Amination of Activated Carbon and Adsorption Characteristics of Its Aminated Surface Masahiko Abe, Keiko Kawashima, Kozo Kozawa, Hideki Sakai, and Katsumi Kaneko Faculty of Science and Technology, Science University of Tokyo, 2641 Yamazaki, Noda-shi, Chiba 278-8510, Japan, Institute of Colloid and Interface Science, Science University of Tokyo, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan, and Faculty of Science, Chiba University, 1-38 Yayoi-cho, Inage-ku, Chiba-shi, Chiba 263-0022, Japan The ACS Journal of Surfaces and Colloids Reprinted from Volume 16, Number 11, Pages 5059-5063Langmuir 2000, 16, 5059-5063 5059 Amination of Activated Carbon and Adsorption Characteristics of Its Aminated Surface Masahiko Abe,**# Keiko Kawashima,’ Kozo Kozawa,' Hideki Sakai,"* and Katsumi Kaneko! Faculty of Science and Technology, Science University of Tokyo, 2641 Yamazaki, Noda-shi, Chiba 278-8510, Japan, Institute of Colloid and Interface Science, Science University of Tokyo, 1-8 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan, and Faculty of Science, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba-shi, Chiba 263-0022, Japan Received July 21, 1999. In Final Form: February 29, 2000 ‘An investigation was conducted on the introduction of amino groups to the surface of activated carbon and the adsorption characteristics of the aminated surface. The organic chemical reactions allowed us to introduce amino groups to the surface of activated earbon without affecting the phy: al structure of the adsorbent. The introduction of amino groups lowered the adsorbancy of activated carbon in the adsorption of benzoic acid from solution, while it produced a remarkably favorable effect in the adsorption of NO in the gas pha 1. Introduetion Since the adsorbancy of activated carbon depends mainly on its surface area and pore distribution, we have totakenote ofthe pore structure of the carbon used. There are some cases, however, where additional factors should be taken into consideration. For example, in liquid phase adsorption, if the carbon surface has oxygen-containing functional groups (surface funetional groups), water molecules adsorb preferentially to these groups to form complexes, thereby preventing molecules of target ad- sorbate from adsorbing on the adsorbent.'”® In gas adsorp- tion, no significant adsorption occurs when the molecular ‘weight of adsorbate is low because ofits weak dispersion interaction with the earbon surface if the solute cannot exchange any other interaction than dispersive ones." ‘The affinity of the surface to target adsorbate should be improved in these eases through a proper surface modification that alters the chemical structure of the carbon surface. There are many reports on the surface modification of activated carbon. For example, several papers deal with the high-temperature surface treatment with hydrogen that. can remove acidic surface functional ‘groups, thereby raising the adsorbancy oftraces of organic substances in aqueous solutions.'"® Another paper de- seribes a method to enhance the adsorbancy of specific substances, in which ehemieally reactive or catalytically active compounds are held in a dispersed state on the surface and the reactivity of the compounds is utilized. Economyetal. reported that activated carbon fibers (ACF) could be nitrided with NF at elevated temperatures to “obtain an ACF with basic characteristics and showed that " Faculty of Science and Technology, Seienee University of Toke. + Institute of Colloid and Interface Science, Science University of Tokyo. ‘Faculty of Scienee, Chiba University. (1) Ogino, Ke Aihara, K:; Ohtsuka, M.; Takahashi, H. J. Jpn. Oi! Chem. Soe, 1979, 8, 61. ‘@) Asakawa, Ogino, K; Yamabe, K Bull. Cher. Soe. Jpn. 1978, 58, 531 4 Ae, ¥; Abe, My; Ono, KJ. Jpn. (A) Teoga, KC Adeorpe. News 1990, 4,1 (6) Kaneko, K; Murata, X; Shimiau, K; Camara, 8; Suauki, 7 Langmuir 1988, 9, 1165. (8) Kaneko, KJ. Jpn: Colour Mater. Soe. 1994, 67,116 such fibers were effective in adsorbing acidic materials such as HCI and SO; However, few papers report the method of promoting the adsorbaney of nitrogen-contain- ing compounds such as ammonia? and NO. In these circumstances, we have attempted to modify the surface of activated carbon by amination utilizing organic reac- tions with a prediction that an amino group, a nitrogen- containing basic functional group, will be effective in the adsorption of these nitrogen-containing compounds. In general, since the surface of carbonaceous materials is composed of condensed aromatic compounds as its