with n-butylamine and n-octylamine

Transcription

1 Originl pprs Prprtion o lnthnum phospht with n-utylmin n n-otylmin # Hiroki Ono, Kiihiro Asi Dprtmnt o Inormtis n Environmntl Sins, Kyoto Prturl Univrsity, 1-5, Shimogmo Nkrgi-yo, Skyo-ku, Kyoto , Jpn # E-mil: ono@kpu..jp Sumitt Novmr 11, 211; pt Mrh 3, 212 Kywors: Lnthnum phospht,chmil synthsis, Amins, Spii sur r N-utylmin n n-otylmin wr to th prprtion o lnthnum phospht rom lnthnum nitrt n phosphori i solutions to otin phospht mtrils tht h lrg spii sur r. Th mixing solution o wtr n thnol ws us to solv ths mins. Th itionl ts o mins n th mixing rtio o solvnt wr stui on th hmil omposition, powr proprtis, n sorption o si stinking gs. Rhophn-typ lnthnum phospht ws otin in spit o th hngs o prprtion onitions. Spii sur r o lnthnum phospht prpr in this work m ovr 1 tims s lrg s tht o stnr phospht. Introution Phosphts hv n us or rmi mtrils, tlysts, sornt, luorsnt mtrils, iltri sustns, mtl sur trtmnt, rtilizr, trgnts, oo itivs, ul lls, pigmnts, n othr itms [1-4]. In ths pplitions, th tlyti n sorptiv proprtis o phosphts wr t rom spii sur r [5-7]. To improv th untionl proprtis, porous phospht, whih h lrg spii sur r, ws prpr in prvious rports [8,9]. Th itivs h som possiility to otin lrg spii sur r in th ils o synthsis o inorgni mtrils [1-13]. Aluminum phosphts ontining ur wr otin in quous solution [14]. By th omposition o ur, this luminum phospht m porous mtril. Th spii sur r o luminum phospht improv rom 124 to 153 m 2 g -1 in this mtho. This mtho init wk point tht th rmin ur in th phospht prtils rs th mount o ii sits on sur o mtrils. Th ii soli stt mtrils hs th possiility to us s n sornt or si mloorous gss. Thror, othr itivs wr xpt to improv th spii sur r n th rmovl ility o suh gss [15]. Ur hs si sits t oth ns. As nw itivs on prprtion o phospht mtril, mloni i hs th ii sits t oth ns n propioni i hs n ii sit t on-si. Glyin hs n ii sit n si sit t h si, n n-utylmin hs on-si si sit. Ths itivs r stui to prpr porous luminum n lnthnum phosphts [16]. Lnthnum phospht prpr with n-utylmin init muh lrgr spii sur r [17]. Bus n-utylmin ws iiult to solv in wtr, th mixing solution o wtr n thnol in th rtio o H 2 O/C 2 H 5 OH=1/1 ws us s solvnt. Thror, it is not lr tht tht th ition o n-utylmin or th mixing solution o wtr n thnol improv th spii sur r o lnthnum phospht. In this work, lnthnum phosphts wr prpr rom lnthnum nitrt n phosphori i solutions, with th hnging th mixing rtio o wtr n thnol s solvnt n th onntrtion o n-utylmin n n-otylmin, n thir proprtis wr stui or sign o untionl mtrils. Th purpos in this work ws to lr th itionl ts o mins n thnol on prprtion n proprtis o lnthnum phospht. Exprimntl.1 mol/l o lnthnum nitrt solution ws mix with.1 mol/l o phosphori i solution in molr rtio o L/P = 1/1. Lnthnum phospht ws xpt to orm in th ollowing qution. L(NO 3 ) 3 + H 3 PO 4 LPO 4 + 3HNO 3 (1) N-utylmin n n-otylmin wr in th phosphori i solution to.2,.1, n.5 mol/l or th mixing. N-utylmin ws us s typil min. N-otyl min ws slt to stimt th inlun o th mins lngth. Th mix solution o wtr/thnol = 2/1 or 1/1 ws us s solvnt to solv ths mins. Thn, th pripitts wr iltr o, wsh with wtr, n ri. 12 Crmis Silikáty 56 (2) (212)

