Decoding the Hume-Rothery Rule in a Bifunctional Tetra-metallic Alloy for Alkaline Water Electrolysis.
basic_science · Level V
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- Record sourced from PubMed, PMID 39818956.
- Also identified by DOI 10.1021/acs.nanolett.4c04412.
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Abstract
The 90-year-old Hume-Rothery rule was adapted to design an outstanding bifunctional tetra-metallic alloy electrocatalyst for water electrolysis. Following the radius mismatch principles, Fe (131 pm) and Ni (124 pm) are selectively incorporated at the Pd (139 pm) site of Mo<sub>0.30</sub>Pd<sub>0.70</sub> nanosheets. Analogously, Cu (132 pm) alloys with only Pd, while Ag (145 pm) alloys with both Pd and Mo (154 pm). The face-centered cubic Mo<sub>0.30</sub>Pd<sub>0.35</sub>Ni<sub>0.23</sub>Fe<sub>0.12</sub> nanosheets with 10-12 atomic layers, featuring in-plane compressive strain along the {111} basal plane, show 1/3 (422) reflection from local hexagonal symmetry. The more electronegative Pd attracts electron density from Ni/Fe in Mo<sub>0.30</sub>Pd<sub>0.35</sub>Ni<sub>0.23</sub>Fe<sub>0.12</sub>, synergistically boosting the mass activities for hydrogen and oxygen evolution reactions to 89 ± 5 and 38.6 ± 3.1 A g<sup>-1</sup> at ±400 mV versus RHE, respectively. Full water electrolysis continues for ≥550 h, requiring cell voltages of 1.51 and 1.63 V at 10 and 100 mA cm<sup>-2</sup>, delivering 45 mL h<sup>-1</sup> green H<sub>2</sub>.