Single-atom transition metals supported on black phosphorene for electrochemical nitrogen reduction

Liu, Kang; Fu, Junwei; Zhu, Li; Zhang, Xiaodong; Li, Hongmei; Liu, Hui; Hu, Junhua; Liu, Min

doi:10.1039/c9nr09117c

Cited by 121 publications

(73 citation statements)

References 55 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…1c, Supplementary Figs. 3 and 4) 31 . As predicted, the FeAB-O shows much higher O 2 adsorption energy of 0.92 eV than that of FePc/AB with 0.72 eV.…”

Section: Resultsmentioning

confidence: 99%

Iron phthalocyanine with coordination induced electronic localization to boost oxygen reduction reaction

et al. 2020

Self Cite

View full text Add to dashboard Cite

Iron phthalocyanine (FePc) is a promising non-precious catalyst for the oxygen reduction reaction (ORR). Unfortunately, FePc with plane-symmetric FeN 4 site usually exhibits an unsatisfactory ORR activity due to its poor O 2 adsorption and activation. Here, we report an axial Fe-O coordination induced electronic localization strategy to improve its O 2 adsorption, activation and thus the ORR performance. Theoretical calculations indicate that the Fe-O coordination evokes the electronic localization among the axial direction of O-FeN 4 sites to enhance O 2 adsorption and activation. To realize this speculation, FePc is coordinated with an oxidized carbon. Synchrotron X-ray absorption and Mössbauer spectra validate Fe-O coordination between FePc and carbon. The obtained catalyst exhibits fast kinetics for O 2 adsorption and activation with an ultralow Tafel slope of 27.5 mV dec −1 and a remarkable half-wave potential of 0.90 V. This work offers a new strategy to regulate catalytic sites for better performance.

show abstract

“…1c, Supplementary Figs. 3 and 4) 31 . As predicted, the FeAB-O shows much higher O 2 adsorption energy of 0.92 eV than that of FePc/AB with 0.72 eV.…”

Section: Resultsmentioning

confidence: 99%

Iron phthalocyanine with coordination induced electronic localization to boost oxygen reduction reaction

et al. 2020

Self Cite

View full text Add to dashboard Cite

show abstract

Section: Applications Of Emsi In Electrocatalysismentioning

confidence: 99%

“…The WP 3 acts as an intermediary for accelerating electron transfer to activate N 2 and regulates the charge transition between the intermediates during NRR and BP as well. [ 113 ]…”

Section: Applications Of Emsi In Electrocatalysismentioning

confidence: 99%

Electronic Metal–Support Interaction of Single‐Atom Catalysts and Applications in Electrocatalysis

et al. 2020

View full text Add to dashboard Cite

between the electronic structure and catalytic efficiency of heterogenous catalysts. Dating back to 1930s, the concept of "electronic factor" was proposed by G. M. Schwab to describe the influence of electronic interaction on catalytic behavior of supported catalyst and divided the interaction into two parts, structural and synergetic ones. [4] Electrons transferring between the metal and the support was first under consideration when it came to the catalysis. After that, S. J. Tauster used the term of "strong metal-support interaction" (SMSI) to describe the chemisorption properties of group VIII elements supported by a metal oxide (e.g. SiO 2 , MgO) in 1978. [5] Later the concept was broadened to interaction between any metallic species and support, based on the experimental phenomena. [6] Till that time, based on the early characterization of surface science, researchers had realized that the active site might change during the process from metallic to an SMSI state, which was indicated to be covered or encapsulated by the support. [7] Among many hypotheses concerning the mechanism of SMSI, electron transfer between the metal and the support has been adapted by many researchers, and was confirmed by Rodriguez based on X-ray crystallography and UV photoemission spectroscopy in 1990s. [8] Then almost at the same time that the term of SACs was formally put forward, C. T. Campbell proposed the concept of "electronic metal-support interaction" (EMSI). As Campbell described, the chemical and catalytic properties might be affected by the electronic perturbations (i.e., shifts in the energy of d-band center) due to the EMSI. [9] In other words, the EMSI gave a much more detailed explanation of the enhanced properties of supported catalysts than SMSI, indicating that the study on catalysis was finally pushed to the electronic scale after so many years. [9b,c,10] Unfortunately, for metal particles or clusters, the accurate identification of electronic state is often difficult or even impossible. [11] The most reliable way to overcome the barrier above is to develop the catalyst based on single-atom metal that avoids intrinsic metal effects, including the electronic quantum size effect as well as structure-sensitivity geometrical effect. [12] Therefore, the rise of SACs provides a nearly perfect model to study the EMSI. As the supported metal species downsize to the single atom, the interaction between active site and support is always uniform, which can be much easier to be characterized by both experiment and theoretical calculation. [13] With the help of advanced techniques, for instance, X-ray absorption spectroscopy (XAS), the information about electronic The electronic metal-support interaction (EMSI), which acts as a bridge between theoretical electronic study and the design of heterogenous catalysts, has attracted much attention. Utilizing the interaction between the metal and the support is one of the most essential strategies to enhance electrocatalytic efficiency due to structural and synergetic promotion. To ...

