Preparation of High-Performance Pd/ZrO2 Catalyst for Methane Combustion AITranslate
Abstract AITranslate
Methane，as a primary component of natural gas，is widely used in power generation and heating applications. The emission of unburned methane causes air pollution and energy waste. Catalytic methane combustion is an effective and economical strategy to obtain high energy transforming efficiency and low emissions of toxic pollutants. Noble metal Pd-based catalysts are the most effective catalysts for methane combustion currently. The property of the support is one of the main factors affecting catalytic performance. Pd/ZrO2 catalyst has good hydrothermal stability but its methane combustion activity needs to be further improved. The methane catalytic combustion performance of the Pd/ZrO2 catalyst was enhanced by optimizing the preparation conditions of ZrO2 support and the preparation methods of catalysts in this work. X-ray diffraction （XRD） results showed that the preparation conditions would affect the crystal phase and grain size of the ZrO2. The grain size of ZrO2 gradually decreased with the increase of pH value and the decrease of calcination temperature. Meanwhile，with the increase in pH value，part of m-ZrO2 was gradually transformed into t-ZrO2，and the increase in temperature could make t-ZrO2 gradually transformed into m-ZrO2. The optimized catalytic performance and water-resistant of the Pd/ZrO2 catalyst for methane combustion could be obtained when the precipitation pH value was 12 and the calcination temperature was 700 ℃ during the ZrO2 support preparation process. Two kinds of Pd/ZrO2 catalysts were then prepared by deposition precipitation （DP） method and incipient wetness impregnation （IM） method using ZrO2 which was synthesized under the optimized preparation conditions as the support. The Pd/ZrO2 catalysts prepared by the DP method showed better catalytic performance for methane combustion （the methane complete conversion temperature reached 347 ℃，and had good water resistance） than that of the Pd/ZrO2 catalysts prepared by the IM method （the methane complete conversion temperature was 378 ℃）. The CO pulse experiments revealed that Pd/ZrO2 catalyst prepared by the DP method （Pd dispersion was 29%） had better dispersion of Pd species than that of the Pd/ZrO2 catalyst prepared by the IM method （Pd dispersion was 34%）. High-angle annular dark field scanning transmission electron microscopy （HAADF-STEM） and corresponding energy dispersive spectrometer （EDS）-mapping images showed that some aggregated Pd species existed in both catalysts prepared by different methods but more abundant smaller size Pd species could be observed in Pd/ZrO2 catalysts prepared by the DP method，which was consistent with CO pulse experiments. The influence of the preparation method on the redox performance of the catalyst and the chemical state of the Pd species was investigated by combining with H2-temperature programmed reduction （H2-TPR），O2-temperature programmed desorption （O2-TPD），and X-ray photoelectron spectroscopy （XPS）. XPS signals of Pd 3d indicated that the Pd species on Pd/ZrO2 catalyst prepared by DP method existed in a more electron-deficient oxidation state compared with the Pd/ZrO2 catalyst prepared by IM method. XPS signals of O 1s showed that there was more chemically adsorbed oxygen on the surface of the Pd/ZrO2 catalyst prepared by DP method，which had a stronger ability to adsorb and activate oxygen. H2-TPR results suggested that the introduction of Pd significantly changed the reduction performance of the catalyst，and the valence state of PdOx species in Pd/ZrO2 catalyst prepared by DP method was higher than that of Pd/ZrO2 catalyst prepared by IM method，which was consistent with XPS results. O2-TPD experiment further demonstrated this point. These results showed that the Pd species in the catalyst prepared by the DP method had more high valence state of Pd species and with more surface adsorbed oxygen which could improve the ability of the catalyst to adsorb and activate oxygen，which was beneficial to improve the catalytic performance for methane combustion.
