Wang Xiuwen, Su Tingting, Lu Zhaohui, Yu Lan, Sha Ning, Lv Chunmei, Xie Ying, Ye Ke
Heilongjiang Provincial Key Laboratory of Surface Active Agent and Auxiliary, Qiqihar University, Qiqihar 161006, China.
Heilongjiang Provincial Key Laboratory of Surface Active Agent and Auxiliary, Qiqihar University, Qiqihar 161006, China.
J Colloid Interface Sci. 2025 Aug;691:137389. doi: 10.1016/j.jcis.2025.137389. Epub 2025 Mar 19.
Developing feasible synthetic strategies for preparing advanced nanomaterials with narrow size distributions and well-defined structures represents a cutting-edge field in alkaline water and seawater electrolysis. Herein, the monodispersed CoP nanocrystals with tunable morphologies, namely one-dimensional nanorods (CoP-R), nanoparticles (CoP-P), and nanospheres (CoP-S), were controllably synthesized by using a Schlenk system through optimizing the reactivity of cobalt- and phosphorus-based sources. The resulting CoP-R exhibited superior electrocatalytic activity for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in 1.0 M KOH, simulated seawater, and natural seawater. Impressively, the reconstructed active species effectively avoid the chlorine evolution on CoP-R surface and facilitate OER process. Density functional theory (DFT) calculations revealed that CoP-R exhibited an optimal d-band center (ε) and a lower energy barrier for the rate-determining steps in both HER and OER processes in comparison with CoP-P and CoP-S. Additionally, the CoP-R showed a more favorable water adsorption energy (E) over Cl adsorption energy (E), which contributes to its enhanced seawater electrolysis performance. The CoP-R||CoP-R electrolyzer achieves a low voltage of 1.70, 1.76, and 1.76 V at 100 mA cm in alkaline freshwater, simulated seawater, and natural seawater, respectively, and demonstrates stable operation for 200 h at 100 mA cm.
开发可行的合成策略以制备具有窄尺寸分布和明确结构的先进纳米材料是碱性水电解和海水电解领域的前沿课题。在此，通过使用Schlenk体系，通过优化钴源和磷源的反应活性，可控地合成了具有可调形态的单分散CoP纳米晶体，即一维纳米棒（CoP-R）、纳米颗粒（CoP-P）和纳米球（CoP-S）。所得的CoP-R在1.0 M KOH、模拟海水和天然海水中对析氢反应（HER）和析氧反应（OER）均表现出优异的电催化活性。令人印象深刻的是，重构的活性物种有效地避免了CoP-R表面的析氯反应，并促进了OER过程。密度泛函理论（DFT）计算表明，与CoP-P和CoP-S相比，CoP-R在HER和OER过程中的速率决定步骤表现出最佳的d带中心（ε）和较低的能垒。此外，CoP-R对水的吸附能（E）比对Cl的吸附能（E）更有利，这有助于其增强的海水电解性能。CoP-R||CoP-R电解槽在碱性淡水、模拟海水和天然海水中，在100 mA cm时分别实现了1.70、1.76和1.76 V的低电压，并在100 mA cm下稳定运行200 h。
