5-羟甲基糠醛在CuPd(111)上的加氢反应机理研究

Study on the mechanism of hydrogenation reaction of 5-hydroxymethyl furfural on CuPd(111)

采用密度泛函理论,利用包含零点能校正的PBE-D3方法研究了5-羟甲基糠醛在双金属催化剂CuPd(111)上表面的加氢还原反应,考虑了两种反应路径,第一种反应路径是侧链上的醛基氧首先发生加氢反应生成F-CHOH中间体,然后F-CHOH中间体继续加氢生成2,5-二羟甲基呋喃;第二种反应路径是侧链上的醛基碳先加氢原还原生成F-CH_(2)O中间体,生成的F-CH_(2)O进一步加氢还原生成2,5-二羟甲基呋喃.计算了两种竞争反应路径的活化能垒和反应热,结果表明,5-羟甲基糠醛在CuPd(111)面加氢还原生成2,5-二羟甲基呋喃的最佳反应路径为:F-CHO→F-CHOH→F-CH_(2)OH.

The hydrogenation-reduction reaction of 5-hydroxymethylfurfural on CuPd(111)surface was investigated by using the PBE-D3 method including zero-point energy corrections under density functional theory method.Two reaction paths were studied,the first reaction path begins with hydrogen addition to the oxygen atom of the aldehyde group to generate F-CHOH intermediate,followed by an addition of a hydrogen atom to F-CHOH to form 2,5-dimethylolfuran;the second reaction path is that the branched carbon on the aldehyde group is first hydrogenated to form the F-CH_(2)O intermediate,and the resulting F-CH_(2)O is further hydrogenated to produce 2,5-dihydroxymethylfuran.The activation energy barriers and reaction heats of the two competitive reaction paths were computed,and the results show that the best reaction path for the hydrogenation of 5-hydroxymethyl furfural to 2,5-dihydroxymethylfuran on the CuPd(111)surface is:F-CHO→F-CHOH→F-CH_(2)OH.