论文标题
HXWO3中的质子极性子通过同步光发射和DFT建模
Proton polarons in HxWO3 by synchrotron photoemission and DFT modelling
论文作者
论文摘要
X射线光电子光谱法对氢诱导的过渡金属氧化物电子结构的测量是一项艰巨的努力,因为光电子的起源不能明确分配给氢。 H诱导的三氧化钨的电子结构变化已有100多年了,但仍引起争议。争议源于由于氧不足的影响而导致的解剖作用的困难。使用X射线光电子光谱的膜方法,与可调的同步子辐射结合使用,我们同时测量核心水平和价带至1000 MBAR的氢压。氢化后,W $^{5+} $核心水平的强度和接近Fermi水平的状态在压力组合等温线曲线后增加,g $ _x $ _x $ wo $ _3 $。结合实验数据和密度功能理论,通过质子极性模型对氢诱导着色的描述得到了证实。尽管氢是电子结构在费米边缘附近发生变化的起源,但现在的价带边缘由钨轨道而不是氧气主导,而不是原始氧化物的情况,对其作为(光电化学)催化剂的使用具有更大的影响。
The measurement of hydrogen induced changes on the electronic structure of transition metal oxides by X-ray photoelectron spectroscopy is a challenging endeavor, since the origin of the photoelectron cannot be unambiguously assigned to hydrogen. The H-induced electronic structure changes in tungsten trioxide have been known for more than 100 years, but are still being controversially debated. The controversy stems from the difficulty in disentangling effects due to hydrogenation from the effects of oxygen deficiencies. Using a membrane approach to X-ray photoelectron spectroscopy, in combination with tuneable synchrotron radiation we measure simultaneously core levels and valence band up to a hydrogen pressure of 1000 mbar. Upon hydrogenation, the intensities of the W$^{5+}$ core level and a state close to the Fermi level increase following the pressure-composition isotherm curve of bulk H$_x$WO$_3$. Combining experimental data and density-functional theory the description of the hydrogen induced coloration by a proton polaron model is corroborated. Although hydrogen is the origin of the electronic structure changes near the Fermi edge, the valence band edge is now dominated by tungsten orbitals instead of oxygen as is the case for the pristine oxide having wider implication for its use as (photo-electrochemical) catalyst.