Crystal Facet-Manipulated 2D Pt Nanodendrites to Achieve an Intimate Heterointerface for Hydrogen Evolution Reactions

Abstract

Despite the Pt-catalyzed alkaline hydrogen evolution reaction (HER) progressing via oxophilic metal-hydroxide surface hybridization, maximizing Pt reactivity alongside operational stability is still unsatisfactory due to the lack of well-designed and optimized interface structures. Producing atomically flat two-dimensional Pt nanodendrites (2D-PtNDs) through our 2D nanospace-confined synthesis strategy, this study tackles the insufficient interfacial contact effect during HER catalysis by realizing an area-maximized and firmly bound lateral heterointerface with NiFe-layered double hydroxide (LDH). The well-oriented {110} crystal surface exposure of Pt promotes electronic interplay that bestows strong LDH binding. The charge-relocated interfacial bond in 2D-PtND/LDH accelerates the hydrogen generation steps and achieves nearly the highest reported Pt mass activity enhancement (∼11.2 times greater than 20 wt % Pt/C) and significantly improved long-term operational stability. This work uncovers the importance of the shape and facet of Pt to create heterointerfaces that provide catalytic synergy for efficient hydrogen production.

Charge transfer modulated heterointerfaces for hydrogen production at all pH values

“…23 Zeta potential ( ζ ) analysis shows a negatively charged phosphorous-rich CoP surface ( ζ = −22.4 mV), and NV-31 too has a negatively charged surface of −31.2 mV originating from the hydroxyl ion surface. In general, the LDH surface has an abundance of cations and shows a positive ζ , 24,25 but this can be reversed by surface modification. In this case, LDH is electrodeposited under a negative bias, where at first the positively charged cations were attracted towards the working electrode, and thereafter water was reduced to OH − , followed by its adsorption by the surface adsorbed cations.…”

Surface-Regulated Platinum–Copper Nanoframes in Electrochemical Reforming of Ethanol for Efficient Hydrogen Production

“…In order to figure out the unique catalytic activity of PtCu NF/C, we first used XPS to analyze their electronic structure (Figures , S26 and S27). It can be seen in Figure a that there are two peaks belonging to the states of Pt 4f 7/2 and Pt 4f 5/2 in the Pt 4f spectrum of PtCu NF/C, and each peak can be further divided into two double peaks related to Pt 0 and Pt 2+ , respectively. , As for Cu, Cu 2p 3/2 and Cu 2p 1/2 can be also divided into two doublets of Cu 0 and Cu 2+ . , Compared with PtCu ND/C, the Pt 4f 7/2 peak of the PtCu NF/C slightly shifts to the higher value (Figure a), while the Cu 2p binding energy in PtCu NF/C shifts to the lower binding energy (Figure S27), indicating that the electron transfer and electronic structure changes of Pt and Cu occurred after the dealloying process. Besides, the change in the electronic structure is also likely associated with the abundant high-index facets on the PtCu NF/C surface, which would provide more possibilities for the adsorption, activation, and dissociation of intermediates, resulting in enhanced catalytic performance.…”

“…It can be seen in Figure 4a that there are two peaks belonging to the states of Pt 4f 7/2 and Pt 4f 5/2 in the Pt 4f spectrum of PtCu NF/C, and each peak can be further divided into two double peaks related to Pt 0 and Pt 2+ , respectively. 34,35 As for Cu, Cu 2p 3/2 and Cu 2p 1/2 can be also divided into two doublets of Cu 0 and Cu 2+ . 36,37 Compared with PtCu ND/C, the Pt 4f 7/2 peak of the PtCu NF/C slightly shifts to the higher value (Figure 4a), while the Cu 2p binding energy in PtCu NF/C shifts to the lower binding energy (Figure S27), indicating that the electron transfer and electronic structure changes of Pt and Cu occurred after the dealloying process.…”

Two-Dimensional Nanomaterial-Templated Composites

“…74 As a result, fcc Au@Pt rhombic core−shell nanoplates exposing a unique (101) f basal plane and a small amount of fcc Au@Pt square core−shell nanoplates with a novel (100) f orientation (Figure 4 Specifically, Rh nanorods can be selectively deposited on different regions of Au nanosheets, i.e., two 2H/fcc heterophase basal planes and two pairs of opposite edges with fcc phase and 2H/fcc heterophase, respectively, leading to the rational construction of three kinds of distinct 1D/2D Rh−Au composites (Figure 4k). In addition to the aforementioned metal−metal heterostructures, the synthesis of other composites consisting of 2D metal templates and metal compounds, e.g., MOFs, 75 metal oxides, 76 metal hydroxides, 77 etc., has also been explored. For example, Zhang et al achieved the preparation of a novel Pd/MOF Janus structure via the selective growth of a MOF on one basal plane of Pd nanosheets.…”