CAJ | 학술논문

采用石墨还原法成功制备了富氧相Ce2 Zr2 O8，选用缺氧相Nd2 Zr2 O7替代其前驱体CeZrO3．5＋δ进行结构对比分析，利用X射线衍射（XRD）、拉曼光谱（Raman）、红外光谱（IR）及X射线光电子能谱（XPS）对样品体、表晶体结构进行表征。XRD结果表明，Ce2 Zr2 O8相具有典型烧绿石结构特征，表征Ce／Zr 阳离子有序排列的超结构峰非常明显，但其Zr-O配位体由前驱体中的[ZrO6]八面体转变为[ZrO8]立方体，[ZrO8]配位体形成大大降低了Ce2 Zr2 O8的结构稳定性。Raman和IR结果表明，Ce2 Zr2 O8相的振动光谱谱带比其前驱体替代物Nd2 Zr2 O7显著增多，说明氧离子的富集导致Ce2 Zr2 O8相中某些振动简并峰消除简并，该结果进一步证实了其结构对称性较前驱体更低。XPS结果表明，Ce2 Zr2 O8相表面Ce（Ⅳ）特征峰（916．3 eV）非常明显，没有Ce（Ⅲ）特征峰（885 eV）出现，说明该相前驱体中的Ce3＋已被完全氧化成Ce4＋；Ce2 Zr2 O8相中Zr（3d）结合能与萤石相Gd1．2 U0．8 Zr2 O7＋y接近证实其表面形成了与体相一致的[ZrO8]配体；O（1s）低位结合能升高表明Ce2 Zr2 O8体相氧种介于晶格氧和吸附氧之间，高位氧峰出现说明其表面含有吸附氧，吸附氧与Ce2 Zr2 O8体相结合强度介于CeO2和Nd2 Zr2 O7之间。
채용석묵환원법성공제비료부양상Ce2 Zr2 O8，선용결양상Nd2 Zr2 O7체대기전구체CeZrO3．5＋δ진행결구대비분석，이용X사선연사（XRD）、랍만광보（Raman）、홍외광보（IR）급X사선광전자능보（XPS）대양품체、표정체결구진행표정。XRD결과표명，Ce2 Zr2 O8상구유전형소록석결구특정，표정Ce／Zr 양리자유서배렬적초결구봉비상명현，단기Zr-O배위체유전구체중적[ZrO6]팔면체전변위[ZrO8]립방체，[ZrO8]배위체형성대대강저료Ce2 Zr2 O8적결구은정성。Raman화IR결과표명，Ce2 Zr2 O8상적진동광보보대비기전구체체대물Nd2 Zr2 O7현저증다，설명양리자적부집도치Ce2 Zr2 O8상중모사진동간병봉소제간병，해결과진일보증실료기결구대칭성교전구체경저。XPS결과표명，Ce2 Zr2 O8상표면Ce（Ⅳ）특정봉（916．3 eV）비상명현，몰유Ce（Ⅲ）특정봉（885 eV）출현，설명해상전구체중적Ce3＋이피완전양화성Ce4＋；Ce2 Zr2 O8상중Zr（3d）결합능여형석상Gd1．2 U0．8 Zr2 O7＋y접근증실기표면형성료여체상일치적[ZrO8]배체；O（1s）저위결합능승고표명Ce2 Zr2 O8체상양충개우정격양화흡부양지간，고위양봉출현설명기표면함유흡부양，흡부양여Ce2 Zr2 O8체상결합강도개우CeO2화Nd2 Zr2 O7지간。
Pyrochlore-type oxygen-rich Ce2 Zr2 O8 phase was prepared successfully by graphite reduction method. With the oxy-gen[U8]-defective Nd2 Zr2 O7 substituting for the oxidized precursor phase CeZrO3. 5+δwas carried out the structure comparative analysis with Ce2 Zr2 O8. The X-ray diffraction (XRD),Raman spectroscopy (Raman),infrared spectroscopy (IR)and X-ray photoelectron spectroscopy (XPS)were used to characterize the crystal structure of samples. The XRD experimental results show that Ce2 Zr2 O8 bulk phase contains the typical structure of pyrochlore,the superstructure peaks that characterize Ce/Zr cations ordering arrangement are very obvious,but the Zr-O ligands had also transformed from octahedrons of the co-top connection in the precursor to cubes of co-edge connection in the Ce2 Zr2 O8 ,and the formation of [ZrO8 ]ligand reduced greatlly the structural stability of Ce2 Zr2 O8 phase. Raman and IR results show that vibrational spectra bands of Ce2 Zr2 O8 phase increased significantly, meaning that the enriched oxygen ions result in a removal of the degeneracy peak for Ce2 Zr2 O8 phase,which confirms further the structural symmetry of Ce2 Zr2 O8 phase lower than its precursor. XPS results show that Ce (Ⅳ)characteristic peak (9 1 6. 3 eV) in the Ce2 Zr2 O8 phase surface is very obvious. No the appearance of Ce (Ⅲ)peak (885 eV)suggests that Ce3+ from the precur-sor has been completely oxidized into Ce4+ in the Ce2 Zr2 O8 phase;the Zr (3d)binding energy is close to fluorite phase with Zr4+,which confirms that [ZrO8 ]ligand in the Ce2 Zr2 O8 surface is consistent with the bulk phase. The increasing low binding energy of O(1s)shows that oxygen species in the Ce2 Zr2 O8 bulk phase are between lattice oxygen and adsorbed oxygen,the presence of high oxygen peak suggests that the surface of Ce2 Zr2 O8 contains adsorbed oxygen,and the bonding strength between adsorption oxygen and Ce2 Zr2 O8 bulk phase is between CeO2 and Nd2 Zr2 O7.