Studies of the Catalytic Reactivity of the Adsorbates on Solid Surfaces

固体表面吸附物催化反应活性的研究

• 批准号: 01470081
• 负责人: TSUCHIYA Susumu
• 金额: $ 4.29万
• 依托单位: Yamaguchi University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-01470081/
• 关键词: Acid-base titration; n-Butenes isomerization; H_2-C_2 exchange; Graphite compound; TPD; Sm_2O_3 catalyst; Infrared spectroscopy; C-H; C-D exchange; 酸化サマリウム; ブテン異性化反応; メトキシド吸着種; CーH,CーD交換反応; ギ酸イオン吸着種; グラファイト層間化合物触媒; セリウムイオン添加TiO_2; 水素ー重水素交換

The n-butenes isomerization profile over Li_2O was cis convex type and basic site was observed by titration. Basic strength distribution and basicity were markedly different at various MgO prepared different way and n-butenes isomerization profiles were different at each MgO. Acid strength distribution and acidity were markedly different at various kinds of TiO_2. The cis convex type profile was observed over pretreated TiO_2 and basic sites was confirmed by titration. 1-Butene isomerization rapidly proceeded on Sm_2O_3. The ratio, cis-2-/trans-2-butene, from1-butene was 22.2.Three kinds of hydrogen on Pt were observed by TPD and reactivities of each hydrogen to adsorbed ammonia was different. Protium-deuterium exchange reaction was performed over tetracyanoethylene and terachloro-p-benzoquinon modified Mg_2Ni. The hydrogen in gas phase exchange either one or two of its hydrogen atoms per reactive collision with the absorbed hydrogen.The double bond migration and the cis-trans isomeriz … More ation of cis-2-butene, cis-2-pentene, and 2-methyl-2-butene took place over KC_<24> and RbC_<24>. cis-2-Butene was the most reactive. The reactivities of olefins over styrene modified KC_<24> were examined.Characteristic hydrogen on Sm_2O_3 at 300 K are observed by infrared spectroscopy. Formation of three kinds of formates over Sm_2O_3 were observed at 373 K. In vacuo, the formates were reacted to bidentate formate and decomposed to OH and carbonate over 533 K. Isotopic effect was observed at decomposition of formate. C-D/C-H exchange reaction of d-formate accompanied with decomposition was observed over 543 K under hydrogen. The site of C-D and H-H activation were the same and at higher pressure H-H activation was prior to C-D activation. Adsorption and reactivities of methoxide on Sm_2O_3 were observed. In vacuo over 573 K, this species gradually decomposed to OH and carboxylate. In oxygen, this species oxidized to formate over 373 K. C-D/C-H exchange reaction of d_3-methoxide was observed over 533 K. The same behavior was observed in the case of formate. Less

正丁烯在Li_2O上的异构化分布为顺凸型，并通过滴定观察到碱性位点。不同制备方法制备的MgO的碱性强度分布和碱度有显著差异，不同MgO的正丁烯异构化谱也不同。不同种类TiO_2的酸强度分布和酸度有显著差异。在预处理TiO_2上观察到顺凸型轮廓，并通过滴定确定了碱性位点。1-丁烯在Sm_2O_3上迅速异构化。顺式-2-丁烯与反式-2-丁烯的比值为22.2。用TPD法观察了铂上的三种氢，每种氢对吸附氨的反应活性不同。在四氰乙烯和四氯对苯醌改性的Mg_2Ni上进行了质子-氘交换反应。气相中的氢每次与被吸收的氢发生反应碰撞，交换一个或两个氢原子。在KC_<24>和RbC_<24>上，顺-2-丁烯、顺-2-戊烯和顺-2-甲基-2-丁烯发生了更多的基化。顺式-2-丁烯反应性最强。考察了烯烃在KC_<24>改性苯乙烯上的反应性。用红外光谱法观察了300 K时Sm_2O_3表面的特征氢。在373 K的温度下，Sm_2O_3表面形成了三种甲酸酯。在真空条件下，甲酸酯在533 K下反应为双齿甲酸酯，并分解为OH和碳酸盐。在甲酸盐分解过程中观察到同位素效应。在543 K条件下，d-甲酸酯的C-D/C-H交换反应伴随分解。C-D和H-H的活化位点相同，在高压下H-H的活化先于C-D的活化。观察了甲氧基氧化物在Sm_2O_3上的吸附和反应活性。在超过573 K的真空中，该物种逐渐分解为OH和羧酸盐。在氧气中，该物种在373 K以上氧化成甲酸盐。在533 K条件下，d_3-甲氧基的C-D/C-H交换反应被观察到。在甲酸盐的情况下也观察到相同的行为。少

项目成果

S.Tsuchiya,M.Yoshinobu,H.Imamura: "Hydrogenation of Phenylacetylene over KC_8,RbC_8,KC_<24> and RbC_<24>." Chem.Express. 4. 273-276 (1989)

S.Tsuchiya，M.Yoshinobu，H.Imamura：“苯乙炔在 KC_8、RbC_8、KC_<24> 和 RbC_<24> 上的氢化。”

Y.NaKashima,Y.Sakata,H.Imamura,S.Tsuchiya: "The Catalytic Isomerization of Butenes over a Samarium Oxide." Bull.Chem.Soc.Jpn.63. 3313-3314 (1990)

Y.NaKashima、Y.Sakata、H.Imamura、S.Tsuchiya：“丁烯在氧化钐上的催化异构化”。

S. Tsuchiya, K. Fujii, Y. Sakata, H. Imamura: "The Reaction. Profile of n-Butenes over a Sulfuric Acid, a Nickel Sulfate, and a Sulfuric Acid Graphite." Chem. Express. 4(9). 633-636 (1989)

S. Tsuchiya、K. Fujii、Y. Sakata、H. Imamura：“反应。正丁烯在硫酸、硫酸镍和硫酸石墨上的剖面。”

Susumu Tsuchiya: "The Catalytic Isomerization of Butenes over a Samarium Oxide" Bull.Chem.Soc.Jpn.63. 3313-3314 (1990)

Susumu Tsuchiya：“丁烯在氧化钐上的催化异构化”Bull.Chem.Soc.Jpn.63。

S.Tsuchiya,K.Konishi,T.Kawashita,H.Imamura: "Hydrogenation and Isomerization of Olefins over Alkali MetalーGraphite Intercalation Compounds." J.Mol.Catal.57. 13-21 (1989)

S.Tsuchiya、K.Konishi、T.Kawashita、H.Imamura：“碱金属石墨插层化合物上的烯烃氢化和异构化”，J.Mol.Catal.57（1989）。