Fernandez-Delgado Olivia, Puente Santiago Alain R, Galindo Betancourth Jolaine, Sanad Mohamed F, Sreenivasan Sreeprasad T, Echegoyen Luis
Department of Chemistry and Biochemistry, University of Texas at El Paso, 500 West University Avenue, El Paso, TX, 79968, USA.
Department of Chemistry, Universidad del Valle, Cali, Colombia.
Nanoscale. 2022 Mar 10;14(10):3858-3864. doi: 10.1039/d1nr05498h.
Considerable efforts are being made to find cheaper and more efficient alternatives to the currently commercially available catalysts based on precious metals for the Hydrogen Evolution Reaction (HER). In this context, fullerenes have started to gain attention due to their suitable electronic properties and relatively easy functionalization. We found that the covalent functionalization of C, C and ScN@C with diazonium salts endows the fullerene cages with ultra-active charge polarization centers, which are located near the carbon-diazonium bond and improve the efficiency towards the molecular generation of hydrogen. To support our findings, Electrochemical Impedance Spectroscopy (EIS), double layer capacitance () and Mott-Schottky approximation were performed. Among all the functionalized fullerenes, DPyScN@C exhibited a very low onset potential (-0.025 V RHE) value, which is due to the influence of the inner cluster on the extra improvement of the electronic density states of the catalytic sites. For the first time, the covalent assembly of fullerenes and diazonium groups was used as an electron polarization strategy to build superior molecular HER catalytic systems.
人们正在做出巨大努力，寻找比目前市售的基于贵金属的析氢反应（HER）催化剂更便宜、更高效的替代品。在这种背景下，富勒烯因其合适的电子性质和相对容易的功能化而开始受到关注。我们发现，用重氮盐对C、C和ScN@C进行共价功能化，使富勒烯笼具有超活性电荷极化中心，这些中心位于碳-重氮键附近，提高了分子产氢的效率。为了支持我们的发现，进行了电化学阻抗谱（EIS）、双层电容（）和莫特-肖特基近似。在所有功能化富勒烯中，DPyScN@C表现出非常低的起始电位（-0.025 V RHE）值，这是由于内部簇对催化位点电子密度态的额外改善的影响。首次将富勒烯与重氮基团的共价组装用作电子极化策略，以构建优异的分子HER催化体系。
