Top

Journal of Nanoparticle Research

Published in:

01-11-2018 | Research Paper

Surface voltammetric dealloying investigation on PdCu/C electrocatalysts toward ethanol oxidation in alkaline media

Authors: Chan Zhu, Yao-Yue Yang, Zhi-Gang Zhao

Published in: Journal of Nanoparticle Research | Issue 11/2018

Activate our intelligent search to find suitable subject content or patents.

search-config

AI-assisted search

Off

Abstract

Voltammetric dealloying is employed here to investigate the correlations between catalytic performance and surface composition and structure, taking ethanol oxidation reaction (EOR) on Pd-Cu alloy surface as a case study. First, home-made PdCu/C with a mean particle size of ca. 3.11 ± 0.6 nm is dealloyed by repetitive potential cycling in 0.5 M H₂SO₄. With dealloying cycles rising, the Cu component is gradually leached out and the corresponding Pd/Cu atomic ratio gradually increases from ca. 2.1 to 4.0; meanwhile, SEM images display that Pd-rich porous shell is formed due to dealloying-induced surface structural rearrangement, being verified by the appearance of ear-like peaks at − 0.015 V (vs. SCE) in CVs collected in 0.5 M H₂SO₄; furthermore, XPS spectra indicate that core-level binding energies of Pd 3d_5/2 first positively shift to 336.1 eV and then oppositively move down to 334.9 eV, indicating that the d-band center of Pd composition is modulated by the dealloying treatment. Moreover, the voltammetric peak current densities for EOR follow the order of PdCu/C-DA15 > as-prepared PdCu/C ˃ > PdCu/C-DA30 ˃ commercial Pd/C ˃ PdCu/C-DA75, due to the modest downshift of Pd d-band center resulted by charge transfer and surface atomic rearrangement. In addition, the EOR durability gradually decays with the continuous loss of Cu, indicating that electro-oxidation of surface species also follows the so-called bi-functional mechanism. This work might provide some new insights into the catalysis enhancement by tuning the surface/interfacial structure of catalysts.

previous article Effect of the size on the aggregation and sedimentation of graphene oxide in seawaters with different salinities

Dont have a licence yet? Then find out more about our products and how to get one now:

Springer Professional "Wirtschaft+Technik"

Online-Abonnement

Mit Springer Professional "Wirtschaft+Technik" erhalten Sie Zugriff auf:

über 102.000 Bücher
über 537 Zeitschriften

aus folgenden Fachgebieten:

Automobil + Motoren
Bauwesen + Immobilien
Business IT + Informatik
Elektrotechnik + Elektronik
Energie + Nachhaltigkeit
Finance + Banking
Management + Führung
Marketing + Vertrieb
Maschinenbau + Werkstoffe
Versicherung + Risiko

Jetzt Wissensvorsprung sichern!

inform now

Springer Professional "Technik"

Online-Abonnement

Mit Springer Professional "Technik" erhalten Sie Zugriff auf:

über 67.000 Bücher
über 390 Zeitschriften

aus folgenden Fachgebieten:

Automobil + Motoren
Bauwesen + Immobilien
Business IT + Informatik
Elektrotechnik + Elektronik
Energie + Nachhaltigkeit
Maschinenbau + Werkstoffe

Jetzt Wissensvorsprung sichern!

inform now

Available only for authorised users

Abild-Pedersen F, Greeley J, Norskov JK (2005) Understanding the effect of steps, strain, poisons, and alloying: methane activation on Ni surfaces. Catal Lett 105:9–13CrossRef

Austin N, Mpourmpakis G (2014) Understanding the stability and electronic and adsorption properties of subnanometer group XI monometallic and bimetallic catalysts. J Phys Chem C 118:18521–18528CrossRef

Babu SP, Elumalai P (2017) Tunable compositions of Pd100-xCux catalysts towards the electrooxidation of ethanol and ethylene glycol. New J Chem 41:13812–13822CrossRef

Bianchini C, Shen PK (2009) Palladium-based electrocatalysts for alcohol oxidation in half cells and in direct alcohol fuel cells. Chem Rev 109:4183–4206CrossRef

Bligaard T, Norskov JK (2007) Ligand effects in heterogeneous catalysis and electrochemistry. Electrochim Acta 52:5512–5516CrossRef

Cai JD, Zeng YZ, Guo YL (2014) Copper@palladium-copper core-shell nanospheres as a highly effective electrocatalyst for ethanol electro-oxidation in alkaline media. J Power Sources 270:257–261CrossRef

Demirci UB (2007) Theoretical means for searching bimetallic alloys as anode electrocatalysts for direct liquid-feed fuel cells. J Power Sources 173:11–18CrossRef

