Talanta 47 (1998) 1099 – 1106

Electrochemical behaviour of gold, silver, platinum and palladium on the glassy carbon electrode modified by chitosan and its application
Xianzeng Ye *, Qinghua Yang, Yan Wang, Nanqiang Li
Department of Chemistry,Peking Uni6ersity, Beijing 100871, People’s Republic of China Received 21 August 1997; received in revised form 5 January 1998; accepted 28 April 1998

Abstract The chitosan-modified glassy carbon electrode can be used as a working electrode for the determination of precious metal elements: Au, Ag, Pt, Pd. In low pH medium, the complex anions of these precious elements combine with the + protonated group NH3 in the chitosan molecule in the form of an ion-association complex. These metal ions were selectively enriched and we got sensitive anodic stripping current. These elements content in ore, welding material have been determined by this method. The results were consistent with those from standard sample and ICP atomic emission spectrometry method. The possible mechanism of electrochemical reaction has been proposed by the study of CV, UV and FT-Raman spectrometry. © 1998 Elsevier Science B.V. All rights reserved. Keywords: Chemically modified electrode; Chitosan; Precious metal element; Glassy carbon electrode; Anodic stripping voltammetry

1. Introduction Chitosan is the main component of the shell of shrimps, crabs and insects, with the following structure:

* Corresponding author. Fax: + 86 10 62751708; e-mail; yexz@chemms.chem.pku.edu.cn

It has not only hydrophilic and hydrophobic groups but also complex groups such as NH2 and OH. It is chemically stable and is widely used in medicine, agriculture, sewage treatment and fibre manufacture etc. [1,2]. In analytical chemistry, it is used to separate and enrich trace amounts of Ni(II), Cu(II), Cd(II) [3]. It can be used as a modifying reagent to prepare chemically modified electrode. Its application to determine trace Fe(III) [4] and Pb(II) [5] has been reported. So far, there are few electrochemical studies on the analysis of precious metal elements. Therefore, we attempted to use the chitosan-modified glassy carbon electrode to assay trace Au, Ag, Pt,

0039-9140/98/$ - see front matter © 1998 Elsevier Science B.V. All rights reserved. PII S0039-9140(98)00189-1

2 V (b) DP = − 0.567 mg ml − 1. respectively. Fig. DT = 2 min. 2. Experimental 2. Au(III) standard solution was prepared by dissolving 0. A three-electrode system was used for all experiments. Anodic stripping votammogram of Pt(II).0 mol l − 1 HCl solution. Ag(I) standard solution was prepared by dissolving 0. .1000 g PdCl2 in 10 ml 1.2. USA).2.7458 g AuCl3 · HCl · 4H2O in 6 mol l − 1 HCl solution.04 mol l − 1). and the measurements were carried out under an atmosphere of nitrogen at 209 2°C.1100 X. HCl–KCl (0. 2. The concentration was 400 mg ml − 1. (a) DP =0. Finally. The concentration was 600 mg ml − 1. More dilute metal solutions were prepared from these standard solution. Apparatus The electrochemical experiments were carried out by using a PAR M270A electrochemical system (EG&GPARC. other conditions are the same as in Fig. 6 = 0. All other reagents were of analytical grade. transferring to 100 ml volumetric flask. Fig. diluting to volume.0540 g pure silver wire in 5% HNO3 solution. Cyclic voltammogram of Pt(II). pH 2.10 mg ml − 1 solution. A glassy carbon electrode with chitosan coating is used as a working electrode.0402 g pure platinum wire in 10 ml aqua regia. 1. HCl was added gradually in order to eliminate HNO3. Pt(IV) standard solution was prepared by dissolving 0. We got a good result and the mechanism of electrode process for this chemically modified electrode has been investigated in detail. The concentration was 3. dilute the stock solution with 6 mol l − 1 HCl to get 0. / Talanta 47 (1998) 1099–1106 Pd by anodic stripping voltammetry in the present paper. Pt(IV) (4 mg ml − 1). Water was quartz-distilled twice. DP = − 0. transferring to 50 ml volumetric flask. heating to boiling. 1c. A saturated calomel electrode and a platinum electrode are used as reference electrode and counter electrode.3 V. (a) Base solution (b) bare glassy carbon electrode (c) glassy carbon electrode modified with chitosan. Reagents 1% chitosan solution was prepared by dissolving 0. and diluting to volume. It’s concentration was 1.01996 g chitosan in 2 ml of 2 mol l − 1 HAc solution.3 V. transferring to 100 ml volumetric flask. 2.2 V s − 1. it was dissolved in 10 ml of 1. High purity nitrogen was used for deaeration for 15 min. Pd(II) standard solution was prepared by dissolving 0. Before use.0 mol l − 1 HCl solution and transferred to 100 ml volumetric flask. The Raman spectra were recorded by means of Nicolet 910 FT-Raman spectrometer with YAG laser source (1064 nm).08 mg ml − 1. 3 mg ml − 1 Pt(IV). Ye et al.1.

