路易斯酸碱相互作用的氧化物支持增强C-C偶联和脱氧反应

IF 6.5 1区 化学 Q2 CHEMISTRY, PHYSICAL
Kishore Rajendran , Dipika Rajendra Kanchan , Ajaikumar Samikannu , Petter Tingelstad , Zhihui Li , Albert Miró i Rovira , Arghya Banerjee , Jyri-Pekka Mikkola , Kumar Ranjan Rout , De Chen
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引用次数: 0

摘要

向可持续能源系统的过渡需要有效的催化剂,能够将生物质转化为液体燃料和平台化学品,以满足未来的能源需求。金属氧化物作为双功能催化剂的载体,由于其提供活性位点、产生氧空位缺陷和促进电子转移的能力而起着关键作用。虽然这些性质在金属纳米颗粒的存在下得到了很好的研究,但单独的氧化物载体的内在活性和表面性质仍未得到充分的研究。本研究探讨了裸金属氧化物(TiO2, ZrO2和Al2O3)在山毛榉生物质蒸汽的直接蒸汽升级中的作用,该过程包括非催化加氢热解步骤和非原位催化升级两阶段。比较了金属氧化物与SiO2等非金属氧化物的性能。通过广泛的表征(H2-TPR, NH3-TPD, O2-TPD, CO2-TPD, BET, XRD和Pyridine-FTIR),我们确定了TiO2的高弱酸性,强碱性和还原性的组合导致了优异的催化性能。在生物油中,TiO2脱位升级获得了最低的氧碳比(O/C = 0.09),最高的C2+分数(98.7 %)和最大的C8-C16分数(49.9 %),同时最大限度地减少了轻分子的形成(16.5 %)。结合能分析进一步表明,与其他氧化物相比,模型化合物(丙酮、乙酸、愈木酚)在TiO2(101)表面发生弱吸附,突出了其特殊的脱氧和C-C偶联性能。这项工作首次建立了氧化物载体的催化性能与其使用实际生物质原料的表面性质之间的全面相关性,从而为设计用于生物质升级的先进催化剂提供了有价值的见解。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Lewis acid-base interactions of oxide support for enhanced C–C coupling and deoxygenation reactions

Lewis acid-base interactions of oxide support for enhanced C–C coupling and deoxygenation reactions

Lewis acid-base interactions of oxide support for enhanced C–C coupling and deoxygenation reactions
The transition to sustainable energy systems requires efficient catalysts capable of upgrading biomass into liquid fuels and platform chemicals to meet future energy demands. Metal oxides, as supports in bifunctional catalysts, are pivotal due to their ability to provide active sites, create oxygen vacancy defects, and facilitate electron transfer. While these properties are well-studied in the presence of metal nanoparticles, the intrinsic activity and surface properties of stand-alone oxide supports remain underexplored.
This study investigates the role of bare metal oxides (TiO2, ZrO2, and Al2O3) in the direct vapor upgrading of beechwood biomass vapors via a two-stage process comprising a non-catalytic hydropyrolysis step followed by ex-situ catalytic upgrading. The performance of metal oxides was compared with non-metal oxide such as SiO2. Through extensive characterization (H2-TPR, NH3-TPD, O2-TPD, CO2-TPD, BET, XRD, and Pyridine-FTIR), we establish that the combination of high weak acidity, low strong basicity, and reducibility of TiO2 results in superior catalytic performance. Ex-situ upgrading over TiO2 achieves the lowest oxygen-to-carbon ratio (O/C = 0.09) in bio-oil, the highest C2+ fraction (98.7 %), and the largest C8-C16 fraction (49.9 %), while minimizing light molecule formation (16.5 %). Binding energy analyses further reveal that weak adsorption of model compounds (acetone, acetic acid, guaiacol) occurs on the TiO2 (101) surface compared to other oxide surfaces, highlighting its exceptional properties for deoxygenation and C–C coupling. This work establishes the first comprehensive correlation between the catalytic performance of oxide supports and their surface properties using actual biomass feedstock, thus offering valuable insights for designing advanced catalysts for biomass upgrading.
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来源期刊
Journal of Catalysis
Journal of Catalysis 工程技术-工程:化工
CiteScore
12.30
自引率
5.50%
发文量
447
审稿时长
31 days
期刊介绍: The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes. The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods. The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.
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