of various strengths of MSI is lacking. Herein, three Cu/ZnO-SiO2 catalysts with different strengths of MSI, namely, normal precipitation Cu/ZnO-SiO2 (Nor-CZS), co-precipitation Cu/ZnO-SiO2 (Co-CZS), and reverse precipitation Cu/ZnO-SiO2 (Re-CZS), were successfully prepared to determine the role of such interactions in the hydrogenation of CO2 to methanol. The results of temperature-programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS) characterization illustrated that the MSI of the catalysts was considerably affected by the precipitation sequence. Fourier transform infrared reflection spectroscopy (FT-IR) results indicated that the Cu species existed as CuO in all cases and that copper phyllosilicate was absent (except for strong Cu-SiO2 interaction). Transmission electron microscopy (TEM), X-ray diffraction (XRD), and N2O chemical titration results revealed that strong interactions between the Cu and Zn species would promote the dispersion of Cu species, thereby leading to a higher CO2 conversion rate and improved catalytic stability. As expected, the Re-CZS catalyst exhibited the highest activity with 12.4% CO2 conversion, followed by the Co-CZS catalyst (12.1%), and the Nor-CZS catalyst (9.8%). After the same reaction time, the normalized CO2 conversion of the three catalysts decreased in the following order: Re-CZS (75%) > Co-CZS (70%) > Nor-CZS (65%). Notably, the methanol selectivity of the Re-CZS catalyst was found to level off after a prolonged period, in contrast to that of Co-CZS and Nor-CZS. Investigation of the structural evolution of the catalyst with time on stream revealed that the high methanol selectivity of the catalyst was caused by the reconstruction of the catalyst, which was induced by the strong MSI between the Cu and Zn species, and the migration of ZnO onto Cu species, which caused an enlargement of the Cu/ZnO interface. This work offers an alternative strategy for the rational and optimized design of efficient catalysts. 相似文献
36.
共沉淀浸渍法制备由合成气直接合成二甲醚的Cu-Mn催化剂 总被引:9,自引:4,他引:9
采用共沉淀浸渍法,制备了直接合成二甲醚的Cu-Mn-Zn催化剂,通过对组成成分及其配比的研究,发现Cu含量一定的条件下,n(Zn)/n(Mn)摩尔比对催化剂性能有较大的影响,当n(Zn)/n(Mn)=1/3~1/2时,催化剂对CO的转化率和对二甲醚的选择性达到最佳,分别为53.6%和63.5%;如锰添加比例过大,对催化剂催化合成二甲醚有微弱抑制;添加锌比例过大,会大大降低CO的转化率。载体Y分子筛的含量对催化剂性能也有影响,用量过大将降低催化剂的活性和对二甲醚的选择性,当其含量为33%时,催化剂上CO转化率和选择性可分别达到66%和68%,且催化剂活性随分子筛含量减少不再有明显的变化。 相似文献
37.
负载型TiO2-聚酰亚胺亲水复合膜的制备与分离性能 总被引:4,自引:1,他引:4
采用溶解-流涎法,湿相转换法和干湿相转换法制轩了负载型TiO2-聚酰亚胺亲水复合膜,采用扫描电镜,红外光谱,压汞和透气性实验等手段对该膜的孔径分布,表面结构及扩散性能进行了表征,并讨论了制备亲水对膜孔结构的影响,实验结果表明,三种膜均具有很好的亲水性能,而干湿相转换膜具有良好的孔径分布和分离性能。 相似文献
38.
研究了一些氧化物的H2-TPR及CO-TPR行为,结果发现,Co3O4/Al2O3,NiO/SiO2,NiO和Pd/NiO的H2-TPR温度要低于它们的CO-TPR温度,特别是Pd/NiO样品,它的H2-TPR温度为598K,而其CO-TPR温度高达949K,差别为351K,因此有可能利用Pd/NiO在一定温度下选择性地与CO中的H2反应而将其除去. 实验结果表明,Pd/NiO可在603K及4000h-1的条件下从H2(0.34%),CO(50%)和N2(余)的混合气中选择性地除去90%以上的H2,吸氢容量为每克样品55mL标准态H2. 相似文献
39.
The efficient utilization of carbon dioxide (CO2) as a C1 feedstock is of great significance for green and sustainable development. Therefore, the efficient chemical conversion of CO2 into value-added products has recently attracted a lot of research attention in recent years. The transformation of CO2 generally requires high-energy substrates, specific catalysts, and harsh reaction conditions due to its high thermodynamic stability and kinetic inertness. Consequently, several efforts have been dedicated toward the development of high-performance catalysts and new reaction routes for CO2 conversion over the last few decades. To date, many routes of convert CO2 into value-added chemicals have been proposed, together with the development of heterogeneous and homogeneous catalysts. Among the advanced catalysts reported to date, ionic liquids (ILs) have been widely investigated and show great potential for the efficient, selective, and economical conversion of CO2 into highly valuable products under mild conditions, even under ambient conditions. Some task-specific ILs have been designed with unique functional groups (e.g., —OH, —SO3H, —NH2, —COOH, and —C≡N), which can act as the solvent, absorbent, activating agent, catalyst, or cocatalyst to realize the transformation of CO2 under metal-free and mild conditions. In addition, a variety of catalytic systems composed of ILs and metal catalysts have also been reported for the transformation of CO2, in which the combination of the IL and metal catalyst is responsible for CO2 conversion with high efficiency. In this review article, we summarize the recent advances in IL-mediated CO2 transformation into chemicals prepared via C—O, C—N, C—S, C—H, and C—C bond forming processes. ILs that can chemically capture CO2 with high capacity are first introduced, which can activate CO2 via the formation of IL-based carbonates or carbamates, thus realizing the transformation of CO2 under metal-free and mild conditions. Recent progress in IL-mediated CO2 transformations to form carbonates and various kinds of N- and S-containing compounds (e.g., oxazolidinones, ureas, benzimidazolones, formamides, methylamines, benzothiazoles, and other chemicals) as well as CO2 hydrogenation to give formic acid, methane, acetic acid, low-carbon alcohols, and hydrocarbons has been summarized in this review with a focus on the reaction routes, catalytic systems, and reaction mechanism. In these reactions, ILs can simultaneously activate the substrate via strong H-bonding in addition to activating CO2, and the cooperative effects among the ionic and molecular species and metal catalysts accomplish the reactions of CO2 with various kinds of substrates to afford a wide range of value-added chemicals. Finally, the shortcomings and perspectives of ILs are discussed. In short, IL-mediated CO2 transformations provide green and effective routes for the synthesis of high-value chemicals, which may have great potential for a wide range of applications. 相似文献
40.
Reactions in a Mixture of CH4 and CO2 under the Aciton of Microwave Discharge at Atmospheric Pressure
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Reactions between CH4 and CO2 under the action of continuous microwave discharge at atmospheric pressure were studied in a special homemade reactor,The main products were CO and H2,while acetylene and ethylene were also found in the products.Experimental results show that conversions of CH4 and CO2 could be higher than 90% without the presence of any catalyst,Effects of CO2/CH4 molar ratio and total flow rate of the feed gas on the reaction were also investigated. 相似文献