Promotion of Electrocatalytic Hydrogen Evolution Reaction on Nitrogen-Doped Carbon Nanosheets with Secondary Heteroatoms

Abstract

Dual heteroatom-doped carbon materials are efficient electrocatalysts via a synergistic effect. With nitrogen as the primary dopant, boron, sulfur, and phosphorus can be used as secondary elements for co-doped carbons. However, evaluation and analysis of the promotional effect of B, P, and S to N-doped carbons has not been widely researched. Here we report a robust platform that is constructed through polydopamine to prepare N,B-, N,P-, and N,S-co-doped carbon nanosheets, characterized by similar N species content and efficient B, P, and S doping. Systematic investigation reveals S to have the greatest promotional effect in hydrogen evolution reactions (HER) followed by P and that B decreases the activity of N-doped carbons. Experimental and theoretical analyses show the secondary heteroatom promotional effect is impacted by the intrinsic structures and extrinsic surface areas of both materials, i.e., electronic structures exclusively determine the catalytic activity of active sites, while large surface areas optimize apparent HER performance.

Doping of Carbon Materials for Metal‐Free Electrocatalysis

“…In particular, they clearly pointed out, theoretically and experimentally, the well-confirmed B, N-codoped graphene had the highest catalytic capability with the optimized ratio between B, C, and N of 12:77:11 among all the BCN samples (Figure 4c,d). [84] It was found that S codoping maximized the HER performance, followed by P, whereas B codoping decreased the catalytic activity of the N-doped carbons, due to delicate effects of the secondary heteroatom-doping on electronic structures of the catalytic active sites (Figure 4f). [84] It was found that S codoping maximized the HER performance, followed by P, whereas B codoping decreased the catalytic activity of the N-doped carbons, due to delicate effects of the secondary heteroatom-doping on electronic structures of the catalytic active sites (Figure 4f).…”

“…[84][85][86][87][88][89] Of particular importance, Zhang et al, reported the first N and P codoped nanocarbon foams with a mesoporous structure (NPMC) under different pyrolysis temperatures (e.g., NPMC-1000 or NPMC-1100, as shown in Figure 5a,b) as efficient bifunctional catalysts for ORR and OER (Figure 5c) in high-performance Zn-air batteries, including the primary and rechargeable ones. This significant advantage allows for the design of new C-MFCs capable of catalyzing different (electro)chemical reactions simultaneously, such as the ORR, OER, HER, attractive for integrated clean energy technologies, such as metal-air batteries, water splitting, and their integrations.…”

“…Reproduced with permission [84]. b) LSVs of various electrodes in O 2 -saturated 0.1 m KOH electrolyte.…”

Carbon-Based Metal-Free Electrocatalysis for Energy Conversion, Energy Storage, and Environmental Protection

“…This is because increased numbers of dopant heteroatoms and electronic interactions between different doped heteroatoms often generate additional synergistic effects than single heteroatom-doped counterparts [104]. With N as the primary dopant, B, S, and P can be used as secondary elements for co-doping carbon [4,105]. Here, it was found that S-doping, followed by P-doping, greatly promotes HER.…”

CoP Embedded in Hierarchical N‐Doped Carbon Nanotube Frameworks as Efficient Catalysts for the Hydrogen Evolution Reaction

“…Further, intertwined N‐CNTs and rough surface on the polyhedron frameworks play critical role in the enhanced performance due to superior conductivity and significant exposure active sites in the harsh electrolyte condition ,. The larger amount of N‐doping in carbon ring can increase the binding energy and improve the stability during HER . Moreover, nitrogen has a chemical interaction with the nearby carbon/metal cores and changes their electronic states, including the structural defects in the carbon matrix …”