KeyWords AITranslate
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Basic Information:
DOI：10.13373/j.cnki.cjrm.XY22050045
Chinese Library Classification Number:TF803.21
Citation Information:
Methane，as a primary component of natural gas，is widely used in power generation and heating applications. The emission of unburned methane causes air pollution and energy waste. Catalytic methane combustion is an effective and economical strategy to obtain high energy transforming efficiency and low emissions of toxic pollutants. Noble metal Pd-based catalysts are the most effective catalysts for methane combustion currently. The property of the support is one of the main factors affecting catalytic performance. Pd/ZrO2 catalyst has good hydrothermal stability but its methane combustion activity needs to be further improved. The methane catalytic combustion performance of the Pd/ZrO2 catalyst was enhanced by optimizing the preparation conditions of ZrO2 support and the preparation methods of catalysts in this work. X-ray diffraction （XRD） results showed that the preparation conditions would affect the crystal phase and grain size of the ZrO2. The grain size of ZrO2 gradually decreased with the increase of pH value and the decrease of calcination temperature. Meanwhile，with the increase in pH value，part of m-ZrO2 was gradually transformed into t-ZrO2，and the increase in temperature could make t-ZrO2 gradually transformed into m-ZrO2. The optimized catalytic performance and water-resistant of the Pd/ZrO2 catalyst for methane combustion could be obtained when the precipitation pH value was 12 and the calcination temperature was 700 ℃ during the ZrO2 support preparation process. Two kinds of Pd/ZrO2 catalysts were then prepared by deposition precipitation （DP） method and incipient wetness impregnation （IM） method using ZrO2 which was synthesized under the optimized preparation conditions as the support. The Pd/ZrO2 catalysts prepared by the DP method showed better catalytic performance for methane combustion （the methane complete conversion temperature reached 347 ℃，and had good water resistance） than that of the Pd/ZrO2 catalysts prepared by the IM method （the methane complete conversion temperature was 378 ℃）. The CO pulse experiments revealed that Pd/ZrO2 catalyst prepared by the DP method （Pd dispersion was 29%） had better dispersion of Pd species than that of the Pd/ZrO2 catalyst prepared by the IM method （Pd dispersion was 34%）. High-angle annular dark field scanning transmission electron microscopy （HAADF-STEM） and corresponding energy dispersive spectrometer （EDS）-mapping images showed that some aggregated Pd species existed in both catalysts prepared by different methods but more abundant smaller size Pd species could be observed in Pd/ZrO2 catalysts prepared by the DP method，which was consistent with CO pulse experiments. The influence of the preparation method on the redox performance of the catalyst and the chemical state of the Pd species was investigated by combining with H2-temperature programmed reduction （H2-TPR），O2-temperature programmed desorption （O2-TPD），and X-ray photoelectron spectroscopy （XPS）. XPS signals of Pd 3d indicated that the Pd species on Pd/ZrO2 catalyst prepared by DP method existed in a more electron-deficient oxidation state compared with the Pd/ZrO2 catalyst prepared by IM method. XPS signals of O 1s showed that there was more chemically adsorbed oxygen on the surface of the Pd/ZrO2 catalyst prepared by DP method，which had a stronger ability to adsorb and activate oxygen. H2-TPR results suggested that the introduction of Pd significantly changed the reduction performance of the catalyst，and the valence state of PdOx species in Pd/ZrO2 catalyst prepared by DP method was higher than that of Pd/ZrO2 catalyst prepared by IM method，which was consistent with XPS results. O2-TPD experiment further demonstrated this point. These results showed that the Pd species in the catalyst prepared by the DP method had more high valence state of Pd species and with more surface adsorbed oxygen which could improve the ability of the catalyst to adsorb and activate oxygen，which was beneficial to improve the catalytic performance for methane combustion.
quote
| GB/T 7714-2015 | [1] Xuan Tang, Bingjing Tang, Ying Liu, et al. Preparation of High-Performance Pd/ZrO2 Catalyst for Methane Combustion[J]. Chinese Journal of Rare Metals, 2025, 49(8): 1200-1213. DOI:10.13373/j.cnki.cjrm.XY22050045. |
| MLA | [1] Xuan Tang, et al., "Preparation of High-Performance Pd/ZrO2 Catalyst for Methane Combustion." Chinese Journal of Rare Metals, vol. 49, no. 8, 2025, pp. 1200-1213, https://doi.org/10.13373/j.cnki.cjrm.XY22050045. |
| APA | [1] Xuan Tang, Bingjing Tang, Ying Liu, Yanglong Guo, Qiyuan Gu, Xiaogang Miao, Wangcheng Zhan, Li Wang, & Yun Guo. (2025). Preparation of High-Performance Pd/ZrO2 Catalyst for Methane Combustion. Chinese Journal of Rare Metals, 49(8), 1200-1213. https://doi.org/10.13373/j.cnki.cjrm.XY22050045 |
| IEEE | [1] Xuan Tang, Bingjing Tang, Ying Liu, Yanglong Guo, Qiyuan Gu, Xiaogang Miao, Wangcheng Zhan, Li Wang, and Yun Guo, "Preparation of High-Performance Pd/ZrO2 Catalyst for Methane Combustion," Chinese Journal of Rare Metals, vol. 49, no. 8, pp. 1200-1213, 2025, doi: 10.13373/j.cnki.cjrm.XY22050045. keywords: {palladium;methane combustion;catalyst;high performance} |