新型双功能Cu(Ⅰ)/沸石羰基化催化剂的制备与表征  

PREPARATION AND CHARACTERIZATION OF A NEW TYPE OF BIFUNCTIONAL Cu(Ⅰ)/ZEOLITE CARBONYLATION CATALYST

作　　者：施其宏[1] 赵修华[1] 张佐良[2] 梁瑜[2] 朱起明[2] 

机构地区：[1]汕头大学科学院,汕头515063 [2]清华大学化学系一碳化工国家重点实验室,北京100084

出　　处：《催化学报》1999年第2期125-128,共4页

基　　金：国家自然科学基金!(2967025);广东省自然科学基金!(950823)资助

摘　　要：报道了双功能Ｃｕ（ Ⅰ）／ 沸石羰基化催化剂的制备及其ＦＴＩＲ 和ＸＰＳ表征结果． 催化剂兼具酸性和金属羰基两类活性中心，能够在较温和的条件（ ～５２３ Ｋ， 常压） 下催化醇与ＣＯ的羰基化合成反应． 以异丁醇为原料时，其Ｃ５ 羧酸和异戊酸异丁酯的总收率可达２０－４ ％ ． 催化剂的ＸＰＳ和ＩＲ表征结果证实，铜以Ｃｕ（ Ⅰ） 价态存在，吸附ＣＯ后，形成金属羰基活性中心Ｃｕ（ＣＯ） ＋２ ． 可能的反应机理是： 母体沸石Ｈβ或ＨＺＳＭ５ 中的酸性中心使醇质子化，形成碳正离子，随后邻近的金属羰基中心Ｃｕ（ＣＯ）＋２ 提供ＣＯ， 协同催化使之生成羧酸或最后转变为羧酸酯．The preparation of a bifunctional Cu(Ⅰ)/zeolite carbonylation catalyst as well as its FT IR and XPS characterization results are described for the first time. This catalyst possesses both acid and metal carbonyl active sites and catalyzes successfully the synthesis of carbonyl compound from alcohol and CO under mild conditions (～523 K and 0 1 MPa). The total yield 20 4% of both carboxylic acids and carboxylic esters could ve reached when i butanol was used as starting material. It is demonstrated by IR and XPS characterization that the copper exists in Cu(Ⅰ) and from which the metal carbonyl active site of Cu(CO) + 2 is formed by CO adsorption. The alcohol is protonized at acidic sites of the parent zeolites HZSM 5 or Hβ, so that the carbonium ion is formed, then the carboxylic acids are synthesized or the carboxylic esters are finally produced by cooperative catalysis of the adjacent metal carbonyl sites from which the CO is supplied.

关 键 词：沸石 异丁醇 羰基化 双功能 催化剂 铜 

分 类 号：O643.36[理学—物理化学] TQ426.94[理学—化学]