Rh/Al2O3催化剂在丙烷脱氢反应中的表面变化

doi:10.1016/S1872-2067(24)60063-X

摘要/Abstract

摘要：

丙烯是一种重要的化工原料, 需求量较大且逐年增加. 丙烷脱氢(PDH)是一种高效的生产丙烯过程, 正逐步取代石脑油裂解成为重要的丙烯生产工艺. 开发高效且稳定的PDH催化剂将对PDH工业发展起到积极的推动作用. Rh因其较好的C-H键活化能力, 展现出作为PDH催化剂的巨大潜力, 但关于Rh应用于PDH的报道较少. 明确Rh物种尺寸对PDH产物选择性的影响, 对后续设计高效且稳定的Rh基PDH催化剂至关重要. 多相催化反应主要发生在催化剂的表面, 因此, 催化剂的表面状态对其催化性能具有重要的影响. 在催化反应过程中, 一些催化剂的表面状态会发生显著变化, 这些变化会导致活性、产物选择性明显变化. 通过采用(准)原位表面研究手段, 能够清晰地了解催化剂在反应过程中的表面变化, 这对于建立催化剂结构与反应性能之间的构效关系具有非常重要的意义.

本文通过沉积-沉淀法制备了不同负载量的Rh/Al₂O₃催化剂, 旨在探究Rh物种尺寸对PDH产物选择性的影响. 球差电镜(AC-HAADF-STEM)观察显示, Rh物种以团簇和单原子的形式共存于Al₂O₃载体上. 进一步通过准原位X射线光电子能谱(XPS)证实了不同化学态的Rh物种. 通过固定床反应器对Rh/Al₂O₃催化剂的PDH性能进行测试, 结果表明, 催化剂在反应初始阶段需要经历诱导期. 在此期间, 甲烷的选择性显著降低, 而丙烯的选择性显著升高, 同时, 丙烷的转化率显著降低. 碳平衡计算表明, 诱导期内产生了大量积碳. 采用准原位XPS、低能离子散射谱(LEIS)和CO吸附红外光谱(CO-FTIR)研究了Rh/Al₂O₃催化剂在诱导期的表面变化. 结果表明, 在反应初始阶段, 催化剂表面有大量积碳产生, 这些积碳主要聚集在Rh物种表面, 覆盖了Rh团簇, 而Rh单原子则保持暴露状态, 并作为PDH反应的活性中心. AC-HAADF-STEM结果表明, PDH反应4 h后, 仍有Rh单原子存在于催化剂表面. 结合Rh/Al₂O₃催化剂的PDH性能和准原位表征结果认为, 丙烷在Rh团簇表面发生C-C键断裂反应, 生成甲烷和积碳. 积碳对Rh团簇的覆盖抑制了丙烷裂解反应, 导致甲烷的选择性在诱导期显著降低; 而Rh单原子则仍然暴露, 具有催化PDH反应活性, 并且是高选择性地生成丙烯的位点. 该选择性的差异由丙烯在不同尺寸Rh物种上的吸附方式不同引起的, 在Rh团簇表面以di-σ键吸附方式为主, 吸附强度较强, 丙烯不易脱附, 并进一步发生裂解产生甲烷和积碳; 而在Rh单原子上, 丙烯以π键吸附方式存在, 吸附强度较弱, 不易发生副反应. 对反应后的Rh/Al₂O₃催化剂进行分析, 发现积碳主要为碳氢化合物和石墨碳, 且随着反应进行, 积碳从Rh团簇表面向Al₂O₃载体上转移.

综上所述, 本文通过使用准原位XPS, LEIS和CO-FTIR等技术探究了Rh/Al₂O₃催化剂在PDH反应中的表面变化, 揭示了Rh物种尺寸对PDH产物选择性的影响. 结果表明, Rh单原子对丙烯选择性有利, 而在Rh团簇表面PDH产物主要为甲烷并产生积碳, 同时积碳导致了催化剂在反应初始阶段的快速失活. 本工作为后续高效Rh基PDH催化剂的设计提供参考.

