Dynamic coordination engineering of 2D PhenPtCl<sub>2</sub> nanosheets for superior hydrogen evolution.

Shao, Gonglei; Jing, Changfei; Ma, Zhinan; Li, Yuanyuan; Dang, Weiqi; Guo, Dong; Wu, Manman; Liu, Song et al. · Nat Commun · 2024

basic_science · Level V

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Abstract

Exploring the dynamic structural evolution of electrocatalysts during reactions represents a fundamental objective in the realm of electrocatalytic mechanism research. In pursuit of this objective, we synthesized PhenPtCl<sub>2</sub> nanosheets, revealing a N<sub>2</sub>-Pt-Cl<sub>2</sub> coordination structure through various characterization techniques. Remarkably, the electrocatalytic performance of these PhenPtCl<sub>2</sub> nanosheets for hydrogen evolution reaction (HER) surpasses that of the commercial Pt/C catalyst across the entire pH range. Furthermore, our discovery of the dynamic coordination changes occurring in the N<sub>2</sub>-Pt-Cl<sub>2</sub> active sites during the electrocatalytic process, as clarified through in situ Raman and X-ray photoelectron spectroscopy, is particularly noteworthy. These changes transition from Phen-Pt-Cl<sub>2</sub> to Phen-Pt-Cl and ultimately to Phen-Pt. The Phen-Pt intermediate plays a pivotal role in the electrocatalytic HER, dynamically coordinating with Cl<sup>-</sup> ions in the electrolyte. Additionally, the unsaturated, two-coordinated Pt within Phen-Pt provides additional space and electrons to enhance both H<sup>+</sup> adsorption and H<sub>2</sub> evolution. This research illuminates the intricate dynamic coordination evolution and structural adaptability of PhenPtCl<sub>2</sub> nanosheets, firmly establishing them as a promising candidate for efficient and tunable electrocatalysts.