Carbon Vol. 28, No. 5, pp. 675482. Printed in Great Britain.

1990

copyright 0 1990 Pergamon

lYEma23/90

s3.00+ .oo Press plc

EFFECT OF HN03 TREATMENT ON THE SURFACE ACIDITY OF ACTIVATED CARBONS

JOONG S. NOH and JAMES A. SCHWARZ* Department of Chemical Engineering and Materials Science, Syracuse University,
Syracuse, NY 13244 (Received 30 October 1989; accepted in revked form 18 Jununry 1990)

Abstrati-A homologous series of activated carbon samples was prepared from a low ash source carbon by controlled oxidation using nitric acid. The physicochemical properties (specifically, BET surface area, ash content, acid/base neutralization, and ammonia adsorption) were determined. Each property value changed systematically with increasing oxidation treatment; the more oxidized sample showed
higher surface acidities without significant changes in BET area or ash content. The point of zero charge (PZC) of each sample was determined by mass and acid/base potentiometric titration. The PZC values also changed systematically with the extent of oxidation; the more oxidized the carbon, the lower its PZC. It is concluded that the PZC can be used as a convenient index for correlating changes in surface

acidity of carbons. Key Words-nitric acid, surface area, PZC values.

1. INTRODUCTION

Important properties of solid/liquid systems are influenced by the electric charges on the particle surface. When immersed in an electrolyte solution, a charged particle will be surrounded by ions of opposite sign so that, from a distance, it appears to be electrically neutral. Many inorganic oxides in aqueous solution are represented as[ 11: -MOH, or -MOH; = -MOH + H+:K, = {-MOH}[H+] {-MOH,} & -MOH & -MO(1)

(2)
-MOH = -MO+ H+:K, = {-MO-}[H+] {-MOH} (3) where [ ] and { } indicate concentrations of species in the aqueous phase and concentrations of surface species respectively. The determination of the equilibrium constants, often called ionization constunts or acidity constants, such as K, and K2, is the first and an important step in interpreting adsorption data in association with the above surface ionization mechanism. Since activated carbons have been shown to exhibit amphoteric behavior in aqueous suspension[2,3], the surface ionization model can be applied to a carbon system provided the carbon contains little dissolvable ash.
*To whom all the correspondence should be made.

The pH value required to give zero net surface charge[4], designated the point of zero charge (PZC), is related to the two intrinsic acidity constants. Acid/base titration has been widely used to determine the PZC[5-81. However, this method has had limited success in determining the PZC for activated carbons. One reason for this is the three curves at different ionic strengths should intersect at a single point. However, the three curves often develop a zone of intersection with three cross points, one at each of two curves. Noh and Schwarz[9] proposed an alternative method to the conventional acid/base titration technique. This is designated mass titration, and it is used to estimate the PZC of amphoteric solids including inorganic oxides and activated carbons which can be described accurately by the surface ionization model[3,10-121. The purpose of the present study is to investigate the effect of surface modification by HNOJ on the PZC of an activated carbon. In order to compare the PZC results with the changes in other surface chemical properties caused by HNO, treatment, acid/base neutralization (according to Boehms procedures[l3]) and ammonia adsorption were also carried out.

2. EXPERIMENTAL

2.1 Preparation of carbons North American carbon (G-21, lot #4033-4, less than 2% ash content) was used as the source carbon in this study. The physical properties are shown in Table 1. Carbons were prewashed for 18 hours with deionized water using a soxhlet extractor. The source carbon was treated in HN03 solution at different concentration levels: 0.2M, 0.4M, lM, and 2M. NAO, NA0.2M, NA0.4M, NAlM, and NA2M
675

