Photoassisted Electrochemical Hydrogen Evolution Reaction of MFe2O4@Ultrathin Black Phosphorus Amorphous-Crystalline Interface

Changchun Fan; Zhenzhen Wan; Meiling Pan; Juan Hou; Yulin Shi; Wen Guo; Gang Wang; Shanglong Peng; Qun Jing; Long Chen

doi:10.1021/acsami.2c16543

Photoassisted Electrochemical Hydrogen Evolution Reaction of MFe₂O₄@Ultrathin Black Phosphorus Amorphous-Crystalline Interface

ACS Appl Mater Interfaces. 2022 Dec 14;14(49):54748-54757. doi: 10.1021/acsami.2c16543. Epub 2022 Dec 1.

Authors

Changchun Fan^{1

2}, Zhenzhen Wan³, Meiling Pan³, Juan Hou¹, Yulin Shi¹, Wen Guo¹, Gang Wang¹, Shanglong Peng⁴, Qun Jing³, Long Chen^{1

4}

Affiliations

¹ School of Chemistry and Chemical Engineering/State Key Laboratory Incubation Base for Green Processing of Chemical Engineering, Shihezi University, Shihezi 832003, P. R. China.
² Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology, Ministry of Education, School of Chemistry, Beihang University, Beijing 100191, P. R. China.
³ School of Physical Science and Technology, Xinjiang University, 666 Shengli Road, Urumqi 830046, P. R. China.
⁴ National & Local Joint Engineering Laboratory for Optical Conversion Materials and Technology, School of Physical Science and Technology, Lanzhou University, Lanzhou 730000, P. R. China.

PMID: 36458335
DOI: 10.1021/acsami.2c16543

Abstract

Exploring highly active, stable, and low-cost catalysts for photoelectrochemical hydrogen evolution reaction (PE-HER) is vital in the field of energy conversion. Herein, we construct a new amorphous crystalline interface that amorphous iron-based spinel oxide (A-MFe₂O₄ (M = Ni, Co, Zn)) is uniformly anchored on the crystalline exfoliated black phosphorus (C-EBP) nanosheets via electrochemical and solvothermal strategies. Among these A-MFe₂O₄@C-EBP catalysts, more oxygen defects of A-NiFe₂O₄@C-EBP interface provide a larger effective electrochemical active area of 32.33 mF cm^-2 as well as a turnover frequency of 0.44 s^-1 and allow for an optimum equilibrium of the hydrogen-containing adsorption intermediates. Furthermore, A-NiFe₂O₄@C-EBP exhibits significant PE-HER performance with an overpotential of 42 mV at 10 mA cm^-2 under visible-light irradiation. Density functional theory (DFT) calculations show that the amorphous-crystalline composite structure causes a large number of oxygen defects enhancing the intrinsic activity of A-NiFe₂O₄@C-EBP, which A-NiFe₂O₄@C-EBP significantly improves its adsorption capacity for H* for HER and has the lowest Gibbs free energy change for HER. This study not only provides a superior multifunctional amorphous-crystalline interface catalysts but also helps to understand the catalytic mechanism of PE-HER.

Keywords: NiFe oxides; amorphous−crystalline composite structure; black phosphorus nanosheets; catalytic mechanism; oxygen defects; photoelectrochemical hydrogen evolution reaction.