Dong Q, Zhao Y, Han X, Wang Y, Liu MC, Li Y (2014) Pd/Cu bimetallic nanoparticles supported on graphene nanosheets: facile synthesis and application as novel electrocatalyst for ethanol oxidation in alkaline media. Int J Hydrog Energy 39:14669–14679CrossRef

Douk AS, Saravani H, Noroozifar M (2017) Novel fabrication of PdCu nanostructures decorated on graphene as excellent electrocatalyst toward ethanol oxidation. Int J Hydrog Energy 42:15149–15159CrossRef

Dutta A, Datta J (2014) Energy efficient role of Ni/NiO in PdNi nano catalyst used in alkaline DEFC. J Mater Chem A 2:3237–3250CrossRef

Gao CY, Xia HR, Xu JQ, Zhou CL, Si SC, Zhang HJ, Wang JY (2009) Photorefractive dynamic properties of Ca²⁺-doped strontium barium niobate crystals. Appl Opt 48:161–166CrossRef

Hammer B, Morikawa Y, Norskov JK (1996) CO chemisorption at metal surfaces and overlayers. Phys Rev Lett 76:2141–2144CrossRef

Hammer B, Norskov JK (2000) Theoretical surface science and catalysis - calculations and concepts. Adv Catal 45(45):71–129

Hong W, Wang J, Wang EK (2014) Synthesis of porous PdAg nanoparticles with enhanced electrocatalytic activity. Electrochem Commun 40:63–66CrossRef

Hu CG, Zhai X, Zhao Y, Bian K, Zhang J, Qu L, Zhang H, Luo H (2014) Small-sized PdCu nanocapsules on 3D graphene for high-performance ethanol oxidation. Nanoscale 6:2768–2775CrossRef

Jiang K, Wang Y, Lin T, Cai WB (2014) Electrocatalytic oxidation of formate on Pd-Cu/C—effect of dealloying pretreatment. J Electrochem 20:343–348

Kibler LA, El-Aziz AM, Hoyer R, Kolb DM (2005) Tuning reaction rates by lateral strain in a palladium monolayer. Angewandte Chemie-Int Edition 44:2080–2084CrossRef

Kitchin JR, Norskov JK, Barteau MA, Chen JG (2004) Role of strain and ligand effects in the modification of the electronic and chemical properties of bimetallic surfaces. Phys Rev Lett 93:156801–1–156810-4CrossRef

Koh S, Strasser P (2007) Electrocatalysis on bimetallic surfaces: modifying catalytic reactivity for oxygen reduction by voltammetric surface dealloying. J Am Chem Soc 129:12624–12625CrossRef

Kong QQ, Lian LX, Liu Y, Zhang J, Wang L, Feng W (2015) Bulk hierarchical nanoporous palladium prepared by dealloying PdAl alloys and its electrochemical properties. Microporous Mesoporous Mater 208:152–159CrossRef

Li QX, Mao HM, Zhu PP, Cao XL, Lu TH, Xu QJ (2014) Electrocatalytic performance of Pd-Sn/C catalyst prepared with different complexants for ethanol oxidation in alkaline solution. Chem J Chin Univ-Chin 35:602–607

Lim EJ, Kim Y, Choi SM, Lee S, Noh Y, Kim WB (2015) Binary PdM catalysts (M = Ru, Sn, or Ir) over a reduced graphene oxide support for electro-oxidation of primary alcohols (methanol, ethanol, 1-propanol) under alkaline conditions. J Mater Chem A 3:5491–5500CrossRef

Mani P, Srivastava R, Strasser P (2011) Dealloyed binary PtM₃ (M = Cu, Co, Ni) and ternary PtNi₃M (M = Cu, Co, Fe, Cr) electrocatalysts for the oxygen reduction reaction: performance in polymer electrolyte membrane fuel cells. J Power Sources 196:666–673CrossRef

Mao H, Huang T, Yu AS (2015) Surface palladium rich Cu_xPd_y/carbon catalysts for methanol and ethanol oxidation in alkaline media. Electrochim Acta 174:1–7CrossRef

Mao JJ, Liu YX, Chen Z, Wang DS, Li YD (2014) Bimetallic Pd-Cu nanocrystals and their tunable catalytic properties. Chem Commun 50:4588–4591CrossRef

Modibedi RM, Masombuka T, Mathe MK (2011) Carbon supported Pd-Sn and Pd-Ru-Sn nanocatalysts for ethanol electro-oxidation in alkaline medium. Int J Hydrog Energy 36:4664–4672CrossRef

