Highly Crystalline Pd₁₃Cu₃S₇ Nanoplates Prepared via Partial Cation Exchange of Cu_1.81S Templates as an Efficient Electrocatalyst for the Hydrogen Evolution Reaction

Abstract

Chemical transformations via postsynthetic modification of colloidal nanocrystals have received great attention as a rational synthetic route to unprecedented nanostructures. In particular, the cation exchange reaction is considered as an effective method to alter the composition of the starting nanostructures while maintaining the initial structural characteristics. Herein, we report the synthesis of highly crystalline Pd 13 Cu 3 S 7 nanoplates (NPs) via partial cation exchange of the Cu 1.81 S phase by Pd cations, with Cu 1.94 S NPs and Pd 13 Cu 3 S 7 /Cu 2−x S janus heterostructure as the intermediate phases. The highly crystalline Pd 13 Cu 3 S 7 ternary NPs exhibit excellent electrocatalytic performance toward the hydrogen evolution reaction (HER) under acidic conditions. The HER activity of Pd 13 Cu 3 S 7 NPs with its overpotential as low as 64 mV at −10 mA cm −2 is superior to those of amorphous PdCuS and commercial Pd/C catalysts, demonstrating the importance of nanocrystal crystallinity in boosting the HER activity. They also exhibit excellent stability as compared to commercial Pt/C and Pd/C under strongly acidic conditions.

Cation/Anion Exchange Reactions toward the Syntheses of Upgraded Nanostructures: Principles and Applications

“…Manna and colleagues reported the synthesis of InP by a CER between Cu 3Àx P and In 3+ , which was due to the similar anion frameworks of Cu 3Àx P and wurtzite InP. 119 Similar in situ transformations due to the preservation of anionic frameworks were reported among other NCs, especially Cu-based NCs, such as Pd 13 Cu 3 S 7 by CER between Cu 1.81 S and Pd 2+ , 39 PbS by Pb 2+ and Cu 2Àx S, 115 Cu 2 ZnSnS 4 by Sn 4+ , Zn 2+ , and Cu 29 S 16 , 120 and Cu 2 SnS 3 by Cu + and SnS 2 . 121 Apart from transformations of metal chalcogenide 2D NCs, Kondo and colleagues reported the synthesis of hydrogen boride sheets derived from MgB 2 via CER, which provided new opportunities for versatile synthesis of boron-based 2D materials.…”

“…169 Based on CER-enabled composition and phase tailoring, Lee and colleagues reported the synthesis of highly crystalline Pd 13 Cu 3 S 7 nanoplates by partial CER of Cu 1.81 S nanoplates, which exhibited enhanced activity for an electrocatalytic hydrogen evolution reaction (HER), compared with Cu 1.81 S templates and amorphous PdCuS nanoplates. 39 The synthesis of hollow Mn-hexacyanoferrate prepared via CER between dense Co-hexacyanoferrate cube and Mn 2+ was reported by Wei and colleagues, which also exhibited high performances for Na-ion hybrid supercapacitors. 17 In addition, hybrid nanostructures prepared via partial CER also exhibited efficient electrocatalytic properties, such as a Mn 3 O 4 @CoMn 2 O 4 -Co x O y core-shell for ORR and OER.…”

“…(C) Teranishi et al38 Copyright 2016, the American Association for the Advancement of Science. (D) Joo and Lee et al39 Copyright 2018, American Society of Chemistry. (E) Zhang et al31 Copyright 2015, Wiley-VCH.…”

Ion exchange: an advanced synthetic method for complex nanoparticles

“…When the cation exchange reaction occurred, the six corners of the hexagonal Cu 1.81 S nanoplates acted as cation exchange sites and the direction of the cation exchange was determined by the cation species. Based on this study, Pd 13 Cu 3 S 7 NPs have been synthesized by the cation exchange reaction of Cu 1.81 S NPs [68]. Similar to the previous experiment, anisotropic diffusion appeared during the cation exchange leading to a Janus-like heterostructure.…”

“…Numerous applications were reported by utilizing ion exchanged-NPs in various devices such as solar cells, photocatalysts, and lithium batteries. In such applications, their performances were enhanced when the NPs were synthesized via ion exchange method [59, 60, 65–68].…”