在CeO2载体上原子分散的Pt和Pt团簇通过低温水气转换反应制氢

IF 9.1 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Progress in Solid State Chemistry Pub Date : 2025-04-29 DOI:10.1016/j.progsolidstchem.2025.100520

Liping Du, Aishu Li, Song Hu, Sheng Su, Yi Wang, Long Jiang, Jun Xu, Kai Xu, Jun Xiang

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引用次数: 0

摘要

水气转换反应在碳基燃料的蒸汽重整制氢过程中起着至关重要的作用。Pt-CeO2催化剂因其优异的低温活性而备受关注，优化催化体系性能对降低能耗至关重要。在这项研究中，我们从氧空位和金属-载体相互作用的角度研究了金属分散差异对ceo2负载簇和原子分散Pt催化剂催化活性的影响。结果表明，Pt的氧化态和聚集对CO在催化剂表面的吸附能力有显著影响，原子分散的Pt0对CO具有更强的亲和力。由于Pt离子进入CeO2晶格，形成Pt- o - ce复合键，从而增强了Pt在CeO2表面的可及性，金属-载体相互作用明显。所有样品均表现出优异的催化性能，在低温下CO转化率超过70%，H2产率超过150 mL g - 1。由于Ce3+在不饱和配位态的部分还原，IMP-Pt的氧空位浓度（OVC）提高了3.99 × 1021 cm−3，CO转化率下降了~ 10%，T50升高了~ 20°C。Ptδ+的存在削弱了CO的吸附，但促进了碳化反应的发生。原子分散Pt- ceo2催化剂优越的晶格氧迁移率和动态氧存储能力使得暴露Pt原子的计算反应速率更快，周转频率更高。

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Atomically dispersed Pt and Pt clusters on CeO2 supports for H2 production via low-temperature water-gas shift reaction

Water-gas shift (WGS) reaction plays a crucial role in the steam reforming of carbon-based fuels for hydrogen production. Pt-CeO₂ catalysts have attracted significant attention due to their excellent low-temperature activity, and optimizing the catalytic system performance is essential for reducing energy consumption. In this study, we investigated the impact of metal dispersion differences on the catalytic activity of CeO₂-supported clusters and atomically dispersed Pt catalysts from the perspectives of oxygen vacancies and metal-support interactions. The results indicated that the adsorption capacity of CO on the catalyst surface was significantly influenced by the oxidation state and aggregation of Pt, with atomically dispersed Pt⁰ exhibiting a stronger affinity for CO. The metal-support interaction was evident in the formation of Pt-O-Ce composite bonds resulting from the incorporation of Pt ions into the CeO₂ lattice, which enhanced Pt accessibility on the CeO₂ surface. All samples demonstrated outstanding catalytic performance, achieving CO conversion exceeding 70 % and H₂ yield surpassing 150 mL g⁻¹ at low temperatures. The IMP-Pt characterized by an elevated oxygen vacancy concentrations (OVC) of 3.99 × 10²¹ cm⁻³, arising from partially reduced Ce³⁺ in unsaturated coordination states, exhibited a ∼10 % decline in CO conversion and a ∼20 °C increase in T₅₀. Undercoordinated Pt clusters led to strong CO binding and high CO vibration frequencies, while the presence of Pt^δ+ weakened CO adsorption but promoted carbonation reactions. The superior lattice oxygen mobility and dynamic oxygen storage capacity of atomically dispersed Pt-CeO₂ catalysts resulted in faster calculated reaction rates on exposed Pt atoms and higher turnover frequencies.

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来源期刊

Progress in Solid State Chemistry 化学-无机化学与核化学

CiteScore

14.10

自引率

3.30%

发文量

期刊介绍： Progress in Solid State Chemistry offers critical reviews and specialized articles written by leading experts in the field, providing a comprehensive view of solid-state chemistry. It addresses the challenge of dispersed literature by offering up-to-date assessments of research progress and recent developments. Emphasis is placed on the relationship between physical properties and structural chemistry, particularly imperfections like vacancies and dislocations. The reviews published in Progress in Solid State Chemistry emphasize critical evaluation of the field, along with indications of current problems and future directions. Papers are not intended to be bibliographic in nature but rather to inform a broad range of readers in an inherently multidisciplinary field by providing expert treatises oriented both towards specialists in different areas of the solid state and towards nonspecialists. The authorship is international, and the subject matter will be of interest to chemists, materials scientists, physicists, metallurgists, crystallographers, ceramists, and engineers interested in the solid state.