676

J. S. NOHand J. A. SCHWARZ Table 1. Properties of North American carbon in increments of 100 mmHg until 700 mmHg was reached. The pressures were measured by an MKS Capacitance Manometer Model 222B. 2.2.4 Ash analysis. The total ash content was determined by burning the carbon. A crucible containing 1 g of carbon was placed in a furnace for 24 h at 900C. The ash was then weighed on a Mettler balance. The ash components for each carbon were also analyzed by the x-ray microscope at Brookhaven National Laboratory. 2.2.5 Mass titration. To measure the PZC of the carbon samples, three different initial pH solutions were prepared using HNO, (0.1 M Fisher Reagent Grade) and NaOH (0.1 M Fisher Reagent Grade); for example, pH = 3,6, or 11. NaNO, was used as the background electrolyte. For each initial pH, six containers were filled with 100 ml of the solution, and different amounts of carbon sample were added (O.OS%, O.l%, 0.5%, l%, 5%, and 10% by weight). The equilibrium pH was measured after 24 h. 2.2.6 Acidlbase potentiometric titration. Acid/ base titration was also carried out to obtain the point of zero charge. HNO,, NaOH, and NaNO, were the acid, base, and electrolyte, respectively, used in the titration. For each carbon, eleven vials of 20 ml capacity were used. They were filled with 20 ml of NaNO, 0.1 M solution, and 200 mg of carbon was weighed and placed into each bottle. Different amounts of acid or base were added to each bottle: five bottles for acid, five for base, and one without acid or base. A 10 p,l micropipette was used to add the acid or base, and the amounts were recorded. The bottles were then placed on a shaker and allowed to obtain equilibrium over two days. They were filtered after shaking was finished. The pH values of each solution were measured. These procedures were repeated for different ionic strengths of the NaN03 solution: 1O-3 M, 1O-2 M, and 10-l M.
3. RESULTS

Type BET surface area Particle size Density (Skeleton) Bulk density Intraparticle porosity

G210R (Coconut base carbon) 110&1200 m*/g 8 x 16 mesh 1.67 glml 0.736 g/ml 39.9%

denote the carbon samples thus prepared. NAO denotes the untreated sample. The HNO, solution used was Fisher Reagent ACS Grade. For each of these samples, 100 grams of carbon was treated for 18 hours in 500 ml of HN09 solution, at its boiling temperature, using a soxhlet extractor. The carbons were then filtered and kept in an oven at 110C. 2.2 Surface characterization 2.2.1 BET surface area. Nitrogen BET surface areas were obtained on a Quantachrome Quantasorb system at liquid nitrogen temperature. The carbon sample (about 500 mg) was weighed in a Mettler balance and then heated at 110C in a flow of helium gas for 18 hours. BET surface area measurements were carried out at gas phase compositions of 7% and 15% nitrogen in helium mixtures. All the mixtures and gases used were of Primary Standard or Ultra High Purity Grade with a minimum purity of 99.999% supplied by Linde Gas Company. As recommended in the procedure manual, the surface area measurements were evaluated on the basis of desorption amounts. The area of a nitrogen molecule was taken to be 0.162 nm2 in the calculation of the surface area. 2.2.2 Boehms acidity. To evaluate the acidic and basic properties of each of the surface modified activated carbons, a scheme suggested by Boehm[l3] that measures the amount of acid/base uptake by carbon by neutralizing titration was followed. The reagents used were HCI, NaOH, NaHCO,, and Na,CO, solutions. Four parts, about 200 mg each in weight, of a sample were placed in four separate glass bottles containing 20 ml of 0.02 M solution of each reagent aforementioned. The bottles were gently shaken for 48 hours on a Wrist Shaker Model 75, Burrel Corporation. The solutions were then filtered using Fisher Scientific P2 filter paper. The amount of each reagent adsorbed was determined by back titration of the solution. Hydrochloric acid was the titer for the three basic solutions, and sodium hydroxide was used to titrate the hydrochloric acid solution. 2.2.3 Ammonia aakorption. Ammonia adsorption isotherms were measured at room temperature using a Cahn Electromicrobalance 1000. Ammonia anhydride supplied by Matheson was used. A carbon sample of 50 mg was first placed on the balance pan. The sample was dehydrated by evacuating the system at 110C for 18 hours. Ammonia gas was introduced into the system until a desired pressure was achieved, and after 30 minutes, the pressure was increased to another value. This step was repeated