2 Prprtion o lnthnum phospht with n-utylmin n n-otylmin A prt o th pripitts ws issolv in hyrohlori i solution. Th rtio o phosphorus n lnthnum in th pripitts wr lso lult rom ICP rsults o ths solutions, using SPS15VR, Siko Instrumnts In. Th thrml hvior o ths mtrils ws nlyz y TG-DTA n XRD. TG n DTA urvs wr msur with Shimzu DTG-6H t hting rt o 1 C/min unr ir. XRD pttrns wr ror on Rigku Dnki RINT 12M X-Ry irtomtr using monohromt CuKα rition. Snning ltron mirosopy (SEM) imgs o lnthnum phosphts wr osrv using JGM-551LV, JEOL Lt. Th prtil siz istriutions o ths mtrils wr msur with lsr irtion/sttring prtil siz istriution HORIBA LA-91. Th spii sur r o phosphts ws lult rom th mount o nitrogn gs sor t th tmprtur o liqui nitrogn y BET mtho with Blsorp mini rom Bl Jpn. Th sorption o trimthylmin gs on phosphts ws stimt t room tmprtur. A totl o.1g o smpl ws pl in gs g (3 m 3 ) o polythyln, whih ws thn ill with trimthylmin gs (15.9 ppm). Th onntrtion o trimthylmin gs tr stning or 1 minuts ws trmin with Kitgw gs ttor. Rsults n isussion Prprtion o lnthnum phospht with mins Tl 1 shows L/P rtios in pripitts prpr with vrious itivs. Th inrs o thnol rtio in solvnt h lss inlun on th L/P rtio in pripitts. By th ition o n-utylmin n n-otylmin, th L/P rtio m littl lrgr. It is th sm phnomn tht th rtio o tion/phosphorus inrs y th ition o n-utylmin in prvious pprs [16,17]. A smll mount o lnthnum hyroxi ws onsir to orm in ths onitions. In th onitions o.1 mol/l Tl 1. L/P rtio o smpls rom ICP rsults. wtr/thnol itiv onntrtion L/P 1/ no mol/l /1 no mol/l 1.1 1/1 no mol/l 1.1 1/1 n-utylmin.2 mol/l /1 n-otylmin.2 mol/l /1 n-utylmin.1 mol/l 1/1 n-otylmin.1 mol/l 1/1 n-utylmin.5 mol/l o mins, lnthnum phospht ws not pripitt. It ws onsir tht lnthnum tion orm th omplx with mins in th rtio o L/min = 1/1 n tht this omplx prvnt th ormtion o lnthnum phospht. Smpl prpr in th onition o.5 mol/l o n-utylmin init highr L/P rtio. Bus.5 mol/l o n-otylmin ws too high onntrtion to solv in th solvnt, smpl oul not prpr. Figur 1 shows TG urvs o smpls prpr in vrious onitions. Smpls prpr with.5 mol/l o n-utylmin h muh lrgr wight loss thn othrs. Th wight loss t 32 C ws onsir to u to th voltiliztion n omustion o n-utylmin. Othr smpls init similr TG urv. Wight loss ws rlt with th mount o mins in phospht mtrils. Th mixing rtio n th ition o low onntrtion o mins h smll hng o wight loss. Wight loss (%) Figur 2 shows DTA urvs o smpls prpr in vrious onitions. Smpl prpr with.5 mol/l o n-utylmin h lrg xothrmi pk t 32 C (Figur 2). This pk ws rom th omustion o n-utylmin. Smll nothrmi pks t 7 n 26 C wr osrv in DTA urvs o othr smpls. Ths pks wr u to th voltiliztion o sor n rystllin wtr, rsptivly [14,17]. Th smll nothrmi pk t 26 C ws ovr y th ov lrgr xothrmi pk in DTA urv t smpl prpr with.5 mol/l o n-utylmin. Figur 3 shows XRD pttrns o smpls prpr in vrious onitions. All smpls init th pk pttrn o Rhophn-typ lnthnum phospht [18]. 1 Figur 1. TG urvs o lnthnum phosphts prpr in vrious onitions; ) no itiv, H 2 O/C 2 H 5 OH = 1/, ) H 2 O/ n-utylmin.2 mol/l, ) H 2 O/C 2 H 5 OH = 1/1, n-otylmin.2 mol/l, ) H 2 O/C 2 H 5 OH = 1/1, n-utylmin.5 mol/l. Crmis Silikáty 56 (2) (212) 13

