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    Real Surface Area Measurements of Pt3Co - C Catalysts

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    Journal of Eleetoanalyical Chemistry 62 (2010) 52-60 Contents lists available at ScienceDirect, Journal of Electroanalytical Chemistry ELSEVIER journal homepage: www.elsevier.com/locate/jel Real surface area measurements of Pt3Co/C catalysts H. Schulenburg*, J. Durst®, E. Maller”, A. Wokaun®, G.G. Scherer* raul scheme si, Ekeochemsty Labora, CH 5252 Villigen PS, Sze electra erscopy ET Zari EZ C003 uch Sitzeriand ARTICLE INFO ABSTRACT ‘ace ison [An evzor analysis for real surface area (Ay) measurements of PLCoJC catalysts is presented. The real sur- Received ne 2009, face area was measured by X-ray diffraction (XRD), high resolution transmission electron microscopy Received in revised form 2 January 2010 ‘cepted | Febraaty 2010, ‘alle online 10 Febrsary 2010, (HRTEM, desorption of underpotental deposited hytogen (Hea) and CO-stripping voltammetry All ‘easements were arred aut after an electrochemical activation by cycle vltammety in perchloric acid. The real surface area decreases in the sequence Ay(XRD) ~ Ay(HRTEM) > Ay(CO-strip- fins) ~ Acta) HITE provides he highest elaiy othe mvetigated metas. The eceweche- Can Fea methods are questionable for PCoiC east. They ye surface ares which are 23-02 lower pesca than dtermiod Oy ne Te sey conse af ube and Co appre ower on een Sorc a compare oPtnanopartcls, Cyl vlan of Paco ialtalne eof suggests tha the Su ors {Sve i leached Co nanparles const of ur Suracecompestion 1. Introduction In heterogeneous catalysis a variety of factors influence the activity of a catalyst, including composition, electronic properties, real surface area and the presence of poisons. The knowledge of the real surface area is important for the discussion of catalytic activity. I helps to understand whether new catalysts perform bet- ter or worse due to their surface composition or their different spe- cifle surface area. For industrial applications, high surface area ‘catalysts are favored, because they offer many active sites per cat- lyst volume and mass. Aa consequence, most heterogeneous cat- alysts are supported nanoparticles. For heterogeneous catalysts ‘experimental methods to determine the real surface area have been reviewed by Bergeret and Gallezot [1], electrachemical meth- ‘ods were reviewed by Trasatti and Petri 2}. ‘Catalysts for the oxygen reduction reaction (Eq. (1)) in polymer electrolyte fuel cells (PEFCs) are carbon supported Pt or Pt-alloy nanoparticles. 0, +411" +4e- 24,0 a ‘The real surface area of Pt- and Ptalloy catalysts is frequently investigated by. in situ electrochemical methods, where a (submonolayer of species lke hydrogen [3] carbon monoxide [4] oF copper [5] is adsorbed and desorbed from the nanoparticle surface. The surface area is then calculated from the charge that © Corespanding autor. Fax: +41 56.310 4415 mal eae: henrikschulenburesps ch (H, Schuler. 1572665718 - ee font matter © 2010 vier BY, Al ahs reserved © 2010 Elsevier RV. All rights reserved “originates from the adsorption andl desorption ofthese test species. Most popular ex situ methods are (high-resolution) transmission ‘electron microscopy (HRTEM) and X-ray diffractometry (XRD), less ‘common are EXAFS (6] or anomalous small-angle X-ray scattering [7], TEM analysis allows the determination of the particle size dis- tribution and therefore the calculation of surface areas, whereas the broadening of XRD reflections provides information about the size of crystalline domains if the domain size is smaller than ~100 nm, In contrast to HRTEM and the electrochemical methods, the XRD analysis yields a volume averaged crystallite size. ‘An extensive amount of work is dedicated to surface area deter- ‘minations of carbon supported Pt nanoparticles [4]. Much less is known about PtsCo nanoparticles, despite their higher catalytic activity for oxygen reduction [8], Frequently, the surface area determination of Pt:Co nanoparticles relies solely on the Haya ‘method [9-11], In addition Paulus et al. [8] investigated carbon supported Pt,Co nanoparticles by TEM. Hypa surface areas were about 40% lower than TEM surface areas, The presence of Co sur~ face atoms, which do not participate inthe Hy. reaction was given as explanation