fundamental structure and has various surface functional groups," these functional groups should be usable in ‘ertain appropriate organic chemical reactions. Even so, there have been relatively few studies" that make use of organic chemical reactions to modify the surface of carbonaceous materials such as activated carbon. In the present study, we have attempted to introduce amino groups onto the surface of activated carbon, a model ‘of carbonaceous materials, and performed adsorption ‘experiments using the surface-modified activated earbon as the adsorbent and NO (in gaseous phase) as the adsorbate, respectively, based on the idea that the introduction of amino groups to carbonaceous materials must be effective to remove nitrogen-containing com- pounds by adsorption in gaseous phase. 2, Experimental Method 2.1. Activated Carbon Sample. Coconut charcoal CG-10 (Fatamura Chemical Ind, L14,]wastused asthe activated carbon sample. CG-10 was vacuum-dried at 110°C for 24h after being washed with deionized water until the electroconductivity of filtrate became nearly the sameas that of the water. Itwas then ‘treated with hydrogen at 100°C aecording tothe previous report? ()Besnomy, dz Foster, Kz Andreopoulon, Ai Jung. H. Chemiech 1993, 897 mines (8) Kaneko, K:; Kotor, Ts Shimizu, K: Shindo, Ni Maeda, T. J Cham, Soe, Faraday Trans. 1882, 88,1905, (@) Kondo, 8; fahikawa,'T3 Abe,” Science Seminar 16, Science of ‘Adsorption: Maruzen: Tokyo, 1983 ‘GO)Sanada, ¥; Suzuki Me; Pulimoto, K. New Edition, Activated Carton: Pundimentlsond Applicetions; Kadanaba Scene: Tokyo, Gi) Inada, T3 Ogino, K; Sakai, th; Nishiyama, K; Watanabe, T; ‘Abe, Mes pn Oil Chem, Soe. 1896, 99, 688. 10.1021/1a980976t CCC: $19.00 © 2000 American Chemical Society ‘Published on Web 04/18/20005060 Langmuir, Vol. 16, No. 11, 2000 of Activated Carbon Modified ‘Amino Group Scheme 1. Synthe: = roving > Ns:0. 1) (emscOHD ar aed a styNopae Hert ae to remove acidic surface functional groups before use. This activated carbon is hereafter abbreviated to He-AC. Surface modification was done by nitrating the earbon surface through electrophilic substitution and then aminating it through reduction. Reagent grade acetic anhydride, fuming nitric acid, and sulfuric aeid were used as supplied in nitration. Distilled water for injection asthe solvent (Ohtsuka Pharmaceutical Co, Ltd.), 289% aqueous ammonia, and reagent grade sodium hy- Arosulfite were employed as purchased in amination. 2.2, Surface Modification of Activated Carbon. Surface tmoification of the earbon was performed according to Scheme 1. Nitration was allowed to proceed in a 1000 mb, three-neck faske containing Ho-AC, acetic anhydride, and concentrated sulfuric acid with dropwise addition of fuming nitric acid in 5 h while keeping the temperature below 5 °C. The reaction was completed after 19 h of stirring at room temperate. Modified Hp-AC thus obtained was thoroughly washed with deionized ‘water until the electroconductivity of filtrate attained a value nearly the same as that of the water and vacuum-dried for 24 hat 110 °C. The nitrated CG-10 is hereafter abbreviated to HyNOrAC. ‘Reduction of the nitrated activated earbon was permitted to proceed in a 1000 ml. flask containing deionized water, 28% {Aqueous ammonia, sodium hydrosulfite, and the carbon with stirring for 24 h in nitrogen atmosphere at room temperature. ‘Theaminated activated carbon thus obtained was vacuum- Hy-NHp-AC > Hy-NO»-AG, indicating that the introduction of nitrogen-containing functional ‘groups to activated carbon was not useful to improve the adsorbancy of benzoie acid from aqueous solutions. In particular, since the AR term reflects the magnitude of adsorption heat," the interaction between benzoic acid and amino groups is suggested to be weak in aqueous solutions. Itis also reported thatthe adsorption of organic ‘molecules decreases ifacidie functional groups are present at the mouth of pores because water molecules adsorb preferentially at acidic groups to prevent the diffusion of the organie molecules into the pores."