网状缺陷型碳化钼材料催化合成气经草酸二甲酯加氢合成乙醇

doi:10.1016/S1872-2067(25)64713-9

摘要/Abstract

摘要：

合成气经草酸二甲酯加氢合成乙醇是合成气间接转化制备含氧化合物的途径之一, 是实现煤炭资源清洁高效利用的重要环节. 然而, 在乙醇合成的过程中存在反应条件苛刻, 反应副产物复杂, 反应机理尚不明确等问题. 碳化钼材料由于其出色的反应活性在多种催化反应领域有着广泛应用, 并可作为主要活性物种催化草酸二甲酯加氢, 在相对温和的条件下合成乙醇等含氧化合物. 通过新型合成方法设计高效的碳化钼催化剂, 阐明构效关系, 为开发高效催化剂奠定了技术基础, 对实现合成气转化制乙醇具有重要意义.

本工作利用火焰喷射裂解法与物理溅射法共同构筑了一种缺陷型的碳化钼催化剂并将其应用于草酸二甲酯加氢合成乙醇. 区别于传统的催化剂合成方法, 火焰喷射裂解法通过高温瞬时淬火, 制备的氧化钼前驱体具有丰富的氧空位与缺陷; 同时, 物理溅射法通过用高能氩离子轰击金属靶材, 可以在原子尺度上精确操纵金属铜的电子结构, 可作为结构助剂改变氧化钼的形貌与晶格结构, 还能有效提升催化剂的整体性能. 该催化剂由镂空的网格状基本单元组成, 互相交叠成具有缺陷的多边形结构, 进一步在空间中交错相连, 生成了独特的三维立体网状结构形貌. 物理溅射法引入的铜作为结构助剂负载于具有氧空位的氧化钼前驱体上, 这种方法不仅确保了铜的均匀分布, 同时促进了具有亚稳态结构的Mo₁₇O₄₇物种生成. 与普通正交相MoO₃不同, 这种不饱和氧化钼在碳化过程中能够进一步影响碳化钼的晶体结构, 使生成的β-Mo₂C具有明显的晶格畸变与缺陷. 同时, 本文通过不同方法引入不同状态及含量的结构助剂负载于各类氧化钼前驱体上, 探究了不同钼物种在加氢过程中的作用. 并通过中子衍射等表征手段证明, 相对于没有缺陷的碳化钼或氧化钼物种, 这种具有缺陷的β-Mo₂C不仅具有较高的反应活性, 而且还可以在反应前后稳定存在, 能够作为主要活性位点促进C=O加氢过程, β-Mo₂C的缺陷程度与其深度加氢活性呈现正相关趋势. 在实际应用中, 该催化剂实现了较温和条件下(230 ^oC, 氢酯比120)催化草酸二甲酯加氢反应中83.1%的乙醇收率. 此外, 在反应过程中, 催化剂可保持良好的反应稳定性.

设计温和条件下高效加氢的催化剂是合成气转化制取乙醇等高附加值含氧化合物的重要环节. 新型催化剂合成方法与先进表征手段的耦合可拓展催化剂的可控合成途径, 通过结构和性能的协同优化为催化剂的设计提供指导. 希望本文可为拓展碳化钼材料的设计及其在C=O键加氢中的应用提供新思路.

关键词: 合成气, 草酸二甲酯, 加氢, 乙醇, 碳化钼

Abstract:

Molybdenum carbide has shown great potential in various hydrogenation reactions, and serves as a primary active species for synthesis of ethanol from dimethyl oxalate hydrogenation process which is a crucial step in the efficient utilization of coal resources. In this study, a molybdenum carbide catalyst with a three-dimensional mesh-like hollow structure and lattice defects was carefully designed. The MoO₃ precursor with abundant oxygen vacancies and defects was prepared by flame spray pyrolysis, and a structural modifier, Cu, was introduced by sputtering. The Cu deposited by sputtering affected the carburization and phase evolution processes. A three-dimensional mesh-like hollow structure composed of defective molybdenum carbide is formed, with the β-Mo₂C exhibiting lattice distortions and defects. This defective β-Mo₂C exhibits high reactivity, and facilitates the C=O hydrogenation process, showing a high reactivity of 83.1% yield in the hydrogenation of dimethyl oxalate. This work provides a new approach to the design and application of molybdenum carbide catalysts.

Key words: Syngas, Dimethyl oxalate Hydrogenation, Ethanol, Molybdenum carbides

孙艳楠, 俞佳枫, 孙兴涛, 韩誉, 葛庆杰, 孙剑. 网状缺陷型碳化钼材料催化合成气经草酸二甲酯加氢合成乙醇[J]. 催化学报, 2025, 73: 234-241.

Yannan Sun, Jiafeng Yu, Xingtao Sun, Yu Han, Qingjie Ge, Jian Sun. Designing mesh-like defective molybdenum carbides for ethanol synthesis via syngas-derived DMO hydrogenation[J]. Chinese Journal of Catalysis, 2025, 73: 234-241.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64713-9

https://www.cjcatal.com/CN/Y2025/V73/I6/234

图/表 7

Fig. 1. The catalytic performance of different Mo-based catalysts. Reaction conditions: T = 230 °C, H2/DMO = 120, p = 3.0 MPa, LHSV = 0.3 h-1 (*SP-Cu/FSP-MoO3 at a LHSV = 0.15 h-1).

Fig. 2. The TEM images of spent catalysts. (a) The comm-MoO3 catalyst; (b) The FSP-MoO3 catalyst; (c) The IM-Cu/FSP-MoO3 catalyst.

Fig. 3. The TEM images of the spent SP-Cu/FSP-MoO3 catalyst.

Fig. 4. XRD patterns of the fresh (a), carburized (b), and spent (c) catalysts and the standard JCPDF cards.

Fig. 5. Rietveld XRD patterns of the carburized samples of IM-Cu/FSPMoO3 and SP-Cu/FSP-MoO3 catalysts and the structure of β-Mo2C from the Rietveld XRD results.

Fig. 6. Neutron diffraction patterns of carburized and spent samples of the SP-Cu/FSP-MoO3 catalyst and the models of β-Mo2C according to the corresponding fittings.

Fig. 7. (a) Rietveld XRD patterns of the spent samples of SP-Cu/FSP-MoO3 catalysts with different sputtering time. (b) The structure of β-Mo2C from the Rietveld XRD results.

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