MoO3和Nb2O5助剂对Pt/ZrO2催化剂上短链烷烃燃烧反应的不同促进作用

doi:10.1016/S1872-2067(20)63771-8

催化学报 ›› 2021, Vol. 42 ›› Issue (12): 2287-2295.DOI: 10.1016/S1872-2067(20)63771-8

MoO₃和Nb₂O₅助剂对Pt/ZrO₂催化剂上短链烷烃燃烧反应的不同促进作用

岑丙横, 汤岑, 鲁继青, 陈建^#(), 罗孟飞^*()

浙江师范大学物理化学研究所,先进催化材料教育部重点实验室,浙江省固体表面反应化学重点实验室, 浙江金华321004

收稿日期:2020-12-23 接受日期:2020-12-23 出版日期:2021-12-18 发布日期:2021-01-31
通讯作者: 陈建,罗孟飞
基金资助:
国家自然科学基金面上项目(21872124);国家自然科学基金面上项目(22072137)

Different roles of MoO₃ and Nb₂O₅ promotion in short-chain alkane combustion over Pt/ZrO₂ catalysts

Bingheng Cen, Cen Tang, Jiqing Lu, Jian Chen^#(), Mengfei Luo^*()

Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua 321004, Zhejiang, China

Received:2020-12-23 Accepted:2020-12-23 Online:2021-12-18 Published:2021-01-31
Contact: Jian Chen,Mengfei Luo
About author:# E-mail: jianchen@zjnu.cn
* E-mail: mengfeiluo@zjnu.cn;
Supported by:
National Natural Science Foundation of China(21872124);National Natural Science Foundation of China(22072137)

摘要/Abstract

摘要：

贵金属Pt催化剂具有高活性和热稳定性, 广泛应用于催化挥发性有机物的完全氧化反应(燃烧反应). 短链烷烃(甲烷、乙烷、丙烷等)化学性质稳定, 是最难氧化的一类有机物, 常用作考察燃烧反应催化剂性能的模型反应物. 然而, 目前报道的研究工作通常仅限于针对某一种烷烃底物的催化燃烧, 系统考察催化剂以及助剂对不同短链烷烃的催化燃烧活性鲜有报道. 在短链烷烃中, 甲烷只有C-H键; 而其它烷烃除了C-H键; 还有C-C键. 因此, 研究催化剂对甲烷、乙烷和丙烷燃烧反应催化性能的差异性, 对于认识催化剂上C-H键和C-C键的活化具有非常重要的意义.

本文制备了MoO₃或Nb₂O₅修饰的Pt/ZrO₂催化剂并用于短链烷烃的燃烧反应. 研究发现, MoO₃助剂对甲烷燃烧有明显的抑制作用, 但对乙烷, 丙烷和正己烷燃烧反应具有促进作用, 促进作用随着烷烃碳链的增长逐渐增加; Nb₂O₅助剂对甲烷、乙烷、丙烷和正己烷燃烧反应均具有促进作用, 然而促进作用随着碳链的增长而逐渐减弱. MoO₃和Nb₂O₅助剂的不同促进作用与助剂影响催化剂表面酸性以及Pt物种的氧化或还原态有关. NH₃-TPD结果表明, MoO₃助剂可以显著增加Pt/ZrO₂催化剂表面强酸位点数量, 而Nb₂O₅助剂可以显著增加Pt/ZrO₂催化剂表面中强酸位点数量. HTEM结果表明, 两种助剂的添加都不会明显改变Pt物种的颗粒尺寸. 在Pt-Mo/ZrO₂催化剂上, MoO₃覆盖部分Pt物种形成丰富的Pt-MoO₃界面, 促进了金属Pt物种和强表面酸性位点的生成, 提高了丙烷燃烧反应活性; Pt-Nb/ZrO₂催化剂上载体表面的部分Nb₂O₅被Pt物种包覆, 使得生成的表面Pt-Nb₂O₅界面低于Pt-Mo/ZrO₂催化剂, 但由于催化剂表面酸性位的提升, 也促进了丙烷燃烧反应活性的提高. XPS结果表明, 在甲烷燃烧反应中, Pt-Nb/ZrO₂催化剂上Ptⁿ⁺物种能够更加稳定地存在, 这可能是Nb₂O₅助剂提高Pt-Nb/ZrO₂催化剂上甲烷燃烧活性的关键. 而Pt-Mo/ZrO₂催化剂上Ptⁿ⁺物种在甲烷反应中可以更容易地被还原, 并且由于MoO₃的包裹导致暴露的Pt位点数量降低, 使催化剂催化甲烷燃烧的活性受到抑制. 可见, MoO₃助剂更有利于C-C键活化, 而Nb₂O₅助剂更有利于高键能的C-H键活化.

