Liu Lin,Yunming Xu,Yiting Han,Ruikun Xu,Tongyue Wang,Zemin Sun,Zhenhua Yan
A deep understanding of the mechanism for the spin-magnetic effect on O–H cleavage is crucial for the development of new catalysts for water oxidation. Herein, we designed and synthesized the crystalline Fe-DABDT and Co-DABDT (DABDT = 2,5-diaminobenzene-1,4-dithiol) and optimized an effective magnetic moment to explore the role of the spin-magnetic effect in the regulation of water oxidation activity. It can be found that the OER activity of the catalyst is positively correlated with its effective magnetic moment. Under the external magnetic field, Fe-DABDT with more spin single electrons has a stronger spin-magnetic response to water oxidation than Fe/Co-DABDT and Co-DABDT. The increase in OER current of Fe-DABDT is nearly 2 times higher than that of Co-DABDT. Experimental and density functional theory studies show that magnetized Fe sites could realize nucleophilic reaction, accelerate the polarization of electron spin states, and promote the polar decomposition of O–H and the formation of the O–O bond. This study provides mechanistic insight into the spin-magnetic effect of oxygen evolution reaction and further understanding of the spin origin of catalytic activity, which is expected to improve the energy efficiency of hydrogen production.
The sp 3 hybridization of surface sulfur in metallic phase molybdenum disulfide (1T MoS 2 ) is identified as the intrinsic bottleneck for alkaline hydrogen production (HER), where their electron-saturated nature elevates the kinetic barrier for water dissociation. To overcome this limitation, a charge-buffered sulfidation strategy is reported to stabilize anionic boron (B δ− ) within 1T MoS 2 . By employing molybdenum aluminum boride as the precursor, the B δ− dopants can be efficiently preserved via the topological confinement imposed by Mo─B─Mo network. This approach also maintains the 1T phase integrity through Al-mediated electron compensation. Theoretical and experimental analyses reveal that B δ− substitution generates vertically oriented empty p z orbitals through sp 2 hybridization, which elevates orbital energy to align with molecular orbitals of water, significantly reducing the O─H cleavage barrier by over 80% compared to 1T MoS 2 . Concurrently, the B─Mo─S networks upshift adjacent sulfur 3p band centers to optimize the hydrogen adsorption path. These dual functionalities endow the p z -functionalized 1T MoS 2 with a low overpotential of −30 mV at 10 mA cm −2 , and high-current operation of 1 A cm −2 at 1.779 V in an anion-exchange membrane electrolytic cell. This work not only establishes orbital alignment as a transformative design principle for advanced electrocatalysts, but also paves a novel synthetic pathway for 1T transition metal disulfides.
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