富缺陷<strong>Pd</strong>纳米片的合成和对甘油的电催化氧化性能

doi:10.11901/1005.3093.2024.443

材料研究学报

2025, Vol. 39

Issue (8): 632-640 DOI: 10.11901/1005.3093.2024.443

研究论文

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富缺陷Pd纳米片的合成和对甘油的电催化氧化性能

谭德新, 陈诗慧, 罗小丽, 宁小媚, 王艳丽(

)

岭南师范学院化学化工学院湛江 524048

Synthesis of Pd Nanosheets with Numerous Defects and Their Electrocatalytic Oxidation Performance for Glycerol

TAN Dexin, CHEN Shihui, LUO Xiaoli, NING Xiaomei, WANG Yanli(

)

School of Chemistry and Chemical Engineering, Lingnan Normal University, Zhanjiang 524048, China

引用本文:

谭德新, 陈诗慧, 罗小丽, 宁小媚, 王艳丽. 富缺陷Pd纳米片的合成和对甘油的电催化氧化性能[J]. 材料研究学报, 2025, 39(8): 632-640.
Dexin TAN, Shihui CHEN, Xiaoli LUO, Xiaomei NING, Yanli WANG. Synthesis of Pd Nanosheets with Numerous Defects and Their Electrocatalytic Oxidation Performance for Glycerol[J]. Chinese Journal of Materials Research, 2025, 39(8): 632-640.

全文: PDF(9954 KB) HTML

摘要:

以Pd(NO₃)₂·2H₂O为前驱体，在水/乙醇(体积比4∶1)体系中调控十六烷基三甲基溴化铵(CTAB)的用量构建软模板体系，用超声辅助模板技术制备出富缺陷Pd纳米片，使用XRD、FESEM、TEM、UV-vis等手段对其表征，研究了对甘油的电催化氧化(GOR)性能。结果表明，这种富缺陷Pd纳米片有大量的缺陷(晶面扩张、晶格畸变、位错、孪晶界)，厚度约为8.10 nm。这种富缺陷Pd纳米片在碱性介质中对甘油的电催化质量活度为4179.82 mA/mg (是商用Pd/C(562.77 mA/mg)的7.43倍)，比表面活度为9.12 mA/cm²(是商业Pd/C(1.57 mA/cm²)的5.81倍)。同时，这种Pd纳米片还具有对GOR的高抗中毒性和良好的稳定性。

关键词 ：金属材料, 钯纳米片, 电催化氧化, 缺陷

Abstract：

A soft template was constructed by adjusting the amount of CTAB in a water/ethanol solution (volume ratio 4:1) with Pd(NO₃)₂·2H₂O as the Pd precursor, then Pd nanosheets were prepared via ultrasonic-assisted template technology. The nanosheets were characterized by XRD, FESEM, TEM, and UV-vis spectroscopy, and their electrocatalytic oxidation of glycerol was investigated by cyclic voltammetry and chronoamperometry methods. The results revealed that the obtained Pd nanosheets possessed abundant defects, including crystal face expansion, lattice distortion, dislocation, and twin boundary etc. These nanosheets had a thickness of approximately 8.10 nm and exhibited a mass activity of 4179.82 mA/mg for glycerol oxidation in alkaline media, which was 7.43 times higher than that of commercial Pd/C (562.77 mA/mg). Furthermore, the specific activity of the Pd nanosheets was 9.12 mA/cm², which was 5.81 times greater than that of the commercial Pd/C (1.57 mA/cm²). In addition, these Pd nanosheets also demonstrated high resistance against poisoning and excellent stability during glycerol oxidation reaction (GOR).

Key words： metallic materials Pd nanosheet electrocatalytic oxidation defect

收稿日期: 2024-10-29

ZTFLH:

TG146.3+6

基金资助:广东省基础与应用基础研究基金(2022A1515011970);岭南师范学院科研团队项目(LT2409)

通讯作者: 王艳丽，教授，ylwang1998@163.com，研究方向为纳米材料构建及电催化性能调控

Corresponding author: WANG Yanli, Tel: (0759)3174029, E-mail: ylwang1998@163.com

作者简介: 谭德新，男，1977年生，副教授

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https://www.cjmr.org/CN/10.11901/1005.3093.2024.443 或 https://www.cjmr.org/CN/Y2025/V39/I8/632

图1 CTAB的紫外可见光谱以及第一和第二CMC

图2 PdNSs的FESEM图和厚度分布

图3 PdNSs的TEM照片和XRD谱

图4 PdNSs的HRTEM图、实线框的FFTs和虚线框放大图

图5 在Pd(NO3)2溶液逐步加入KBr和CTAB的紫外吸收光谱

图6 PdNSs的生长机理演示图

图7 PdNSs和商业Pd/C的循环伏安曲线 (溶液：1 mol/L KOH；扫描速率：50 mV/s)

图8 PdNSs和商业Pd/C的Pd质量归一化CV曲线、ECSA归一化CV曲线、催化剂相应的质量活度和比表面活度(溶液：1 mol/L C3H8O3 + 1 mol/L KOH；扫描速率：50 mV/s)

图9 500次循环加速耐久性实验前后PdNSs和商业Pd/C的CV曲线、基于500次循环起始峰值电流密度PdNSs和商业Pd/C的耐久性以及500次循环后的标准化质量活性(溶液：1 mol/L C3H8O3 + 1 mol/L KOH；扫描速率：50 mV/s)

Catalysts	Electrolyte	Scan rate / mV·s^-1	ECSA / m²·g^-1	Specific activity / mA·cm^-2	Mass activity / mA·mg $- 1$	i_b / i_f	Ref.
PdNSs	1 mol/L KOH + 1 mol/L glycerol	50	46.31	9.12	4179.82	0.25	This work
Pd NPs/C110	0.5 mol/L KOH + 1 mol/L glycerol	50	22.69	-	1026	0.34	[35]
PdFe/C	0.5 mol/L KOH + 1 mol/L glycerol	50	38.99	1.10	-	0.64	[36]
PdNi/C	1 mol/L KOH + 0.5 mol/L glycerol	50	-	2.2	211	-	[37]
Pd/C	1 mol/L KOH + 1 mol/L glycerol	50	43.30	-	1150	-	[38]
AgPd (1∶1)/C	2 mol/L KOH + 1.5 mol/L glycerol	20	-	-	220.27	-	[39]
Pd₃Pb	1 mol/L KOH + 1 mol/L glycerol	50	-	-	916	-	[40]

表1 近年来关于Pd基催化剂对GOR行为的研究成果[35~40]

图10 PdNSs和商业Pd/C分别在0和-0.3 V电压下的计时电流曲线(溶液：1 mol/L C3H8O3 + 1 mol/L KOH；扫描速率：50 mV/s)

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