for this effec. Liu eta. [12] investigated PtsCo par- ticles prepared by a reverse micelle method and annealed the cat- alysts at temperatures of 200°C or 300°C. Surface areas were ‘measured by XRD, TEM and Hyoo. The ex sit techniques were ap- plied prior £0 Hyj. XRD and TEM analysis gave comparable results, ‘whereas Hypa areas were roughly 50% smaller. ‘Chen eta [13] studied as received and heat-treated Pt,Co/C by HRTEM and Hyoy- TEM and Hyog areas of the as received catalysts ‘were similar in this study. After heat-treatment Ayj.yq Was about 430% smaller than Arey. 1H Schueny Journalo lectroanaytal Chemistry 642 (2010) 52-60 Surprisingly, little work discusses CO-stripping voltammetry of t,Co nanoparticles in liquid electrolytes although this method has bbeen studied for the analysis of Pr nanoparticles in detail [4,1429,31,32,35-42]. Hernandez-Fernindez et al. [15] used CO- tipping voltammetry for surface area measurements of PtCo nanoparticles. Very recently Mayrhofer et al. [16] studied CO-sti ping of Pt,Co in alkaline solutions. In this work we analyze real surface areas of two commercial PCo[C catalysts by HRTEM and XRD. As electrochemical methods ‘we employed the H,,, technique and also CO-stripping voltamme- {ry Unlike in previous work [8.9.12,13}, the ex situ measurements HRTEM and XRD were carried out after applying the electrochem- Jcal methods, because surface areas may change during electro- chemical measurements due to sintering, ripening or cobalt dissolution. ‘A main goal of this work is to provide an error analysis of the different techniques, which allows recommending the most reli able method for Pr,Co/C surface area determination. 2. Experimental 2.1, Catalysts Pr,Co[C catalysts were obtained from E-TEK (Summerset, NJ, USA) and TKK (Tanaka Kikinzoku Kogyo KK. Tokyo, Japan), For E-TEK catalysts Vulcan XC72 was used as carbon support. The su port of TKK catalysts was HSAC, high surface area carbon [17]. Ci ‘bon supported cobalt nanoparticles with 12% metal loading were prepared according to Re. 48. 22. Inductive coupled plasma-optical emission spectroscopy (ICP-OES) For determination of metal loadings and stoichiometry all cata~ sts were decomposed by aqua tegia, diluted with water and ana- lyzed by ICP-OES (Vista Pro Axial from Varian) 23, Blectrochemical measurements For Hypg- and CO-stripping voltammetry a three compartment cell was used, Glassware was cleaned similar to the procedure de- scribed by Angerstein-Kozlowska [18], but piranha solution (H:S04/H,02) was used instead of chromic-sulfuric acid for rea- sons of environmental protection. The electrolyte, 0.1 M perchloric acid, was prepared from redistilled 70% perchloric acid (99.999%, Sigma) and water (resistivity 182 M&cm). A platinum coil was used as counter electrode. Saturated Ag/AgCl (Meinsberg) served as reference electrode. The reference electrode was separated from the working electrode compartment by a closed electrolyte bridge to avoid chloride contamination. The potential of the reference electrode was calibrated using the hydrogen oxidation/reduction reaction on a platinum working electrode. All potentials are re- ferred to the reversible hydrogen electrode (RHE) Catalyst inks |19] were prepared from 25mg catalyst, 20% water (182 MQ.em), 0.1 ml Nafiont17-solution (5%, Fluka) filled up to a total volume of 25 ml with 2-propanol (CHROMASOLY, Riedel). After ultrasonic dispersion an aliquot was dropped onto 2 glassy carbon electrodes (A=0.283 cm", SIGRADUR K, TW Hochtemperaturwerkstofle GmbH) and dried at room temperature in an argon stream. Prior to use, glassy carbon electrodes were cleaned ultrasonically in water (182 MO cm), 2-propanol and again water. For Hy q measurements, vollammogramms were re- corded at 0.045, 0.05, 0.055, and 0.06 V as lower potential limit. For subsequent’ measurements of CO oxidation, a potential of (0.05 V was fixed for 10 min and the electrolyte was saturated with CO (Messer Griesheim 5.0). The electrolyte was purged with argon {or 30 min to remove dissolved CO. The CO-stripping curves were recorded with a scan rate of 50 mV/s and the upper potential limit ‘was set to 1.2V (RHE). Catalyst Suspensions for measurements in alkaline solutions ‘were prepared without ionomer. The electrolyte was prepared by cliluting 1 M KOH (Fluka) with water (182 MO cm). All measure- ‘ments were cartied out at room temperature, Surface areas are de- noted as averages with standards deviations obtained from four independent measurements. 