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

doi:10.11901/1005.3093.2024.443

Chinese Journal of Materials Research

2025, Vol. 39

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

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

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

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

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TAN Dexin, CHEN Shihui, LUO Xiaoli, NING Xiaomei, WANG Yanli. Synthesis of Pd Nanosheets with Numerous Defects and Their Electrocatalytic Oxidation Performance for Glycerol. Chinese Journal of Materials Research, 2025, 39(8): 632-640.

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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

Received: 29 October 2024

ZTFLH:

TG146.3+6

Fund: Guangdong Basic and Applied Basic Research Foundation(2022A1515011970);Lingnan Normal University School Project(LT2409)

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

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	TAN Dexin
	CHEN Shihui
	LUO Xiaoli
	NING Xiaomei
	WANG Yanli

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https://www.cjmr.org/EN/10.11901/1005.3093.2024.443 OR https://www.cjmr.org/EN/Y2025/V39/I8/632

Fig.1 UV-vis spectra (a), and the first and second CMCs (b) of CTAB

Fig.2 FESEM image (a) and thickness distribution images (b, c) of PdNSs

Fig.3 TEM images (a, b) and XRD pattern (c) of PdNSs

Fig.4 HRTEM image of PdNSs (a) and FFTs from the solid boxes (a1, a2), magnification HRTEM images from the dashed boxes (b-e)

Fig.5 UV-vis spectra of Pd(NO₃)₂ solution upon the addition of KBr (a) and CTAB (b)

Fig.6 Illustration of the growth mechanism of PdNSs

Fig.7 CV curves of PdNSs (a) and commercial Pd/C (b) (solution: 1 mol/L KOH; scan rate: 50 mV/s)

Fig.8 Pd-mass (a) and ECSA (b) normalized CVs of the PdNSs and commercial Pd/C, and corres-ponding mass activities and specific activities of catalysts (c) (solution: 1 mol/L C₃H₈O₃ + 1 mol/L KOH; scan rate: 50 mV/s)

Fig.9 CVs obtained before and after accelerated durability tests for PdNSs (a) and commercial Pd/C (b) for 500 cycles, durability properties of PdNSs and commercial Pd/C based on the onset peak current density for 500 cycles (c), normalized mass activity of catalysts after 500 cycles (d) (solution: 1 mol/L C₃H₈O₃ + 1 mol/L KOH; scan rate: 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]

Table 1 Glycerol oxidation reaction performance of Pd-based catalysts published in recent years^[35~40]

Fig.10 Chronoamperometric curves of PdNSs and commercial Pd/C at a fixed potential of 0 V (a) and -0.3 V (b) (solution: 1 mol/L C₃H₈O₃ + 1 mol/L KOH; scan rate: 50 mV/s)

