Preparation of Molybdenum Phosphide⁃based Catalyst and Its Application in Water Electrolysis

doi:10.19894/j.issn.1000-0518.210086

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (3): 439-450.DOI: 10.19894/j.issn.1000-0518.210086

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Preparation of Molybdenum Phosphide⁃based Catalyst and Its Application in Water Electrolysis

Bo-Yang CUI, Hong-Da WU, Zong-Bao YU, Zong-Xing GENG, Tie-Qiang REN, Chun-Wei SHI, Zhan-Xu YANG()

School of Petrochemical Engineering，Liaoning Petrochemical University，Fushun 113001，China

Received:2021-03-01 Accepted:2021-06-23 Published:2022-03-01 Online:2022-03-15
Contact: Zhan-Xu YANG
About author:zhanxuy@126.com
Supported by:
the National Natural Science Foundation of China(21671092);Liaoning Provincial Science and Technology Innovation Leading Talent Project(XLYC1802057);the Joint Research Fund of Liaoning?Shenyang National Laboratory for Materials Science, China(2019010280?JH3/301);Fushun Youth Talents Project(FSYC202007001)

Abstract

Abstract:

With dodecyl amine intercalated orthorhombic molybdenum trioxide as the precursor， PH₃ was produced by decomposition of sodium hypophosphite as the phosphorus source， in a confined space by in-situ carbonization and phosphating method to synthesize “N-doped MoP/graphite” composite materials. The microstructure and physicochemical properties of the catalyst samples obtained at different phosphating temperatures of 700， 800 and 900 ℃ were characterized by scanning electron microscopy （SEM）， transmission electron microscopy （TEM）， X-ray diffraction （XRD）， X-ray photoelectron spectroscopy （XPS）， Raman spectroscopy （Raman）， and specific surface area measurement （BET）. The catalytic performance in the hydrogen evolution reaction （HER） of water was investigated. The results show that part of dodecyl amine decomposes to form N-doped graphite as the conductive structure， and the other part decomposes to form nitrogen-doped molybdenum phosphide. The 800 ℃ phosphating sample has the largest pore size ratio and electrochemically active surface area， and shows the best catalytic performance （overpotential η_onset=111 mV， Tafel slope b=70 mV/dec and excellent stability of 27 hours） which is better than those of most reported molybdenum phosphide catalysts.

Key words: Catalyst, Electrolyzed water, Hydrogen production, Molybdenum phosphide

CLC Number:

O614.6

Bo-Yang CUI, Hong-Da WU, Zong-Bao YU, Zong-Xing GENG, Tie-Qiang REN, Chun-Wei SHI, Zhan-Xu YANG. Preparation of Molybdenum Phosphide⁃based Catalyst and Its Application in Water Electrolysis[J]. Chinese Journal of Applied Chemistry, 2022, 39(3): 439-450.

Figures/Tables 10

Fig.1 XRD patterns of MoO3， MoO3/DDA（A）， MoP-700， MoP-800， MoP-900 and MoO2 （B）

Fig.2 FT-IR spectra of MoO3/DDA and MoO3 precursor

Fig.3 SEM images of α-MoO3 （A）， MoO3/DDA （B）， MoP-700 （C）， MoP-800（D）， MoP-900 （E） and MoO2 （F）

Fig.4 TEM （A） and HRTEM （B） images of MoP-800； EDX images of MoP-800（C）

Fig.5 XPS spectra of MoP-800：Mo 3d （A）， P 2p （B）， C 1s （C）， N 1s （D）

Fig.6 Raman patterns of MoP-700， MoP-800， MoP-900 and MoO2 （A）；The fitted Raman D and G peaks of MoP-700 （B）， MoP-800 （C） and MoP-900 （D）

Table 1 The nitrogen and carbon content of the catalyst

样品

Samples

氮元素含量

X（N）/%

碳元素含量

X （C）/%

Fig.7 N2 adsorption-desorption isotherms of MoP-700， MoP-800， MoP-900 and MoO2 （A）； Pore size distribution curves of MoP-700， MoP-800， MoP-900and MoO2 （B）

Fig.8 Electrochemical test results of MoP-700， MoP-800， MoP-900 and MoO2： Polarization curves（A）； Tafel plots （B）； Nyquist plots （C）； Cdl of different materials （D）； Electrolysis curve of MoP-800 at a fixed current of -10 mA for more than 27 h （E）； The stability test of MoP-800 with an initial LSV curve and after 1000 cycles （F）

Table 2 Comparison of HER parameters of several molybdenum phosphide catalysts

催化剂 Catalysts	电解液 Electrolyte	过电势 η₁₀/（mA·cm^-2）	塔菲尔斜率 Tafel slope/（mV·dec^-1）	参考文献 Ref.
MoP?RGO	0.5 mol/L H₂SO₄	117	62	37
MoP@C@rGO	0.5 mol/L H₂SO₄	168.9	79	38
MoP@NPC?S	0.5 mol/L H₂SO₄	141	61	39
MoP/NPG	0.5 mol/L H₂SO₄	148	49	40
MoP/Mo₂N	0.5 mol/L H₂SO₄	89	51	41
CoMoP	0.5 mol/L H₂SO₄	39	73.3	42
MoC?MoP/BCNC	0.5 mol/L H₂SO₄	158	58	43
MoP/Co₂P	0.5 mol/L H₂SO₄	140	80	44
HF?MoSP?800 硫化钼/磷化钼复合材料	0.5 mol/L H₂SO₄	108	82	45
MoP/N掺杂石墨 MoP/N doped graphite	0.5 mol/L H₂SO₄	111	70	本文 This work

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Preparation of Molybdenum Phosphide⁃based Catalyst and Its Application in Water Electrolysis

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