2.4, Electron microscopy ‘After electrochemical experiments catalysts were removed from the electrodes with 2-propanol in an ultrasonic bath. A vol- ‘ume of the obtained suspension was pipetted onto a carbon coated copper grid. HRTEM was carried out on a Phillips CM 30 ST oper- ated at 300 kV. Particle size distributions were determined using the UTHSCSA Image tool by measuring the particle sizes from sev- eral high resolution images of different catalyst regions. 25. X-ray difractometry (XRD) For XRD measurements after electrochemical activation, a lar- ser glassy carbon electrode (A= 28 cm") was covered with catalyst suspensions. Catalyst coated electrodes were inserted to the argon (60, Messer-Griessheim) saturated electrolyte at a potential of (0.05 V (RHE) and activated by recording 20 cyclic voltammograms in the potential range from 0.05 to 1.2 V (RHE) at a scan rate of '50 mVjs. Catalysts were removed from the glassy carbon electrode by a PTFE spatula. The spatula was inserted to a glass vessel con- taining 2-propanol. After treatment in an ultrasonic bath the cata- lyst suspension was dropped to a XRD sample holder. About 1 mg. ‘catalyst was attached to the sample holder. Powder difractograms ‘were recorded on a Bruker D8 ADVANCE diffractometer with Bragg-Brentano geometry using a Cu Ka source, The step size ‘was 0.02° with a step time of 20. The 20 range was 30-90". Crys- talline phases were assigned with the ICDD database, The instru- mental broadening was measured with a NayAlyCasF standard. 3. Results 3.1, 1CP-OES analysis For the accurate determination of the Pt- and Co-loading, all PriCo[C catalysts were decomposed in aqua regia, diluted and analyzed by ICP-OES. The results of this analysis are summed up in Table 1. The decomposition experiments were carried out twice. ‘rable P-OFS analysis of PoC eats Gale ‘etal ening (2) Pleading) Co osding (2) Sticiomey "Coaching (2) "Co esching 2(3) _ Stichiomety afer aching PHCoICETER 16403 1452021852005 PCy 70 ° Pian Poe@eTeK 461208 20205 4132007 Gayle ° Pol ~ obal achins daring 20 ci olammoarams, 50-1200 mi (RHE. 0.1 M CIO, 20°C and w= 50s * Coat leaching afer addtenal 20 cee voammogramms in fesh electra a 1 Schulnburg tl aura of Eetroanaytil Chemiry G2 (2010) 52-60 In case of the E-TEK catalyst the results differ significantly from the values that are reported on the label (20% metal loading). Addi- tional leaching tests were carried out with the Pr,Co[C catalysts to determine the Co-loss during the electrochemical activation. For these experiments the catalysts were exposed to electrolyte (0.1 M HClO.) and cycled 20 times between 50 and 1200mV (RHE) at room temperature with a scan rate of 50 mV/s. Measure- ‘ents ofthe cobalt concentration show that 23% of the initial Cois leached out of the PtsCo(C-E-TEK catalyst and 7% of the PtsCo[C- TKK catalyst. After addition of fresh electrolyte and 20 additional ‘voltammograms in the same potential range, no more cobalt was found in the electrolyte. Therefore, we assume that the cobalt leaching stops during the first 20 cycles. The catalysts stoichiome- try after this leaching is close to PrsCo, 3.2. XRD Ierystallites are less than approximately 100 nm in size, appre- cable broadening of the diffraction peaks occurs. The real surface ‘area measurement by XRD takes advantage of this effect. The ‘quantitative relation between peak broadening by nanocrystals, ‘and the crystallite size was deduced by Scherrer in 1918 [20], (Eq. (2), Ki Bs,cos) o In this expression D is the crystal dimension normal to the liffracting planes, K the Scherrer constant, 2 the wavelength of Cu Ka. source (1.542 A), Bao the integral breath of the diffraction, peak in terms of the 20 angle in radians, and @is the angle at the peak maximum. Instead of the integral breath, the full width at halt ‘maximum (FWHM) is frequently used in Eq. (2). Other factors that influence the peak broadening are stress and strain effects, stack- ing faults, structural disorder and instrumental. broadening. ‘Assuming spherical crystallites the real surface area is calculated by dividing the particle surface with the particle mass (Eq. (3). 