Dissolution Rates of Precious Metal Compounds in Acid

1Hideaki

Sasaki, 2Masao Miyake and 1Masafumi Maeda

1. International Research Center for Sustainable Materials, Institute of Industrial Science, The University of Tokyo 2. Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign

Introduction
Precious metals (Pt, Pd, Rh, Au .......) in industry
Recovery from used products economically important

Pt, Pd, Rh in automotive catalyst

Au, Pd, Ag in electronic device

Recovery involves a large environmental load because of chemical stability ex. Leaching requires a large amount of strong acid

Investigative purpose Development of a method to dissolve precious metal in aqueous solution easily

Previous work
Some precious metal compounds dissolved at higher rate than pure precious metals in aqua regia.Ref. 1 Compounds consisted of Pt, Pd or Rh and Ca, Mg or Zn When pure Pt was dissolved ....
Aqua regia

1h Pt Pt

14% of total Pt was dissolved

When Pt-Zn was dissolved ....

Pt-Zn

1h

Contained Pt was dissolved totaly

Ref. 1 T. H. Okabe et al., J. Mater. Res., Vol. 18, 8 (2003) T. H. Okabe et al., Materials Transactions, Vol. 44, No. 7 (2003) Y. Kayanuma et al., Journal of Alloys and Compounds 365 (2004) Y. Kayanuma et al.,Metallurgical and Materiaks Transactions, 35B (2004)

Novel recovery process

Process
Scraps Precious metal In the pretreatment Precious metals and zinc form compounds which dissolve easily

Zinc vapor treatment

Precious metal compound

The use of acid and processing time can be reduced

Acid leaching

Dissolution mechanism of the compounds has not been clarified. Further investigation is required.

Solution containing precious metals

Ceramics etc.

What compounds should be formed to dissolve precious metals easily ? 3

Fig. Novel recovery process for precious metal using Zn vapor

Experimental
Compounds synthesis by exposing precious metals to Zn vapor Electrochemical measurement of dissolution rates of compounds

Compound synthesis
Isopiestic vapor pressure method Ref. 1

Zn

Ti wire
(Deoxidizing agent)

Pt or Au sheet
(Supported by W)

T1

nt gradie e u t a r Tempe

T2

Fig. Schematic representation of synthesis method

Activity of Zn in formed compound can be controlled by temperature gradient

aZn = p
Ref. 1

Zn at

T1

Zn at

T2
5

S. Thimmaiah et al.; Solid State Science, 5, 1309-1317 (2003)

Specimens
Table List of obtained compounds

Obtained compound composition Pt-50%Zn Pt-Zn Pt-75%Zn Au-40%Zn Au-Zn Au-75%Zn structure

1 2
Confirmed by XRD 6

Estimated from gain in weight (Homogeneity was confirmed by SEM observation)

Specimens
1200 1100

Temperature / K

1000 900

(Pt) PtZn

*
1

Temperature / K

*
( )
Pt3Zn PtZn1.7

1400

1200 1000 (Au) 800 600 400 200 1 AuZn ()

L
(Zn)

PtZn8

800 700 600 500

()

*
2
60

2 2 20

Au5Zn3

1
40

Pt

20

40

60

80

Zn

500

Au

80

Zn

Zn concentration / atom% Fig. Phase diagram for Pt-Zn system Ref .1

Zn concentration / atom% Fig. Phase diagram for Au-Zn system Ref. 1

Ref. 1 T. B. Massalski et al. BINARY ALLOY PHASE DIAGRAMS, ASM (1986)

Channel flow double electrode (CFDE)

Working electrode ( Pt-Zn or Au-Zn ) 5 molL-1 HCl Gear pump 100 mLmin-1 10 mm Collecting electrode ( Glassy carbon ) Reference electrode ( Ag/AgCl ) 1 mm

iW iC
Dissolution current of PM

Counter electrode ( Pt wire )

Fig. Schematic representation of CFDE

: iPM : iZn

PM + xCl- [PMClx]y-x + yeDissolution current of Zn Zn Zn2+ + 2e-

[PMClx]y-x Zn2+

Collection efficiency (N) can be calculated theoretically from geometric parameters of electrodes Ref. 1

iPM = - iC / N iW= iZn + iPM iC= - iPM N iZn = iW - iPM

8

(In following parts, iPt, iAu and iZn represent dissolution currents of Pt, Au and Zn determined using equations above)
Ref. 1 K. Aoki et al., J. Electroanal. Chem., 195, 229-249 (1985)