3.1 Surface characterization 3.1.1 BETsu$ace area. BET areas of the carbon samples treated in different concentrations of HN03 solution are listed in Table 2. Although the apparent surface areas appear to decrease with nitric acidic treatment (except with 2M HN03), the changes are nominal. (The accuracy of the BET area measurement is +7%.) It has been reported that the treatment of carbons with HN03 does not affect their physical morphology but alters their surface chemical properties[l4, 151, and that HNO, treatment is the most effective one to make carbons acidic. 3.1.2 Boehms titration. The changes in the surface acidity brought about by treatment with HN03 can be detected classically with Boehms titration measurement; the results are shown in Table 2. The three bases used in his titration are regarded as approximate probes of a distribution of acidic surface groups according to the scheme: NaHCOJ (car-

Surface acidity of activated carbons Table 2. Characterization HNO, treatment BET area, mVg Total ash, % PZC Neutralization me& HCI NaOH Na,COj NaHCO, Ammonia acidity mmollg Ash analysis K ppm Ca Mn Fe Ni cu Rb of carbon samples 0.4M 1020 0.6 6 l.OM 1015 0.8 5.5 2.OM 1150 0.6 3.5

677

llkM 1.1
10 0.738 0.04

0.2M 1055 :.*

0.599

0.276 -

3
86.19

0.314 0.478 0.127 4.24 638.10 17.08 2.40 6.81 0.86 1.69 0.41

0.163 0.887 0.351 0.334 5.18 533.33 24.33 2.48 38.54 0.27 1.25 0.41

0.143 1.709 0.503 0.117 6.41 302.38

2.35 214.29 6.92 0.61 9.20 0.32 0.37 0.73

3.63 0.71 25.92 0.60 0.72 0.68

27.61 0.24 0.58 0.36

boxyl), Na,CO, (carboxyl and f-lactonic), and NaOH (carboxyl, f-lactonic, and phenolic). It is assumed that the HCl neutralization result represents the amount of surface basic groups. Although this interpretation is not universally accepted, it gives a semiquantitative measure of the surface functionalities[l2]. The results (Table 2) indicate that the oxidation treatment produces more acidic sites, and that leads to an increase in the amount of base required to neutralize the oxidized carbon. At the same time, the amount of acid needed to neutralize the basic sites decreases as the oxidation intensity increases. It is clear that the nature of surface chemical functionalities is significantly altered by the nitric acid treatment. 3.1.3 Ammonia adsorption. Ammonia adsorption was carried out to test whether the changes in surface acidic properties caused in the HN03 treatment are also detected in gaseous titration. The ammonia adsorption isotherms at room temperature are shown in Fig. l(a). These isotherms do not show the typical behavior of a plateau as the pressure increases. In fact, they appear to follow Freundlich-type isotherms as shown in Fig. l(b). This is likely a consequence of the contribution of selective chemisorption of ammonia on acidic sites and physical adsorption. Since the BET surface areas do not change significantly, it is reasonable to assume that the physical adsorption component to the measured weight change is a constant at a fixed pressure and temperature. The increase in adsorbed amount at, for example, 300 mmHg of NH3 pressure is then proportional to the increase in the chemisorbed component of NH3 on more acidic carbons. Ammonia, a basic molecule, has been used to probe for the presence of and the nature of surface acidic sites of solid adsorbents[l6, 171. It has been shown that the values of acidity obtained by ammonia adsorption (for example, the amount of NH3

irreversibly adsorbed at a pressure of 300 mmHg at 25C) agree well with those obtained by other techniques such as n-heptaneln-butylamine titration[l8, 191. This technique has also been used for carbon systems[2&22]. Bastick et al.[20] demonstrated a relation between the presence of carboxyl groups and the amount of ammonia adsorption. Similar trends were also observed in this study. The oxidation treatment was found to increase the amount of ammonia adsorbed, as shown in Fig. l(a). Although the interpretation of ammonia adsorption is particularly useful in the study of the gaseous adsorption phenomena[21], the results based on gaseous adsorption are not necessarily related to the aqueous adsorption phenomena, because many other important variables such as pH are involved in aqueous adsorption. Control of experimental parameters when studying aqueous adsorption is more difficult than when studying gaseous adsorption[23]. Therefore, investigations that can compare aqueous and gaseous adsorption data are necessary to illuminate the weak areas in the former[23]. To that end, a correlation can be found between the aqueous base uptake and the amount of ammonia adsorbed. Figure 2(a) shows that NaOH uptake increases with the amount of ammonia adsorbed at a pressure of 300 mmHg. Unfortunately, however, results like those shown in Fig. 2(a) still do not establish an absolute measurement for the surface acidity of the carbon. 3.1.4 Ash analysis. The total amount of ash of the as-received carbon, after water washing, was 1.1%. The total ash contents for oxidized carbons are listed in Table 2; all values are below 1% . Although I-INO, oxidation treatment appears to reduce the ash content, the changes are marginal, probably because the initial ash content is low. Therefore, it is assumed that the effect of ash on the surface properties is identical for all the carbon samples.

