Synergy of the catalytic activation on Ni and the CeO2-TiO2/Ce2Ti2O7 stoichiometric redox cycle for dramatically enhanced solar fuel production
Synergy of the catalytic activation on Ni and the CeO2-TiO2/Ce2Ti2O7 stoichiometric redox cycle for dramatically enhanced solar fuel production
复制标题
Ni 催化活化和 CeO2-TiO2/Ce2Ti2O7 化学计量氧化还原循环的协同作用可显着提高太阳能燃料产量
DOI：
10.1039/c8ee03069c
复制
发表时间：
2019
影响因子：
32.5
通讯作者：
Wang Xiaodong
中科院分区：
文献类型：
--
作者：
Ruan Chongyan;Huang Zheng Qing;Lin Jian;Li Lin;Liu Xiaoyan;Tian Ming;Huang Chu;e;Chang Chun Ran;Li Jun;Wang Xiaodong
太阳能热化学方法分解二氧化碳和水已成为太阳能燃料生产的一种有吸引力的途径。然而，在较低温度下高效生产具有高氧化还原动力学和产率的太阳能燃料仍然是一个主要挑战。在这项研究中，开发了镍促进的二氧化铈-钛氧化物 (CeO2-TiO2) 氧化还原催化剂，用于在 900 °C 下高效热化学 CO2 和 H2O 分解以及 CH4 的部分氧化。与目前最先进的太阳能热化学二氧化碳分解和水分解工艺相比，CO 和 H2 的生产率和生产率分别高出约 10-140 和 5-50 倍，同时实现了接近完全的 CH4 转化和对合成气的高选择性。通过结合实验表征和密度泛函理论（DFT）计算，研究了异常反应性能的潜在机制。结果表明，金属Ni和Ni/氧化物界面对CH4活化和CO2或H2O解离表现出催化活性，而CeO2-TiO2通过CeO2-TiO2/Ce2Ti2O7化学计量氧化还原循环增强晶格氧传输，用于CH4部分氧化以及随后由催化活性Ni促进的CO2或H2O分解。这些发现证实了催化位点反应物活化与控制氧离子传输的化学计量氧化还原化学之间协同作用的重要性，为设计用于可持续太阳能燃料生产的前瞻性材料铺平了道路。
Solar thermochemical approaches to CO2 and H2O splitting have emerged as an attractive pathway to solar fuel production. However, efficiently producing solar fuel with high redox kinetics and yields at lower temperature remains a major challenge. In this study, Ni promoted ceria–titanium oxide (CeO2–TiO2) redox catalysts were developed for highly effective thermochemical CO2 and H2O splitting as well as partial oxidation of CH4 at 900 °C. Unprecedented CO and H2 production rates and productivities of about 10–140 and 5–50 times higher than the current state-of-the-art solar thermochemical carbon dioxide splitting and water splitting processes were achieved with simultaneous close to complete CH4 conversions and high selectivities towards syngas. The underlying mechanism for the exceptional reaction performance was investigated by combined experimental characterization and density functional theory (DFT) calculations. It is revealed that the metallic Ni and the Ni/oxide interface manifest catalytic activity for both CH4 activation and CO2 or H2O dissociation, whereas CeO2–TiO2 enhances the lattice oxygen transport via the CeO2–TiO2/Ce2Ti2O7 stoichiometric redox cycle for CH4 partial oxidation and the subsequent CO2 or H2O splitting promoted by catalytically active Ni. Such findings substantiate the significance of the synergy between the reactant activation by catalytic sites and the stoichiometric redox chemistry governing oxygen ion transport, paving the way for designing prospective materials for sustainable solar fuel production.