English

Amorphous-Crystalline Interfaces Coupling of CrS/CoS₂ Few-Layer Heterojunction with Optimized Crystallinity Boosted for Water-Splitting and Methanol-Assisted Energy-Saving Hydrogen Production

• Shi-Yu Lu ^{1, ,} ,
• Wenzhao Dou ^2, ,
• Jun Zhang ^1, ,
• Ling Wang ^2, ,
• Chunjie Wu ^2, ,
• Huan Yi ^2, ,
• Rong Wang ^{1, ,} ,
• Meng Jin ^{1, ,}

• 1.

  College of Metallurgy and Materials Engineering, Chongqing University of Science and Technology, Chongqing 401331, China

• 2.

  College of Chemistry and Chemical Engineering, Chongqing University of Science and Technology, Chongqing 401331, China

Corresponding author: Email: lushiyu@cqust.edu.cn (S.L.); Email: rongwang@cqust.edu.cn (R.W.); Email: jinmeng@cqust.edu.cn (M.J.)

• Received Date: 15 August 2023
  Accepted Date: 27 September 2023
  Revised Date: 26 September 2023
  Available Online: 15 August 2024
• Fund Project:

  the Young Elite Scientists Sponsorship Program by CAST 

  Natural Science Foundation of Chongqing 

  Natural Science Foundation of Chongqing 

  Natural Science Foundation of Chongqing 

  Talent Introduction of Chongqing University of Science and Technology 

  Talent Introduction of Chongqing University of Science and Technology 

  Talent Introduction of Chongqing University of Science and Technology 

  Science and Technology Research Program of Chongqing Municipal Education Commission 

  Science and Technology Research Program of Chongqing Municipal Education Commission 

  Science and Technology Research Program of Chongqing Municipal Education Commission 

  National Natural Science Foundation of China 

  Open Research Fund of CNMGE Platform & NSCC-TJ 

Abstract: Large-scale hydrogen production through the electrochemical water splitting technique is an important way for addressing the impending energy and environmental crisis. This approach requires highly efficient and robust bifunctional cost-effective electrocatalysts. Engineering amorphous and crystalline phases within electrocatalysts is a key method for enhancing the catalytic kinetics of water electrolysis, due to their unique physicochemical properties. The interface and amorphous regions constructed within heterostructures serve as highly active sites that play a crucial role in electrochemical reactions. On the other hand, highly crystalline regions within the heterostructure demonstrated high tolerance in harsh environments, which helps to improve the stability of the overall catalyst. However, effectively tailoring the crystalline state of catalysts within a microenvironment presents a significant challenge. Herein, construction of a novel CrS/CoS₂ heterojunction with precise control over crystallinity were presented. The optimized amorphous CrS/highly crystalline CoS₂ heterojunction (A-CrS/HC-CoS₂) exhibits a low overpotential of 90.6 mV (at 10 mA∙cm⁻²) and 370.5 mV (at 50 mA∙cm⁻²) for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations reveal that charge redistribution induces variations in the d-band center value at the A-CrS/HC-CoS₂ heterostructure interface, enhancing the catalytic activity for both HER and OER. The displacement of the d-band due to charge redistribution in the Cr―S―Co bond within A-CrS/HC-CoS₂ contributes to the modulation of the adsorption capacity of H* and OOH* intermediates on the catalyst surface, thereby optimizing the rate-determining step for HER and OER. The amorphous/highly crystalline structure also facilitates the structural and compositional evolution of A-CrS/HC-CoS₂ during water electrolysis, ensuring excellent stability. As a bifunctional catalyst in a methanol-assisted energy-saving hydrogen production device, A-CrS/HC-CoS₂ operates at a low cell voltage of 1.51 Ⅴ to deliver a current density of 10 mA∙cm⁻², making it a promising candidate among metal-based catalysts. The well-preserved amorphous/crystalline heterointerfaces in A-CrS/HC-CoS₂, along with favorable changes in surface composition, contribute to robust HER and OER stability. This work provides valuable insights into the manipulation of catalytic activity through crystalline control within amorphous/crystalline heterojunctions for bifunctional transition metal compound electrocatalysts.

Key words:
• Amorphous-crystalline interface
•  /  Heterostructure
•  /  Crystalline degree modulation
•  /  Water-splitting
•  /  Energy-saving hydrogen device

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