3m 38 sane a. 3 3) im Seda Sai er [ with the surface area A, particle mass m, particle density p, particle radius r and the number of crystallites n, Using the Scherrer equa- tion one assumes a uniform particle radius. The density of Pt,Co ‘was calculated using Eq. (4) with XRD data obtained from Fig. 1 m_xMy +yMo, Vania 4 where Vis the volume and m the mass ofthe unit cell. M is the mo- Jar mass of platinum and cobalt, Ns the Avogadro constant and athe lattice parameter. For the stoichiometric coefficients x and y the relation x+y=4 is valid. The stoichiometry and therefore the mass ‘of the unit cell can be estimated using Vegards law which allows the ‘determination of the atomic fraction of cobalt xe. ab Xe 6) Constants m and are calculated from literature values for fee- Px,Co.(00-029-0499) and. fec-PICo_(03-065-8970). The lattice parameters a for fee-PrxCo and fee-PICo are 3.85410 and 3.7440 A, respectively. With the atomic fraction of these com- pounds, xp 025 and xo, 05 one obtains m= -0.4404 A and = 3.9682 From the difractograms in Fig. 1 we obtain latice parameters of a= 3.848 £0007 A for PrCo|C-E-TEK and a= 3.84001 A for PLCo[C-TKK, With Ea (4 yielding xe, "0.26 + 0.02 for Pt,CofC-E- TEK and acy" 027 + 0.02 for PUsCofC-TKK, which results in astoi- chiometry of PtzsnaorC®;oqage and for Pt,CojCE-TEK and PLesninmsC0} 2009 for PLCO/CTKK. With Eq, (4) and the exvors forthe estimation of the lattice parameter we obtain density of 186205gem * for PLCojC-E-TEK and 185205gcm ° for PLCo/C-TKK. Combining Eqs. (2) and (3) gives an expression for the surface area calculation (Ea. (6). A. 6B cos(0) im pki 6) 32.1. Error analysis ‘The error for the rea surface area determination by XRD, AA/m, is calculated with, A [2A/m) 9 JarA/m|., , OAM), JavA/m)| in Pa « Pees a e+ Pa a Following errors are estimated: ABs» #103", A= 202°, AK =#0.05 and Ap=205. The results for the determination of the real surface area and the error are displayed in Table 2. The rel- ative ertor is in the range of 13-21% The main source of error for both catalysts is the determination of the correct peak width, ‘which contributes with more than 50% to AA/m. The second largest error source is the uncertainty of the Scherrer constant K which was expected to be 0.94 + 005. In contrast, the error forthe deter- ‘mination of the peak maximum and the density is very small. Error sources that have been neglected in this analysis are the ‘existence of a particle size distribution, the presence of X-ray PICoJC TKK 25 oD Pyco en ttt SH 40 50 60 70 80 40. 50 60 70 80 Fig 1. Background coreted powder diactosrams of PColC catalysts ae tic voltammetry 0.1 MHCIOg sets show the PC (20) reflexes which were we for 1H, Staenbury l/Jouralo Hlectrosnaytal Chemistry 642 (2010) 52-60 RD stays of PoC catalys, Gault Tate parameicr evn putide —BVEM———~Peakimaximum —-PLor Pico Scherrer Alaa) Relative a szetm) 220.200) 2007, density (gem!) __ constant er (8) PuGolCETEK 348 0.007 2 24203 6a0s02 135205 0942005 7as16 a PuGoICTKK 3842001 40 25203 oazs02 185205 ostsos we 20 amorphous material, stress and strain effects, a non-spherical par- ticle shape and the chance that crystallites consist of several crys- {allite grains. The quantification ofthese error sources is dificult or impossible without help of other analytical techniques, e.g. elec- ‘won mieroscopy. More advanced methods of X-ray analysis are based on assuming a lognormal particle size distribution [21,22] ‘The analysis of stress and strain effects and the separation from le size broadening is not possible by single reflection analysis the Scherrer equation, The Warren-Averbach [23-25] and Williamson-Hall [26-28] analysis have been used and modified for separation of size and strain broadening, These methods re- quire a peak shape analysis of more than one peak, which is not straightforward for the catalysts investigated in this study. AS Fig. 1 shows, only for the 220 reflection no peak deconvolution is needed and an unambiguous background correction is possible. 