X. The real surface area of the CME was determined to be 0.0 s. The peak half-width W1/2 =65 mV was acquired from the plot and it was increased with the pulse height. 2. DT= 0. 3.20 V.3. Glassy carbon electrode modified with chitosan. The film thickness is 1. Pt(II) (20 mg ml − 1). / Talanta 47 (1998) 1099–1106 1101 Fig. the pulse width is 40 ms. but Pt(IV) cannot. The value of W1/2 = 65 mV was approximate to 60 mV (paper value). The stripping peak current is proportional to 6 over the range of 10 100 mV s − 1 is not proportional to 6 1/2. The potential difference between reduction and oxidation peaks (DEp) is 40 mV.This illustrates that it is PtCl2 − which 4 can be enriched in the coating film. 3. 2.1 mm according to the density of chitosan (1. 2a).3 0. Cyclic voltammogram of Pt(II). So we concluded that PtCl2 − 4 combined with chitosan. 1. The cyclic voltammograms at different deposit potential are shown in Fig.3 V (Fig. The NH2 group of chitosan is protonated in low pH solution. The electrode was permitted to be used for a new run after it had been dipped in 2 mol l − 1 NaCl solution for 5 min and washed with distilled water. the peak current at the modified electrode is 10 times higher than that of the bare electrode. Ye et al. and the electron transfer number was equal to two [8]. Preparation and regeneration of CME The surface of glassy carbon electrode was polished with alumina slurry and sonicated with deionized water and ethanol. for 3 min. The durability of the chitosan CME was more than a month. It means PtCl2 − 6 cannot be enriched in the coating film.0 ml of 1% chitosan solution with a microinjector. the scan rate is 5 mV s − 1 and the scan range is −0. The CME was placed under infrared light for 30 min and the chitosan CME was acquired. The differential pulse voltammetric curve of Pt have been made in 0. Therefore.16 V. Pt(II) is active enough to react with the reagent.04 mol l − 1 HCl–KCl (pH 2. After sonication.2) solutions at 293 K. the electrode process can be expressed as follows: enriching process: C6H11O4N. the use of chitosan CME made it possible to improve the sensitivity for the determination of Pt greatly. However. These data indicate that the redox of electroactive material in the film belongs to a surface-confined quasi-reversible wave [7]. Based on the above results. The peaks are observed at a potential of −0.2 V (Fig. where the pulse height is 50 mV. The cyclic voltammogram of Pt(II) also shows that there is no redox peaks when the CME is deposited at + 0. Results and discussion 6= 200 mV s − 1) are shown in Fig. Then the electrode was coated by injecting 4. respectively. 2b). The redox peaks appear when the CME is deposited at −0. the electrode was rinsed with deionized water and allowed to dry in the air.285 cm2 by small amplitude triangular potential scanning method [6] (a method to calculate the real surface area by determining differential capacitance). Generally.29 g cm − 3).

ed + H + = C6H11O4NH + .

ed PtCl2 − + 2e=PtCl2 − + 2Cl − 6 4 C6H11O4NH + .

ed + PtCl2 − 4 = C6H11O4NH + PtCl2 − .

