Guo Yingying, Wu Donghai, Li Minhan, Wang Kaixi, Zhang Shouren, He Guangli, Yin Hengbo, Huang Chenyu, Yang Baocheng, Zhang Jianan
Henan Provincial Key Laboratory of Nanocomposite and Applications Institute of Nanostructured Functional Materials Huanghe Science and Technology College Zhengzhou Henan 450006 P. R. China.
College of Materials Science and Engineering Zhengzhou University Zhengzhou 450001 P. R. China.
Small Sci. 2022 Aug 11;2(10):2200035. doi: 10.1002/smsc.202200035. eCollection 2022 Oct.
The lack of highly efficient, inexpensive catalysts severely hinders the large-scale application of electrochemical energy conversion technologies (e.g., electrochemical hydrogen evolution reaction (HER) for hydrogen production, metal-air batteries (Cathode: oxygen reduction reaction (ORR))). As a new class of nanomaterials with a high ratio of surface atoms and tunable composition and electronic structure, metal nanocluster (NCs) are promising candidates as catalysts. Herein, a novel catalyst using S,N-doped carbon matrix (NSCSs) is synthesized to efficiently stabilize high density and ultra-uniform ruthenium (Ru) nanoclusters (Ru@NSCSs) by small-molecule self-assembly pyrolysis approach. The obtained Ru@NSCSs catalyst exhibits outstanding HER activity in all pH conditions (especially with a low overpotential of 5 mV at a current density of 10 mA cm in 1 m KOH) and excellent ORR performance (half-wave potential ( ) of 0.854 V in 0.1 m KOH). Based on the experimental investigations and theoretical calculations, it is discovered that the S-atom can modulate the electronic structure and optimization of redox states on the surficial sites of Ru NCs during the ORR process. This work provides a feasible strategy for understanding and regulating the metal-support interface of ultra-uniform nanoclusters catalysts.
高效、廉价催化剂的缺乏严重阻碍了电化学能量转换技术的大规模应用（例如，用于制氢的电化学析氢反应（HER）、金属空气电池（阴极：氧还原反应（ORR）））。作为一类具有高表面原子比、可调组成和电子结构的新型纳米材料，金属纳米团簇（NCs）有望成为催化剂。在此，通过小分子自组装热解方法合成了一种使用S、N掺杂碳基质（NSCSs）的新型催化剂，以有效稳定高密度和超均匀的钌（Ru）纳米团簇（Ru@NSCSs）。所获得的Ru@NSCSs催化剂在所有pH条件下均表现出出色的HER活性（特别是在1 m KOH中电流密度为10 mA cm时过电位低至5 mV）以及优异的ORR性能（在0.1 m KOH中的半波电位（ ）为0.854 V）。基于实验研究和理论计算，发现S原子在ORR过程中可以调节Ru NCs表面位点的电子结构并优化氧化还原状态。这项工作为理解和调控超均匀纳米团簇催化剂的金属-载体界面提供了一种可行的策略。
