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催化磷化 1

异质纳米晶 1

快速充电 1

磷化锡 1

锂离子电池 1

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>In situ growth of phosphorized ZIF-67-derived amorphous CoP/Cu₂O@CF electrocatalyst for efficient hydrogen evolution reaction

《化学科学与工程前沿（英文）》 2023年第17卷第10期页码 1430-1439 doi: 10.1007/s11705-023-2320-1

摘要： Transition metal phosphides have been extensively studied for catalytic applications in water splitting. Herein, we report an in situ phosphorization of zeolitic imidazole frameworks (ZIF-67) to generate amorphous cobalt phosphide/ZIF-67 heterojunction on a self-supporting copper foam (CF) substrate with excellent performance for hydrogen evolution reaction (HER). The needle-leaf like copper hydroxide was anchored on CF surface, which acted as implantation to grow ZIF-67. The intermediate product was phosphorized to obtain final electrocatalyst (CoP/Cu₂O@CF) with uniform particle size, exhibiting a rhombic dodecahedron structure with wrinkles on the surface. The electrochemical measurement proved that CoP/Cu₂O@CF catalyst exhibited excellent HER activity and long-term stability in 1.0 mol·L^–1 KOH solution. The overpotential was only 62 mV with the Tafel slope of 83 mV·dec^–1 at a current density of 10 mA·cm^–2, with a large electrochemical active surface area. It also showed competitive performance at large current which indicated the potential application to industrial water electrolysis to produce hydrogen. First-principle calculations illustrated that benefit from the construction of CoP/ZIF-67 heterojunction, the d-band center of CoP downshifted after bonding with ZIF-67 and the Gibbs free energy (ΔG_H*) changed from –0.18 to –0.11 eV, confirming both decrease in overpotential and excellent HER activity. This work illustrates the efficient HER activity of CoP/Cu₂O@CF catalyst, which will act as a potential candidate for precious metal electrocatalysts.

关键词： CoP/Cu₂O@CF electrocatalyst phosphorization HER DFT

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原子界面催化合成SnP/CoP异质纳米晶嵌入碳杂化物用于高功率型锂离子电池 Article

胡晨, 胡彦杰, 陈爱平, 段学志, 江浩, 李春忠

《工程（英文）》 2022年第18卷第11期页码 154-160 doi: 10.1016/j.eng.2021.11.026

摘要：

磷化锡（SnP）具有极佳的锂离子扩散能力和高理论比容量，是高功率锂离子电池的理想负极材料。然而，SnP的合成难度高，大尺寸晶粒导致的电化学不可逆也阻碍了其应用。根据密度泛函理论（DFT）计算，使用原位催化磷化方法可以显著降低SnP的相对生成能。因此，在还原氧化石墨烯（rGO）包裹的碳骨架内合成了SnP/CoP异质纳米晶。所得复合材料具有超快充放电能力（50 A·g⁻¹时容量为260 mA·h·g⁻¹），且循环1500次不会出现容量衰减（2 A·g⁻¹时容量为645 mA·h·g⁻¹）。充放电机理分析表明尺寸为4.0 nm的SnP/CoP纳米晶具有高反应可逆性，且CoP在较高电位生成的金属Co加速了低电位SnP反应的动力学，从而赋予材料超快充放电能力。相对电流密度的有限元模拟进一步验证了这一现象。

关键词：催化磷化磷化锡异质纳米晶快速充电锂离子电池