综上, 本文系统性地研究MoO₃助剂和Nb₂O₅助剂对Pt/ZrO₂催化剂上不同短链烷烃的燃烧反应的影响, 证实了两种助剂的促进作用与碳链长度的关系是截然不同的.

关键词: Pt/ZrO₂催化剂, 烷烃燃烧, MoO₃助剂, Nb₂O₅助剂, 活性位点

Abstract:

Pt/ZrO₂ catalysts promoted with MoO₃ and Nb₂O₅ were tested for the combustion of short-chain alkanes (namely, methane, ethane, propane, and n-hexane). For short-chain alkane combustion, the inhibition of MoO₃ (for the methane reaction) dramatically transformed to promotion (for the ethane, propane, and n-hexane reactions) as the carbon chain length increased, whereas the remarkable promotion of Nb₂O₅ gradually weakened with an increase in the carbon chain length. Based on a detailed study of the oxidation reactions of methane and propane over the catalysts, the different roles of the promoters in the reactions were ascribed to differences in the acidic properties of the surface and the oxidation or reduction states of the Pt species. The MoO₃ promoter could decorate the surface of the Pt species for a Pt-Mo/ZrO₂ catalyst, whereas the Nb₂O₅ promoter on the support could be partially covered by Pt particles for a Pt-Nb/ZrO₂ catalyst. The formation of accessible Pt-MoO₃ interfacial sites, a high concentration of metallic Pt species, and a high surface acidity in Pt-Mo/ZrO₂ were responsible for the enhanced activity for catalytic propane combustion. The lack of enough accessible Pt-Nb₂O₅ interfacial sites but an enhanced surface acid sites in Pt-Nb/ZrO₂ explained the slight improvement in activity for catalytic propane combustion. However, the stabilized Ptⁿ⁺ species in Pt-Nb/ZrO₂ were responsible for the much-improved activity for methane combustion, whereas the Ptⁿ⁺ species in Pt-Mo/ZrO₂ could be reduced during the oxidation reaction, and the fewer exposed surface Pt species because of MoO₃ decoration accounted for the inhibited activity for methane combustion. In addition, it can be concluded that MoO₃ promotion is favorable for the activation of C-C bonds, whereas Nb₂O₅ promotion is more beneficial for the activation of C-H bonds with high energy.

Key words: Pt/ZrO₂ catalyst, Alkanes combustion, MoO₃ promoter, Nb₂O₅ promoter, Active site

岑丙横, 汤岑, 鲁继青, 陈建, 罗孟飞. MoO₃和Nb₂O₅助剂对Pt/ZrO₂催化剂上短链烷烃燃烧反应的不同促进作用[J]. 催化学报, 2021, 42(12): 2287-2295.

Bingheng Cen, Cen Tang, Jiqing Lu, Jian Chen, Mengfei Luo. Different roles of MoO₃ and Nb₂O₅ promotion in short-chain alkane combustion over Pt/ZrO₂ catalysts[J]. Chinese Journal of Catalysis, 2021, 42(12): 2287-2295.

