Chen Jianmin, Wang Yajing, Zhou Mingjun, Li Yingwei
State Key Laboratory of Pulp and Paper Engineering, School of Chemistry and Chemical Engineering, South China University of Technology Guangzhou 510640 China
Chem Sci. 2022 Mar 30;13(16):4647-4653. doi: 10.1039/d2sc00038e. eCollection 2022 Apr 20.
The conversion of biomass-derived platform molecules (, 5-hydroxymethyl furfural (HMF)) represents a sustainable route to produce value-added chemicals. Here we report the fabrication of an N-doped carbon nanotube assembled yolk-shell polyhedron with embedded Co-CoS nanoparticles (NPs) (Y-Co-CoS @CN) for efficient HMF electrooxidation. DFT calculations demonstrate that the formation of the heterojunction could intensify spin polarization in Co-CoS, thus achieving effective d-p coupling between the catalyst and reactant/intermediate. As expected, Y-Co-CoS @CN exhibits excellent HMF electro-oxidation activity at a low applied potential of 1.29 V RHE at 10 mA cm in 0.1 M KOH with 5 mM HMF, affording an FDCA yield of 96% and FE of 93.5%. This work not only sheds light on the catalytic nature of the heterojunction and the underlying mechanisms for the enhancement of HMF electro-oxidation activity, but would also provide a descriptor for the rational design of advanced electro-catalysts.
生物质衍生平台分子（如5-羟甲基糠醛（HMF））的转化是生产高附加值化学品的可持续途径。在此，我们报道了一种用于高效HMF电氧化的氮掺杂碳纳米管组装的蛋黄壳多面体，其内部嵌入了Co-CoS纳米颗粒（Y-Co-CoS@CN）。密度泛函理论（DFT）计算表明，异质结的形成可以增强Co-CoS中的自旋极化，从而实现催化剂与反应物/中间体之间有效的d-p耦合。正如预期的那样，Y-Co-CoS@CN在0.1 M KOH中含5 mM HMF、电流密度为10 mA cm时，在1.29 V（相对于可逆氢电极（RHE））的低施加电位下表现出优异的HMF电氧化活性，FDCA产率为96%，法拉第效率（FE）为93.5%。这项工作不仅揭示了异质结的催化本质以及增强HMF电氧化活性的潜在机制，还将为先进电催化剂的合理设计提供一个描述符。