The anodic stripping voltammetric curve at the CME and bare glassy carbon electrode in 0.3 V (versus SCE).2. . Voltammetric beha6iours of Pt on the chitosan/GC CME The working electrode was dipped into Pt solution and deposited for two min at −0.04 mol l − 1 KCl – HCl supporting electrolyte (pH 2.1.ed 4 3.

1102 X.32 Added amount (mg ml−1) Detected amount (mg ml−1) Recovery (%) 0. Ye et al.68 1.31 0.34 0.70 1. / Talanta 47 (1998) 1099–1106 Table 1 The content of platinum in ore and recovery Recovery Sample 1 2 3 Mean Pt content (mg ml−1) 0.43 98 102 100 stripping process: C6H11O4NH + PtCl2 − .32 0.40 0.

ed + 2Cl − 4 − 2e=C6H11O4NH .

6 = 0. We have used SnCl2 reducing Pt(IV) to Pt(II) and scanned directly (not having been electroenriched). We have used this technique to assay the platinum content in ore without separation. ipa (mA) = 0.2 V. 4. but it disappears in chitosan+ PtCl2 − 6 4 system.3 mg l − 1 Pd(II). Cyclic voltammogram of Pd(II). The method is as follows: The ore sample Fig.0 V. but the latter has a strong absorption peak at 251 nm. 3.0. 2. 3).02 mol l − 1). correlation coefficient r= 0. The method can assay 0. DP = −0.0 mg ml − 1. The peak potential is in good agreement with the above plot (Fig. First scanning. pH 2. This indicates that new component of C6H11O4NH + PtCl2 − was produced. Fig. The oxidation peak current can also be obtained. 5. 4 Under the above conditions. The determination results is consistent with the standard sample.98c[Pt(IV)].1 V s − 1. DT= 60 s. the anodic stripping peak current is proportional to the concentration of Pt(IV) over the range of 0. Anodic stripping voltammogram of Pd(II).9984. DP= 0. 1. second scanning.5 5. . then enriched and oxidized.025 mg ml − 1 Pt(IV) if the electrode preconcentrates for 10 min.557−5. We compared the UV spectra of chitosan + PtCl2 − and chitosan+ PtCl2 − system. 1. There is a vibrational peak of N H bond at 3300 3500 cm − 1 in chitosan + PtCl2 − . (a) Base solution (b) bare glassy carbon electrode (c) glassy carbon electrode modified with chitosan. HCl – KCl (0. other conditions are the same as in Fig. It indicates that Pt(IV) is reduced to Pt(II) first. The Raman spectrogram 4 also proves this point.5 mg l − 1 Pd(II).ed +PtCl + 2− 6 The following experiments prove the mechanism further. This illustrates that PdCl2 − combined with 4 chitosan and produced a new component C6H11O4NH + PtCl2 − . The for6 4 mer has an absorption peak at 224 nm which is consistent with the absorption peak of chitosan. 4.