* In view of this, the decrease in adsorption of benzoic acid in the present work would be due toa competitive adsorption of the acid with water to yield the decreasing order of He-AC > HzNH,-AC > Hz-NO;-AC. ‘The adsorption isotherms of NO are shown in Figure 4 for the carbon samples, in which the amount of NO adsorption is seen to be remarkably higher for Hy NHAC than for Hy-AC. The adsorbed amounts at saturation determined using the Langmuir equation (Table 5) were about 96 meg for Hy-NHz-AC and about (07) Jaroniec, M; Choma, J; Burakiewiex Morike, W. Carbon 1991, 29, 1294 '18) Kawezoe, $3 Astakbor, V. As Kaveai, T; Eguchi, Y. Ka gokukaganu 1971, 31, 68Soe Langmuir, Vo 16.1, 200 ated at ae - 7 ¥* z : z i 2 al os o s 10 1s 20 Ey 30 a € 7 2 o 1° 7 2 ad LP, Pa =. Figure 4. Adsorption isotherms of NO on He-treated activated carbons at 303 K. Figure 5, Extended DR plots for NO adsorption. ‘Table 6. Characteristic Adsorption Energy JF) and ‘Saturated Vapor Pressure Puy for NO ‘Table 5. Saturation Amount of NO Adsorption Wi samples BBs (emo) Pa tkPa) We Heac 73 167.7 Hp-NH-AC ns 102.7 samples ave mail? Teac “62 a0 ‘Table 7. Characteristics Adsorption Energy AE y and Hy NHeAC 96.1 143 ‘duigrte for NO “Amount of NO adsorption per unit weight of sample. samples (BB (ean) deegnie (keno) » Amount of NO adsorption per micropore volume of sample. HeAC 79 217 HpNHyAC ng 287 45 mg/g for Hy-AC, respectively, showing a little over 2.fold increase in adsorption amount brought about by the introduction of amino groups. An approximately 10 times increase in the amount of NO adsorption was also found in the low-pressure region for Hy-NHz-AC over HyAC. ‘An extended DR equation (4) proposed by Kaneko et al." that is useful for analyzing the adsorption data for supereritical gases was then used to thermodynamically ‘examine the adsorbed state of NO molecules in adsorbent pores. ns)? = (RT/BE Mn P,,- InP) (4) where W is the adsorption amount, Wi is the adsorbed amount at saturation, f is an affinity factor, By is the characteristic energy of adsorption, Pis pressure, and Pua ig the quasi-saturated vapor pressure of a supercritical gas, which was defined assuming that the gas changes to, vapor even if it is supercritical one sinee a strong adsorption field is generated by the superposition of potentials extended from the opposing pore walls in micropores with diameters less than 2 nm. Ifa straight ine is obtained when thelleft side of eq 4 is plotted against In P, the value of P,is then calculated from the slope and the intercopt of the line. ‘In Figure 5 are shown the results obtained by plotting the NO adsorption data in Figure 4 using the extended DR equation. The plots gave a straight line for all carbon, samples, and the values of BE> and Py, were calculated from the slope and the intercopt of the line (Table 6). The value of Py, was smaller for Hy-NH,-AC than for Hy-AC ‘as seen from the table, suggesting that NO condenses ‘more easily onto Hy-NH,-AC than onto Hy-AC. ‘The quantity AB in the first term on the right side of eq 4 reflects isostericheat of adsorption of the gas and the following relation holds for it.* Ing=ve = AH + BEy ©) where qs.9-1e 8 the isosterie adsorption heat of NO at an adsorption ratio of 1/e and AH is the liquefaction heat of the gas (13.8 kJ/mol), respectively. Table 7 shows the for the samples used. Modifi- ‘ation of the surface of activated carbon brought about an increase in the values of both #Ep and gy.y-we as shown in the table. The increase observed in the case of Ha- NH;-AC would be caused by the increased interaction between the amino groups on the surface and NO molecules. Unlike benzoic acid adsorption from aqueous solutions, existence of acidic functional group does not affect the adsorption significantly. Since Kaneko et al.” reported that NO molecules adsorb forming dimers in ‘mieropores even at room temperature, the increased NO adsorption onto the modified carbon surface observed in the present work would also be due to a dimer formation enhanced by the amino groups in micropores on thecarbon surface, 3. Conclusions Amino groups were introduced onto the activated car- bon surface, and the adsorption characteristics of the aminated surface were examined in both liquid and gaseous phases. () It was confirmed through elemental analysis, XPS ‘measurement, and Neadsorption that amino groups could grQi) Rone, Ks Shins, Ks Burak, TJ. Chem, Phy. 199897, (@0) Kaneko, K; Pukuraki, Nj Kakel, K; Sunuk, T; Ozeki, §. Langmuir 1988, 5, 960.Amination of Activated Carbon be successfully introdueed without causing changes in the pore structure of activated carbon. (2) The introduction of amino groups to the carbon increased the adsorption of NO considerably in the gas phase beeause ofa strong interaction of the amino groups ‘with NO molecules. Langmuir, Vol. 16, No. 11, 2000 5063 ‘Acknowledgment, Part of the present work was financially supported by a Grant-in-Aid for Scientific Research on Priority Area of Carbon Alloy from the ‘Ministry of Education, Sports, and Culture, Japan. La9909767