二氧化铈-铈掺杂锰氧化物纳米复合物高效紫外-可见-红外光热催化净化乙酸乙酯

doi:10.1016/S1872-2067(21)63816-0

摘要/Abstract

摘要：

乙酸乙酯是一种重要的有机溶剂, 广泛应用于涂料、粘合剂和塑料及石化等工业生产, 但作为一种主要的挥发性有机污染物(VOCs), 其对大气环境造成严重污染. 目前工业上主要采用负载型贵金属催化剂催化燃烧的方法进行净化处理, 但该方法存在催化剂价格昂贵和能耗高的问题, 迫切需要开发活性高、稳定性好、成本低及能耗小的催化新方法和新材料.
本文以硝酸铈和高锰酸钾为原料制备了二氧化铈和具有隐钾锰矿结构的铈掺杂纳米复合物(CeO₂-CeOMS-2). 该纳米复合物在紫外-可见-红外光照射下对乙酸乙酯具有极高的光热催化活性、很低的乙醛(副产物)选择性以及较好的催化稳定性, 在光照下持续反应45 h, 乙酸乙酯的转化率仍然稳定在90%左右; 而纳米CeO₂, OMS-2以及纳米TiO₂(P25)光热催化活性很低, 且乙醛选择性较高. CeO₂-CeOMS-2初始5 min CO₂生成速率高达1102.5 μmol g ^-1 min ^-1, 分别是纳米CeO₂, OMS-2和P25的137, 17和30倍. CeO₂-CeOMS-2在波长大于420和560 nm的可见-红外光照射下也具有良好的光热催化活性, 甚至在波长大于830 nm的红外光照射下仍具有较好的光热催化活性. 同位素标记、程序升温还原以及拉曼光谱实验结果表明, CeO₂-CeOMS-2的催化活性远高于CeO₂和OMS-2的主要是由于铈掺杂显著提高了OMS-2的晶格氧活性. 乙酸乙酯在CeO₂-CeOMS-2催化剂上被 ¹⁸O₂氧化的FTIR光谱结果表明, 其在CeO₂-CeOMS-2上的催化氧化遵循Mars-van-Krevelen氧化还原机理, CeO₂的光催化与铈掺杂OMS-2的光致热催化之间存在协同作用, 显著提高了催化活性. CeO₂-CeOMS-2还存在与常规半导体光催化不同的光活化效应, 进一步提高了其催化活性.

关键词: 光催化, 光热催化, 挥发性有机污染物, 乙酸乙酯氧化, 锰氧化物

Abstract:

A unique nanocomposite of CeO₂nanoparticles and Ce-doped manganese oxide nanofibers having a crystalline cryptomelane-type octahedral molecular sieve (KMn₈O₁₆·nH₂O, abbreviated as OMS-2) structure (denoted CeO₂-CeOMS-2) was prepared by the reaction of Ce(NO₃)₃and KMnO₄ at 90 °C. CeO₂-CeOMS-2 shows extremely high photothermocatalytic activity, very low selectivity for acetaldehyde (an unfavorable byproduct), and excellent durability for ethyl acetate removal under UV-visible-infrared (UV-vis-IR) irradiation. In striking contrast, pure CeO₂, pure OMS-2, and TiO₂ (P25) showed much lower photothermocatalytic activities and higher selectivities for acetaldehyde. The CO₂ production rate within the first five minutes (r_CO2) of reaction with CeO₂-CeOMS-2 was as high as 1102.5 μmol g ^-1 min ^-1, which is 137, 17, and 30-times higher than those of pure CeO₂, pure OMS-2, and TiO₂ (P25), respectively. CeO₂-CeOMS-2 also shows good photothermocatalytic activity under vis-IR (λ > 420 or 560 nm) irradiation. Further, even under vis-IR (λ > 830 nm) irradiation, efficient photothermocatalytic activity was achieved. In addition, the catalytic activity of CeO₂-CeOMS-2 is far superior to those of pure CeO₂ and OMS-2, which is attributed to the fact that Ce doping significantly improves the lattice oxygen activity of OMS-2. The high photothermocatalytic activity of CeO₂-CeOMS-2 arises from the synergy between the photocatalytic effect of the CeO₂ nanoparticles and light-driven thermocatalysis of the Ce-doped OMS-2. The novel photoactivation of Ce-doped OMS-2, which is unlike that of conventional photocatalysis on semiconductor photocatalysts, further promotes the catalytic activity because the surface oxygen activity of Ce-doped OMS-2 is promoted upon UV-vis-IR or vis-IR (λ > 560 nm) irradiation.

