钴基水滑石衍生物催化甲醛氧化活性成分的探究（英文）
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摘要
甲醛是一种常见的室内污染气体,可对人类健康产生极大危害.如何高效环保地去除甲醛已成为亟待解决的问题.催化氧化降解法去除甲醛由于其高效、持久、产物清洁环保而被广泛研究.催化氧化法要求催化剂在反应过程中具有良好的氧化还原特性,因此,一般采用拥有多重价态的过渡金属氧化物作为催化剂材料.近年来,钴氧化物由于拥有多种价态且来源广泛,被广泛用于催化领域.目前已有关于钴基氧化物改性方面的研究报道.此外,许多关于钴基氧化物活性机理的研究也开展.这些研究对新催化材料的合成具有十分重要的指导意义.本文通过在空气氛围和氮气氛围中对钴基水滑石进行煅烧,得到了不同的衍生材料.利用氢气程序升温还原、X射线光电子能谱(XPS)、高分辨透射电镜、扫描电镜、比表面分析及拉曼光谱等表征手段发现,在氮气氛围中煅烧的材料,其表面含有更多的八配位二价钴以及表面活性氧物种,更有利于在反应过程中氧化甲醛分子,并更容易解离空气中的氧气分子.此外,还利用原位红外光谱对反应过程进行了表征,由氮气煅烧得到的钴基材料在甲醛催化降解过程中遵循M-K机理,甲醛分子首先由表面活性氧物种(O_2~–,O~–)氧化为中间体亚甲二氧基(DOM),之后该中间体转化为甲酸盐物种,后者进一步分解生成最终产物H_2O和CO_2.在该过程中,甲酸盐分解为控速步骤.根据XPS和拉曼光谱的结果,氮气煅烧材料比空气煅烧材料含有更多的二价钴,且在甲醛催化降解实验中,氮气煅烧材料表现出更好的转化能力.二价钴通常被认为是惰性的,并不具备催化氧化甲醛的活性.然而在本体系中,氮气煅烧材料表面含有一种八配位的二价钴,该配位环境与传统的活性三价钴的配位环境相同.此外,该二价钴拥有更高的表面能且更容易与氧气接触.另一方面,氮气煅烧材料表面含有更多的表面活性氧物种,能够提高材料的氧化还原能力.因此我们推测,在本文体系中,氮气煅烧材料能够拥有更好的活性主要是由于存在Co~(2+)-O~–-Co~(3+)和Co~(2+)-O_2~–-Co~(3+)这两种成分.在利用原位红外表征手段对反应中间过程进行探究时,为了证明氧的重要作用,我们分别向催化剂表面通入甲醛+氮气和甲醛+氧气+氮气两种气流.结果显示,在有氧气参与的过程中,主要产物为甲酸盐和碳酸盐,而在没有氧气参与的过程中,在催化剂表面观察到DOM、碳酸盐、甲酸盐和甲醛的吸附峰.这说明有氧气参与时催化剂能够快速地将甲醛氧化,而在不通入氧气的情况下,DOM先快速生成,之后有甲酸盐生成.这说明氧气将甲醛先氧化为DOM,再进一步转化为甲酸盐.甲酸盐的分解较慢,不断累积,导致在氧气充足的情况下,依旧可以观察到材料表面大量的甲酸盐.因此,甲酸盐的分解为该体系的控速步骤.
A series of Co-based oxide catalysts were prepared by calcining hydrotalcite precursors in different atmospheres and studied for HCHO catalytic oxidation.The N_2-calcined catalyst exhibits enhanced HCHO oxidation and superior stability.On the basis of H_2-TPR,X-ray photoelectron spectroscopy,and Raman characterizations,this can be ascribed to better redox ability,octahedrally coordinated Co~(2+) ions derived from the CoO phase,and other surface oxygen species,such as O_2–or O–.The extra octahedrally coordinated Co~(2+) ions may reside in a more open framework site than the inactive tetrahedrally coordinated Co~(2+) ions.This species of Co2+can easily make contact with oxygen and oxidize.The surface oxygen species,along with the octahedrally coordinated Co~(2+) ions,and a part of the Co~(3+) species constitute the Co~(2+)-oxygen species-Co~(3+) sites,which enhance the catalytic activities.According to DRIFTS,Co~(2+)-oxygen species-Co~(3+) makes oxidation of HCHO and conversion of DOM to formate easier.
A series of Co-based oxide catalysts were prepared by calcining hydrotalcite precursors in different atmospheres and studied for HCHO catalytic oxidation.The N_2-calcined catalyst exhibits enhanced HCHO oxidation and superior stability.On the basis of H_2-TPR,X-ray photoelectron spectroscopy,and Raman characterizations,this can be ascribed to better redox ability,octahedrally coordinated Co~(2+) ions derived from the CoO phase,and other surface oxygen species,such as O_2–or O–.The extra octahedrally coordinated Co~(2+) ions may reside in a more open framework site than the inactive tetrahedrally coordinated Co~(2+) ions.This species of Co2+can easily make contact with oxygen and oxidize.The surface oxygen species,along with the octahedrally coordinated Co~(2+) ions,and a part of the Co~(3+) species constitute the Co~(2+)-oxygen species-Co~(3+) sites,which enhance the catalytic activities.According to DRIFTS,Co~(2+)-oxygen species-Co~(3+) makes oxidation of HCHO and conversion of DOM to formate easier.
引文
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