678

J. S. NOH and J. A. SCHWARZ

Ammonia Adsorption hotherm

-1 I

bons are shown in Fig. 3. As mentioned earlier, it appears difficult to determine a single common intersection point among the three curves. The acid/ base titration results for activated carbons, in many cases, were not successful in producing a distinct intersection point; see Figs. 3(a), 3(d), and 3(e). Also, the three intersection points are often scattered over one or two pH units, as in Figs. 3(b) and 3(c). This is probably because background electrolytes may be specifically adsorbed onto the carbon surface to a certain degree. Acid/base titration requires a variation of the electrolyte concentration by 100 times, which may significantly affect the acid/ base titration results for activated carbons. If specific adsorption occurs, the PZC determination by acid/ base titration becomes difficult[24].
4. DLWXJSSION

200

400

ooo
A

m
xl&w

OllM

tnAom

*aEc
(4 Ammonia Adaorptii mwnr

SAY

laotherm

Table 3 is the comparison between the mass titration results and the acid/base titration results. The value of PZC estimated by mass titration is comparable to the PZC value determined by the conventional method, acid/base titration. In the PZC determination for activated carbons, mass titration is more advantageous than acid/base titration for the following reasons: 1. Operationally, it is more convenient to obtain a consistent PZC value from mass titration experiments than from acid/base titration experiments. Mass titration requires the determination of the asymptotic values for three different initial pH conditions. Each asymptotic value can be obtained from each curve independently. Each value can also be an estimate of the PZC. On the other hand, acid/ base titration requires the intersection point among the curves for three different ionic strength conditions. At least two curves are required to intersect each other. It is often troublesome to determine the intersection point. Also, the accuracy of mass titration technique appears to be as good as the acid/ base titration technique. 2. The variation in the concentration of electrolyte solution is not necessary. This is very useful when specific adsorption of background electrolyte ions occurs. Mass titration can give an estimate of the PZC at a given ionic strength condition. 3. Mass titration can provide a standardized procedure in delineating useful information on the carbon suspension pH. Although the pH information on the activated carbon suspension has been considered important, the pH measurement has not yet been standardized[l2]. Oxidation by HNO, lowers the PZC (Table 2). This phenomenon indicates the fact that additional acidic groups, such as carboxyl groups, can be formed by HNOJ oxidation. If the value of the Boehms titration result and the ammonia acidity are plotted against the PZC, good correlations are found (Fig. 4). This consistent trend between various measurements supports the fact that acidic groups de-

Fig. 1. Ammonia adsorption results (a) ammonia adsorption isotherm; (b) Freundlich isotherm.

3.1.5 Determination of the PZC. The mass titration results for each carbon are shown in Fig. 2.. These graphs plot pH values as a function of the mass fraction of carbon in the solution. They also demonstrate that a plateau is found in the plot of pH versus mass fraction. It is noted that there are some deviations in the asymptotic values of the curves for different initial pH conditions. The discrepancy is possibly due to the specific adsorption of background electrolyte ions such as Na+ and NO, ions; however, the discrepancy seems to be marginal. The PZC of activated carbons can be estimated from the mass titration results within an error of -1-0.2pH unit, if the average value of the three asymptotic pH values is taken as the PZC. Acid/base potentiometric titration results for car-

Surfaceacidityof activatedcarbons
NAO NAO2M

679

* PHo* 3.0 . PHCy 5.6 & P*Ila

() pno 3.0 l P&J * 5.6 A pHo* 11.0

*0 1

2 1

4 1 Solid Fraction (a)