[1]	Braun M, Santana C S, Garcia A C, et al. From waste to value-glycerol electrooxidation for energy conversion and chemical production [J]. Curr. Opin. Green Sustainable Chem., 2023, 41: 100829
[2]	Velázquez-Hernández I, Álvarez-López A, Álvarez-Contreras L, et al. Electrocatalytic oxidation of crude glycerol from the biodiesel production on Pd-M (M = Ir, Ru or Pt) sub-10 nm nanomaterials [J]. Appl. Surf. Sci., 2021, 545(15): 149055
[3]	Arjona N, Rivas S, Álvarez-Contreras L, et al. Glycerol electro-oxidation in alkaline media using Pt and Pd catalysts electrodeposited on three-dimensional porous carbon electrodes [J]. New J. Chem., 2017, 41(4): 1854
[4]	Saravani H, Farsadrooh M, Mollashahi M S, et al. Two-dimensional engineering of Pd nanosheets as advanced electrocatalysts toward formic acid oxidation [J]. Int. J. Hydrog. Energy, 2020, 45(41): 21232
[5]	Liu J F, Liu H T, Wang Q X, et al. Phosphorus doped PdMo bimetallene as a superior bifunctional fuel cell electrocatalyst [J]. Chem. Eng. J., 2024, 486(15): 150258
[6]	Wang J, Zhang W, Dong Z M, et al. One-step CO assisted synthesis of hierarchical porous PdRuCu nanosheets as advanced bifunctional catalysts for hydrogen evolution and glycerol oxidation [J]. Int. J. Hydrog. Energy, 2022, 47(78): 33319
[7]	Zhang X T, Hui L, Yan D X, et al. Defect rich structure activated 3D palladium catalyst for methanol oxidation reaction [J]. Angew. Chem.-Int. Edit., 2023, 62(40): e202308968
[8]	Yan D F, Li Y X, Huo J, et al. Defect chemistry of nonprecious-metal electrocatalysts for oxygen reactions [J]. Adv. Mater., 2017, 29(48): 1606459
[9]	Cai L, He J F, Liu Q H, et al. Vacancy-induced ferromagnetism of MoS₂ nanosheets [J]. J. Am. Chem. Soc., 2015, 137(7): 2622
[10]	Ling T, Yan D Y, Jiao Y, et al. Engineering surface atomic structure of single-crystal cobalt (II) oxide nanorods for superior electrocatalysis [J]. Nat. Commun., 2016, 7(1): 12876
[11]	Gao S, Lin Y, Jiao X C, et al. Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel [J]. Nature, 2016, 529: 68
[12]	Nosheen F, Wasfi N, Aslam S, et al. Ultrathin Pd-based nano-sheets: syntheses, properties and applications [J]. Nanoscale, 2020, 12(7): 4219 doi: 10.1039/c9nr09557h pmid: 32026907
[13]	Yadav D D, Jha R, Singh S, et al. Synthesis and characterisation of Nickel oxide nanoparticles using CTAB as capping agent [J]. Mater. Today Proc., 2023, 73(2): 333
[14]	Ma C S, Li G Z, Xu Y M, et al. Determination of the first and second CMCs of surfactants by adsorptive voltammetry [J]. Colloids Surf., 1998, 143A(1) : 89
[15]	Shah S K, Chatterjee S K, Bhattarai A. Micellization of cationic surfactants in alcohol—water mixed solvent media [J]. J. Mol. Liq., 2016, 222: 906
[16]	Lu H J, Chen C, Guo H T, et al. Determination of the second critical micelle concentration of CTAB by UV spectra without probe [J]. Acta Chim. Sin., 2006, 64: 2437
	卢惠娟, 陈冲, 郭宏涛等. 无探针紫外光谱法测定CTAB的第二临界胶束浓度 [J]. 化学学报, 2006, 64: 2437
[17]	Dong M, Hu H L, Ding S J, et al. Flexible non-enzymatic glucose biosensor based on CoNi₂S₄ nanosheets grown on nitrogen-doped carbon foam substrate [J]. J. Alloy. Compd., 2021, 883: 160830
[18]	Wang Y H, Zhu Z Z, Xu K, et al. Palladium nanobelts with expanded lattice spacing for electrochemical oxygen reduction in alkaline media [J]. ACS Appl. Nano Mater., 2021, 4(2): 2118
[19]	Foley D J, Coleman S P, Tschopp M A, et al. Correlating deformation mechanisms with X-ray diffraction phenomena in nanocrystalline metals using atomistic simulations [J]. Comput. Mater. Sci., 2018, 154: 178
[20]	Srivastava S C, Newman L. Mixed ligand complexes of palladium (II) with chloride and bromide [J]. Inorg. Chem., 1966, 5(9): 1506
[21]	Berhault G, Bausach M, Bisson L, et al. Seed-mediated synthesis of pd nanocrystals: factors influencing a kinetic- or thermodynamic-controlled growth regime [J]. J. Phys. Chem., 2007, 111C(16) : 5915
[22]	Buettner J, Gutierrez M, Henglein A. Sonolysis of water-methanol mixtures [J]. J. Phys. Chem., 1991, 95(4): 1528
