| Citation: |
Quan Zhang, Pengcheng Liu, Wenxian Liu, Zhiwei Wang, Jia He, Guangzhi Hu, Xijun Liu. Strong 3d–4d orbital coupling mechanism in high-entropy alloys enables industrial-level alkaline seawater electrolysis[J]. Energy Lab. doi: 10.54227/elab.20250009
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Strong 3d–4d orbital coupling mechanism in high-entropy alloys enables industrial-level alkaline seawater electrolysis
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Abstract
Continuous seawater electrolysis for mass production of hydrogen suffers drawbacks from electrode corrosion and low efficiency due to the presence of multivalent ions in feed seawater. Herein, a strong 3d–4d orbital coupling mechanism is discovered in a FeNiCoMnRh high-entropy alloy (HEA), which can optimize the electron structure near the Fermi energy and reduce the universal reaction energy barrier. The HEA catalyst shows excellent hydrogen/oxygen evolution reactions with overpotentials of 21 and 297 mV at 10 mA cm−2, respectively, better than those of Pt/C and RuO2. Accordingly, it delivers 500 mA cm−2 at 2.02 V and superior durability over 250 hours in an anion exchange membrane (AEM) seawater electrolyzer. More importantly, the AEM electrolyzer only requires 0.66 V to deliver 500 mA cm−2 when it coupling with hydrazine oxidation. Thus, the 3d–4d orbital coupling mechanism in HEA can guide the development of green hydrogen fuel production.
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References
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Quan Zhang, Pengcheng Liu, Wenxian Liu, Zhiwei Wang, Jia He, Guangzhi Hu, Xijun Liu. Strong 3d–4d orbital coupling mechanism in high-entropy alloys enables industrial-level alkaline seawater electrolysis[J]. Energy Lab. doi: 10.54227/elab.20250009
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Figure 1.
Theoretical analyses and preparation of HEAs. a Schematic of 3d- and 4d-orbits metal element atomic orbital profile. b pCOHP profiles of FeNiCoMn, FeNiCoMnCu, and FeNiCoMnRh. c SEM image and partial enlarged SEM image, d and e TEM and High-resolution TEM (HRTEM) images of FeNiCoMnRh/NC. f HRTEM image corresponding to different crystal faces spacing (inset: corresponding FFT pattern and line profile). g HR-STEM image (inset: corresponding FFT pattern and line profile) and h HAADF-STEM image and elemental mapping of FeNiCoMnRh/NC.
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Figure 2.
HER and OER performance in alkaline seawater. a LSV curves of HER. b Tafel slope of HER. c Durability test of FeNiCoMnRh/NC at 10 mA cm−2 (inset: LSV in HER before and after stability). d LSV curves of OER. e Tafel slope of OER. f Durability test of FeNiCoMnRh/NC at 10 mA cm−2 (inset: LSV in OER before and after stability). g Performance of different catalysts in HER and OER (the corresponding references are listed in Supplementary Tables 3 and 5).
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Figure 3.
SWE performance in two-electrode electrolyzer. a LSV curves. b Voltage–time curves for FeNiCoMnRh/NC||FeNiCoMnRh/NC at j = 10, 50, 100 mA cm−2. c Overpotentials of different catalysts at j = 10 mA cm−2 in SWE. d Multiple chronoamperometry test in alkaline seawater. e Volumes of gaseous H2 and O2 (reaction products) at j = 50 mA cm−2. f j–V characteristics of solar panels.
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Figure 4.
Hydrazine-assisted seawater electrolysis. a LSV curves of all the tested electrocatalysts in alkaline seawater with 0.5 M N2H4. b LSV curves for SWE and OHzS using FeNiCoMnRh/NC. c Timing voltage curves for FeNiCoMnRh/NC at j = 10, 50, 100 mA cm−2 in alkaline seawater with 0.5 M N2H4. d Schematic image of AEM water electrolyzer. e, f Polarization curves of the AEM electrolyzer for SWE and hydrazine-assisted SWE. g Comparison of SWE performance between FeNiCoMnRh/NC and the reported catalysts. h Durability tests of FeNiCoMnRh/NC toward SWE and hydrazine-assisted SWE (inset shows FE throughout the test of H2 produced in SWE and hydrazine-assisted SWE).
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Figure 5.
Theoretical calculation of HER, OER, and HzOR activation energy on FeNiCoMnRh alloy catalysts. a Schematic of HER, OER, and HzOR processes catalyzed by FeNiCoMnRh HEA. b−d Schematic of free energy changes during the HER, OER, and HzOR. e Schematic of the HzOR progress with time for FeNiCoMnRh based on Ab-initio molecular dynamics simulations (AIMD).