3 Ono H., Asi K. Bus smpl prpr with.5 mol/l o n-utylmin inlu lrg mount o min, th pk intnsity m wk (Figur 3). Othr smpls h th sm rng o XRD pk intnsity, us th irn o wight loss in TG urvs ws smll (Figur 1). By hting up to 4 C, thr is no hng on XRD pk pttrn rom smpls without hting. Th inlu mins h no inlun on hmil omposition o phospht mtrils. Eno. Exo Figur 2. DTA urvs o lnthnum phosphts prpr in vrious onitions; ) no itiv, H 2 O/C 2 H 5 OH = 1/, ) H 2 O/ n-utylmin.2 mol/l, ) H 2 O/C 2 H 5 OH = 1/1, n-otylmin.2 mol/l, ) H 2 O/C 2 H 5 OH = 1/1, n-utylmin.5 mol/l. Intnsity Powr proprtis o lnthnum phosphts Figur 4 shows SEM imgs o lnthnum phosphts prpr in vrious onitions. Smpls prpr without thnol n mins h th smll homogniz prtils (Figur 4). Lrg prtils wr osrv in SEM imgs o othr smpls. In prtil siz istriution o smpls without hting, th ition o thnol n mins m th mo o prtil siz lrgr. Th mo o prtil siz m muh lrgr y hting. Th prtil siz istriutions o smpls ht t 4 C r shown in Figur 5. Th prtil siz o smpl prpr without thnol n mins ws rng rom 5 to 5 µm (Figur 5). On th othr hn, othr smpls init high rtio o lrgr prtils thn 1 µm. Th ition o thnol prou th ggrgtion o phospht mtrils in this prprtion. Tl 2 shows th spii sur rs o lnthnum phosphts prpr in vrious onitions. Bus smpls wr ht t 1 C or 2 hours to rmov th sor wtr s prtrtmnt o BET mtho, spii sur r o smpls without hting oul not msur. In ll onitions, spii sur r m lrgr thn tht o stnr lnthnum phospht. Th mixing o thnol in solvnt improv th spii sur r. Th low onntrtion o mins supprss this improvmnt. Smpl prpr with.5 mol/l o n-utylmin h muh lrgr spii sur r. It ws onsir rom tht th voltiliztion o mins prou th pors on phospht prtils. Th ition o n-otylmin muh improv th spii sur r o lnthnum phospht thn tht o n-utylmin t sm onntrtion. By hting t highr tmprtur, smpls h lrgr spii sur r θ ( ) Figur 3. XRD pttrns o lnthnum phosphts prpr in vrious onitions; ) no itiv, H 2 O/C 2 H 5 OH = 1/, ) H 2 O/ n-utylmin.2 mol/l, ) H 2 O/C 2 H 5 OH = 1/1, n-otylmin.2 mol/l, ) H 2 O/C 2 H 5 OH = 1/1, n-utylmin.5 mol/l. Tl 2. Spii sur r o smpls prpr with vrious itivs (m 2 /g). wtr/ itiv onntrtion tmprtur ( C) /thnol (mol/l) / / / /1 n-utylmin /1 n-otylmin /1 n-utylmin Crmis Silikáty 56 (2) (212)

4 Prprtion o lnthnum phospht with n-utylmin n n-otylmin Figur 4. SEM imgs o lnthnum phosphts prpr in vrious onitions; ) no itiv, H 2 O/C 2 H 5 OH = 1/, ) H 2 O/ n-utylmin.2 mol/l, ) H 2 O/C 2 H 5 OH = 1/1, n-otylmin.2 mol/l, ) H 2 O/C 2 H 5 OH = 1/1, n-utylmin.5 mol/l. Numr o prtils (%) Asorptio rtio (%) Prtil siz (µm) Figur 5. Prtil siz istriution o smpls prpr in vrious onitions n thn ht t 4 C; ) no itiv, H 2 O/C 2 H 5 OH = 1/, ) H 2 O/C 2 H 5 OH = 2/1, ) H 2 O/C 2 H 5 OH = 1/1, ) H 2 O/C 2 H 5 OH = 1/1, n-utylmin.2 mol/l, ) H 2 O/ C 2 H 5 OH = 1/1, n-otylmin.2 mol/l, ) H 2 O/C 2 H 5 OH = 1/1, n-utylmin.5 