IP Library › Granted Patent US 12,251,692
Granted Patent B2
US 12,251,692 · App. 17/303,005 · Granted Mar 18, 2025

Method of synthesizing high-efficiency bifunctional electrocatalysts

Inventors: Yang Yang (Orlando, FL); Jinfa Chang (Orlando, FL)
Assignee: University of Central Florida Research Foundation, Inc.
B01J37/348B01J27/1853B01J35/00B01J35/30B01J37/0238B01J37/28C25B1/04C25B11/091B82Y40/00
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Quick Facts
Patent No.
US 12,251,692
App. No.
17/303,005
Granted
Mar 18, 2025
Kind
B2
Abstract

The design of bifunctional catalysts for water splitting by modifying the electronic structure of the catalyst. That bifunctional catalyst that is synthesized is a quaternary FeNi—PSe nanoporous film (FeNi—PSe NF). A self-supported FeNi—PSE NF is synthesized and used as an anode and a cathode in a two-electrode electrolytic cell. The cell is subjected to a water source, and the FeNi—PSe NFs split the water molecules to produce hydrogen fuel. The slightly oxidized FeNi—PSe surface serves as an active site for oxygen evolution reactions, making hydrogen evolution reactions and oxygen evolution reactions well-balanced, thereby improving electrolysis efficiency.

Claims (50)

1. A method of synthesizing a bifunctional catalyst for water splitting applications, the method comprising the steps of:

forming a self-supported quaternary iron-doped nickel phosphoselenide nanoporous film by:

performing a top-down anodic conversion of an iron-doped nickel alloy film to form an iron-doped nickel-oxygen nanofilm;

thermally treating, via a tube furnace, the iron-doped nickel-oxygen nanofilm via a phosphorization treatment using a bottom-up chemical vapor deposition, forming an iron-doped nickel-phosphorus nanofilm;

subsequent to forming the iron-doped nickel-phosphorus nanofilm, cooling the tube furnace to room temperature for a predetermined period of time; and

thermally treating, via the tube furnace, the iron-doped nickel-phosphorus nanofilm with selenium vapor, using the bottom-up chemical vapor deposition, to partially substitute selenium for phosphorus, forming a quaternary iron-doped nickel phosphoselenide nanoporous film bifunctional catalyst;

wherein the quaternary iron-doped nickel phosphoselenide nanoporous film bifunctional catalyst comprises high valence nickel;

wherein the selenium stabilizes the bifunctional catalyst and improves an electrical conductivity of the bifunctional catalyst;

wherein the quaternary iron-doped nickel phosphoselenide nanoporous film includes an oxidized surface as an active site for oxygen evolution reactions, such that the quaternary iron-doped nickel phosphoselenide nanoporous film is capable of both hydrogen evolution reactions and oxygen evolution reactions during a water splitting application, thereby improving electrolysis efficiency; and

wherein the quaternary iron-doped nickel phosphoselenide nanoporous film exhibits a rate-determining final electron transfer process (hereinafter “RDS”) for hydrogen evolution reactions, whereby the RDS is dominated by the Heyrovsky step.

2. The method of claim 1 , further comprising the step of forming a plurality of pores disposed through the quaternary iron-doped nickel phosphoselenide nanoporous film, such that the plurality of pores improve a transportation of mass through the nanoporous film.

3. The method of claim 1 , wherein the quaternary iron-doped nickel phosphoselenide nanoporous film includes a thickness of 5 μm.

4. The method of claim 3 , wherein the quaternary iron-doped nickel phosphoselenide nanoporous film is disposed on a surface of an unreacted iron-nickel alloy matrix.

5. The method of claim 1 , wherein the quaternary iron-doped nickel phosphoselenide nanoporous film includes at least 10 wt % iron, at least 65 wt % nickel, at least 0.5 wt % phosphorus, and at least 23 wt % selenium.

6. The method of claim 1 , further comprising the step of subjecting the quaternary iron-doped nickel phosphoselenide nanoporous film to an amount of water.