6 I ht.% t

8 1

IO i

4 Solid Fraction (b)

6 tit M

IO

NA IM NA04M

II.0

4 SolId @I

6 Fraction (wt %I

IO

*0

I ,4 Solid Fraction WI

I 6 (wt.%)

I
0

NA 2M

4pH0'3.0 l PI+,* 5.6 A pHoll.0

21 0

I
Solid

I
4 Fraction

I
8

I
IO

(wt %I

Fig. 2. Mass titration results (a) as-receivedcarbon; (b) NAO.ZM carbon; (c) NA0.4Mcarbon; (d) NAlM carbon; (e) NA2Mcarbon. ahties. The PZC is not only a ~mp~ative measure of surface acidity, but also a the~~yna~c quantity; thus the PZC may be usefuliy related to other important thermodynamic properties of the aetivated carbons. Activated carbons contain a certain amount of ash substances and thus discussion of their impact re-

(a) velop as the oxidation level increases and they dominate the surface charge development. This qualitative trend has also been documented in the literature[l5,25]. The substantive point is that mass titration can serve to show qualitative trends as well as provide a quantitative characterization index for the oxidation effect on surface chemical function-

680

J. S. NOH and J. A. !W-IWARZ

PZC NAOl

PZC MAo4)

Fig. 3. Potentiometric titration results (a) as-received carbon; (b) NAO.ZM carbon; (c) NA0.4M carbon; (d) NAlM carbon; (e) NAZM carbon.

Surface acidity of activated carbons

Table 3. Determination of PZC for activated carbons Mass titration

NAO NA0.2M NA0.4M NAl.OM NA2.0M 10.0 7.75 6.04 5.54 3.53 + 0.12 f 0.19 f 0.19 + 0.10 r?:0.10

Acid/base titration
10.07 7.35 5.83 5.57 3.60 + + lr f z 0.71 0.10 0.11 0.14 0.33

quires further consideration. The presence of ash ingredients complicates interpretation of surface phenomena of carbon. Mineral substances that originated from the raw materials may influence the formation of functional groups during the course of activation. Comparison among carbons of various ash composition is not well defined unless the influence of the content of each mineral component becomes clear. Some ash species dissolve in water; others do not. The undissolved mineral can exist in various forms as compounds with carbon, oxygen, and hydrogen. For this reason, any interpretation based on the analysis of surface groups, however accurate it may be, is in vain when the carbon contains significant amounts of ash substances. In order to minimize the ambiguities caused by ash substances, the present study employed carbons with an ash content below 1% in total. (See Table 2.) The content of potassium, which appears to be the leading component of the species analyzed by X-ray microscope, was less than 0.05% by weight. Additionally, the variation in ash composition among the samples is small as far as the absolute weight of each species is concerned. It is assumed that the effect of ash substances on the mass titration analysis is negligible, but it is important to note that the mineral centers which are not soluble should be considered as part of the active surface site inventory[26]. In other words, the mineral sites can take part in the charge development on the carbon surface as these impurity metal oxides become charged in aqueous suspension. In this respect, the surface ionization model describes the nature of charge development on the carbon surface as a lumped parameter. It is also important to note that most analytical measurements such as infrared, x-ray, and electron microscopy require that the sample particles be ground. Grinding the carbon in the presence of air is believed to affect the surface chemical properties significantly[27,28].

Jll-LLdo
3 5 7 9 PZC

Fig. 4. Correlation of PZC with ammonia/Boehms ities.

acid-

in the surface acid/base properties due to oxidation treatment by HN09 acid. The major findings in this study are: 1. HN09 oxidation treatment is effective in altering the surface chemical properties of the activated carbon without affecting the surface area significantly. The treatment increases the surface acidity of the carbons. 2. The simple amphoteric surface ionization model is useful in interpreting the meaning of the carbon suspension pH. The pH value, which does not change with an increase in the mass fraction of the suspension, is found to be an estimate of the PZC. This mass titration procedure is found to be more consistent and convenient in determining the PZC for activated carbons than acid/base potentiometric titration. 3. As the carbon surface becomes oxidized, its PZC value is lowered. This trend is consistent with base neutralization and ammonia adsorption results. Therefore, the PZC can be a convenient index for correlating changes in surface acidity in relation to the acidic/basic properties of carbons.

