分子氮的电催化还原

Electrocatalytic Reduction of Dinitrogen

对温和条件下分子氮的络合活化已有研究,但用修饰电极法电催化固氮成氨(或肼)尚未见报道,Shilov等曾发现在V(OH)_2-Mg(OH)_2的悬浮液中,V(Ⅱ)可起络合及还原作用,钒固氮酶在缺钼条件下也可活化分子氮,其活性中心可能与钼酶相似,也是通过有机硫配体而定位在蛋白质的肽链上,能否用含有机硫配体的钒表面配合物模拟钒酶,用电催化方法进行电子与能量的偶联从而固氮成氨?本文对此进行了研究。

Dinitrogen can be reduced to ammonia under the condition of controlled potential electrolysis in the presence of the chemically modified electrode containing vanadium surface complex in 0. 02 moI/L KCl/HOAc(pH4. 0) aqueous solution. The maximum current efficiency in the electrochemical reduction is 15% for the reduction of dinitrogen under the controlled potential electrolysis conditions (at -0.8 V vs SCE).