7. The method of claim 6 , further comprising the step of converting, via the hydrogen evolution reactions, the amount of water into hydrogen fuel that is usable as a renewable energy source.

8. The method of claim 6 , wherein the quaternary iron-doped nickel phosphoselenide nanoporous film exhibits a turnover frequency of about 3.48 s −1 for oxygen evolution reactions.

9. A method of improving electrolysis efficiency during water splitting applications for improved hydrogen fuel production, the method comprising the steps of:

forming a self-supported quaternary iron-doped nickel phosphoselenide nanoporous film by:

performing a top-down anodic conversion of an iron-doped nickel alloy film to form an iron-doped nickel-oxygen nanofilm;

thermally treating, via a tube furnace, the iron-doped nickel-oxygen nanofilm via a phosphorization treatment using a bottom-up chemical vapor deposition, forming an iron-doped nickel-phosphorus nanofilm;

subsequent to forming the iron-doped nickel-phosphorus nanofilm, cooling the tube furnace to room temperature for a predetermined period of time;

thermally treating, via the tube furnace, the iron-doped nickel-phosphorus nanofilm with selenium vapor, using the bottom-up chemical vapor deposition, to partially substitute selenium for phosphorus, forming a quaternary iron-doped nickel phosphoselenide nanoporous film bifunctional catalyst;

forming a plurality of pores disposed through the quaternary iron-doped nickel phosphoselenide nanoporous film;

wherein the quaternary iron-doped nickel phosphoselenide nanoporous film bifunctional catalyst comprises high valence nickel; and

wherein the quaternary iron-doped nickel phosphoselenide nanoporous film exhibits a rate-determining final electron transfer process (hereinafter “RDS”) for hydrogen evolution reactions, whereby the RDS is dominated by the Heyrovsky step;

subjecting the quaternary iron-doped nickel phosphoselenide nanoporous film to an amount of water and flowing the amount of water through the plurality of pores disposed through the quaternary iron-doped nickel phosphoselenide nanoporous film; and

converting the amount of water into hydrogen fuel that is usable as a renewable energy source by splitting the amount of water into hydrogen molecules and oxygen molecules by capturing the oxygen molecules on an oxidized surface of the quaternary iron-doped nickel phosphoselenide nanoporous film to perform oxygen evolution reactions, such that the hydrogen molecules are recovered via hydrogen evolution reactions.

10. The method of claim 9 , wherein the quaternary iron-doped nickel phosphoselenide nanoporous film includes a thickness of 5 μm.

11. The method of claim 10 , wherein the quaternary iron-doped nickel phosphoselenide nanoporous film is disposed on a surface of an unreacted iron-nickel alloy matrix.

12. The method of claim 9 , wherein the quaternary iron-doped nickel phosphoselenide nanoporous film includes at least 10 wt % iron, at least 65 wt % nickel, at least 0.5 wt % phosphorus, and at least 23 wt % selenium.

13. The method of claim 9 , wherein the quaternary iron-doped nickel phosphoselenide nanoporous film exhibits a turnover frequency of about 3.48 s −1 for oxygen evolution reactions.

14. A method of synthesizing a high-efficiency bifunctional electrocatalyst, the method comprising the steps of:

forming a self-supported quaternary iron-doped nickel phosphoselenide nanoporous film by:

performing a top-down anodic conversion of an iron-doped nickel alloy film to form an iron-doped nickel-oxygen nanofilm;

thermally treating, via a tube furnace, the iron-doped nickel-oxygen nanofilm via a phosphorization treatment using a bottom-up chemical vapor deposition, forming an iron-doped nickel-phosphorus nanofilm;

subsequent to forming the iron-doped nickel-phosphorus nanofilm, cooling the tube furnace to room temperature for a predetermined period of time;

thermally treating, via the tube furnace, the iron-doped nickel-phosphorus nanofilm with selenium vapor, using the bottom-up chemical vapor deposition, to partially substitute selenium for phosphorus, forming a quaternary iron-doped nickel phosphoselenide nanoporous film bifunctional catalyst;

forming a plurality of pores disposed through the quaternary iron-doped nickel phosphoselenide nanoporous film; and