关键词: 丙烷脱氢, 铑, 积碳, 单原子, 准原位谱学, 表面变化

Abstract:

The surface structures of heterogeneous catalysts significantly impact catalytic performance, especially for structure-sensitive reactions. In this study, we employed surface techniques such as low-energy ion scattering spectroscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy with CO as a probe (CO-FTIR) to investigate the surface dynamics of Rh/Al₂O₃ catalysts for propane dehydrogenation (PDH). We observed a notable induction process for PDH on Rh/Al₂O₃ catalysts, marked by significant variations in propane conversion, methane, and propylene selectivities. These changes were attributed to substantial coke formation. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy) and CO-FTIR revealed the coexistence of Rh nanoparticles, clusters, and single atoms on the surface. Through various dynamic quasi in-situ characterizations, we found that coke preferentially covered Rh clusters, thereby inhibiting C-C bond breaking and methane formation. Meanwhile, Rh single atoms were less affected by coke coverage and remained exposed as active and selective sites for PDH, favoring propylene production. This work underscores the sensitivity of PDH to the sizes of Rh species, with isolated Rh single atoms promoting propylene formation.

Key words: Propane dehydrogenation, Rhodium, Coke, Single atom, Quasi in-situ spectroscopy, Surface dynamics

李书毅, 穆长乐, 何念秋, 徐杰, 郑燕萍, 陈明树. Rh/Al₂O₃催化剂在丙烷脱氢反应中的表面变化[J]. 催化学报, 2024, 62: 145-155.

Shuyi Li, Changle Mu, Nianqiu He, Jie Xu, Yanping Zheng, Mingshu Chen. Surface dynamics of Rh/Al₂O₃ during propane dehydrogenation[J]. Chinese Journal of Catalysis, 2024, 62: 145-155.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60063-X

https://www.cjcatal.com/CN/Y2024/V62/I7/145

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Fig. 1. AC-HAADF-STEM images of Rh/Al2O3 catalysts with varying Rh loadings: 3% (a,b), 1% (c), 0.5% (d), 0.1% (e), and 0.03% (f). (Red circles: Rh clusters, yellow circles: Rh single atoms).

Fig. 2. (a) Model of a Rh/Al2O3 catalyst (yellow balls: metallic Rh atoms, purple balls: interfacial Rh atoms, green balls: Rh single atoms). XPS Rh 3d spectra of the Rh/Al2O3 catalysts: 3% (b), 1% (c), and 0.5% (d).

Fig. 3. Catalytic performance of Rh/Al2O3. (a) Propane conversion; (b) propylene selectivity; (c) methane selectivity; (d) ethene selectivity; (e) ethane selectivity; (f) carbon balance.

Fig. 4. Propane-pulse tests of 3% Rh/Al2O3 (a), 1% Rh/Al2O3 (b), 0.5% Rh/Al2O3 (c), 0.1% Rh/Al2O3 (d) and 0.03% Rh/Al2O3 (e). (f) The propane consumption amounts of the Rh/Al2O3.

Fig. 5. LEIS spectra (He+) of the Rh/Al2O3 catalysts before and after propane treatment. (a,b) 3% Rh/Al2O3; (c,d) 1% Rh/Al2O3. The spectra were adjusted to have a comparable peak height of O.

Fig. 6. CO-FTIR spectra of the Rh/Al2O3 catalysts: Models of CO adsorbed on Rh species (a), 3% Rh/Al2O3 (b), 1% Rh/Al2O3 (c), 0.5% Rh/Al2O3 (d), 0.1% Rh/Al2O3 (e), and 0.03% Rh/Al2O3 (f).

Fig. 7. (a) Schematic of surface dynamics of the Rh/Al2O3 catalysts before and after the induction process. (b) Adsorption types of propylene on the Rh species.

Fig. 8. (a) TPOC of the spent 3% Rh/Al2O3 (m/e = 18, 28, and 44 for H2O, CO, and CO2, respectively). (b) TPOC of the spent Rh/Al2O3 catalysts and the Al2O3 support (m/e = 44 for CO2). HAADF-STEM image (c) and TEM image (d) of the spent 3% Rh/Al2O3. (blue circle: coke, yellow circle: Rh clusters. Two Rh clusters inside the red circles were selected as a reference to prove that these two images were obtained in the same area.)

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Rh/Al₂O₃催化剂在丙烷脱氢反应中的表面变化

Surface dynamics of Rh/Al₂O₃ during propane dehydrogenation

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