氢氧化物协同钯双活性位点用于大电流和pH通用析氢反应

doi:10.11949/0438-1157.20241430

摘要/Abstract

摘要：

开发高效催化剂对于电解水析氢反应（HER）至关重要。在乙酸锰与氯化钠混合溶液刻蚀处理的泡沫镍（NF）上电沉积钯（Pd）纳米颗粒，合成了电解水析氢催化剂（PdMn/NF-45m），Pd含量为0.52%（质量分数）。该催化剂在宽pH范围内表现出优异的HER性能，在1 mol/L KOH、0.5 mol/L H₂SO₄和1 mol/L磷酸盐缓冲液（PBS）电解液中达到1000 mA/cm²电流密度时所需的过电位仅为302、67和645 mV。溶液刻蚀增加了NF的活性表面积，Mn掺杂降低了Pd的氢吸附自由能。此外，金属氢氧化物促进了水分解为吸附氢，进而与Pd活性位点结合生成氢气，提高了析氢效率。在1000 mA/cm²的电流密度下，该催化剂在1 mol/L和6 mol/L KOH电解液中均可稳定运行240 h；在0.5 mol/L H₂SO₄溶液中可稳定运行76 h；在1 mol/L PBS溶液中可稳定运行230 h。

关键词: 低温电刻蚀, 电子结构, 析氢反应, 亲水疏气表面, 电流密度

Abstract:

The development of efficient catalysts is crucial for hydrogen evolution reaction (HER). In this study, palladium (Pd) nanoparticles were electrodeposited on nickel foam (NF) etched with a mixed solution of manganese acetate and sodium chloride to synthesize an HER catalyst (PdMn/NF-45m) with a Pd content of 0.52%(mass). This catalyst exhibited excellent HER performance over a wide pH range, requiring over potentials of only 302, 67 and 645 mV to achieve a current density of 1000 mA/cm² in 1 mol/L KOH, 0.5 mol/L H‍₂SO‍₄, and 1 mol/L phosphate-buffered saline (PBS) electrolytes, respectively. Solution etching increases the active surface area of NF, and Mn doping reduces the hydrogen adsorption free energy of Pd. Moreover, the presence of metal hydroxides promoted the dissociation of water to adsorbed hydrogen, which then combined with the active sites on the Pd surface to generate H₂, enhancing the hydrogen evolution efficiency. At a current density of 1000 mA/cm², the catalyst demonstrated stable operation for 240 h in both 1 mol/L and 6 mol/L KOH electrolytes, 76 h in 0.5 mol/L H₂SO₄ solution, and 230 h in 1 mol/L PBS solution.

Key words: low-temperature electro-etching, electronic structure, hydrogen evolution reaction, hydrophilic-hydrophobic surface, current density

中图分类号:

O 646

李同辉, 回天力, 郑涛, 张睿, 刘海燕, 刘植昌, 徐春明, 孟祥海. 氢氧化物协同钯双活性位点用于大电流和pH通用析氢反应[J]. 化工学报, 2025, 76(7): 3671-3685.

Tonghui LI, Tianli HUI, Tao ZHENG, Rui ZHANG, Haiyan LIU, Zhichang LIU, Chunming XU, Xianghai MENG. Synergistic palladium double active sites with hydroxide for high current density and pH-universal hydrogen evolution reaction[J]. CIESC Journal, 2025, 76(7): 3671-3685.

图/表 9

图1 (a) 裸露NF,(b) PdMn/NF-15m,(c) PdMn/NF-30m,(d) PdMn/NF-45m,(e) PdMn/NF-60m的SEM图像;(f) ~ (j) PdMn/NF-45m的SEM图像和EDS元素分布图像;(k) PdMn/NF-45m的制备过程示意图

Fig.1 SEM images of (a) NF, (b) PdMn/NF-15m, (c) PdMn/NF-30m, (d) PdMn/NF-45m and (e) PdMn/NF-60m; (f) — (j) SEM and EDS elemental mapping images of PdMn/NF-45m; (k) Schematic illustration of the fabrication procedure of PdMn/NF-45m

图2 (a),(b) PdMn/NF-45m的TEM图像;(c) PdMn/NF-45m的SAED图像;(d) ~ (h)PdMn/NF-45m的TEM-EDS图

Fig.2 (a), (b) TEM images of PdMn/NF-45m; (c) SAED image of PdMn/NF-45m; (d) — (h) TEM-EDS images of PdMn/NF-45m

图3 PdMn/NF-45m的XRD谱图

Fig.3 XRD pattern of PdMn/NF-45m

图4 PdMn/NF-45m XPS光谱的(a) 全谱,(b) Ni 2p,(c) Mn 2p,(d) Pd 3d,(e)O 1s,(f) C 1s;PdMn/NF-15m、PdMn/NF-30m、PdMn/NF-45m和PdMn/NF-60m的(g)Pd 3d和(h)Mn 2p XPS光谱

Fig.4 (a) Full survey spectrum, (b) Ni 2p, (c) Mn 2p, (d) Pd 3d, (e) O 1s, (f) C 1s XPS spectra of PdMn/NF-45m; (g) Pd 3d and (h) Mn 2p XPS spectra of PdMn/NF-15m, PdMn/NF-30m, PdMn/NF-45m and PdMn/NF-60m

图5 (a) PdMn/NF-45m和(b) NF的固液接触角;在1 mol/L KOH溶液中,以500 mA/cm²的电流密度对(e)裸露NF和(d)PdMn/NF-45m电极表面氢气释放行为的原位观察;(e) NF和(f) PdMn/NF-45m的固气接触角

Fig.5 Solid-liquid contact angle of (a) PdMn/NF-45m and (b) pristine NF; Insitu observation of hydrogen evolution behavior on the surface of (c)pristine NF and (d) PdMn/NF-45m electrodes under a current density of 500 mA/cm² in 1 mol/L KOH solution; Solid-gas contact angle of (e) pristine NF and (f) PdMn/NF-45m

图6 不同刻蚀时间催化剂在碱性条件下的电化学性能表征

Fig.6 Electrochemical performance characterization of catalysts with different etching times under alkaline conditions

图7 不同刻蚀时间催化剂在酸性条件下的电化学性能表征

Fig.7 Electrochemical performance characterization of catalysts with different etching times under acidic conditions

图8 不同刻蚀时间催化剂在中性条件下的电化学性能表征

Fig.8 Electrochemical performance characterization of catalysts with different etching times under neutral conditions

图9 催化剂在碱性、酸性和中性稳定性测试后XRD、XPS和SEM对比图

Fig.9 Comparison of XRD, XPS and SEM after stability tests of the catalysts under alkaline, acidic and neutral conditions

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