wherein the quaternary iron-doped nickel phosphoselenide nanoporous film bifunctional catalyst comprises high valence nickel;

wherein the quaternary iron-doped nickel phosphoselenide nanoporous film includes at least 10 wt % iron, at least 65 wt % nickel, at least 0.5 wt % phosphorus, and at least 23 wt % selenium;

wherein the selenium stabilizes the bifunctional catalyst and improves an electrical conductivity of the bifunctional catalyst;

wherein the quaternary iron-doped nickel phosphoselenide nanoporous film includes an oxidized surface as an active site for oxygen evolution reactions, such that the quaternary iron-doped nickel phosphoselenide nanoporous film is capable of both hydrogen evolution reactions and oxygen evolution reactions during a water splitting application, thereby improving electrolysis efficiency;

wherein the quaternary iron-doped nickel phosphoselenide nanoporous film exhibits a rate-determining final electron transfer process (hereinafter “RDS”) for hydrogen evolution reactions, whereby the RDS is dominated by the Heyrovsky step; and

wherein the iron-doped nickel phosphoselenide nanoporous film is disposed upon at least one portion of a surface of an unreacted iron-nickel alloy.

15. The method of claim 14 , wherein the quaternary iron-doped nickel phosphoselenide nanoporous film includes a thickness of 5 μm.

16. The method of claim 14 , further comprising the step of subjecting the quaternary iron-doped nickel phosphoselenide nanoporous film to an amount of water.

17. The method of claim 16 , further comprising the step of flowing the amount of water through the plurality of pores disposed through the quaternary iron-doped nickel phosphoselenide nanoporous film.

18. The method of claim 16 , further comprising the step of converting, via the hydrogen evolution reactions, the amount of water into hydrogen fuel that is usable as a renewable energy source.

