Li Rui-Qing, Guo Songyun, Wang Xiaojun, Wan Xiaoyu, Xie Shuixiang, Liu Yu, Wang Changming, Zhang Guangyu, Cao Jun, Dai Jiamu, Ge Mingzheng, Zhang Wei
School of Textile and Clothing, Nantong University Nantong 226019 PR China
Department of Physics, Zhejiang Sci-Tech University Hangzhou 310018 PR China
Chem Sci. 2024 May 16;15(26):10084-10091. doi: 10.1039/d4sc01160k. eCollection 2024 Jul 3.
Electrocatalytic hydrogen production in seawater to alleviate freshwater shortage pressures is promising, but is hindered by the sluggish oxygen evolution reaction and detrimental chloride electrochemistry. Herein, a dual strategy approach of Fe-doping and CeO-decoration in nickel phosphide (Fe-NiP/CeO) is rationally designed to achieve superior bifunctional catalytic performance for the hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR) in seawater. Notably, the two-electrode Fe-NiP/CeO-based hybrid seawater electrolyzer realizes energy-efficient and chlorine-free hydrogen production with ultralow cell voltages of 0.051 and 0.597 V at 10 and 400 mA cm, which are significantly lower than those needed in the hydrazine-free seawater electrolyzer. Density functional theory calculations manifest that the combination of Fe doping and heterointerface construction between Fe-NiP and CeO can adjust the electronic structure of the NiP and optimize the water dissociation barrier and hydrogen adsorption free energy, leading to improvement of the intrinsic catalytic performance. This route affords a feasible solution for future large-scale hydrogen generation using abundant ocean water.
利用海水进行电催化制氢以缓解淡水短缺压力具有广阔前景，但析氧反应缓慢和有害的氯化物电化学过程对其形成了阻碍。在此，合理设计了一种在磷化镍（Fe-NiP/CeO）中进行铁掺杂和氧化铈修饰的双策略方法，以实现海水中析氢反应（HER）和肼氧化反应（HzOR）的优异双功能催化性能。值得注意的是，基于Fe-NiP/CeO的两电极混合海水电解槽在10和400 mA cm时实现了节能且无氯的制氢，其超低的电池电压分别为0.051和0.597 V，这显著低于无肼海水电解槽所需的电压。密度泛函理论计算表明，铁掺杂与Fe-NiP和CeO之间异质界面的构建相结合，可以调节NiP的电子结构并优化水离解能垒和氢吸附自由能，从而提高本征催化性能。该途径为未来利用丰富的海水进行大规模制氢提供了一种可行的解决方案。