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图/表 12

Fig. 1. XRD patterns of Pt/ZrO2, Pt-Mo/ZrO2, and Pt-Nb/ZrO2 catalysts.

Fig. 2. TEM images (a-c) and particle size distributions (d-f) of Pt/ZrO2 (a,d), Pt-Mo/ZrO2 (b,e), and Pt-Nb/ZrO2 (c,f) catalysts.

Fig. 3. Raman spectra of Pt/ZrO2, Pt-Mo/ZrO2, and Pt-Nb/ZrO2 catalysts.

Fig. 4. NH3-TPD profiles of Pt/ZrO2, Pt-Mo/ZrO2, and Pt-Nb/ZrO2 catalysts.

Fig. 5. DRIFT spectra of CO adsorption on Pt/ZrO2, Pt-Mo/ZrO2, and Pt-Nb/ZrO2 catalysts at 25 °C.

Fig. 6. Catalytic activity of methane and propane combustion over the Pt/ZrO2, Pt-Mo/ZrO2, and Pt-Nb/ZrO2 catalysts and the Mo/ZrO2 and Nb/ZrO2 supports (C1 = methane, C3 = propane).

Table 1 CO chemisorption, speciﬁc reaction rates, and turnover frequencies (TOFs) of Pt/ZrO2, Pt-Mo/ZrO2, and Pt-Nb/ZrO2 catalysts.

Catalyst	Pt content (wt.%)	Pt dispersion^a (%)	CO uptake^a (μmol g_pt^-1)	Speciﬁc reaction rate^b (μmol g_Pt^-1 s^-1)		TOF (×10^-3 s^-1) ^c
Catalyst	Pt content (wt.%)	Pt dispersion^a (%)	CO uptake^a (μmol g_pt^-1)	methane	propane	methane	propane
Pt/ZrO₂	2.1	30.0	30.7	45.9	15.9	29.4	10.2
Pt-Mo/ZrO₂	2.0	22.5	23.0	21.6	44.2	18.1	37.1
Pt-Nb/ZrO₂	2.0	31.4	32.2	96.6	19.0	57.4	11.3

Fig. 7. Stability tests of Pt/ZrO2, Pt-Mo/ZrO2, and Pt-Nb/ZrO2 catalysts at different temperatures for propane (0.2% C3H8 + 2% O2 + 97.8% N2, S.V. = 20000 h-1).

Fig. 8. Pt 4f XPS spectra of Pt/ZrO2, Pt-Mo/ZrO2, and Pt-Nb/ZrO2 catalysts.

Table 2 Analysis of Pt species content on fresh and spent catalyst surfaces.

Catalyst	Fresh catalyst (%)			After methane combustion ^a(%)			After propane combustion ^b(%)
Catalyst	Pt⁰	Pt²⁺	Pt⁴⁺	Pt⁰	Pt²⁺	Pt⁴⁺	Pt⁰	Pt²⁺	Pt⁴⁺
Pt/ZrO₂	0	62.0	38.0	20.5	56.7	22.8	11.9	56.0	32.1
Pt-Mo/ZrO₂	6.2	56.6	37.2	23.6	54.3	22.1	28.9	51.8	19.3
Pt-Nb/ZrO₂	4.2	53.7	42.1	13.4	61.3	25.3	20.1	54.8	25.1

Scheme 1. Structure models for propane and methane combustion over Pt/ZrO2, Pt-Mo/ZrO2, and Pt-Nb/ZrO2 catalysts.

Fig. 9. Relationship between ethane (a) and n-hexane (b) conversion rates and reaction temperatures for Pt/ZrO2, Pt-Mo/ZrO2, and Pt-Nb/ZrO2 catalysts.

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MoO₃和Nb₂O₅助剂对Pt/ZrO₂催化剂上短链烷烃燃烧反应的不同促进作用

Different roles of MoO₃ and Nb₂O₅ promotion in short-chain alkane combustion over Pt/ZrO₂ catalysts

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