23, HRTEM HRTEM is a useful tool for analyzing particles which are larger than Inm. It allows the determination of reliable particle size distributions and is suitable for particle shape analysis. Iregular particle shapes othe presence of agglomerates may hamper the Getermination of the real surface area, For E-TEK PECOIC and TKK PtsCo/C catalysts those irregular particles and agglomerates are very rare (Fig. 2). Separated particles supported by carbon black Bre visible. Histograms for both PryCo catalysts afer leaching are displayed in Fig. 3. We obtain average particle sizes of 4.1 nm (E- ‘Tek catalyst) and 45 nm (TKK catalyst) The absence of agglomer- ation isa prerequisite forthe accurate determination ofthe surface fea by HRTEM, but the shape of the particles i important too. In previous investigations of Pr nanopaticls a spherial shape was usually assumed, but also a cubooctahedral shape [29]. According to Fig. 2, the assumption of spherical particles seems appropiate, although few ellipsoids and particles with facets are present. Assuming a spherical parte shape the real surface area is given ty: yam 3n, Eon slp Caley : where A is the surface area, m the particle mass, 9 the patticle density, r the particle radius and the n the number of particles Fig. 2. HRTEM images of PCO} catalysts after eyelic voltammetry in Ot M HCO, PI,CoIC E-TEK 15 ® tam 310 a PL,ColC TKK ,=4.5nm Particle size / nm. i 2. Paice sie itbutions of Caf catalysts rey vltmety in 0.1 BCI 1 Schuler et laura of etroanaytil Chemiry 62 (2010) 52-60 2 E 40 PI,ColC E-TEK 3 ‘Aim = 8240m*9,, & 120 & 5 100 8 20 it 2 Lf PI,ColC TKK Alm = 7429m‘/g,, 080100 150 200 0 80 100 180 200 Measured particles ig. 4. Average surtace area measured by HRTEM a function ofthe numberof measured parties, For each catalyst the particle size was determined from several HRTEM images. To get an impression how many particles should be counted to get reasonable statistics, Fig. 4 displays the surface ‘areas a5 a function of the counted particles. The areas approach a ‘constant value after counting about 100 particles. Therefore, it seems sufficient to count around 200 particles to get a reliable value for the mean particle size. 33.1, Eror analysis “The error for the real surface area calculation is given by: A ® {As forthe XRD calculation a Pt,Co density of 18.6 + 0.5 g/cm? for, PLsCo/C-E-TEK and 18.5 +0.5 glem? for PLsCojC-TKK is assumed. The error for the measurement of the particle size Ar is 40.15 nm. The results are summarized in Table 3. Notably, the rel- ative error is 11-12% which demonstrates a high reliability ofthis, ‘method. The error for the PrsCo catalysts consists of contributions from the particle radius on one hand! and the density on the other hand. Bath errors are about equal Ifthe surface area is calculated ‘with the number average mean diameter [1] and not by Eq. (8), one ‘obtains slightly smaller numbers, namely 80 m:/gPr (Pt,Co/C- TTEK) and 73 m")gPt (Pt:Co{C-TKK), which is a difference of fess than 3% to the more accurate values, obtained from the particle size distribution (Table 3). ‘An error source that has been neglected is porosity or surface roughness of the particles, which cannot be resolved by HRTEM, however, this morphology is unlikely due to the high surface en= ‘ergy which favors the formation of smooth particle surfaces. Efforts to further improve the real surface area measurements, may rely ‘on improving the resolution [13] or to determine the particle den- sity with a higher accuracy. The estimation of the Pt;Co density from XRD measurements is possible for the investigated E-TEK and TKK catalyst, since they consist mainly of one crystalline phase, which is fce-Pt,Co, Other Pt-alloy catalysts may consist of a mixture of different crystalline phases [48], which would compli Table3 HRTEM analysis of PCo cats Gataist———1 V (RHE) (Fig. 5). The upper integration limit was therefore set to around 1 V were the CO-stripping peak tails out. Ina study of PYC catalysts CO-stripping peaks were observed at potentials >1 V (RHE) 35}, but in Fig. 5 no distinct peaks are present which point to CO-stripping at potentials higher than 1 V. We subtracted the ‘current of the base line voltammogram in the potential region of the CO oxidation peak (Fig. 5). After background correction the ‘remaining charge originates mainly from CO oxidation (Ea. (12) PL-CO+H,0 — Pt-+ CO, + 2H" +20 (12) In CO-stripping voltammetry of PIjC catalysts a charge of 420 Clem? is commonly used [4]. For Pr,Co[C catalysts in this study, we used the same value for surface area calculation (Ea, (13)). The calculated surface areas are displayed in Table 4, A 0/420 pC em? ‘The validity of this method to correct the double layer charge was discussed by Gomez et