Influence of the Rh Nanoparticle Size and Rh Precursor Nature on Decalin Ring Opening over Rh/Al2O3 Catalysts

IF 2.3 4区化学 Q3 CHEMISTRY, PHYSICAL

Catalysis Letters Pub Date : 2025-01-21 DOI:10.1007/s10562-024-04925-2

Elena D. Finashina, Olga P. Tkachenko, Kristina E. Kartavova, Alexander A. Greish, Alexander L. Kustov, Nikolay A. Davshan, Nikolay N. Tolkachev, Leonid M. Kustov

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Abstract

A series of 1%Rh/γ-Al₂O₃ catalysts was prepared using different Rh-containing precursors (chloride, nitrate, and complex [Rh(NH₃)₅Cl]Cl₂). The catalysts prepared in this work were characterized by various physicochemical methods. Textural and acid–base properties, metal dispersion and metal charge state were characterized by nitrogen adsorption–desorption analysis, scanning electron microscopy with the energy dispersive X-ray analysis, diffuse-reflectance Fourier-transform infrared spectroscopy, transmission electron microscopy, CO chemisorption, X-ray photoelectron spectroscopy. The activity and selectivity of the catalysts were tested in the reaction of decalin ring opening under high pressures. The XPS study showed that rhodium in the surface layers of the samples is present in a metallic state. However, a small positive charge (δ+) is observed on the rhodium atoms due to the interaction of dispersed metal particles with the carrier. This effect is especially noticeable for the sample prepared using the Rh(NO₃)₃ precursor. According to the data, all studied catalysts allow one to obtain a similar set of reaction products, where C₁₀ alkylcyclohexanes predominate. The catalyst activity decreases in the NO₃⁻ > Cl⁻ > [Rh(NH₃)₅Cl]Cl₂ series, that is in the inverse correlation with the rhodium particle size 1.5 nm < 2.2 nm < 17.2 nm (determined by the CO chemisorption method) and 1.7 nm < 2.3 nm < 6.6 nm (determined by TEM). The catalyst synthesized on the basis of rhodium nitrate demonstrates a reaction selectivity close to 74% for the partial ring opening at the total decalin conversion of 67%. The highest activity and selectivity for this catalyst are possibly accounted for by the relatively small size of metal particles formed on the alumina support. Also, some changes in the activity and selectivity of the catalysts observed with variation of the major reaction parameters, such as temperature, pressure, space velocity and H₂/C₁₀ molar ratio were determined.

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Rh纳米颗粒尺寸和Rh前驱体性质对Rh/Al2O3催化剂上十萘环开度的影响

采用不同的含Rh前驱体（氯化物、硝酸盐和配合物[Rh(NH3)5Cl]Cl2）制备了一系列1%Rh/γ-Al2O3催化剂。用各种物理化学方法对所制备的催化剂进行了表征。通过氮吸附-解吸分析、扫描电子显微镜与能量色散x射线分析、漫反射傅里叶变换红外光谱、透射电子显微镜、CO化学吸附、x射线光电子能谱等手段表征了金属的织构和酸碱性质、弥散和电荷态。在高压开环反应中测试了催化剂的活性和选择性。XPS研究表明，样品表层中的铑以金属态存在。然而，由于分散的金属粒子与载体的相互作用，在铑原子上观察到一个小的正电荷（δ+）。这种效应对于使用Rh(NO3)3前驱体制备的样品尤其明显。根据数据，所有研究的催化剂都可以得到一组相似的反应产物，其中C10烷基环己烷占主导地位。NO3 - > Cl - > [Rh(NH3)5Cl]Cl2系催化剂活性下降，与铑粒径1.5 nm < 2.2 nm < 17.2 nm （CO化学吸附法测定）和1.7 nm < 2.3 nm < 6.6 nm （TEM测定）成反比。以硝酸铑为原料合成的催化剂在总十烯烃转化率为67%的情况下，部分开环的反应选择性接近74%。该催化剂的最高活性和选择性可能是由于在氧化铝载体上形成的金属颗粒相对较小。同时，考察了催化剂的活性和选择性随反应温度、压力、空速和H2/C10摩尔比等主要反应参数的变化。图形抽象

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来源期刊

Catalysis Letters 化学-物理化学

CiteScore

5.70

自引率

3.60%

发文量

327

审稿时长

1 months

期刊介绍： Catalysis Letters aim is the rapid publication of outstanding and high-impact original research articles in catalysis. The scope of the journal covers a broad range of topics in all fields of both applied and theoretical catalysis, including heterogeneous, homogeneous and biocatalysis. The high-quality original research articles published in Catalysis Letters are subject to rigorous peer review. Accepted papers are published online first and subsequently in print issues. All contributions must include a graphical abstract. Manuscripts should be written in English and the responsibility lies with the authors to ensure that they are grammatically and linguistically correct. Authors for whom English is not the working language are encouraged to consider using a professional language-editing service before submitting their manuscripts.