A combined DFT-Experimental study on FSP-made Ru/Ti-SiO2 catalysts for CO2 methanation

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis Pub Date : 2025-05-05 DOI:10.1016/j.mcat.2025.115179

Okorn Mekasuwandumrong , Tinnakorn Saelee , Jakapob Noppakhun , Meena Rittiruam , Patcharaporn Khajondetchairit , Damien P. Debecker , Supareak Praserthdam , Piyasan Praserthdam

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Abstract

Flame spray pyrolysis (FSP) was employed to synthesize Ti-modified SiO₂ in a single step, serving as the support for Ru-based catalysts in CO₂ methanation reactions. The addition of Ti led to the formation of anatase and rutile TiO₂ phases, enhancing the catalytic activity of Ru/Ti-SiO₂ catalysts. Benchmarking between Ru/Ti-SiO₂ catalysts of various Ti concentrations prepared using one-step FSP techniques indicated significantly higher catalytic activity for the impregnation-made catalysts compared to the FSP-made ones, where diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) revealed different CH₄ formation mechanisms between two techniques. For FSP-made catalysts, it predominantly occurred through the CO route, whereas the impregnation-made proceed via both the dissociative adsorption of CO₂ (CO route) and through surface formate species formation. To explain the effect of Ti loading on Ru/SiO₂ catalysts, a multiscale analysis combining density functional theory (DFT) and microkinetic modeling was performed to study the adsorption behavior of CO₂ on different catalysts. The results revealed that a high amount of Ti reduced the adsorption strength of CO₂ on Ru/SiO₂ catalysts, indicating a modified interaction between CO₂ and the catalyst surface.

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fsp制备Ru/Ti-SiO2 CO2甲烷化催化剂的联合dft -实验研究

采用火焰喷雾热解法（FSP）一步合成ti改性SiO 2，作为CO 2甲烷化反应中ru基催化剂的载体。Ti的加入导致锐钛矿和金红石型tio2相的形成，增强了Ru/Ti- sio2催化剂的催化活性。对一步FSP技术制备的不同Ti浓度的Ru/Ti- sio₂催化剂进行基准测试表明，浸渍法制备的催化剂的催化活性明显高于FSP法制备的催化剂，漫反射红外傅立叶变换光谱（DRIFTS）揭示了两种技术之间不同的CH₄形成机制。对于fsp制备的催化剂，主要通过CO途径进行，而浸渍制备的催化剂则通过CO 2的解离吸附（CO途径）和表面甲酸酯的形成进行。为了解释Ti负载对Ru/SiO₂催化剂的影响，采用密度泛函理论（DFT）和微动力学模型相结合的多尺度分析方法研究了不同催化剂对CO₂的吸附行为。结果表明，高含量的Ti降低了CO₂在Ru/SiO₂催化剂上的吸附强度，表明CO₂与催化剂表面的相互作用发生了改变。

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来源期刊

Molecular Catalysis Chemical Engineering-Process Chemistry and Technology

CiteScore

6.90

自引率

10.90%

发文量

700

审稿时长

40 days

期刊介绍： Molecular Catalysis publishes full papers that are original, rigorous, and scholarly contributions examining the molecular and atomic aspects of catalytic activation and reaction mechanisms. The fields covered are: Heterogeneous catalysis including immobilized molecular catalysts Homogeneous catalysis including organocatalysis, organometallic catalysis and biocatalysis Photo- and electrochemistry Theoretical aspects of catalysis analyzed by computational methods