al. [50], who studied the CO sorption at Pe-group single crystals by electrochemical and spectroscopic methods. IRspectroscopic analysis yielded lower CO surface cover- ge deo than determined by CO-sripping voltammetry using the (13) 8 1 Schulenburg et laura of Betroanaytil Chemistry 642 (2010) 52-60 Galt ‘Aim mln)® — Relative Ama)” — Relative ror) ere)” PuGiceTeR 5729 16 9 7 PLCOICTR, 6 10 56 " Double layer charge crectin according i 5 according oa (19 conventional method to correct double layer charges [2151-54] (Fig. 6). An explanation for this discrepancy could be anion adsorp- tion occurring rapidly after CO oxidation, This additional charge would contribute to the CO-stripping peak and cause inaccurate values for to. Therefore Gomer proposed to use Eq, (14) for cor- rection of double layer charges. oer = Qa ~ (5 + Qu) 4) here Qc isthe charge exclusively originating from CO eletro- ‘oxidation, Qn the total anodic charge and Q, the background charge in absence of CO. All these values refer toa potential range fim E, to E, which includes the CO oxidation peak [50 The charge Qusre- fers to processes which are coupled (othe CO oxidation, for instance anion adsorption. The measurement of Ques cartied out by holding the working electrode ata constant potential E under inert gas fol- towed by bubbling CO into the electrolyte which may lead to di placement of anions (A) by CO (Eq, (15)) [50.55]: PL-A+COFE —Pt-CO+A (15) Applying this method to the PtsCo/C catalysts yields Quserex = 111 C)gre and Qeree = ~10.1 + 0.3 Clix when CO is bubbled at 05 V (RHE). The reverse ofthis charge is used to calcu- late the Qcor Values (Eq, (14) and the corrected sutface areas (Ta- ble 4), The negative values for Qu, point to adsorption displacement of anions by CO. Since the experiments were carried ‘out in 0.1 M perchlotic acid a displacement of perchlorate ions is ‘obvious. Adsorption of residual chloride could contribute 0 Quis to0 [56,57], since perchlorate is often regarded as weakly or non- adsorbing ion [56,57] on Pt. Also a displacement of adsorbed oxy- Assumption and ecor analysis for el surace rez measurements of PCC catalts. _genated species (OH) by CO may cause Qu. In case of both inves- figated PE,Co/C catalysts the correction with Quy results in slightly lower surface areas (Table 4). 3.5.1. Eror analysis ‘The results of the real surface area determination are summed up in Fig. 6 and Table 4. The error is calculated as the standard ‘deviation of four independent measurements. Not included are er rors, which originate from background current correction and devi- ations from the value of 420 jC [tis assumed that no surface ‘area is lost due to contact of the Pt;Co particles with the carbon support. 4. Discussion 4.1. Differences between electrochemical and TEM/XRD surface areas ‘A comparison of the surface areas for both PtsCojC catalysts is depicted in Fig. 6. The surface areas were caleulated by XRD, ‘TEM, Hypa and CO-stripping voltammetry. The XRD areas agree fairly well with the HRTEM areas, whereas the electrochemical ‘metitods clearly yield lower surface areas. The Hypa method results in Iower surface areas than CO-stripping voltammetry ifa constant ‘capacitive current is assumed for the Haga charge estimation. Ifwe use the CO-stripping base lin for correction of capacitive currents, the agreement between Hq and CO-stripping is excellent, which ‘was also observed in studies of PU/C catalysts [22]. Nevertheless, these in situ surface areas are 30% (E-TEK catalyst) of 23% (TKK cat” lyst) lower than the corresponding TEM surface areas. Ths differ- ‘ence is significant. 42. Contact area catalyst-support ‘With Table 5 in mind, which lists the assumptions and error sources for the measurements, one may speculate that a part of the PtsCo particle surface is blocked by the carbon support. This ef- fect was discussed by Ferrera et al. [58] who studied the ageing ‘mechanisms of PU/C catalysts in PEFCS. The Hyyq sutface area was roughly 70% of the TEM area in PEFC cathodes. This difference is similar to the results for PtsCojC in our study. Ferreira et al. (58] Method Asem Consiered ror sures Relative er RD Spherical paride shape Full- width at half max 20-21 Uniform particle os ‘Absence OF Kray amorphous phases Peak maximum, ‘Absence of ses and trainees Scherrer constant Each particle consist of ne crystal