Mn Doping Regulates Surface Oxygen Defects of ZnOx to Promote Tandem CO2 Hydrogenation to Light Olefins

IF 2.5 4区化学 Q3 CHEMISTRY, PHYSICAL

Catalysis Letters Pub Date : 2026-08-21 DOI:10.1007/s10562-026-05501-6

Tao Peng, Liang Ma, He Xu, Rong Liu, Wenzhuo Bao, Xiaoyan Liu, Ting Su, Kai Wu, Yu Meng

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引用次数: 0

Abstract

Mn-doped ZnO_x composite oxides with tunable Mn/(Mn + Zn) molar ratios were synthesized by co-precipitation and integrated with SAPO-34 to construct bifunctional tandem catalysts for CO₂ hydrogenation to light olefins. The effects of Mn incorporation on phase evolution, surface oxygen vacancies, adsorption–activation properties, and reaction intermediates were systematically elucidated. Moderate Mn incorporation modifies the local ZnO structure, whereas excessive Mn induces ZnMn₂O₄ spinel formation. Among the catalysts, 30%Mn-ZnO_x exhibits the highest fraction of defect/adsorbed oxygen species which is accompanied by enhanced CO₂ adsorption and H₂ activation behavior. H₂-TPD, CO₂-TPD, and DRIFTS collectively indicate improved activation matching and the formation of HCOO* and CH₃O* intermediates, suggesting a possible formate-related hydrogenation route. When coupled with SAPO-34, 30%Mn-ZnO_x/SAPO-34 achieves a CO₂ conversion of 12.57% and ca. 80% light-olefin selectivity under optimized conditions, while maintaining stable performance over 100 h. This work highlights Mn-induced vacancy engineering as an effective strategy for designing Zn-based oxide/zeolite tandem catalysts.

Graphical Abstract

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Mn掺杂调控ZnOx表面氧缺陷促进CO2串联加氢制轻烯烃

采用共沉淀法合成了Mn/(Mn + Zn)摩尔比可调的Mn掺杂ZnOx复合氧化物，并与SAPO-34集成，构建了CO2加氢制轻烯烃的双功能串联催化剂。系统地阐明了Mn掺入对相演化、表面氧空位、吸附活化性能和反应中间体的影响。适量Mn的掺入改变了ZnO的局部结构，而过量Mn则诱导了ZnMn2O4尖晶石的形成。在催化剂中，30%Mn-ZnOx表现出最高的缺陷/吸附氧，并伴有增强的CO2吸附和H2活化行为。H2-TPD、CO2-TPD和DRIFTS共同表明活化匹配改善，HCOO*和ch30 *中间体形成，提示可能与甲酸相关的加氢途径。当与SAPO-34偶联时，30%Mn-ZnOx/SAPO-34在优化条件下实现了12.57%的CO2转化率和约80%的轻烯烃选择性，同时在100小时内保持稳定的性能。该研究表明，mn诱导空位工程是设计zn基氧化物/沸石级联催化剂的有效策略。图形抽象

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来源期刊

Catalysis Letters 化学-物理化学

CiteScore

5.70

自引率

3.60%

发文量

327

审稿时长

1 months

期刊介绍： Catalysis Letters aim is the rapid publication of outstanding and high-impact original research articles in catalysis. The scope of the journal covers a broad range of topics in all fields of both applied and theoretical catalysis, including heterogeneous, homogeneous and biocatalysis. The high-quality original research articles published in Catalysis Letters are subject to rigorous peer review. Accepted papers are published online first and subsequently in print issues. All contributions must include a graphical abstract. Manuscripts should be written in English and the responsibility lies with the authors to ensure that they are grammatically and linguistically correct. Authors for whom English is not the working language are encouraged to consider using a professional language-editing service before submitting their manuscripts.