N2O Adsorption and Photochemistry on Ceria Surfaces
N2O Adsorption and Photochemistry on Ceria Surfaces
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二氧化铈表面的 N2O 吸附和光化学
DOI：
10.1021/acs.jpcc.1c10181.s001
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发表时间：
2022-01
期刊：
影响因子：
--
通讯作者：
Christof Wöll
中科院分区：
文献类型：
--
作者：
Chengwu Yang;Yunjun Cao;Philipp N. Plessow;Jia Wang;Alexei Nefedov;Stefan Heissler;Felix Studt;Yuemin Wang;Hicham Idriss;Thomas G. Mayerhöfer;Christof Wöll
一氧化二氮（N2 O）是一种主要的臭氧层破坏物质，也是第三大温室气体，催化分解N2 O是控制N2 O排放的最有希望的方法之一。用偏振相关红外吸收光谱（IRRAS）、芯能级（XPS Ce 3d和NEXAFS）和价带（Ce 4f）谱以及密度泛函理论（DFT+U）计算研究了N2 O在宏观单晶CeO2（111）表面的吸附和光致分解. 110K时的IRRAS结果表明，N2O吸附态的ν as（NNO）不对称伸缩振动在较低的N2O覆盖度下，在p偏振光谱中出现带分裂.这种带分裂归因于吸收带的偏振相关移位。在还原的CeO2（111）表面上，IRRAS提取的N2O的脱附能（0.37eV）高于氧化表面。这种结合能的增加归因于从体相迁移的极化子与表面Ce4+还原形成的Ce3+阳离子的吸引耦合。通过IRRAS（5 × 10 − 19 cm 2）测定的还原CeO2（110）表面的光反应截面（在T = 120 K时，紫外（UV）光= 365 nm）证实了其比还原CeO2（111）高得多的活性。
: Catalytic decomposition of nitrous oxide (N 2 O) is one of the most promising ways to control N 2 O emissions, the dominant ozone depleting substance and the third most potent greenhouse gas. We have investigated the adsorption and photoinduced decomposition of N 2 O on macroscopic monocrystalline CeO 2 (111) surfaces by polarization dependent infrared re fl ection absorption spectroscopy (IRRAS) in conjunction with core level (XPS Ce 3d and NEXAFS) and valence band (Ce 4f) spectroscopy as well as DFT+U calculations. The IRRAS results at 110 K show that the ν as (NNO) asymmetric stretching vibration of adsorbed N 2 O exhibits band splitting at relatively low N 2 O coverage in p polarized spectra. This band splitting is attributed to polarization dependent shifts of absorption bands. On reduced ceria (111) surfaces, the desorption energy (0.37 eV) of N 2 O extracted by IRRAS is found to be higher than on oxidized surfaces. This increasing binding energy is attributed to the attractive coupling with Ce 3+ cations formed via surface Ce 4+ reduction by by polarons that migrate from the bulk. The photoreaction cross section (with ultraviolet (UV) light = 365 nm at T = 120 K) of the reduced ceria (110) surfaces determined by IRRAS (5 × 10 − 19 cm 2 ) con fi rms their much higher activity than that of the reduced CeO 2 (111).
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