Mukherjee P, Roy PS, Mandal K, Bhattacharjee D, Dasgupta S, Bhattacharya SK (2015) Improved catalysis of room temperature synthesized Pd-Cu alloy nanoparticles for anodic oxidation of ethanol in alkaline media. Electrochim Acta 154:447–455CrossRef

Muneeb O, Estrada J, Tran L, Nguyen K, Flores J, Hu S, Fry-Petit AM, Scudiero L, Ha S, Haan JL (2016) Electrochemical oxidation of Polyalcohols in alkaline media on palladium catalysts promoted by the addition of copper. Electrochim Acta 218:133–139CrossRef

Oliveira MC, Rego R, Fernandes LS, Tavares PB (2011) Evaluation of the catalytic activity of Pd-Ag alloys on ethanol oxidation and oxygen reduction reactions in alkaline medium. J Power Sources 196:6092–6098CrossRef

Rabis A, Rodriguez P, Schmidt TJ (2012) Electrocatalysis for polymer electrolyte fuel cells: recent achievements and future challenges. ACS Catal 2:864–890CrossRef

Ruban A, Hammer B, Stoltze P, Skriver HL, Norskov JK (1997) Surface electronic structure and reactivity of transition and noble metals. J Mol Catal A-Chem 115:421–429CrossRef

Serov A, Asset T, Padilla M, Matanovic I, Martinez U, Roy A, Artyushkova K, Chatenet M, Maillard F, Bayer D, Cremers C, Atanassov P (2016) Highly-active Pd-Cu electrocatalysts for oxidation of ubiquitous oxygenated fuels. Appl Catal B-Environ 191:76–85CrossRef

Shi QR, Zhu CZ, Bi CX, Xia HB, Engelhard MH, Du D, Lin YH (2017) Intermetallic Pd3Pb nanowire networks boost ethanol oxidation and oxygen reduction reactions with significantly improved methanol tolerance. J Mater Chem A 5:23952–23959CrossRef

Strasser P (2009) Dealloyed core-shell fuel cell electrocatalysts. Rev Chem Eng 25:255–295CrossRef

Strasser P, Koh S, Anniyev T, Greeley J, More K, Yu C, Liu Z, Kaya S, Nordlund D, Ogasawara H, Toney MF, Nilsson A (2010) Lattice-strain control of the activity in dealloyed core-shell fuel cell catalysts. Nat Chem 2:454–460CrossRef

Tsui LK, Zafferoni C, Lavacchi A, Innocenti M, Vizza F, Zangari G (2015) Electrocatalytic activity and operational stability of electrodeposited Pd-Co films towards ethanol oxidation in alkaline electrolytes. J Power Sources 293:815–822CrossRef

Wakisaka M, Mitsui S, Hirose Y, Kawashima K, Uchida H, Watanabe M (2006) Electronic structures of Pt-Co and Pt-Ru alloys for Co-tolerant anode catalysts in polymer electrolyte fuel cells studied by EC-XPS. J Phys Chem B 110:23489–23496CrossRef

Wang DL, Yu Y, Xin HL, Hovden R, Ercius P, Mundy JA, Chen H, Richard JH, Muller DA, DiSalvo FJ, Abruña HD (2012a) Tuning oxygen reduction reaction activity via controllable dealloying: a model study of ordered Cu3Pt/C intermetallic nanocatalysts. Nano Lett 12:5230–5238CrossRef

Wang JY, Kang YY, Yang H, Cai WB (2009) Boron-doped palladium nanoparticles on carbon black as a superior catalyst for formic acid electro-oxidation. J Phys Chem C 113:8366–8372CrossRef

Wang KW, Kang WD, Wei YC, Liu CW, Su PC, Chen HS, Chung SR (2012b) Promotion of PdCu/C catalysts for ethanol oxidation in alkaline solution by SnO2 modifier. Chemcatchem 4:1154–1161CrossRef

Wang L, Zhai JJ, Jiang K, Wang JQ, Cai WB (2015a) Pd-Cu/C electrocatalysts synthesized by one-pot polyol reduction toward formic acid oxidation: structural characterization and electrocatalytic performance. Int J Hydrog Energy 40:1726–1734CrossRef

Wang Y-F, Zhu C, Yang Y-Y, Zhao Z-G (2018) Surface-clean low-doped PdB/C as superior electrocatalysts toward ethanol oxidation in alkaline media. J Energy Chem 27:389–394CrossRef

Wang Y, Nguyen TS, Liu XW, Wang X (2010) Novel palladium-lead (Pd-Pb/C) bimetallic catalysts for electrooxidation of ethanol in alkaline media. J Power Sources 195:2619–2622CrossRef

Wang Y, Shi FF, Yang YY, Cai WB (2013) Carbon supported Pd-Ni-P nanoalloy as an efficient catalyst for ethanol electro-oxidation in alkaline media. J Power Sources 243:369–373CrossRef