19. The method of claim 16 , wherein the quaternary iron-doped nickel phosphoselenide nanoporous film exhibits a turnover frequency of about 3.48 s −1 for oxygen evolution reactions.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 3, 2021
From: YANG, YANG; CHANG, JINFA
To: UNIVERSITY OF CENTRAL FLORIDA RESEARCH FOUNDATION, INC.
Reel/Frame 056431/0861 →
Continuity (2)
Provisional Application 63026471 · May 18, 2020
Related Publication 20210354120A1 · Nov 18, 2021
References Cited (24)
US 20150259810A1 · Lewis · 2015 [cited by examiner]
US 20170044679A1 · Jin · 2017 [cited by examiner]
US 20180245741A1 · Etkind · 2018 [cited by examiner]
US 20210002777A1 · Kenney · 2021 [cited by examiner]
Dong, W. J., Song, Y. J., Yoon, H., Jung, G. H., Kim, K., Kim, S., Lee, J.-L., Monolithic Photoassisted Water Splitting Device Using Anodized Ni—Fe Oxygen Evolution Catalytic Substrate, Adv. Energy Mater. Jul. 2017, 170… [cited by examiner]
Yanru Liu, Yunmei Du, Wen-Kun Gao, Bin Dong, Yi Han, Lei Wang, Surface phosphorsulfurization of NiCo2O4 nanoneedles supported on carbon cloth with enhanced electrocatalytic activity for hydrogen evolution, Electrochimic… [cited by examiner]
Sengeni Anantharaj et al., Recent Trends and Perspectives in Electrochemical Water Splitting with an Emphasis on Sulfide, Selenide, and Phosphide Catalysts of Fe, Co, and Ni: A Review, ACS Catalysis 20166 (12), 8069-809… [cited by examiner]
Qian, M., Cui, S., Jiang, D., Zhang, L., Du, P., Highly Efficient and Stable Water-Oxidation Electrocatalysis with a Very Low Overpotential using FeNiP Substitutional-Solid-Solution Nanoplate Arrays, Adv. Mater. 2017, 2… [cited by examiner]
Juanjuan Huo, Yali Chen, Yan Liu, Jiaojiao Guo, Li Lu, Wenxian Li, Yong Wang, Hao Liu, Bifunctional iron nickel phosphide nanocatalysts supported on porous carbon for highly efficient overall water splitting, Sustainabl… [cited by examiner]
Kaili Liu, Fengmei Wang, Tofik Ahmed Shifa, Zhenxing Wang, Kai Xu, Yu Zhang, Zhongzhou Cheng, Xueying Zhana and Jun He, An efficient ternary CoP2xSe2(1-x) nanowire array for overall water splitting, Nanoscale, Sep. 2017… [cited by examiner]
Jiachen Li, Shengwen Li, Jun Pu, Chenglin Zhong, Qingwen Zhou, Zihan Shen, Huigang Zhang, Haixia Ma, Electronic modulation of nickel phosphide by iron doping and its assembly on a graphene framework for efficient electr… [cited by examiner]
Jing-Qi Chi, Xiao Shang, Fei Liang, Bin Dong, Xiao Li, Yan-Ru Liu, Kai-Li Yan, Wen-Kun Gao, Yong-Ming Chai, Chen-Guang Liu, Facile synthesis of pyrite-type binary nickel iron diselenides as efficient electrocatalyst for… [cited by examiner]
Anantharaj, Sengeni et al. Recent Trends and Perspectives in Electrochemical Water Splitting with an Emphasis on Sulfide, Selenide, and Phosphide Catalysts of Fe, Co, and Ni: A Review. ACS Catal. Jun. 2016, 8069-8097. [cited by applicant]
Chang, Jinfa et al. Sulfur-Doped Nickel Phosphide Nanoplates Arrays: A Monolithic Electrocatalyst for Efficient Hydrogen Evolution Reactions. ACS Appl. Mater. Interfaces Oct. 2018, (31), 26303-26311. [cited by applicant]
Chang, Jinfa et al. Ultrathin cobalt phosphide nanosheets as efficient bifunctional catalysts for a water electrolysis cell and the origin for cell performance degradation. Green Chem. 2016, 18 (8), 2287-2295. [cited by applicant]
Chang, Jinfa et al. Cobalt phosphosulfide in the tetragonal phase: a highly active and durable catalyst for the hydrogen evolution reaction. J. Mater. Chem. A 2018, 6 (26), 12353-12360. [cited by applicant]
Chang, Jinfa et al. Stable Fe2P2S6 Nanocrystal Catalyst for High-Efficiency Water Electrolysis. Small Methods 2020, 1900632. [cited by applicant]
Chang, Jinfa et al. Surface Oxidized Cobalt-Phosphide Nanorods As an Advanced Oxygen Evolution Catalyst in Alkaline Solution. ACS Catal. May 2015, 6874-6878. [cited by applicant]
Du, Yeshuang et al. Colloidal synthesis of urchin-like Fe doped NiSe2 for efficient oxygen evolution. Nanoscale Sep. 2017, (20), 6821-6825. [cited by applicant]
Konkena, Bharathi et al. Metallic NiPS3@NiOOH Core—Shell Heterostructures as Highly Efficient and Stable Electrocatalyst for the Oxygen Evolution Reaction. ACS Catal. Jul. 2017, 229-237. [cited by applicant]
Liang, Kun et al. Overall Water Splitting with Room-Temperature Synthesized NiFe Oxyfluoride Nanoporous Films. ACS Catalysis Jul. 2017, (12), 8406-8412. [cited by applicant]
Qian, Manman et al. Highly Efficient and Stable Water-Oxidation Electrocatalysis with a Very Low Overpotential using FeNiP Substitutional-Solid-Solution Nanoplate Arrays. Adv Mater. 2017, 29 (46), 1704075. [cited by applicant]
Wang, Pengyan et al. Coupling NiSe2—Ni2P heterostructure nanowrinkles for highly efficient overall water splitting. Journal of Catalysis 377 (2019) 600-608. [cited by applicant]
Zhou, Haiqing et al. One-step synthesis of self-supported porous NiSe2/Ni hybrid foam: An efficient 3D electrode for hydrogen evolution reaction. Nano Energy (2016) 20, 29-36. [cited by applicant]