本文以具有重要催化应用前景的Ni/CeO2体系为例，借助17O固体核磁共振波谱技术，根据表面氧物种17O NMR信号的变化，尝试分析了Ni/CeO2表面层中镍离子的含量.分析结果显示，10% NiCe-500和20% NiCe-300两种Ni/CeO2样品表面第一和第二金属离子层中Ni离子的含量分别位于9%~17%和8%~15%范围内.这一方法或可推广至研究其它一系列顺磁掺杂氧化物的表面掺杂含量.
王杨
,
杨昌菊
,
温玉洁
,
陈俊超
,
杜佳欢
,
彭路明
. 利用17O固体核磁共振波谱分析Ni/CeO2表面镍离子含量[J]. 波谱学杂志, 2020
, 37(1)
: 52
-60
.
DOI: 10.11938/cjmr20192765
With Ni/CeO2 as an example, which has important applications in catalysis, 17O solid-state nuclear magnetic resonance (NMR) spectroscopy was applied to explore and analyze the concentration of surface Ni ions, according to the changes in the 17O NMR intensity of surface oxygen ions. The results indicate that the Ni concentrations in the first and second top metal ion layers in 10% NiCe-500 and 20% NiCe-300 are within the ranges of 9%~17% and 8%~15%, respectively. This approach may be extended to study the concentration of the doped paramagnetic elements in the surface for a variety of doped oxide materials.
[1] ZIELIŃSKI M, WOJCIECHOWSKA M. Studies of new magnesium fluoride supported nickel catalysts for toluene hydrogenation[J]. Catal Today, 2011, 169(1):175-180.
[2] GONG M, LI Y G, WANG H L, et al. An advanced Ni-Fe layered double hydroxide electrocatalyst for water oxidation[J]. J Am Chem Soc, 2013, 135(23):8452-8455.
[3] VAIDYA P D, RODRIGUES A E. Insight into steam reforming of ethanol to produce hydrogen for fuel cells[J]. Chem Eng J, 2006, 117(1):39-49.
[4] DU X J, ZHANG D S, SHI L Y, et al. Morphology dependence of catalytic properties of Ni/CeO2 nanostructures for carbon dioxide reforming of methane[J]. J Phys Chem C, 2012, 116(18):10009-10016.
[5] THEOFANIDIS S A, GALVITA V V, POELMAN H, et al. Enhanced carbon-resistant dry reforming Fe-Ni catalyst:role of Fe[J]. ACS Catal, 2015, 5(5):3028-3039.
[6] BARRIO L, KUBACKA A, ZHOU G, et al. Unusual physical and chemical properties of Ni in Ce1-xNixO2-y oxides:structural characterization and catalytic activity for the water gas shift reaction[J]. J Phys Chem C, 2010, 114(29):12689-12697.
[7] ZHOU G, BARRIO L, AGNOLI S, et al. High activity of Ce1-xNixO2-y for H2 production through ethanol steam reforming:tuning catalytic performance through metal-oxide interactions[J]. Angew Chem Int Ed Engl, 2010, 49(50):9680-9684.
[8] LIU Z Y, GRINTER D C, LUSTEMBERG P G, et al. Dry reforming of methane on a highly-active Ni-CeO2 catalyst:effects of metal-support interactions on C-H bond breaking[J]. Angew Chem Int Ed Engl, 2016, 55(26):7455-7459.
[9] LI D B, XU S, YU Z W. Application of solid-state NMR to bone and bone biomaterials[J]. Chinese J Magn Reson, 2017, 34(1):115-129. 李东北,许帅, 喻志武. 固体核磁共振技术在骨基生物材料研究中的应用[J]. 波谱学杂志, 2017, 34(1):115-129.
[10] XU X J, WANG S L. Probing membrane protein interactions by 19F solid-state NMR[J]. Chinese J Magn Reson, 2019, 36(2):238-251. 徐小俊, 王申林. 19F固体核磁共振技术研究膜蛋白相互作用的进展[J]. 波谱学杂志, 2019, 36(2):238-251.
[11] SHEN L, PENG L M. 17O solid-state NMR studies of oxygen-containing catalysts[J]. Chin J Catal, 2015, 36(9):1494-1504.
[12] DU J H, PENG L M. Recent progress in investigations of surface structure and properties of solid oxide materials with nuclear magnetic resonance spectroscopy[J]. Chinese Chem Lett, 2018, 29(6):747-751.
[13] SHEN L, WU X P, WANG Y, et al. 17O solid-state NMR studies of ZrO2 nanoparticles[J]. J Phys Chem C, 2019, 123(7):4158-4167.
[14] LI Y H, WU X P, JIANG N X, et al. Distinguishing faceted oxide nanocrystals with 17O solid-state NMR spectroscopy[J]. Nat Commun, 2017, 8(1):581.
[15] WANG M, WU X P, ZHENG S J, et al. Identification of different oxygen species in oxide nanostructures with 17O solid-state NMR spectroscopy[J]. Sci Adv, 2015, 1(1):e1400133.
[16] MAI H X, SUN L D, ZHANG Y W, et al. Shape-selective synthesis and oxygen storage behavior of ceria nanopolyhedra, nanorods, and nanocubes[J]. J Phys Chem B, 2005, 109(51):24380-24385.
[17] HOPE M A, HALAT D M, MAGUSIN P C, et al. Surface-selective direct 17O DNP NMR of CeO2 nanoparticles[J]. Chem Commun (Camb), 2017, 53(13):2142-2145.
[18] HALAT D M, DERVIŞOĞLU R, KIM G, et al. Probing oxide-ion mobility in the mixed ionic-electronic conductor La2NiO4+δ by solid-state 17O MAS NMR spectroscopy[J]. J Am Chem Soc, 2016, 138(36):11958-11969.
[19] HALAT D M, DUNSTAN M T, GAULTOIS M W, et al. Study of defect chemistry in the system La2-xSrxNiO4+δ by 17O solid-state NMR spectroscopy and Ni K-edge XANES[J]. Chem Mater, 2018, 30(14):4556-4570.
