Preparation and Functions of Composits of Metal and Carbon which Contains unsaturated nitrogen-functionalities on its Surface.

本研究的目的是：(1)制备表面含有大量不饱和氮官能团的碳；(2)通过在碳表面分散高金属和金属配合物制备复合材料；(3)研究这些材料的功能及其作用机理。对表面含有大量不饱和氮官能团的碳和纤维碳的制备方法的研究表明，通过(1)聚丙烯腈的选择性脱氢和控制活化，可以制备出这种高氮官能团的碳并在一定程度上控制其含量；(2)用硫酸或二氧化硫联合活化，用氨水处理活性炭和活性炭纤维。特别是后一种方法值得注意，因为无论碳的种类如何，它都具有广泛的适用性。这些方法可以为表面改性提供更高稳定的氮官能团和其他方法无法获得的一些特性。发现这些碳在有或没有适当预处理的情况下表现出非常高的脱nox和脱sox的能力。这种能力比通常的活性炭大得多，因此需要进一步发展。对于金属和这些碳的复合材料，发现用非质子溶剂浸渍可以提供高分散的金属。以氯仿为溶剂制备的Cu和Fe复合材料具有良好的脱硝性能。贵金属复合材料还有望提供选择性氢化芳烃的能力，并提供更高的灰耐久性。这种表现已经被调查过了。虽然大环金属配合物与这些碳之间的加速相互作用尚未完全得到，但它们的催化能力得到了一些进展，增强相互作用的方法可以提供预期的性能。调查正在进行中。少

Objectives of this research are (1)preparation of carbons which contain large amounts of unsaturated nitrogen-functionalities on their surface, (2)preparation of composites by dispersing highly metals and metal-complexes on the carbon surface, and (3)investigation of functions of these materials and of mechanisms in such functions.Investigation of preparation methods for carbons and fibrous carbons which contain large amounts of unsaturated nitrogen-functionalities on the surface revealed that it is possible to prepare such highly nitrogen-functionality containing carbons and to control the contents to some extent by using (1)selective dehydrogenation of polyacrilonitrile and controling the activation, and (2)combination of activation with sulfuric acid or sulfur dioxide and treatment with ammonia against active carbons and active carbon fibers. Especially, the latter method is of value to note because of its wide applicability regardless of the kind of carbons. These methods can provi … More de highly stable nitrogen-functionalities and some characteristics which can not be obtained by other methods for the surface modification.These carbons were found to exhibit remarkably high abilitles for de-NOx and de-SOx of flue gas with or without proper pretreatment. Such abilities are much larger than those of usual active carbons, so that further developments should be required.With respect to composites of metal and these carbons, impregnation by using aprotic solvents was found to provide high dispersion of metals. Cu amd Fe composites which were prepared by using chloroform as a solvent can be expected to exhibit high abilities for de-NOx. Noble metals composites are also expected to provide abilities for selective hydrogenation of aromatic hydrocarbons and provide higher durability for ash. Such performances have been imvestigated. Although the expedted interaction between macrocyclic metal complexes and these carbons unfortunately were not obtained completely, some developments in their catalytic abilities were obtained and enhancing methods for the interaction can provide expected performances. The investigation has been in progress. Less