Sulfur-Phosphorus Doped Metal Composites As Superior Catalyst for Electrolytic Hydrogen Production in Real Seawater
Authors: Yen Yi Chun , Lee Chun-I , Pan Chun-Jern 
Published: August 2024

In the face of the increasingly severe global energy crisis and challenges posed by climate change, promoting energy transition has become an international consensus. Among various renewable energy sources, hydrogen is considered an ideal energy carrier due to its clean and efficient characteristics. The electrolysis of seawater for hydrogen production has garnered widespread attention for its ability to fully utilize abundant seawater resources and the advantage of zero carbon dioxide emissions. However, achieving efficient, stable, and economically viable hydrogen production in seawater still faces many challenges, with catalyst design and optimization being recognized as key issues.
Firstly, NiFe-LDH was synthesized using a simple one-pot solvothermal method. Subsequently, phosphorization, sulfurization, and sulfur-phosphorus co-doping were conducted to obtain samples namely NiFe-P, NiFe-S and NiFe-SP, respectively. Various electrochemical tests, including hydrogen evolution reaction (HER), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were firstly performed in simulated seawater to evaluate the electrochemical performance of the synthesized catalysts. The overall seawater splitting reaction was conducted with the same catalysts for both anode and cathode sides.
After comparing the electrochemical activity of four different catalysts, it was found that NiFe-SP performs superior HER activity in alkaline simulated seawater. NiFe-SP required merely -0.143 V to deliver 100 mA cm-2 current density, which was 95 mV lower than NiFe-LDH to achieve the same current density. In EIS tests, NiFe-SP exhibited a smaller charge transfer resistance than NiFe-LDH, and NiFe-SP had the largest double-layer capacitance (Cdl) value in ECSA measurements, indicating that NiFe-SP possessed and lowest reaction resistance and the maximum electrochemically active surface area.
X-ray Diffraction (XRD) and Raman spectroscopy analyses indicate that the catalyst, after sulfur-phosphorus doping, does not exhibit a pure-phase LDH structure but transforms into a heterogeneous structure of Ni3S2 and FeS2. Scanning Electron Microscopy (SEM) observations suggest that sulfur-phosphorus co-doping causes the original spherical structure of NiFe-LDH to aggregate, with the appearance of some lamellar structures on the surface. Energy Dispersive Spectroscopy (EDS) also confirms the successful doping of sulfur and phosphorus elements into NiFe-LDH, with uniform distribution on the material's surface.
Finally, the catalyst underwent a 2000-hours continuous stability test at a constant current of 100 mA cm-² in real seawater. The results indicate that the potential of NiFe-SP increased by only 5%, demonstrating that the doping of sulfur and phosphorus not only reduces the catalytic overpotential but also significantly sustains potential retention. This suggests that the metal composite structure obtained after sulfur-phosphorus co-doping is well-formed and stable. The systematic electrochemical tests and stability evaluation in this study highlights the potential of sulfur-phosphorus co-doped metal composite NiFe-SP as an efficient and stable catalyst for real seawater electrolysis. This not only contributes to a deeper understanding of the fundamental principles governing catalyst behavior but also opens new possibilities for the practical application of hydrogen production technology.

Figure 1