Cu-Based Catalysts on ZnO Hexagonal Nanorods and Performance in CO₂Hydrogenation Reaction AITranslate

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Basic Information:

DOI：10.13373/j.cnki.cjrm.XY25040017

Chinese Library Classification Number:TQ426.6

Citation Information:

The increasing concentration of atmospheric CO₂ and the escalating severity of global warming have made CO₂ capture, utilization, and storage (CCUS) technologies crucial solutions for reducing carbon emissions and mitigating climate change. CO₂ hydrogenation to methanol represents a crucial pathway for CO₂ recycling. Industrially, Cu-based catalysts are widely employed due to their abundant raw materials, low cost, and excellent stability, with CuZnAl catalysts already being utilized in industrial-scale CO/CO₂ hydrogenation to methanol processes. However, the introduction of ZrO₂ as a promoter, due to its weak alkalinity and weak hydrophilicity, can inhibit the toxic effect of water on the active site during methanol synthesis, playing an important role in CO₂ adsorption and methanol selectivity. In this study, ZnO hexagonal nanorods were used as support to load Cu-ZnO-ZrO₂. Different catalysts were prepared by regulating the content of the loaded substances in the catalyst, changing the morphology of the ZnO support, and with or without the support, and their CO₂ hydrogenation catalytic performance was investigated. The catalysts were characterized by methods such as scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), energy dispersive X-ray spectroscopy (EDX), X-ray powder diffraction (XRD), hydrogen-programmed temperature reduction (H₂-TPR) and X-ray photoelectron spectroscopy (XPS). The morphology, elemental distribution, reducing property and valence state of surface metal elements of the catalysts were analyzed. STEM characterization results showed that 0.33CuZnZr/ZnO-HN and 0.5CuZnZr/ZnO-HN catalysts retained the rod-like structure of the support ZnO hexagonal nanorods in terms of morphology and structure. Due to different loading amounts, there were obvious differences in morphology. 0.5CuZnZr/ZnO-t catalyst retained the granular form of the traditional ZnO support, but the distribution was uneven. The support-free CuZnZr catalyst was composed of randomly piled particles, with smaller particle size and more uniform distribution. XPS spectra showed that Zn species and Zr species existed in the form of ZnO and ZrO₂ phases respectively in all catalysts, and Zn atoms migrated to the surface during the reduction process. Compared with other catalysts, the catalyst supported by ZnO hexagonal nanorods could not completely reduce Cu²⁺ to Cu⁰ in H₂ reduction treatment. H₂-TPR test results showed that the reduction peak of the catalyst supported by ZnO hexagonal nanorods was around 270 ℃, which was much higher than that of other catalysts. This might be due to the stronger interaction between Cu and ZnO, making it more difficult for CuO to be reduced to Cu⁰. It could also be that the loading layer was thicker, significantly reducing the reducing property of the catalyst. The CO₂ hydrogenation performance of all catalysts was tested, and the results showed that the supported materials on 0.5CuZnZr/ZnO-HN catalyst were uniformly dispersed, the interaction between Cu and ZnO was stronger, and the selectivity of methanol at high temperatures was higher. Using ZnO hexagonal nanorods as the support might change the reaction path of CO₂ hydrogenation to methanol. At 290 ℃, the methanol selectivity of 0.5CuZnZr/ZnO-HN catalyst was 34.9%, significantly higher than that of 0.5CuZnZr/ZnO-t (24.1%) and CuZnZr (25.7%), and its methanol space-time yield was 65.9 mg·g_Cu⁻¹·h⁻¹.