Wang Y, Zou SZ, Cai WB (2015b) Recent advances on electro-oxidation of ethanol on Pt- and Pd-based catalysts: from reaction mechanisms to catalytic materials. Catalysts 5:1507–1534CrossRef

Xiong ZP, Yan B, Zhang K, Wang C, Li S, Xu H, du Y, Zhai C (2017) A facile synthesis of 3D network PdCu nanostructure with enhanced electrocatalytic activity towards ethanol oxidation. J Taiwan Inst Chem Eng 75:12–17CrossRef

Yin J, Shan S, Ng MS, Yang L, Mott D, Fang W, Kang N, Luo J, Zhong CJ (2013) Catalytic and electrocatalytic oxidation of ethanol over palladium-based nanoalloy catalysts. Langmuir 29:9249–9258CrossRef

Zhang JY, Feng A, Bai J, Tan Z, Shao W, Yang Y, Hong W, Xiao Z (2017) One-pot synthesis of hierarchical flower-like Pd-Cu alloy support on graphene towards ethanol oxidation. Nanoscale Res Lett 12:521–529CrossRef

Zhang QL, Zheng JN, Xu TQ, Wang AJ, Wei J, Chen JR, Feng JJ (2014) Simple one-pot preparation of Pd-on-Cu nanocrystals supported on reduced graphene oxide for enhanced ethanol electrooxidation. Electrochim Acta 132:551–560CrossRef

Zhang ZH, Wang Y, Qi Z, Zhang WH, Qin JY, Frenzel J (2009) Generalized fabrication of nanoporous metals (Au, Pd, Pt, Ag, and Cu) through chemical dealloying. J Phys Chem C 113:12629–12636CrossRef

Zhang ZH, Zhang C, Sun JZ, Kou TY, Zhao CC (2012) Ultrafine nanoporous Cu-Pd alloys with superior catalytic activities towards electro-oxidation of methanol and ethanol in alkaline media. RSC Adv 2:11820–11828CrossRef

Zhang ZY, Xin L, Sun K, Li WZ (2011) Pd-Ni electrocatalysts for efficient ethanol oxidation reaction in alkaline electrolyte. Int J Hydrog Energy 36:12686–12697CrossRef

Zhao X, Zhang J, Wang LJ, Liu ZL, Chen W (2014) PdxCu100-x networks: an active and durable electrocatalyst for ethanol oxidation in alkaline medium. J Mater Chem A 2:20933–20938CrossRef

Zhao XJ, Dai L, Qin Q, Pei F, Hu CY, Zheng NF (2017) Self-supported D-3 PdCu alloy nanosheets as a bifunctional catalyst for electrochemical reforming of ethanol. Small 13:1602970–1602978CrossRef

Zhou WP, Lewera A, Larsen R, Masel RI, Bagus PS, Wieckowski A (2006) Size effects in electronic and catalytic properties of unsupported palladium nanoparticles in electrooxidation of formic acid. J Phys Chem B 110:13393–13398CrossRef

Zhu FC, Ma GS, Bai ZC, Hang RQ, Tang B, Zhang ZH, Wang XG (2013) High activity of carbon nanotubes supported binary and ternary Pd-based catalysts for methanol, ethanol and formic acid electro-oxidation. J Power Sources 242:610–620CrossRef

Title: Surface voltammetric dealloying investigation on PdCu/C electrocatalysts toward ethanol oxidation in alkaline media
Authors: Chan Zhu
Yao-Yue Yang
Zhi-Gang Zhao
Publication date: 01-11-2018
Publisher: Springer Netherlands
Published in: Journal of Nanoparticle Research / Issue 11/2018
Print ISSN: 1388-0764
Electronic ISSN: 1572-896X
DOI: https://doi.org/10.1007/s11051-018-4423-z

Springer Professional

Abstract

Please log in to get access to your license.

Dont have a licence yet? Then find out more about our products and how to get one now:

Springer Professional "Wirtschaft+Technik"

Springer Professional "Technik"

Other articles of this Issue 11/2018

Influence of size and surface capping on photoluminescence and cytotoxicity of gold nanoparticles

Terahertz-based nanometrology: multispectral imaging of nanoparticles and nanoclusters in suspensions

Facile synthesis of WO3 − x nanorods with controlled dimensions and tunable near-infrared absorption

Reduced graphene oxide-based broad band photodetector and temperature sensor: effect of gas adsorption on optoelectrical properties

First-principles investigation on the interlayer doping of SnSe2 bilayer

Determining surface chemical composition of silver nanoparticles during sulfidation by monitoring the ligand shell

Premium Partners