The sulfion oxidation reaction (SOR) could offer an energy-efficient and tech-economically favorable alternative to the oxygen evolution reaction (OER) for H2 production. Transition metal (TM) based catalysts have been considered promising candidates for SOR but suffer from limited activity due to the excessive bond strength from TM-S2- d-p orbit coupling. Herein, we propose a feasible strategy of screening direct d-p orbit hybridization between TM and S2- by constructing the Turing structure composed of lamellar stacking carbon-confined nickel nanosheets. The optimized p-p orbit coupling between electron-injected carbon and S2- enables exceptional catalytic activity and stability for sulfion degradation and energy-efficient yet value-added H2 production. Specifically, it achieves a current density of 500 mA cm-2 at an ultralow potential of 0.67 V vs. RHE for alkaline SOR. Theoretical calculations indicate that the electron transfer from Ni imparts metallicity and a higher p-band center to carbon shells, thereby contributing to optimized p-p orbit hybridization and a thermodynamically favorable stepwise sulfion degradation. Practically, a two-electrode flow cell achieves an industrial current density of 1 Acm-2 at an unprecedented low voltage of 0.91 V while maintaining stability for over 300 hours, and exhibits high productivities of 3.83 and 0.32 kgh-1m-2 for sulfur and H2, respectively.

中文翻译：

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受约束镍图灵结构中的筛选 d-p 轨道杂交用于硫酸盐离子氧化加速制氢


硫酸盐离子氧化反应 （SOR） 可以为 H2 生产提供一种节能且技术上有利的析氧反应 （OER） 替代方案。基于过渡金属 （TM） 的催化剂被认为是 SOR 的有前途的候选者，但由于 TM-S2-d-p 轨道耦合的键强度过高，其活性受到限制。在此，我们提出了一种可行的策略，通过构建由层状堆叠碳限制镍纳米片组成的图灵结构，筛选 TM 和 S2- 之间的直接 d-p 轨道杂交。电子注入碳和 S2- 之间优化的 p-p 轨道耦合为硫离子降解和节能但增值的 H2 生产提供了卓越的催化活性和稳定性。具体来说，与碱性 SOR 的 RHE 相比，它在 0.67 V 的超低电位下实现了 500 mA cm-2 的电流密度。理论计算表明，来自 Ni 的电子转移赋予碳壳金属丰度和更高的 p 波段中心，从而有助于优化的 p-p 轨道杂化和热力学上有利的逐步硫酸离子降解。实际上，双电极流通池在前所未有的 0.91 V 低电压下实现了 1 Acm-2 的工业电流密度，同时保持了 300 多个小时的稳定性，并且对硫和 H2 的生产率分别为 3.83 和 0.32 kgh-1m-2。