show abstract

“…1 and 2) respectively, indicating that the asymmetric charge localization of Mo in the N-Mo/Co SAA can improve the water dissociation activity. [32][33][34][35][36] The water transition state Bader charge analyses performed to prove charge localization Mo δ+ can effectively boost water dissociation (Fig. 1c).…”

Section: Resultsmentioning

confidence: 99%

Charge localized atomic Moδ+ site boosting hydrogen evolution in alkaline solution

Cao

Liu

Song

et al. 2020

Preprint

Self Cite

View full text Add to dashboard Cite

Electrochemical water splitting has drawn tremendous interest for the scalable and sustainable conversion of renewable electricity to clear hydrogen fuel and chemicals. However, the sluggishly kinetics of water dissociation step in alkaline solutions restrict severely the application of hydrogen evolution reaction (HER). Here, we designed and prepared cobalt layers with nitrogen modified atomically dispersed Mo sites (N-Mo/Co SAA) to boost the activity of HER. Density functional theory (DFT) calculations demonstrated that the N can induce the asymmetry charge localization of Moδ+ to facilitate the water dissociation. The energy barriers of water dissociation reduced from 0.48 to 0.35 eV by the charge localized Moδ+ site. High resolution transmission electron microscope (HRTEM) and synchrotron X-ray absorption spectroscopy (XAS) measurements confirmed the structure of N modified atomically dispersed Moδ+. Ambient pressure X-ray photoelectron spectroscopy (AP-XPS) measurements assessed the atomically dispersed Moδ+ site is the active site for water dissociation. Thus, the obtained N-Mo/Co catalyst exhibits record activity with 12 mV overpotential to achieve the current density of 10 mA cm− 2 and Tafel slope of 31 mV dec− 1 in alkaline media, which are superior to 32 mV overpotential for 10 mA cm− 2 and 38 mV dec− 1 Tafel slope on best commercial 20 wt% Pt/C sample in the same condition. This design strategy provided a new pathway to boost the activity of single atom alloy (SAA) by regulating the charge localization of the active site precisely at the atomic-level.

show abstract

Single-atom transition metals supported on black phosphorene for electrochemical nitrogen reduction

Abstract: Electrochemical nitrogen reduction reaction (NRR) is a promising route to produce ammonia under mild conditions. Single-atom W supported on BP was screened as a promising electrocatalyst with high catalytic activity, stability, and selectively for NRR.

Cited by 121 publications

References 55 publications

Iron phthalocyanine with coordination induced electronic localization to boost oxygen reduction reaction

Iron phthalocyanine with coordination induced electronic localization to boost oxygen reduction reaction

Electronic Metal–Support Interaction of Single‐Atom Catalysts and Applications in Electrocatalysis

Charge localized atomic Moδ+ site boosting hydrogen evolution in alkaline solution

Contact Info

Product

Resources

About