Surface Modification of Diamond by Organic Reactions for Preparation of Advanced Functional Devise

以2,2′-偶氮二异丁腈的无水氯仿溶液为自由基引发剂，硫酰氯为氯化剂，在323 K氩气氛下对氢化金刚石粉末进行了处理。氯化处理后，将溶液彻底蒸发，在不暴露于空气的情况下加入正丁胺。将处理后的金刚石粉末用四氢呋喃和水洗涤去除副产物，并通过红外光谱和闪蒸热解对其进行表征。结果表明，氢化后的金刚石表面在液相中发生了自由基修饰。用乙二胺、丙胺、三乙胺或苯乙胺均可得到类似的结果。氯化金刚石也分别用正丁基锂、叠氮化钠、甲氧基钠或乙氧基钠作为亲核试剂进行了处理。在金刚石表面形成丁基、叠氮基、甲氧基和乙氧基的方法未被FTIR和ESCA证实。这一结果可能是由于金刚石氯化作用不够。金刚石气相直接氯化是为了促进氯化后金刚石表面官能团与碳之间的共价键。

Hydrogenated diamond powder was treated with an anhydrous chloroform solution of 2, 2'-azobisisobutyronitrile as the radical initiator and sulfuryl chloride as the chlorination reagent at 323 K under an Ar atmosphere. After the chlorination process, the solution was exhaustively evaporated and n-butylamine was added without exposure to air. The diamond was then butylaminated at 303 K for 1-24 h. The treated diamond powder was washed with tetrahydrofuran and water to remove by-products, and characterized by infrared spectroscopy and flash pyrolysis. It could be confirmed that the hydrogenated diamond surface was modified by the radical reactions in the liquid phase. The similar results were obtained by using ethylenediamine, propylamine, triethylamine or phenethylamine.Chlorinated diamond was also treated with n-butyllithium, sodium azide, sodium methoxide or sodium ethoxide as the nucleophilic reagent. The formation of butyl, azide, methoxy and ethoxy groups on the diamond surface was not confirmed with FTIR and ESCA.The results might be due to the insufficient chlorination of diamond. Direct chlorination of diamond in the gas phase is carried out for the promoting covalent bonds between functional groups and carbon on the chlorinated diamond surface.