1 2 3 4 Mean Pd content (%) 1. adding HCl to eliminate HNO3.65 V the anodic stripping peak was observed. At potential of 0.35 mg g − 1.1 1. The standard deviation is 0.041 V) is about 600 mV and the anodic peak current and cathodic peak current is intended to be equal when scanning for the second time. the potential difference between anodic peak potential (0. PdCl2 − reacts with 4 chitosan and produces an ionpair. In such way we get a more sensitive anodic stripping voltammetric current.3 mg ml − 1 of Pd(II).4 Added amount (mg l−1) 0. Ye et al.1 V s − 1. 6.0 V for 1 min and scan positively.015 mg g − 1.0. A new component was produced. Finally transferred to 10 ml volumetric flask with 0. pH 2.0 V. 10 times of Au(III). The peak current at modified electrode was 15 times higher than that at bare electrode (Fig. DT= 5 min.29 Recovery (%) 95 93 95 97 95 1103 was incandesced at 600 650°C.30 Detected amount (mg l−1) 0. PdCl2 − in solution combined with the protonated 4 + group NH3 in chitosan molecule and was enriched selectively at electrode surface in the form of C6H11O4NH + PdCl2 − .01 mol l − 1 HCl.6%.X. DP= 0. The amount of modifying reagent was selected for 4. 6= 0.21 0. But when we deposited at 0. KCl – HCl (0. 5).02 mol l − 1 KCl–HCl as supporting electrolyte.2. the relative standard deviation is 4.12 V s − 1 at the concentration of 3.15 0. The chitosan +Pd(II) system produced a new absorption peak at 263 nm compared with the chitosan system.1 mg ml − 1 Au(III).4 1.4 1. So the reversibility of the electrode reaction of Pd(II) is worse than that of Pt(II).0 ml of 1% chitosan solution. If we enrich it only by static charge adsorp- Fig. China Academy of Geology Research 72-Pt-02 sample) the relative error is − 8. . (a) Bare glassy carbon electrode (b) glassy carbon electrode modified with chitosan. so it can be adsorbed and enriched at the electrode surface.1 mol l − 1).0 V for 60 s. pH 2).5 1. 0. Pd(II) In palladium solution (0. Compared with the standard sample (0. 3. Ag(I) did not interfere with determination. In cyclic voltammograms of Pd(II) (Fig.075 0. 4). The determination results are shown in Table 1 under the above conditions.071 0. The coexisting element in ore 20 times of Os(VIII). Anodic stripping voltammogram of Au(III). The residue was dissloved with aqua regia.22 0. 5 times of Ru(III). it was electroreduced to Pd(0). The stripping peak current increases proportionally with the increase of scanning rate over the range of 0. the working electrode was deposited at 0.65 V) and cathodic peak potential (0. / Talanta 47 (1998) 1099–1106 Table 2 The determination results of Pd in 105 deoxycatalyst and recovery Recovery No.14 0.02 0. Then the sample was washed with 4 mol l − 1 HCl to eliminate Cu and Ni. Similarly to Pt(II).7%. This point can also be 4 proved by UV spectra.

/ Talanta 47 (1998) 1099–1106 Table 3 The determination results of Au in ore and recovery Recovery No. The electrode process can be described as follows: enriching process: C6H11O4N.49 3. then scan directly for the second circle).04 1.52 Added amount (mg ml−1) 1. As seen in Fig.59 3. 5. 1 2 3 4 Mean Au content (g T−1) 3.00 2.89 4.00 Detected amount (mg ml−1) 1.1104 X.7 tion.94 2.52 3.5 99.00 4.00 3. the anodic stripping current of the second scan is obviously smaller than the first scan. its anodic stripping current is smaller than that electroreduced. (We have deposited 60 s for the first scan.48 3.06 Recovery (%) 104 97 96.3 101. Ye et al.

ed +H + = C6H11O4NH + .

ed C6H11O4NH + .

ed +PdCl2 − 4 = C6H11O4NH + PdCl2 − .

ed 4 C6H11O4NH + PdCl2 − .

ed +2e 4 = C6H11O4NH + · Cl − · Pd.

ed +3Cl − stripping progress: C6H11O4NH + · Cl − · Pd.

ed + 3Cl − −2e= C6H11O4NH + .