Key words: Photocatalysis, Photothermocatalytis, Volatile orgamic compound, Ethylacetate oxidation, Manganese oxides

张龙, 杨懿, 李远志, 武继春, 吴绍文, 谭鑫, 胡倩倩. 二氧化铈-铈掺杂锰氧化物纳米复合物高效紫外-可见-红外光热催化净化乙酸乙酯[J]. 催化学报, 2022, 43(2): 379-390.

Long Zhang, Yi Yang, Yuanzhi Li, Jichun Wu, Shaowen Wu, Xin Tan, Qianqian Hu. Highly efficient UV-visible-infrared photothermocatalytic removal of ethyl acetate over a nanocomposite of CeO₂and Ce-doped manganese oxide[J]. Chinese Journal of Catalysis, 2022, 43(2): 379-390.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63816-0

https://www.cjcatal.com/CN/Y2022/V43/I2/379

图/表 11

Fig. 1. XRD patterns of CeO2-CeOMS-2 (1), OMS-2 (2), and CeO2 (3).

Fig. 2. TEM image (a), high-resolution (HR)TEM image of nanoparticle (b), and nanofiber (c) of CeO2-CeOMS-2.

Fig. 3. Mn 2p (a), Mn 3s (b), and Ce 3d (c) XPS spectra of CeO2-CeOMS-2.

Fig. 4. Ethyl acetate conversion (a) and acetaldehyde selectivity (b) with time, and initial CO2 production rate (c) of the catalysts under UV-vis-IR irradiation; Long-term photothermocatalytic ethyl acetate oxidation over CeO2-CeOMS-2 under UV-vis-IR irradiation (d).

Fig. 5. Ethyl acetate conversion (a) and acetaldehyde selectivity (b) with time, and CO2 production rate (c) of CeO2-CeOMS-2 under vis-IR and IR irradiation.

Fig. 6. (a) Optical absorption spectra of the catalysts; (b) Photocatalytic activity of CeO2-CeOMS-2 for ethyl acetate oxidation under UV-vis-IR irradiation at near room temperature; The equilibrium temperature (Teq) values of the catalysts under UV-vis-IR irradiation (c) and CeO2-CeOMS-2 under vis-IR and IR irradiation (d).

Fig. 7. Ethyl acetate conversion (a), acetaldehyde selectivity (b), and CO2 yield (c) of the catalysts for thermocatalytic oxidation of ethyl acetate at different temperatures in the dark.

Fig. 8. FTIR spectra obtained during the course of ethyl acetate oxidation over CeO2-CeOMS-2 at 200 °C in the presence of 18O2 (a) and that measured in the presence of 16O2 at 200 °C over the used CeO2-CeOMS-2 sample obtained after the 18O2 isotope experiment (b). Note: The peak corresponding to C16O2 around 2341 cm-1 is overlapped with that of C16O18O at around 2343 cm-1.

Fig. 9. CO-TPR profiles (a) and Raman spectra (b) of CeO2-CeOMS-2, OMS-2, and CeO2.

Fig. 10. Ethyl acetate reaction rates for catalytic ethyl acetate oxidation on CeO2-CeOMS-2 at different temperatures (a) and temperature-programmed reduction of CeO2-CeOMS-2 in the presence of ethyl acetate and the absence of O2 (b) in the dark and under the irradiation of UV-vis-IR and vis-IR (λ > 560 nm).

Scheme 1. Schematic of the synergy between photocatalysis on nano-CeO2, light-driven thermocatalysis on CeO2-CeOMS-2, and photoactivation.

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