Research Progress of Cobalt Phosphide Heterojunction Catalysts for Electrolytic Hydrogen Evolution Reaction

doi:10.19894/j.issn.1000-0518.230135

Chinese Journal of Applied Chemistry ›› 2023, Vol. 40 ›› Issue (8): 1175-1186.DOI: 10.19894/j.issn.1000-0518.230135

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Research Progress of Cobalt Phosphide Heterojunction Catalysts for Electrolytic Hydrogen Evolution Reaction

Wei WANG, Jia-Yuan LI()

School of Chemistry and Chemical Engineering，Northwestern Polytechnical University，Xi′an 710072，China

Received:2023-05-06 Accepted:2023-07-06 Published:2023-08-01 Online:2023-08-24
Contact: Jia-Yuan LI
About author:jiayuanli@nwpu.edu.cn
Supported by:
China Postdoctoral Science Foundation （No.?2021M702667）?, the Fundamental Research Funds for the Central Universities(D5000210829);Guangdong Basic and Applied Basic Research Foundation(2021A1515110643)

Abstract

Abstract:

Hydrogen （H₂）， a renewable green energy source， has been widely focused on tackling environmental issues and fossil energy shortages. The development of low-cost， highly efficient and stable electrocatalysts towards hydrogen evolution reaction （HER） is one of the major challenges facing the large-scale utilization of hydrogen. Cobalt phosphide （CoP） has been widely studied in the field of electrocatalytic HER due to its metal-like properties and corrosion resistance in acid and alkali electrolytes. This review firstly elaborates the major advantages and challenges for CoP heterojunction as electrocatalyst for HER. Next， the different effects of the CoP heterojunction on HER are discussed. Finally， the prospects of CoP heterojunction for HER electrocatalysis are summarized and prospected.

Key words: Hydrogen evolution reaction, Electrocatalysis, Cobalt phosphate, Heterojunction, Catalyst activity, Catalytic mechanism

CLC Number:

O643.3

Wei WANG, Jia-Yuan LI. Research Progress of Cobalt Phosphide Heterojunction Catalysts for Electrolytic Hydrogen Evolution Reaction[J]. Chinese Journal of Applied Chemistry, 2023, 40(8): 1175-1186.

Figures/Tables 7

Table 1 Comparison of HER properties of CoP heterojunction electrocatalysts

Catalysts	Electrolyte	η₁₀/mV	Tafel slope/（mV·dec^-1）	Durability/h	Ref.
CoP nanosheet	1.0 mol/L KOH	175	146.69	—	［7］
CoP	1.0 mol/L KOH	160	106	—	［13］
CoP nanwires	1 mol/L KOH	137	76.8	—	［30］
CoP nanoparticles	0.5 mol/L H₂SO₄	137	67	—	［31］
CoP nanorods	1 mol/L PBS	122.4	81.1	—	［32］
CoP/CeO _x	1.0 mol/L KOH	118	77.26	24	［7］
Pt₂Ir₁/CoP	0.5 mol/L H₂SO₄	η₂₀=7	25.2	500	［10］
CoP/NiCoP	1 mol/L KOH	133	88	24	［13］
O，Cu-CoP	1 mol/L KOH	72	57.6	24	［30］
Ni₂P/CoP	0.5 mol/L H₂SO₄	105	64	—	［31］
CoP@CoOOH	1 mol/L PBS	89.6	64.4	40	［32］
CoP NS/CNTs	1.0 mol/L KOH	68	57	24	［33］
CoP/CoO PNTs	1.0 mol/L KOH	61	78	10	［34］
CoSe₂/CoP	0.5 mol/L H₂SO₄	65	54	50	［35］
CoP/CoMoP	1.0 mol/L KOH	34	33	12	［36］
NiFe-LDH@NiCoP/NF	1 mol/L KOH	120	88.2	100	［37］
CoP-Co _x O _y /CC	1 mol/L KOH	43	64.7	70	［38］
CoP-Mo₂C@NC	1 mol/L KOH	94	79.7	15	［39］
R-Mn-CoP	1 mol/L KOH	117	54	—	［40］
CoP/Co-MOF	0.5 mol/L H₂SO₄	27	43	17	［41］
	1 mol/L PBS	49	63	17
	1 mol/L KOH	34	56	17
N-CoP/CC	0.5 mol/L H₂SO₄	25	49	30	［42］
	1 mol/L PBS	74	69	30
	1 mol/L KOH	39	58	30