mol/l. Figur 6. Asorption o trimthylmin on lnthnum phospht prpr in vrious onitions; ) no itiv, H 2 O/ C 2 H 5 OH = 1/, ) H 2 O/C 2 H 5 OH = 2/1, ) H 2 O/C 2 H 5 OH = 1/1, ) H 2 O/C 2 H 5 OH = 1/1, n-utylmin.2 mol/l, ) H 2 O/ C 2 H 5 OH = 1/1, n-otylmin.2 mol/l, ) H 2 O/C 2 H 5 OH = 1/1, n-utylmin.5 mol/l. Bus o th voltiliztion o th inlu thnol n mins, phospht mtrils wr onsir to porous rom prvious pprs [16,17]. It is th rson tht phospht h lrg spii sur r in spit o lrg prtil siz. Asornt or si stinking gs Figur 6 shows th sorption rtios o trimthylmin on lnthnum phosphts prpr in vrious onitions. Smpl prpr without thnol n mins Crmis Silikáty 56 (2) (212) 15

5 Ono H., Asi K. sor 27% o trimthylmin, n this rtio m smll y hting (Figur 6). Smpl prpr in H 2 O/ C 2 H 5 OH = 2/1 n 1/1 with n without.2 mol/l o mins init highr sorption rtio thn stnr lnthnum phospht (Figur 6-). Th sorption rtios wr low in smpl prpr with.5 mol/l o n-utylmin (Figur 6). High onntrtion o n-utylmin improv spii sur r, howvr lin th sorption rtio o si stinking gs. Th mount o ii sits on sur o mtrils ws onsir to rs with high onntrtion o n-utylmin. Conlusion By th ition o n-utylmin n n-otylmin, th rtio o L/P in pripitt m littl lrgr us o th ormtion o lnthnum hyroxi. From XRD nlyss, th min omposition o pripitt ws Rhophn-typ lnthnum phospht. In th onition with.1 mol/l o n-utylmin n n-otylmin, lnthnum phospht ws not pripitt. Th mixing o thnol to wtr prou lrg spii sur r o this lnthnum phospht. Th ition o n-otylmin muh improv th spii sur r o lnthnum phospht thn tht o n-utylmin t sm onntrtion. Espilly, smpl prpr with.5 mol/l o n-utylmin h muh lrgr spii sur r. Th sorption rtio o trimthylmin ws high in th s o smpls prpr with th mixing solution o wtr n thnol. Rrns 1. Klit S. J., Bhrwj A., Bhtt H. A.: Mtr. Si. Eng. C 27, 441 (27). 2. Elis M., Sv B., Dionu A., Ursu D., Ptrsu R.: J. Non-Cryst. Solis 355, 1877 (29). 3. Rjsh P., Rmsmy P.: Mtr. Ltts. 63, 226 (29). 4. Rsn C. X., Dill J., Pltt G. M., Bstos I. N., Sors G. A.: Mtr. Chm. Phys. 19, 429 (28). 5. Ono H., Nrii H., Moriwki, A., Mki, H., Motook I.: J. Mtr. Chm. 12, 1754 (22). 6. Ono H., Oht T., Tmki J., Kojim K.: Appl. Ctl. A 288, 98 (25). 7. Ono H., Oht T., Tmki J., Kojim K., Nrii H.: Mtr. Chm. Phys. 96, 163 (26). 8. Go, D., Go Q.: Mirop. Msop. Mtr. 85, 365 (25). 9. Montiro V. A. R., Snz E. F., Azvo M. M. M., Glmk F.: J. Coll. Intr. Si. 217, 237 (1999). 1. Knori K., Ikgmi N., Ysukw A., Ishikw T.: J. Coll. Intr. Si. 182, 425 (1996). 11. Hrnz T., Butist C., Mrtin P.: Mtr. Chm. Phys. 92, 366 (25). 12. Trr, A., Bisws S., Prmnik N. K., Prmnik P.: Mirop. Msop. Mtr. 89, 24 (26). 13. Shu C., Ynwi W., Hong L., Zhngzhng P., Kng Y.: Crm. Intr. 31, 135 (25). 14. Ono H., Tniguhi K., Tnk I.: Mirop. Msop. Mtr. 19, 193 (28). 15. Ono H., Ukit S., Hyshi A., Tknk A., Kojim K.: Phosphorus Rs. Bull., 19, 29 (25). 16. Ono H., Fukumur Y., Tknk A.: J. Mtr. Si. Eng. Av. Th. 1, 97 (21). 17. Ono H., Ishim Y., Tknk A., Tnk I.: Mtr. Rs. Bull. 44, 1712 (29). 18. Moony R. C. L.: At Cryst. 3, 337 (195). 16 Crmis Silikáty 56 (2) (212)