grain arte density No mixture of diferent erysalne pases Rr No partes <1 nm Particle density 10-12 Sperial patie shape Partie aus Ht 210 pce, Petoadag on elected as “Appropriate cometion of bacaround currents Covet integration fits Compl catalyst vetting No adsorbed impurities on catalyst parties No ative aca ss det contact with bon Suppor costing 20cm, Petosing on 17 ‘Appoprite cretion nf hacker carers trove Core integration its Complee catalyst vetting No adsorbed impurities o catalyst parties No setve ass de to ott with bon Suppor 1H Schueng Jounlo Electroanaytal Chemistry 642 (2010) 52-60 so explained this difference by non-spherical particle shapes and blocking of active sites by the carbon support. An adeltional prob- Jem for Hypa measurements in PEFCs isthe absence of a reference electrode and incomplete impregnation of catalyst particles with Jonomer. In case of the investigated Pt,CojC particles in our work it appears reasonable to neglect the surface blocking effect of the carbon support, because (i) studies of PUC catalysts in liquid elec- twolyte yielded similar Hyys and TEM surface areas [8 (i) the con- tact area of PtsCo particles and carbon should be very small if the catalyst pattcles and the support are nearly spherical (Fig. 2). Nev- ertheless an analytical quantification ofthe blocked surface would be interesting and might be possible using aberration-corrected ‘3D-HR{S)TEM in several years. 4.3, Presence of surface Co atoms ‘The electrochemical surface areas of Pt,Co nanopartictes in our study are clearly lower than the TEM/XRD surface areas. Is this dif- Terence caused by cobalt atoms atthe surface ofthe alloy nanopat- ticles? These cobalt atoms may not participate in hydrogen and carbon monoxide sorption reactions, but they contribute to the ‘TEM surface area. This explanation was given by Paulus et al. [8] in a study of PLalloy catalysts. For a PtsColC catalyst a surface ‘composition of 58 at% Pr and 42 at-% Co for Pt;Co was calculated under this assumption. On the other hand the presence of Co at the surface is not supported by low-energy scattering spectroscopy ‘of annealed (1000 K) bulk PtsCo, which show that the surface layer consists of 100% Pt [43,44] Molecular dynamics simulations by Chui and Chan [45] point to an incomplete surface segregation of Pt. The surface still consists of both, Pt and Co, however, these calculations do not consider the leaching of Co in acidic electrolyte, which was also observed in this study (Table 1), Monte Caro simulations at T= 600 K show that Pr;Co nanoparticles have a pure Pt monolayer shell and a Co-en- riched sublayer [44], These calculations were supported by aberra- tion-corrected HRSTEM images of annealed Pt;Co nanoparticles [13]. The atomic resolution of these images suggests the segrega- tion of Pt monolayers and the formation of a Co-enriched sublayer. However the presence of Co atoms at the surface can not be excluded, Mayshofer et al. [16] and Duong et al. [49] used cyclic voltam- ‘metry in alkaline solutions to prove the presence or absence of o on Pr,Co nanoparticles. The presence of a redox peak was re- lated to surface cobalt. We adopted this approach to study the surface of the commer- cial Pt,Co[C catalyst before and after leaching (Fig. 7). Both as re- ceived catalysts depict features of a cobalt voltammogram even oto ~~ Paco ETEK as received —Pt.Co E-TEK after leaching cole 0.05 ae 1 amg", 0.00 0.05 00 02 04 06 08 10 12 00 02 E/V(RHE) ‘though the oxidation peak at potentials >1 V is missing. The redox: peak at potentials around 0.44 and 0.70 V (RHE) could be assigned to the oxidation and formation of Co(OH), [46], but also a redox: reaction involving metallic cobalt was discussed [49]. The oxida- tion products may be a mixture of CoO, Co;0, and CoOOH, which ‘were observed by XPS of oxidized Co films [47], After leaching, the catalysts by cyclic voltammetry in perchloric acid another vol- Tammogram ia alkaline electrolyte was recorded, After leaching the characteristic cobalt redox peak is absent, suggesting that Co atoms ae present at the surface before leaching and absent after leaching. In that case the surface of the investigated catalysts seems 10 consist of 100% Pt. Therefore, the discrepancy of the in situ and ex situ measurements in Fig. 6 seems to originate from an incomplete H and CO sorption even though