Rh2P Nanoparticles Stabilized by Carbon Patches for Hydroformylation of Olefins,ACS Applied Nano Materials

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Rh2P Nanoparticles Stabilized by Carbon Patches for Hydroformylation of Olefins
ACS Applied Nano Materials ( IF 5.3 ) Pub Date : 2021-10-01 , DOI: 10.1021/acsanm.1c02194
Carmen Galdeano-Ruano ₁ , Christian Wittee Lopes ₂ , Debora Motta Meira _{3,

4} , Avelino Corma ₁ , Pascual Oña-Burgos _{1,

5}

Affiliation

Rh₂P nanoparticles (NPs) have been identified as suitable mimics of [Rh^I(Ph₃P)₃]⁺, the benchmark of homogeneous catalysts in liquid-phase hydroformylation. For this reason, a fitted synthetic strategy is required to develop catalysts based exclusively on Rh₂P NPs. To attain this, two synthetic pathways have been devised. In the first one, two separate sources of Rh and P were used. In the second one, the Wilkinson complex was employed as a unique source of Rh and P to probe the positive influence of the well-defined molecular organization on the preparation of dispersed and controlled Rh₂P nanoparticles, stabilized by carbon patches formed during the pyrolysis treatment from PPh₃. In addition, metallic Rh nanoparticles were also synthesized to be used as reference. All catalysts have been compared by means of: transmission electron microscopy, X-ray diffraction, and X-ray adsorption spectroscopy. The application of XAS to the study of Rh₂P NPs is unusual and has been essential in the discussion of the results. Starting with a well-defined metal precursor leads to the exclusive formation of Rh₂P NPs with excellent catalytic activity for the liquid-phase hydroformylation. The role of P is to modulate the particle size and the electronic configuration of Rh species, resulting in the improvement of the catalytic performance and the obtention of turnover frequencies of 5236 h^–1 at 60 °C and 17,788 h^–1 at 100 °C.

中文翻译：

用于烯烃加氢甲酰化的碳补丁稳定的 Rh2P 纳米颗粒

Rh ₂ P 纳米颗粒 (NP) 已被确定为 [Rh ^I (Ph ₃ P) ₃ ] ^{+ 的}合适模拟物，后者是液相加氢甲酰化中均相催化剂的基准。因此，需要一种合适的合成策略来开发完全基于 Rh ₂ P NPs 的催化剂。为了实现这一点，已经设计了两种合成途径。在第一个中，使用了两种不同的 Rh 和 P 来源。在第二个研究中，威尔金森配合物被用作 Rh 和 P 的独特来源，以探讨明确定义的分子组织对制备分散和受控的 Rh ₂的积极影响P 纳米颗粒，由 PPh ₃热解处理过程中形成的碳块稳定。此外，还合成了金属 Rh 纳米粒子以用作参考。所有催化剂都通过以下方法进行了比较：透射电子显微镜、X 射线衍射和 X 射线吸附光谱。XAS 在 Rh ₂ P NPs研究中的应用是不寻常的，并且在结果的讨论中是必不可少的。从明确定义的金属前体开始导致独家形成 Rh ₂P NPs 对液相加氢甲酰化具有优异的催化活性。P 的作用是调节 Rh 物种的粒径和电子构型，从而提高催化性能并获得60 °C下 5236 h ^–1和100 °C 下17,788 h ^–1的转换频率.

更新日期：2021-10-22

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