Potential of collecting electrode

1.5 Potential, E / V vs. SHE 1.0 0.5 0 -0.5 -1.0 -1.5

[PtCl6]2[PtCl4]2Pt

Pt(OH)6
Pt( OH )4

Zn7Cl2(OH)12

[PtCl6]2Pt-Zn

Zn(OH)2

Zn2+ Zn
0 4 pH

Zn2+

12

iW= iZn + iPt

iC= - iPt

(0.1 V)
Fig. Reactions on two electrode. The collecting electrode was set at 0.1 V in order to reduce platinum ions generated on the working electrode

Fig. Potential-pH diagram for platinumchloride-Water system at 298.15 K. a of -3 dissolved metals = 10 and aCl-=5. That for Znchloride-water system is shown together

Dissolution of pure Pt (Preliminary examination)

Verification of the calculated collection efficiency

[PtCl6]2Pure Pt

iW
Current density i / mAcm-2
4 4

iC= - iPt N

Fig. Reactions on two electrodes Current density i / mAcm-2

2 2 1.5

Scan rate =10 mVs-1

3

5
2 2 1 0 0

molL-1

HCl

iW

iW
0 0 0.2 0.4 0.4 0.6 0.8 0.8

iPt

iPt

11
0.5 0

1.2 1.2

0 0 0

50

100 100

150

200 200

250

300 300

potential E / V vs. SHE Fig. Linear sweep voltammogram obtained by Pt working electrode.

time t / s Fig. Time variations of iW and iPt at 1.2 V.

iW and iPt were in good agreement Anodic current at Pt-Zn electrode can be separated into iPt and iZn

10

Measurement for Au-Zn

1.5

Potential, E / V vs. SHE

1.0 0.5 0 -0.5 -1.0 -1.5

[AuCl4]Au

Au(OH)3

Zn7Cl2(OH)12

[AuCl4]Zn(OH)2

Au-Zn

Zn2+

Zn2+ Zn
0 4

iW= iAu + iZn

8 pH 12

iC= - iAu

(0.1 V)
Fig. Reactions on two electrode. The collecting electrode was set at 0.1 V in order to reduce gold ions generated on the working electrode

Fig. Potential-pH diagram for a gold-chloridewater system at 298.15 K. a of dissolved metals = 10-3 and aCl-=5 Ref. 1. That for Zn-chloridewater system is shown together.

Ref. 1 G.H. Kelsall et al.,Journal of Electroanalytical Chemistry, 361, 13-24 (1993)

11

Dissolution of pure
Verification of the calculated collection efficiency

(Preliminary examination)
[AuCl4]Pure Au

iW
current density, i / mAcm-2 current density i / mAcm-2

iC= - iAu N

Fig. Reactions on two electrodes 2000 2000 1500 1500 1000 1000 Scan rate =10 mVs-1 5 molL-1 HCl 50 50
40 40

iW
500 500

iAu

30 30
20 20 10 10

iW

iAu

0.4 0.6 0.8 1 1.2 0.4 0.8 1.2 potential, EW / V vs. SHE Fig. Linear sweep voltammogram obtained by Au working electrode

00

0 0

0.2

100 150 200 300 time t / s Fig. Time variations of iW and iAu at 1.0 V.

00

0 0

50 100

iW and iAu were in good agreement Anodic current at Au-Zn electrode can be separated into iAu and iZn

12

Results
Dissolution behaviors of Pt-50%Zn and Au-40%Zn From a linear sweep voltammogram... Zn didnt dissolve preferentially at low potentials Zn and precious metals dissolved simultaneously at high potentials During dissolution at fixed potential... iZn from the compounds increased with time iPt and iAu were higher than from pure precious metals Dissolution behaviors of Pt-75%Zn and Au-75%Zn From a linear sweep voltammogram... Zn dissolved from compounds preferentially even at low potentials During dissolution at fixed potential... iZn from the compounds decayed with time iPt and iAu increased with time iPt was much higher than from Pt-50%Zn. iAu was smaller than from Au-40%Zn.

13

Summary and future work

Pt-50%Zn, Pt-75%Zn, Au-40%Zn and Au-75%Zn was synthesized by exposing precious metals to Zn vapor.

Dissolution rates of precious metals from the compounds were measured by CFDE method. Dissolution rate of Pt was the highest from Pt-75%Zn. Dissolution rate of Au was the highest from Au-40%Zn.

14