the surface is free of cobalt atoms, 4.4, Hypothesis for differences of electrochemical and XRD/TEM areas It seems that the assumption of 210 jCfem for estimation of Hp areas and 420 Clem, for CO-stripping areas are inaccurate Tot PCo particles, even if we assume that the particle surface con- sists of 100% Pt. Surface areas calculated with these values are smaller than values obtained by HRTEM which is more reliable. We speculate that H and CO overlayers have different structures ‘on polycrystalline Pt and Pt;Co surfaces. Obviously the surface cov- erage of H and CO is lower on PtsCo. Even for different Pt facets the surface coverage and structure of overlayers differ alot [4.50.59] and it would not be surprising ifthe surface of PtsCo particles have a different distribution of facets than Pt particles. Additionally the Pt-Pt bond length is different at the surface of Pt-alloys [60,61] which may influence the H and CO sorption properties too. Stamenkovic et al. 43] investigated well-defined PrsCo and Pt surfaces for oxygen reduction, The surface of the annealed PtsCo electrodes consists of 100% Pt which was shown by low-energy Jon-scattering. Inspection of the cyclic voltammogram (Fig. 2 in Ref, [43]) im 0.1 M HClO, shows that the Hy surface area is clearly lower than the area of polycrystalline Pt, however, no numerical values for charges were given. This finding supports our hypothesis that less H is adsorbed per surface area than on polycrystalline Pt. 45. Comparison of measuring methods Of all investigated methods, the HRTEM analysis seems to be the most reliable method for determining surface areas. For PI,ColC nanoparticles, which were investigated in this study, HRTEM appears to be the only method, which allows the Ta= PICO TKK as recewved —Pt.Co TKK after leaching coc 04 06 08 10 12 Fig. 7. Cyclic votammogramm in thaline soltion of reve and Fathed PCa catalysts as wells CofC: Catalyst aching was cared ut by etic otammetry in TM UCia se experimental Hetralyte was OM KOR, SOs 20°C o 1 Schulnburg tourna of Eetroanaytil Chemistry G2 (2010) 52-60 determination of absolute values for the real surface area. Our study shows that if surface areas of Pt,CoC nanoparticles are mea- sured by CO-stripping or Hyya (according to Ref. [32], the values are roughly 25% lower than HRTEM areas. Ifthe real surface area ‘of Pr,Co nanoparticles is measured solely by one of these in situ methods, we propose to ad ~33% to the calculated value to obtain ‘a more accurate value forthe real surface area, 5. Conclusions Real surface areas of electrochemicaly leached Pt,Co|C catalyst supplied by E-TEK and TKK were measured by XRD. HRTEM, Hips and CO-steipping voltammetry, Error sources and assumptions of the methods were discussed. The comparison of the different methods shows that ‘+ HRTEM is most reliable for real surface area measurements of r,Co nanoparticles. The relative error for the real surface area determination is around 11%. ‘The Hyy-technique yield the same surface area as CO-stripping voltammetry, if the CO-stripping curve is used for subtraction of, capacitive currents. + Surface areas determined by HRTEM and XRD are cleary (23- 30%) larger than calculated from CO-stripping voltammetry and Hyp + Ifthe real surface area of PtsCo nanoparticles is measured solely bby Hugs oF CO-stripping voltammetry ~33% should be added to the caleulated value to obtain a more accurate teal surface area, Acknowledgements Dr. C. Weidenthaler (Max-Planck-Insttut fir Kohlenforschung,, Germany) is acknowledged for discussion of XRD data. We thank S. Kochli (PSI, Laboratory for Radiochemistry and. Environmental Chemistry) for ICP-OES analysis, Dr. G. Khelashvili (Forschungszen- trum Karistuhe, Germany) for preparation of Co/C and Dr. K. Pom- Jakushina and R. Frison (PSI, Laboratory of Developments and Methods) for giving us access to the XRD equipment. References 101 6. torgeret Gallet: GH. Kndenge, Shih.) Weitam Randbook of Heterogeneity 2nd vol 2. Wey VCH. Vera, ‘Wirnei, 2008 pp. 738-82. [2} 5 trast, O. Pee, Pure App chom 63 (1991) 711 {3} 6. jew Prog suttSe 57 (1098) 137. and references therein. [aj Ee are W. Vee ns W. Vetch A Lamm, HA. Caster (Eds) Handbook of Fel cells leat va 2, Wiley. West Sse. 2003p. 508-315, and references tern, [5] CLcreen, A Kocernak. Phys. 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