[23]	Li Y, Gong S L, Che Y, et al. Hydroxyl radical scavenging activity and kinetics of Vitamin C [J]. Chin. J. Appl. Chem., 2015, 32(8): 948 doi: 10.11944/j.issn.1000-0518.2015.08.140427
	李艳, 巩士磊, 车影等. Fenton反应考察抗坏血酸清除羟基自由基能力及动力学[J]. 应用化学, 2015, 32(8): 948
[24]	Allen R N, Shukla M K, Reed D, et al. Ab initio study of the structural properties of ascorbic acid (vitamin C) [J]. Int. J. Quantum Chem., 2006, 106(14): 2934
[25]	Zi X H, Wang R, Liu L C, et al. Cetyltrimethylammonium bromide assisted preparation and characterization of Pd nanoparticles with spherical, worm-like, and network-like morphologies [J]. Chin. J. Catal., 2011, 32(5): 827
	訾学红, 王锐, 刘立成等. 十六烷基三甲基溴化铵辅助作用下球形、蠕虫状和网状Pd纳米粒子的制备与表征 [J]. 催化学报, 2011, 32(5): 827 doi: 10.1016/S1872-2067(10)60194-5
[26]	Lam B T X, Chiku M, Higuchi E, et al. Preparation of PdAg and PdAu nanoparticle-loaded carbon black catalysts and their electrocatalytic activity for the glycerol oxidation reaction in alkaline medium [J]. J. Power Sources, 2015, 297: 149
[27]	Ao K L, Li D W, Yao Y X, et al. Electro-catalytic activity of composite films of Pd-doped bacterial cellulose Nano-fibers for ethanol oxidation[J]. Chin. J. Mater. Res., 2018, 32(2): 155 doi: 10.11901/1005.3093.2016.793
	敖克龙, 李大伟, 姚壹鑫等. 载钯细菌纤维素纳米纤维复合膜用于乙醇的电催化氧化[J]. 材料研究学报, 2018, 32(2): 155 doi: 10.11901/1005.3093.2016.793
[28]	Fard L A, Ojani R, Raoof J B, et al. Poly (pyrrole-co-aniline) hollow nanosphere supported Pd nanoflowers as high-performance catalyst for methanol electrooxidation in alkaline media [J]. Energy, 2017, 127: 419
[29]	Simões M, Baranton S, Coutanceau C. Electrooxidation of sodium borohydride at Pd, Au, and Pd _x Au_1- _x carbon-supported nanocatalysts [J]. J. Phys. Chem., 2009, 113C(30) : 13369
[30]	Ran X, Qu Q, Liu C, et al. Highly-effective palladium nanoclusters supported on para-sulfonated calix[8]arene-functionalized carbon nanohorns for ethylene glycol and glycerol oxidation reactions [J]. New J. Chem., 2018, 6: 4631
[31]	Liu X J, Yin X, Sun Y D, et al. Interlaced Pd–Ag nanowires rich in grain boundary defects for boosting oxygen reduction electrocatalysis [J]. Nanoscale, 2022, 12(9): 5368
[32]	Nguyen S T, Law H M, Nguyen H T, et al. Enhancement effect of Ag for Pd/C towards the ethanol electro-oxidation in alkaline media [J]. Appl. Catal., 2009, 91B(1-2) : 507
[33]	Feng Y Y, Liu Z H, Kong W Q, et al. Promotion of palladium catalysis by silver for ethanol electro-oxidation in alkaline electrolyte [J]. Int. J. Hydrog. Energy, 2014, 39(6): 2497
[34]	Habibi E, Razmi H. Glycerol electrooxidation on Pd, Pt and Au nanoparticles supported on carbon ceramic electrode in alkaline media [J]. Int. J.Hydrog. Energy, 2012, 37(22): 16800
[35]	Ivanov R, Nakova A, Tsakova V. Glycerol oxidation at Pd nanocatalysts obtained through spontaneous metal deposition on carbon substrates [J]. Electrochim. Acta, 2022, 427: 140871
[36]	Mphahlele N E, Ipadeola A K, Haruna A B, et al. Microwave-induced defective PdFe/C nano-electrocatalyst for highly efficient alkaline glycerol oxidation reactions [J]. Electrochim. Acta, 2022, 409: 139977
[37]	White J, Terekhina I, Dos Santos E C, et al. Synergistic bimetallic PdNi nanoparticles: enhancing glycerol electrooxidation while preserving C3 product selectivity [J]. ACS Appl. Energy Mater., 2024, 7(5): 1802
[38]	Huang Y F, Wu P, Ma Y Y, et al. Single atom iron carbons supported Pd-Ni-P nanoalloy as a multifunctional electrocatalyst for alcohol oxidation [J]. Int. J. Hydrog. Energy, 2023, 48(37): 13972
[39]	Mares-Briones F, Velázquez-Hernández I, González-Reyna M A, et al. AgPd nanoparticles as a potential electrocatalyst for enhanced performance in direct glycerol fuel cells [J]. Int. J. Hydrog. Energy, 2025, 108: 43
[40]	Duan Y J, Liu Z L, Zhao B, et al. Raspberry-like Pd₃Pb alloy nanoparticles: superior electrocatalytic activity for ethylene glycol and glycerol oxidation [J]. RSC Adv., 2020, 10(27): 15769

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