Dual Graphitic‐N Doping in a Six‐Membered C‐Ring of Graphene‐Analogous Particles Enables an Efficient Electrocatalyst for the Hydrogen Evolution Reaction

Lin, Zhiyu; Yang, Yang; Li, Mengsi; Hu, Wei; Cheng, Ling; Yan, Wensheng; Yu, Zhengkun; Mao, Kaitian; Xia, Guoliang; Lu, Jian; Jiang, Peng; Kang, Yang; Xu, Pengping; Wang, Changlai; Hu, Lin; Chen, Qianwang

doi:10.1002/ange.201908210

Cited by 10 publications

(3 citation statements)

References 37 publications

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“…Even though pristine graphene exhibits inert activity as electrocatalyst, it is possible to tune its electronic structures and correspondingly reactivities by introducing heteroatoms. [ 10‐12 ] For example, nitrogen dopants (generally can be classified as pyridinic N, pyrrolic N and graphitic N according to their configurations as shown in Figure 1a) can tweak the electronic and electrochemical properties of graphene sheet via tailoring the electronic density of C atoms, changing them into active sites. [ 13 ] Moreover, Bao et al .…”

Section: Introductionmentioning

confidence: 99%

MOFs‐Derived N‐Doped Carbon‐Encapsulated Metal/Alloy Electrocatalysts to Tune the Electronic Structure and Reactivity of Carbon Active Sites^†

Yang

Jiang

et al. 2021

Chin. J. Chem.

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Despite progress over the past few years in developing efficient low‐cost catalysts, precious metals are still the best catalysts for hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). However, the natural scarcity and high cost greatly hamper their large‐scale commercialization. The combination of graphene shell with metal core could tune the electronic structure of carbon active sites. Recently, nitrogen doped graphene encapsulated metal or alloy (M@NG) has emerged as novel and fascinating electrocatalysts. In this review, we focus on some recent advances in designing M@NG electrocatalysts for HER, OER and ORR through tuning electronic structure and activity of carbon active sites. We have summarized some facile and universal strategy for synthesizing various M@NG via direct annealing of metal‐organic frameworks (MOFs). With elaborated MOFs precursor design, careful control over the nitrogen doping level, metal element types and alloy structure, the electronic structure of carbon active sites can be rationally tuned to optimize activity for different electrochemical reactions. We hope this review can provide new insights into the design of M@NG with high catalytic activity.

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Section: Introductionmentioning

confidence: 99%

MOFs‐Derived N‐Doped Carbon‐Encapsulated Metal/Alloy Electrocatalysts to Tune the Electronic Structure and Reactivity of Carbon Active Sites^†

Yang

Jiang

et al. 2021

Chin. J. Chem.

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“…N-Zn-C materials retain the structural features of parent ZIF-8 particles. ZIF-8 particles are consisted of a mass of graphene-analogous particles, 33 which can provide rich active sites for implanting heteroatoms. Phosphorus has the same number of valence electrons as nitride [34][35] and a much greater radius than carbon; hence, P-doping in carbon drives local structural distortion in carbon hexagonal framework and enlarges the basal plane spacing, which could facilitate Na-ion transport.…”

Section: Introductionmentioning

confidence: 99%

Heteroatomic Interface Engineering of MOF-Derived Metal-Embedded P- and N-Codoped Zn Node Porous Polyhedral Carbon with Enhanced Sodium-Ion Storage

Zhu¹,

Li²,

Wang

et al. 2020

ACS Appl. Energy Mater.

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Amorphous-ordered mesoporous carbon materials are regarded as the most promising anode candidate for sodium-ion batteries (SIBs) owing to their ecofriendliness, abundance, thermal stability, and low price. However, poor rate, low initial Coulombic efficiency, and poor cycling performance have been the major challenges of SIBs. Herein, we successfully constructed robust phosphorus and nitrogen-codoped Zn node porous polyhedral carbon polyhedron (P-N-Zn-C). The as-prepared P-N-Zn-C anode delivers outstanding electrochemical performance and ultrahigh stability and has achieved a remarkable capacity of 460 mA h g -1 at 100 mA g -1 , long-term cycling stability of up to 100 cycles, and an excellent rate performance even at a current density of up to 1000 mA g -1 . The remarkable performance can be ascribed to the enlarged interlayer distances of carbon and the existence of Zn node, which facilitate the insertion-extraction of Na ions. The first-principle density functional theory calculations revealed that the presence of P, N, and Zn could reduce the band gaps between the valence and conduction bands and accelerate the electron transfer reaction rate. This study underscores the potential importance of heteroatom doping as an effective strategy for improving the performance of carbon electrode materials.

