<br>Co-O3-Zn 电子转移产生富电子 Zn，在氧空位上促进 CO2 甲醇化的氢解吸,Energy & Fuels

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Co-O3-Zn 电子转移产生富电子 Zn，在氧空位上促进 CO2 甲醇化的氢解吸
Energy & Fuels ( IF 5.2 ) Pub Date : 2024-10-30 , DOI: 10.1021/acs.energyfuels.4c03765
Jun Cheng ₁ , Hao Li ₁ , Zhuo Chen _{2,

3} , Yongbin Zhong _{2,

3} , Wentao Du _{2,

3} , Tongyun Zhang _{2,

3} , Jingwen Xu _{2,

3} , Shengxuan Luo ₁ , Zhefeng Li ₁ , Weixin Liu ₁ , Mingxing Zhao ₄

Affiliation

为了加强 ZnZrO_x 催化剂的供电子接受行为以通过 CO₂ 加氢生产甲醇，在 ZnZrO_x 催化剂中通过共沉淀掺杂 Co，生成 Co-O 3-Zn 电子转移，以促进 CO₂ 在富电子 Zn 位点上的氢解吸甲醇化。Zn 物质的富电子状态削弱了 Zn-H 键以促进 H* 物质的解吸，这有利于 Zn 物质的暴露以进一步氢解离。将 Co 掺入 ZnZrO_x 晶格中，以产生更多的氧空位，以促进 CO₂ 吸附在甲醇生产催化剂上。DFT 计算表明，活性氢在 CoZnZrO_x 催化剂上的结合能低于 ZnZrO_x 催化剂。HAADF-STEM 和 XANES/EXAFS 阐明了在 CoZnZrO_x 催化剂中，具有 +2.3 价的原子 Co 分散，平均 Co-O 配位数为 3.1。XPS 证实 Zn 接受 Co 提供的电子以产生富含电子的 Zn 物种。H_2-TPR 显示 CoZnZrO_x-1% 催化剂的低温还原峰移至 305 °C，低于 ZnZrO_x 催化剂的低温还原峰（378 °C）。在 5 MPa、310 °C、H₂/CO₂/Ar = 80：8：12 和 GHSV = 12,000 mL g_cat^–1 h^–1 下，甲醇产率提高了 58%。

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Co–O3–Zn Electron Transfer Generated Electron-Rich Zn to Promote Hydrogen Desorption for CO2 Methanolation over Oxygen Vacancies

In order to strengthen the electron-donating–accepting behavior of ZnZrO_x catalysts to produce methanol with CO₂ hydrogenation, Co was doped in a ZnZrO_x catalyst through coprecipitation to generate Co–O₃–Zn electron transfer to promote hydrogen desorption on electron-rich Zn sites for CO₂ methanolation. The electron-rich state of Zn species weakened the Zn–H bond to promote desorption of H* species, which was favorable to exposure of Zn species for further hydrogen dissociation. Co was incorporated into the ZnZrO_x crystal lattice to create more oxygen vacancies to facilitate CO₂ adsorption on catalysts for methanol production. DFT calculations showed that the binding energy of active hydrogen species on CoZnZrO_x catalysts was lower than that of ZnZrO_x catalysts. HAADF-STEM and XANES/EXAFS clarified that atomic Co with +2.3 valence was dispersed with an average Co–O coordination number of 3.1 in CoZnZrO_x catalysts. XPS confirmed that Zn accepted electrons donated from Co to generate electron-rich Zn species. H₂-TPR revealed that the low-temperature reduction peak of the CoZnZrO_x-1% catalyst shifted to 305 °C, which was lower than that (378 °C) of the ZnZrO_x catalyst. This promoted methanol yield by 58% at 5 MPa, 310 °C, H₂/CO₂/Ar = 80:8:12, and GHSV = 12,000 mL g_cat^–1 h^–1.

更新日期：2024-10-30

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