物理化学学报 >> 1993, Vol. 9 >> Issue (01): 56 -62 .doi: 10.3866/PKU.WHXB19930110

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RuCo催化剂CO加氢形成含氧物的中间体：甲酰基

肖丰收; 市川胜; 郭燮贤   

  1. 吉林大学化学系，长春 130023；北海道大学触媒化学研究中心，日本札幌；大连化学物理研究所国家催化实验室
  • 收稿日期:1991-09-07 修回日期:1992-03-30 发布日期:1993-02-15
  • 通讯作者: 肖丰收

Formyl: An Intermediate for Formation of Oxygenates in CO Hydrogenation Over Supported RuCo Carbonyl Cluser-Derived Catalysts

Xiao Feng-Shou; Shi Chuan-Sheng; Guo Xie-Xian   

  1. Department of Chemsitry, Jilin University, Changchun 130023; Catalysis Research Center, Hokkaido University, Sapporo 060, Japan; National Laboratory for Catalysis, Dalian Institute of Chemical Physics, Dalian 116023
  • Received:1991-09-07 Revised:1992-03-30 Published:1993-02-15
  • Contact: Xiao Feng-Shou

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摘要： 进行了在SiO_2担载的Ru-Co双金属原子簇催化剂上合成气(CO+H_2)反应和模型化合物吸附的红外、质谱研究. 结果表明, 在原子簇制备的Ru-Co/SiO_2催化剂上, 在453 K下合成气(CO+H_2)反应在红外谱图产生了1584 cm~(-1)谱带, 它与CO加氢反应中含氧化台物的生成速率成线性关系. 因此提出了此谱峰对应着在CO加氢反应中生成古氧化合物的一个十分重要的中间体. 以CO+D_2、~(13)CO+H_2和~(13)CO+D_2代替CO+H_2, 在Ru-Co/SiO_2催化剂中, 1584 cm~(-1)谱带分别位移至1575、1542和1539 cm~(-1)处. 还观察到, 1584 cm~(-1)物种与H_2反应, 产物给出了CH_4和CH_3OH; 如果1584 cm~(-1)物种和D_2反应则生成CHD_3和CHD_2OD. 这些结果提出了1584 cm~(-1)谱带归属于表面甲酰基的羰基振动, 这同Ru-Co/SiO_2催化剂吸附甲醛的结果基本一致.

关键词: Ru-Co双金属原子簇, 含氧化合物, CO加氢反应, 表面甲酰基

Abstract: The reaction and adsorption of syngas and paraformaldehyde on Ru-Co/SiO_2 ca-talysts prepared from Ru-Co bimetallic carbonyl clusters have been investigated by infrared, mass spectroscopies. The spectra of reaction of CO+H_2 with Ru-Co/SiO_2 catalysts showed a band appearing at 1584 cm~(-1), which has a good relationship to the activity and selectivity for oxygenates in CO hydrogenation. Thus it was proposed that 1584 cm~(-1) is a possible intermediate to produce oxygenated products. Isotopic tracer studies of D_2 and ~(13)CO suggest that 1584 cm~(-1) can possibly be assigned to the formyl group, which is in good agreement with the adsorption of paraformaldehyde. The chemical trapping of 1584 cm~(-1) adspecies provided an evidence to demonstrate that 1584 cm~(-1) is attributed to formyl. The reaction of 1584 cm~(-1) species with H_2 produced CH_4 and CH_3OH, and the introduction of D_2 into 1584 cm~(-1) species resulted in the formation of CHD_3 and CHD_2OD.

Key words: Ru-Co bimetallic carbonyl cluster, Oxygenates, CO hydrogenation, Surface formyl