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“…For example, Qiao et al reported a nonmetal iodine single-atom electrocatalyst with robust structural stability and exceptional electrocatalytic activity for HER in an alkaline solution [ 31 ]. Lin et al group-fabricated a graphene-analogous material, in which the active carbon atom is displaying unusual activity toward the HER under acidic conditions [ 32 ]. Works in this direction are still at an early stage; there is still a significant challenge in understanding the catalytic reaction mechanism in monoatomic nonmetal catalysts.…”

Section: Introductionmentioning

confidence: 99%

A Unique Ru-N ₄ -P Coordinated Structure Synergistically Waking Up the Nonmetal P Active Site for Hydrogen Production

Ding

Liu

et al. 2020

Research

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Numerous experiments have demonstrated that the metal atom is the active center of monoatomic catalysts for hydrogen evolution reaction (HER), while the active sites of nonmetal doped atoms are often neglected. By combining theoretical prediction and experimental verification, we designed a unique ternary Ru-N4-P coordination structure constructed by monodispersed Ru atoms supported on N,P dual-doped graphene for highly efficient hydrogen evolution in acid solution. The density functional theory calculations indicate that the charge polarization will lead to the most charge accumulation at P atoms, which results in a distinct nonmetallic P active sites with the moderate H∗ adsorption energy. Notably, these P atoms mainly supply highly efficient catalytic sites with ultrasmall absorption energy of 0.007 eV. Correspondingly, the Ru-N4-P demonstrated outstanding HER performance not only in an acidic condition but also in alkaline environment. Notably, the performance of Ru-NPC catalyst at high current is even superior to the commercial Pt/C catalysts, whether in acidic or alkaline medium. Our in situ synchrotron radiation infrared spectra demonstrate that a P-Hads intermediate is continually emerging on the Ru-NPC catalyst, actively proving the nonmetallic P catalytically active site in HER that is very different with previously reported metallic sites.

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Dual Graphitic‐N Doping in a Six‐Membered C‐Ring of Graphene‐Analogous Particles Enables an Efficient Electrocatalyst for the Hydrogen Evolution Reaction

Cited by 10 publications

References 37 publications

MOFs‐Derived N‐Doped Carbon‐Encapsulated Metal/Alloy Electrocatalysts to Tune the Electronic Structure and Reactivity of Carbon Active Sites^†

MOFs‐Derived N‐Doped Carbon‐Encapsulated Metal/Alloy Electrocatalysts to Tune the Electronic Structure and Reactivity of Carbon Active Sites^†

Heteroatomic Interface Engineering of MOF-Derived Metal-Embedded P- and N-Codoped Zn Node Porous Polyhedral Carbon with Enhanced Sodium-Ion Storage

A Unique Ru-N ₄ -P Coordinated Structure Synergistically Waking Up the Nonmetal P Active Site for Hydrogen Production

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Dual Graphitic‐N Doping in a Six‐Membered C‐Ring of Graphene‐Analogous Particles Enables an Efficient Electrocatalyst for the Hydrogen Evolution Reaction

Cited by 10 publications

References 37 publications

MOFs‐Derived N‐Doped Carbon‐Encapsulated Metal/Alloy Electrocatalysts to Tune the Electronic Structure and Reactivity of Carbon Active Sites†

MOFs‐Derived N‐Doped Carbon‐Encapsulated Metal/Alloy Electrocatalysts to Tune the Electronic Structure and Reactivity of Carbon Active Sites†

Heteroatomic Interface Engineering of MOF-Derived Metal-Embedded P- and N-Codoped Zn Node Porous Polyhedral Carbon with Enhanced Sodium-Ion Storage

A Unique Ru-N 4 -P Coordinated Structure Synergistically Waking Up the Nonmetal P Active Site for Hydrogen Production

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MOFs‐Derived N‐Doped Carbon‐Encapsulated Metal/Alloy Electrocatalysts to Tune the Electronic Structure and Reactivity of Carbon Active Sites^†

MOFs‐Derived N‐Doped Carbon‐Encapsulated Metal/Alloy Electrocatalysts to Tune the Electronic Structure and Reactivity of Carbon Active Sites^†

A Unique Ru-N ₄ -P Coordinated Structure Synergistically Waking Up the Nonmetal P Active Site for Hydrogen Production