Interfacial Electron Transfer Strategy to Improve the Hydrogen Evolution Catalysis of CrP Heterostructure

Abstract

Though several Pt‐free hydrogen evolution reaction (HER) catalysts have been reported, their employment for industry is challenging. Here, a facile pyrolysis method to obtain phase‐pure CrP nanoparticles supported on N, P dual‐doped carbon (CrP/NPC) is reported to be tuned toward industrial HER. Interestingly, CrP/NPC exhibits excellent HER activity that requires an overpotential of 34 mV to attain a current density of 10 mA cm−2, which is only 1 mV positive to commercial Pt/C and a potential of 55 mV to achieve a current density of 200 mA cm−2 which is better than Pt/C. In addition, the long‐term durability of CrP/NPC is far superior to Pt/C due to the strong interaction between CrP and C support, restricting any agglomeration or leaching. Density functional theory (DFT) calculations suggest that electronic modulation at the interface (CrP/NPC) optimizes the hydrogen adsorption energy. The Cr–Cr bridge site with required density of states near the Fermi level is found to be the active site. Overall, this report provides a practical scheme to synthesize rarely investigated CrP based materials along with a computational mechanistic guideline for electrocatalysis that can be utilized to explore other phosphides for various applications.

In situ encapsulation of abundant WP/Ni2P heterointerfaces in N,P co-doped two-dimensional carbon frameworks for boosting hydrogen evolution electrocatalysis

“…S1,† two distinct characteristic peaks at 1352 and 1582 cm −1 are linked to the defective and graphitic carbon, respectively. 20 The intensity ratio of I D / I G is found to decrease from 1.29 to 1.03 after introducing the WP and Ni 2 P, which implies that the formation of metal phosphide is helpful to generate more graphitic carbons.…”

“…3d unveil four obvious peaks at 129.74, 130.51, 134.00 and 133.20 eV, which correspond well to P 2p 1/2 , P 2p 3/2 , P–C and P–O, respectively. 20 Therein, the existence of P–C bonds (Fig. 3b and d) demonstrates the doping of P into N-doped carbon frameworks.…”

Designed synthesis of a hierarchical MoSe2@WSe2 hybrid nanostructure as a bifunctional electrocatalyst for total water-splitting

“…Both the experimental and theoretical evidence thus suggest that the rational design of the catalyst should be focused towards maximizing the exposure of edge sites. In this pursuit, interfacial heterostructure engineering [28][29][30][31] with enriched edge sites is one of the most promising strategies to further enhance the watersplitting reaction in alkaline media via the synergistic effect. Hence, engineering the morphology of LMDs and further heterostructure formation can improve their electrochemical activity.…”

Cerium-Doped Nickel Phosphide Nanosheet Arrays as Highly Efficient Electrocatalysts for the Hydrogen Evolution Reaction in Acidic and Alkaline Conditions

“…Because of the cost-effectiveness and great catalytic potential for the HER, nonprecious transition-metal carbides, sulfides, phosphides, and selenides have been widely investigated. − Among them, transition-metal phosphides (TMPs) feature good electrical conductivity, a hydrogenase-like catalytic mechanism, and favorable corrosion resistance, which are favorable for obtaining excellent electrocatalytic performance. ,− As a model catalyst for the HER at the beginning of research studies on transition-metal phosphide research, nickel phosphides have been extensively studied for replacing noble metal-based catalysts. ,, However, compared with other phosphide catalysts, nickel phosphide (Ni 2 P) is currently not an excellent electrocatalyst for the HER. , Generally, the electrocatalyst performance depends on the mass transport properties of the electrode surface, the number of active sites, and the intrinsic activity of each active site . The construction of self-supported electrodes with a three-dimensional open structure facilitates the diffusion of electrolyte ions, release of bubbles, and acquisition of large reaction interfaces with numerous exposed active centers. ,, For instance, Yan et al reported self-supported and hierarchical nickel phosphide nanosheet arrays on nickel foam, which exhibited an open nanostructure with abundant edges .…”

“…20,25,26 However, compared with other phosphide catalysts, nickel phosphide (Ni 2 P) is currently not an excellent electrocatalyst for the HER. 27,28 Generally, the electrocatalyst performance depends on the mass transport properties of the electrode surface, the number of active sites, and the intrinsic activity of each active site. 29 The construction of self-supported electrodes with a three-dimensional open structure facilitates the diffusion of electrolyte ions, release of bubbles, and acquisition of large reaction interfaces with numerous exposed active centers.…”