Acknowledgement-This work was supported by Brookhaven National Laboratory under Contract No. 186193-S. The authors appreciate the assistance of Dr. Keith Jones at Brookhaven National Laboratory in the ash analysis by X-ray microscope.

5. SUMMARY An alternative technique to conventional acid/ base titration for the point of zero charge (PZC) measurement was carried out. This technique is designated mass titration. The asymptotic pH value in the plot of pH versus mass fraction is the PZC. The PZC for the carbons, the base neutralization acidity, and the ammonia acidity showed systematic changes

REFERENCES
1. T. W. Healy and L. R. White, Adv. in Colloid Interface
Sci., 9, 303 (1978). 2. J. S. Mattson and H. B. Mark, Activated Carbon, Mar-

cel Dekker. New York (1971). 3. M. 0. Corapcioglu and C. P. Huang, Carbon, 25,569
(1987). 4. W. Stumm

and J. J. Morgan, Aquatic Chembtry, 2nd

edition, Wiley, New York, 632 (1981).

682

J. S. NOH and J. A. SCHWARZ 18. M. Ai, J. Catal., 49, 305 (19771. 19. J. Lame, S. Yunes, J. B&o, and P. Andreu, J. Catal., 62. 157 (1980). 20. M: Bastick, 6. Dupupet, M. Marlot, J. M. Perrot, and J. Weber, Carbon, 15, 25 (1977). 21. G. Bomchil, N. Harris, M. Leslie, J. Tabony, J. W. White, P. H. Gamlen, R. K. Thomas, and T. D. Trewern, J. Chem. Sot., London Faraday Trans. I, 1535 (1979). 22. W. B. Spencer, C. H. Amberg, R. A. Beebe, J. Phys. Chem., 62, 719 (1958). 23. M. Anderson, C. Bauer, D. Hansmann, and N. Loux, In Adsorption of Inorganics at Solid Interfaces, (Edited by M. A. Anderson, and A. J. Rubin), Ann Arbor Sci., Ann Arbor (1981). 24. J. Lyklema, J. of Colloid Interface Sci., 99,109(1984). 25. C. Ishizaki and I. Marti, Carbon, 19,409 (1981). 26. E. D. Goldberg, Black Carbon in the Environment, Wiley, New York, 18 (1985). 27. J. N. Rouzaud, E. Totino, J. M. Guet, J. Kister, and J. F. Muller, Fuel Processing Technology, 20, 133 (1988). 28. I. Wender, L. A. Heredy, M. B. Neuworth, and I. G. C. Dryden, In Chemistry of Coal Utilization,(Edited by M. A. Elliot), 2nd. Supplementary Vol., Wiley, New York, 479 (1981).

5. K. Takahashi, H. T. Tagaya, K. Higashitsuji, and S. Kittaka, Electrical Phenomena at Interfaces, edited by A. Kitahara and A. Watanabe, Marcel Dekker, New York, 147 (1984). 6. R. 0. James and G. A. Parks, Surface Colloid Sci., l2. 119 (1982). 7. P. H. Tewari and A. B. Campbell, J. Colloid Interface Sci., 55, 531 (1976). 8. Y. G. Berube and P. L. DeBruyn, J. Colloid Interface Sci., 27, 305 (1968). 9. J. S. Noh and J. A. Schwarz, J. Colloid Interface Sci., l30, 157 (1989). 10. C. Muller, C. J. Radke, and J. M. Prausnitz, J. Phys. Chem., 84, 369 (1980). 11. S. M. Ahmed, CanadianJ. of Chem., 73,3546 (1969). 12. T. J. Fabish and D. E. Schleifer, Carbon, 22, 19 (1984). 13. H. P.Boehm, Advan. Catal., 16, 179 (1966). 14. K. Kinoshita. Carbon: Electrochemical and Phvsicochemical Properties, Wiley, New York (1988). 15. 0. P. Mahajan, A. Youseff, and P. L. Walker, Jr., Separation Sci. and Tech., W, 487 (1978). 16. M. C. Kung and H. H. Kung, Catal. Rev.-Sci. Eng., 27, 425 (1985). 17. K. Tanabe, Solid Acids and Base, Academic Press, Tokyo (1970).