Fig.1 Different effects of heterojunction assist in electrolysis of water to produce hydrogen

Fig.2 （a） HER polarization curves of different catalysts in 1.0 mol/L KOH；（b） Comparison of overpotentials at 10 mA/cm2；（c） Tafel plots of different catalysts；（d） Ealculated H2O adsorption energies on different surfaces；（e） Calculated H* adsorption energies on different surfaces；（f） DOSs on CoO， CoP and CoO/CoP heterostructures［34］

Fig.3 （a） HER polarization curves of CoP/CeO x -10∶?1， CoP/CeO x -20∶?1， CoP/CeO x -30∶?1， CoP， and CeO x in 1 mol/L KOH；（b） Tafel plots of CoP/CeO x -10∶?1， CoP/CeO x -20∶?1， CoP/CeO x -30∶?1， CoP， and CeO x in 1 mol/L KOH；（c） Chronoamperometry curve of CoP/CeO x -20∶?1；（d） SEM image of CoP/CeO x -20∶?1 after HER；（e） HAADF-STEM image of CoP/CeO x -20∶?1 after HER；（f） Energy diagrams of CeO x and CoP before and after contact and schematic diagram of the proposed mechanism for catalyzing HER in the CoP/CeO x p-n heterojunction；（g） Partial density of states （PDOS） of the Co3d band of CoP （211）（top panel） and CoP（211）/CeO2（111） heterojunction （bottom panel）. The positions of d-band centers are marked by vertical dashed lines［7］

Fig.4 （a） The schematic diagram to illustrate the fabrication process of CoP/CoMoP via topotactic conversion from CoCH；（b） High-resolution TEM of CoP/CoMoP；（c） The HER iR-corrected polarization curves of CoP/CoMoP， pure-CoP， pure-CoMoP， Pt/C and bare Ni foam with a scan rate of 2 mV/s in 1 mol/L KOH；（d） The corresponding Tafel plots；（e） The mechanisms of the cooperative CoP/CoMoP interfaces acting on HER in alkaline electrolyte［36］

Fig.5 （a） LSV curves of various Pt2M1/CoP and Pt/CoP catalysts （mass percent 1.0%） and Pt/C （mass percent 20%） benchmarks；（b） LSV-derived Tafel plots for various catalysts；（c） Comparisons of the noble-metal utilization activity of Pt2Ir1/CoP （mass percent 1.0%） for HER with those of other well-known noble-metal based catalysts， especially the single-atom Pt catalysts；（d） Catalytic durability of Pt2Ir1/CoP （mass percent 1.0%） through a time-overpotential profile at 40 mA/cm2. Insets are cycle performance of LSV curves and Faradic efficiency；（e） Calculated free energy diagram for HER on Pt2Ir1/CoP paradigm and Pt/CoP benchmark；（f） The optimized H* adsorption structures at various sites；（g） Electron density difference map of interfaces， where a loss of electrons is indicated in blue and electron enrichment is indicated in red［10］

Fig.6 （a） Polarization curves in 1 mol/L KOH；（b） Tafel plots in 1 mol/L KOH；（c） Polarization curves in 0.5 mol/L H2SO4；（d） Tafel plots in 0.5 mol/L H2SO4；（e） Cycle performance of LSV curves of the samples in 1 mol/L KOH and 0.5 mol/L H2SO4；（f） Long-time chronoamperometry tests in 1 mol/L KOH and 0.5 mol/L H2SO4；（g） The optimized hydrogen atom adsorption structure；（h） The optimized hydrogen H2O adsorption structure［13］

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Research Progress of Cobalt Phosphide Heterojunction Catalysts for Electrolytic Hydrogen Evolution Reaction

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