Louis Hitler, Ikenyirimba Onyinye J, Unimuke Tomsmith O, Mathias Gideon E, Gber Terkumbur E, Adeyinka Adedapo S
Computational and Bio-Simulation Research Group, University of Calabar, Calabar, Nigeria.
Department of Pure and Applied Chemistry, University of Calabar, Calabar, Nigeria.
Sci Rep. 2022 Sep 16;12(1):15608. doi: 10.1038/s41598-022-20048-3.
The utilization of nanostructured materials as efficient catalyst for several processes has increased tremendously, and carbon-based nanostructured materials encompassing fullerene and its derivatives have been observed to possess enhanced catalytic activity when engineered with doping or decorated with metals, thus making them one of the most promising nanocage catalyst for hydrogen evolution reaction (HER) during electro-catalysis. Prompted by these, and the reported electrochemical, electronic and stability advantage, an attempt is put forward herein to inspect the metal encapsulated, doped, and decorated dependent HER activity of C engineered nanostructured materials as effective electro-catalyst for HER. Density functional theory (DFT) calculations have been utilized to evaluate the catalytic hydrogen evolution reaction activity of four proposed bare systems: fullerene (C), calcium encapsulated fullerene (CaC), nickel-doped calcium encapsulated fullerene (NiCaC), and silver decorated nickel-doped calcium encapsulated (AgNiCaC) engineered nanostructured materials at the TPSSh/GenECP/6-311+G(d,p)/LanL2DZ level of theory. The obtained results divulged that, a potential decrease in energy gap (E) occurred in the bare systems, while a sparing increase was observed upon adsorption of hydrogen onto the surfaces, these surfaces where also observed to maintain the least E gap while the AgNiCaC surface exhibited an increased electrocatalytic activity when compared to others. The results also showed that the electronic properties of the systems evinced a correspondent result with their electrochemical properties, the Ag-decorated surface also exhibited a proficient adsorption energy [Formula: see text] and Gibb's free energy (ΔG) value. The engineered Ag-decorated and Ni-doped systems were found to possess both good surface stability and excellent electro-catalytic property for HER activities.
纳米结构材料作为多种过程的高效催化剂，其应用已大幅增加。人们观察到，包括富勒烯及其衍生物在内的碳基纳米结构材料，在经过掺杂工程处理或用金属修饰后，具有增强的催化活性，因此使其成为电催化析氢反应（HER）中最有前景的纳米笼催化剂之一。受这些因素以及所报道的电化学、电子和稳定性优势的启发，本文提出尝试研究金属封装、掺杂和修饰的碳基纳米结构材料对析氢反应活性的影响，这些材料可作为有效的析氢反应电催化剂。密度泛函理论（DFT）计算已用于评估四个提议的裸体系的催化析氢反应活性：富勒烯（C）、钙封装富勒烯（CaC）、镍掺杂钙封装富勒烯（NiCaC）以及银修饰镍掺杂钙封装（AgNiCaC）的纳米结构材料，计算采用TPSSh/GenECP/6 - 311 + G(d,p)/LanL2DZ理论水平。所得结果表明，裸体系的能隙（E）出现潜在降低，而氢吸附到表面时观察到略有增加，这些表面在吸附氢时也保持最小的能隙，同时与其他表面相比，AgNiCaC表面表现出增强的电催化活性。结果还表明，体系的电子性质与其电化学性质呈现相应结果，银修饰的表面也表现出较高的吸附能[公式：见原文]和吉布斯自由能（ΔG）值。发现经银修饰和镍掺杂的工程体系对析氢反应活性具有良好的表面稳定性和优异的电催化性能。
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