氧化锌纳米管论文氧化锌纳米管分解H2S,H2O制氢的密度泛函理论研究.docVIP

氧化锌纳米管论文：氧化锌纳米管分解H_2S，H_2O制氢的密度泛函理论研究 【中文摘要】作为一种宽禁带直接半导体,氧化锌在很多领域具有广泛的应用前景。尤其是金属氧化物(包括氧化锌)纳米管具有孔结构和较高比表面积,因此活性组分可以比较均匀的分布在金属氧化物纳米管表面上,负载在纳米管的内部,这会导致催化剂具有一些独特的性质。我们研究了钯(Pd)纳米团簇在ZnO (5, 5) SWNTs外的粘附,三种小分子气体(O2, H2和CO)在完美的ZnO (5, 5), Pd/ZnO SWNTs上的吸附几何性质,并以O2的吸附为例讨论了其电子性质。Pdn(n=1-6)纳米团簇粘附在ZnO (5, 5)的纳米管上主要通过Pd-O键的相互作用。Pd单体在氧化锌外部和内部具有相同的粘附性质。三种小分子气体吸附在完美的氧化锌纳米管内部和外部的吸附能是相似的。当氧气吸附在负载了Pd1氧化锌内部时,不仅仅氧气的吸附能增大了0.16 eV而且吸附位置由在Pd1/ZnO SWNTs体系外面时的顶位变为桥位。我们用密度泛函理论研究了硫化氢(H2S)及产物水在ZnO纳米管和ZnO- ZnS纳米管上的吸附和反应以及S, HS,和H的吸附机理。H2S, HS, S和H分别吸附在Zn的顶位上, Zn-Zn的桥为上,Zn-O的桥位上和O位上。用NEB的方法描绘了H2O在ZnO- ZnS纳米管上的是可能的反应路径势能图。在完美的氧化锌纳米管上生成水需要的反应能垒为40.56 kcal/mol,而在氧化锌-硫化锌纳米管上则只需要14.45kcal/mol。在完美的氧化锌纳米管上生成氢气需要的反应能能垒为88.65 kcal/mol,比在纳米管异质结上的反应能能垒小4.58 kcal/mol。水在纳米管异质结上的解离过程中,水中的氧穿过纳米管,在异质结纳米管内部形成氧气。 【英文摘要】As one kind of wide direct band-gap semiconductor, ZnO has potential applications in several fields. Especially, due to metal oxide nanotube (included ZnO) has the hollow structure and high surface-volume ratio, the active species can distribute on the surface uniformly and locate inside the nanotubes, which leads to novel catalytic properties.We investigated the adhesion of Pd nanoclusters on ZnO (5, 5) and adsorption of probe gas molecules (O2, H2 and CO) on the outside or inside wall of ZnO and Pd1/ZnO SWNTs by means of density functional theory calculations in this study. Our study shows that the binding of Pd clusters on ZnO is mainly via the Pd-O bond interaction. The Pd monomer has the same adhesion ability on both the outside and the inside wall of ZnO SWNTs. However, we found that the adsorption energy of O2 is larger on the inside wall of ZnO and Pd1/ZnO SWNTs than that on the outside one, which is caused by the confinement effect.We further investigated the adsorption and dissociation of H2S on ZnO and ZnO- ZnS SWNTs. It was found that H2S, HS, S, and H preferentially adsorb at the Zn, bridge of Zn- Zn, bridge of Zn-O and O sites, respectively. The potential energy profiles for H2O splitt