It combines with the proto+ nated group NH3 in chitosan group and can be enriched selectively.1 mol l − 1 KCl–HCl solution (pH 1 2.01 mol l − 1 HCl solution and transferred to 25 ml volumetric flask. 6 =100 mV s − 1). The peak current at the modified electrode is 5 times higher than that at the bare electrode (Fig. The standard deviation is 0. − Au(III) exits in the form of AuCl4 in HCl medium (pH 1 2).0%. 6). We have used this method to determine the content of gold in ore. the relative standard deviation is 12%. The result is consistent with that from the ICP-AES method.017%. The correlation coefficient r= 0. A sample of ore (10. The determination results are shown in Table 3 with the above method. The results and percent recovery are shown in Table 2.609 0. The sample was first leached with 6 mol l − 1 HCl several times.2 V for 5 min and scan positively in 0. China Academy of Geology Resarch).1 times of Cu(II). The results are consistent with 3. However.1 mol l − 1 HCl until the filtrate was colourless and transparent.0497. 3. the residual sample was washed with 0. it was dissolved in 0.0050 g) was incandesced at 600 650°C for 1 h to eliminate C and S elements.01 1. HNO3 was eliminated. NO3 did not interfere with determination. The filtrate was heated to dryness.12 g T − 1 of the standard sample (GBW(E) 070023. 0. After filtering. this kind of combination is more relaxed than that of Pt(II) and Pd(II).ed +PdCl2 − 4 Under above conditions we have determined palladium in 105 deoxidized catalyst. large amount of Mn(II).0 mg ml − 1. Au Gold anodic stripping peak was observed at 1. The anodic stripping current is proportional to the concentration of Au(III) over the range of 0. The ionpair of AuCl4 and chitosan is − more relaxed than that of PtCl4 . 150 times of − Ru(III). The standard deviation is 0. 0.3. It must be . Ni(II). the relative standard deviation is 2.00 V when the working electrode was deposited at 0.75 times of Pt(IV) had no interference with determination. then filtered and the residual sample was dissolved with 40 ml aqua regia.9983. So no obvious change is observed in UV and Raman spectra. The electrochemical reaction process is like that − of Pd.

The peak current is obviously higher than that at the bare electrode (Fig. Its dissociation degree is smaller than that of Au(III) and Ag(I). Anodic stripping voltammogram of Ag(I).X.1 mol l − 1). University Chemistry 9 (3) (1994) 22. These metal ions combine in different way with chitosan according to UV and Raman spectra. p. 0. 3. The reality is 1000 mg ml − 1. Chitin. The potential is at − 0.075 V. London. It is ideal to be used as the modifying reagent for CME to determine precious elements such as Au.1 mol l − 1 NH4SCN system (pH 4. Chitosan and Related Enzymes.1 mg ml − 1 Ag(I).4. 0. electroreduced in order to get more sensitive anodic stripping current. Pd. . pH 4. Pt. The combination is relax which is similar to Au(III).0 mg ml − 1. Academic Press. 1984.). DP = − 0. The Ag content in the welding material was also determined with the results of 0. DT =180 s. Conclusion Because chitosan has a wider range of potential window in positive potential with complexing capacity group. References [1] J.0). 6= 0.1 V s − 1. So the metal ions can be enriched selectively and produce sensitive anodic stripping peak current. (Ed. Potassium hydrogen benzene bicarboxylic acid (0. The relative standard deviation is 1. 77.92% while the reality was 1. then electroreduced to Ag. . 7.02 1.P. 4. No obvious change is observed in UV spectra.9989. [2] Jian Xu. The correlation coefficient r= 0. Ye et al. The concentration of Ag(I) is proportional to the anodic stripping peak current over the range of 0. (a) Bare glassy carbon electrode (b) glassy carbon electrode modified with chitosan. Zikakis. The results of determination are consistent with standard sample. XinRong Jin.6% and percent recovery is 97 101%.8 V. / Talanta 47 (1998) 1099–1106 1105 Fig.0%. − The mechanism is that Ag(SCN)2 combined with the protonated group in chitosan molecule. Ag. The ion-association complex of Pt(II) and Pd(II) with chitosan is tighter than that of Au(III) and Ag(I). We have determined silver in standard solution by this method with the average (98729 16) mg ml − 1. Ag Ag(I) also has a good anodic stripping peak in potassium hydrogen benzene bicarboxylic acid+ 0.1 mol l − 1 NH4SCN. In low pH medium. 7). the correlated complex anionic ions of the precious metal combine with the protonated + group NH3 in chitosan molecule when scanning positively.0.

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