Jianxing Gan, Yoshinao Nakagawa, Mizuho Yabushita and Keiichi Tomishige
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Upon the combination of two Mo precursors, <em>i.e.</em> (NH<small><sub>4</sub></small>)<small><sub>6</sub></small>Mo<small><sub>7</sub></small>O<small><sub>24</sub></small> and Na<small><sub>2</sub></small>MoO<small><sub>4</sub></small>, the selectivity of the catalyst (MoO<small><sub><em>x</em></sub></small>–Cu–Na/TiO<small><sub>2</sub></small>) was further enhanced to achieve 81% yield of 2,5-DHF. This catalyst also exhibited broad substrate scope including cyclic and linear alkyl vicinal diols and tartaric ester. Furthermore, MoO<small><sub><em>x</em></sub></small>–Cu–Na/TiO<small><sub>2</sub></small> was reusable at least three times after its calcination as regeneration. The reaction was almost zero-order with respect to the H<small><sub>2</sub></small> pressure and 1,4-AHERY concentration, suggesting that the release of the alkene is the rate-determining step. The comprehensive characterization using STEM, XRD and XAFS provided insights into the surface structure of the catalyst, revealing that H<small><sub>2</sub></small> is activated over Cu particles and subsequently transferred to Mo cluster species on the TiO<small><sub>2</sub></small> surface <em>via</em> the spillover effect to proceed with the DODH reaction.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3000,"publicationDate":"2024-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Non-noble metal heterogeneous catalysts for hydrogen-driven deoxydehydration of vicinal diol compounds†\",\"authors\":\"Jianxing Gan, Yoshinao Nakagawa, Mizuho Yabushita and Keiichi Tomishige\",\"doi\":\"10.1039/D4GC02006E\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Noble-metal-free heterogeneous catalysts for deoxydehydration (DODH) using H<small><sub>2</sub></small> as a reductant were developed. 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引用次数: 0
摘要
以 H2 为还原剂的脱氧脱水(DODH)无贵金属异相催化剂被开发出来。在作为添加剂改性 MoOx/TiO2 催化剂的各种过渡金属中,铜在将 1,4-anhydroerythritol (1,4-AHERY) 转化为 2,5-dihydrofuran (2,5-DHF) 的过程中表现出良好的转化率和选择性。MoOx-Cu/TiO2 催化剂的性能与用 Ag 或 Au 代替 Cu 改性的催化剂相当。将两种 Mo 前驱体(即 (NH4)6Mo7O24 和 Na2MoO4)结合使用后,催化剂(MoOx-Cu-Na/TiO2)的选择性进一步提高,2,5-DHF 的产率达到 81%。这种催化剂还具有广泛的底物范围,包括环状和线性烷基官能团二元醇和酒石酸酯。此外,MoOx-Cu-Na/TiO2 经煅烧再生后至少可重复使用三次。反应与 H2 压力和 1,4-AHERY 浓度几乎呈零阶关系,这表明烯的释放是决定反应速率的步骤。利用 STEM、XRD 和 XAFS 进行的综合表征深入揭示了催化剂的表面结构,揭示了 H2 在 Cu 颗粒上被激活,随后通过溢出效应转移到 TiO2 表面的 Mo 团簇物种上,从而进行 DODH 反应。
Non-noble metal heterogeneous catalysts for hydrogen-driven deoxydehydration of vicinal diol compounds†
Noble-metal-free heterogeneous catalysts for deoxydehydration (DODH) using H2 as a reductant were developed. Among various transition metals examined as additives to modify the MoOx/TiO2 catalyst, Cu showed good conversion and selectivity in the transformation of 1,4-anhydroerythritol (1,4-AHERY) to 2,5-dihydrofuran (2,5-DHF). The performance of the MoOx–Cu/TiO2 catalysts was comparable to those modified with either Ag or Au instead of Cu. Upon the combination of two Mo precursors, i.e. (NH4)6Mo7O24 and Na2MoO4, the selectivity of the catalyst (MoOx–Cu–Na/TiO2) was further enhanced to achieve 81% yield of 2,5-DHF. This catalyst also exhibited broad substrate scope including cyclic and linear alkyl vicinal diols and tartaric ester. Furthermore, MoOx–Cu–Na/TiO2 was reusable at least three times after its calcination as regeneration. The reaction was almost zero-order with respect to the H2 pressure and 1,4-AHERY concentration, suggesting that the release of the alkene is the rate-determining step. The comprehensive characterization using STEM, XRD and XAFS provided insights into the surface structure of the catalyst, revealing that H2 is activated over Cu particles and subsequently transferred to Mo cluster species on the TiO2 surface via the spillover effect to proceed with the DODH reaction.
期刊介绍:
Green Chemistry is a journal that provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998), which defines green chemistry as the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry aims to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. The journal welcomes submissions on all aspects of research relating to this endeavor and publishes original and significant cutting-edge research that is likely to be of wide general appeal. For a work to be published, it must present a significant advance in green chemistry, including a comparison with existing methods and a demonstration of advantages over those methods.