Ding Lan, Xu Jing, Zhang Zeyu, Qi Kezhen, Jin Ge
College of Pharmacy, Dali University, Dali 671000, China.
College of Pharmacy, Dali University, Dali 671000, China.
J Colloid Interface Sci. 2025 Jul;689:137245. doi: 10.1016/j.jcis.2025.03.034. Epub 2025 Mar 4.
Electrocatalytic hydrogen evolution reaction (HER) via water splitting is a prospective technology for achieving the sustainable production of hydrogen. So, ruthenium-based electrocatalysts have been extensively studied. However, metallic ruthenium tends to agglomerate due to the high cohesive energy, resulting in decreased HER performance in practical usage. Introducing sufficient support for dispersing and immobilizing ruthenium-based species is a viable way to enhance the utilization efficiency. MXene-based materials with unique surface termination groups, superior chemical stability, high specific surface area and favorable electrical conductivity have received significant attention as low-cost carriers for the development of active catalysts in HER. Herein, nitrogen (N) and sulfur (S) atom-doped titanium carbide (TiC) quantum dots (QDs) were successfully synthesized as efficient carriers for anchoring ultra-small ruthenium nanoparticles (NPs) toward electrocatalytic HER. Electrochemical tests reveal that the resultant N,S-TiC QDs/Ru displays superior HER performance with low overpotentials of 28, 25 and 56 mV at 10 mA cm current density in 0.5 M HSO, 1 M KOH and 1 M PBS solutions, respectively. Such a low overpotential is comparable to most previously reported non-metallic catalysts, Ru-based electrocatalysts and commercial Pt/C. In addition, N,S-TiC QDs/Ru displays extraordinarily long-term stability over a relatively wide pH range and is indeed a kind of pH-universal catalyst for hydrogen evolution. Furthermore, density functional theory (DFT) calculations demonstrate that the interactions between metal Ru and N,S-TiC MXene QDs effectively regulate the electronic structure of the active site Ru, lowering the energy barrier of the electrocatalytic HER intermediate, thus dramatically enhancing the activity for N,S-TiC QDs/Ru. This work proposes a novel approach to functionalize MXene quantum dots for use as low-cost electrocatalysts with promising practical applications in renewable energy conversion.
通过水分解进行的电催化析氢反应（HER）是实现可持续制氢的一项有前景的技术。因此，钌基电催化剂已得到广泛研究。然而，由于高内聚能，金属钌容易团聚，导致其在实际应用中的析氢性能下降。引入足够的载体来分散和固定钌基物种是提高利用效率的可行方法。基于MXene的材料具有独特的表面端基、优异的化学稳定性、高比表面积和良好的导电性，作为开发用于析氢反应的活性催化剂的低成本载体受到了广泛关注。在此，成功合成了氮（N）和硫（S）原子掺杂的碳化钛（TiC）量子点（QDs），作为锚定超小钌纳米颗粒（NPs）用于电催化析氢反应的高效载体。电化学测试表明，所得的N，S-TiC QDs/Ru在0.5 M H₂SO₄、1 M KOH和1 M PBS溶液中，在10 mA cm⁻²电流密度下分别具有28、25和56 mV的低过电位，表现出优异的析氢性能。如此低的过电位与大多数先前报道的非金属催化剂、钌基电催化剂和商业Pt/C相当。此外，N，S-TiC QDs/Ru在相对较宽的pH范围内表现出超长的长期稳定性，确实是一种用于析氢的pH通用催化剂。此外，密度泛函理论（DFT）计算表明，金属Ru与N，S-TiC MXene QDs之间的相互作用有效地调节了活性位点Ru的电子结构，降低了电催化析氢反应中间体的能垒，从而显著提高了N，S-TiC QDs/Ru的活性。这项工作提出了一种新的方法来功能化MXene量子点，用作低成本电催化剂，在可再生能源转换中具有广阔的实际应用前景。
