Ociober, 1973) BULLETIN OF Tite CHEMICAL SOCIETY OF JAPAN, VoL. 46, 2985—2988 (1973) 2985 Acidic properties of Binary Metal Oxides Katsue Suipara, Tadam su Kryoura, Jun Krracawa, Takashi Suatvosi,* and Kozo Tanane* Central Research Laboratory, Mitssi Toatsu Chemicals, Inc, Totsukaks, Yokohama 247 Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060 (Received February 3, 1973) Eighteen binary metal oxides consisting of TOy-MyOq, Zn1O-M,,O, and AlO;-MyOx (MxO, oxide) were prepared by the usual co-precipitation method, their acid amounts and strengths being determined by n-butylamine titration using various acid-base indicators. The acid strengths of fourteen of the tested binary oxides of molar ratio 1 acid strengths were a8 follows: ~3 for TiO,-CdO, TiO,-SnO, and Zn0-SiO,, HyZ~8.2 for TOS 1 were found to be remarkably higher than those of the component single oxides. High (Oy, Hy: —56 for TiO,-AL,O, and ALO,-ZrO, and Hes “The acid amounts of sixteen binary oxides were larger than those of the component oxides. The effect of the compesition of binary oxides on acidity was examined for TiO, ‘Al,0,, Zn0-Al,0, and Al,0,-Z10,, found’ to be of molar ratio: 1 and for Al,O,-Z10,: ‘The acidity maxima appearing for TiO,-Al,O, and ZnO-Al,O, were ‘A airly good correlation has been demonstrated between the observed highest acid strengths and the average electronegativities of metal ions of binary oxides. Some binary metal oxides such as SiO,-Al,Os, SiO,-ZrO, SiOy-MgO and AlO,-Bi,O, are known to show acidic property and have long been used as solid acid catalysts. ‘These combinations of oxides contain either SiO, or Al,O,, both essential constituents of clay minerals. However, combinations such as TiO-ZnO, TiO,-ZrO, and ZnO-Bi,O, containing no clay mineral component were recently found to exhibit remarkable acidic property!~® and catalytic activity.*9 Since many other combinations are also expected to exhibit acidic property and it is considered important for theoretical development and practical use of mixed oxides to find combinations of oxides giving acidic property and to correlate it with the physico-chemical properties of metal oxides, we prepared various binary oxides and examined their acid amounts and sterngths. ‘The binary oxides are restricted to colorless materials to which an acidity measurement by the amine titra- ion method using indicators can be applied. The observed acid strengths are correlated with the electro- negativities of metal ions of binary oxides. The cflect of the composition of some binary oxides on acidic property was also examined. Experimental Preperation of Metal Oxides. Binary metal oxides were prepared by the thermal decomposition of their hydroxides at 500°C for She. in air. ‘The hydroxides were co-precipitat- ‘ed by adding 28% of ammonia water to the mixed aqueous solution of water soluble metal salts (Table 1). ‘The pre- cipitates were washed thoroughly to remove adhering anions such as chloride ion, Each single oxide was prepared si- milarly as above. Binary oxides containing silica were pre- pared by kneading the wetted hydroxides of silicon and 1) K, Tanabe, “Solid Acids and Bases," Kodansha, Tokyo, Academic Press; New York, London (1971) 2) -K. Tanabe, C. Ishiya, I. Matta, Hattori ‘Thi Bulletin, 45, 47 (1972). 3) K, Shibata and. Kiyoura, J- Res. Ist. Catlin, Hokaido Unis, 19, 35. (197 44)" K. Tanabe, I. Ichikawa, H. Ikeda and H. Hattori, iit 19,185 (1971). '3) -K, Shibata. Kiyoura and K. Tanabe, iid 18, 189 (1970). 6) “Cracking activity and acidity of hydrous oxide composites," Honors Thesis of Mariel Meents (1961) with Profesor J. D. Date forth, Grinnell College, Grinnell, Towa I. Tehikawa, and H. ‘Tamue 1. Sranmino MATERIALS OF OXIDES ‘Oxides Starting materials Oxides Starting materials Tio, BO, ‘BIC, ZO SiO, NaSiO, Sb,0; PbO. Pb(NO,)s 210, cao cach, ALO3 AlCl, SnO, Sn, MgO MgCl, other metal and calcining at 500°C. for Shr after deying at 70—80°C, The silicon hydroxide was prepared from aqueous sodium silicate by adding aqueous hydrochloric acid and drying at 70—80°C for Shr. ‘The amount of oxide ir the binary oxides containing silica was determined by gravimetric analysis of the oxide obtained by calcining the hydroxide. ‘Measurement of Spcife Surface Area and Acidiy. Specie surface aren was obtained by applying the BET method to the adsorption stherm of nitrogen at —196°C. Surface acidity was measured by mbutylamine dtration using the following indicators: methyl red (pK,=+4.8), _phenyle azonaphithylamine (4-40), p-dimethylaminoazobenzene (+53), Denzeneazodiphenylamine (+18), -dicinnamal- acetone (—3,0), benzalacetophenone (—5.6) and anthraquin« one (8.2). ‘X-Ray Diffraction. X-Ray powder diffraction di agrams were recorded with an X-ray diffiactometer ( akudenki, Geigerficx SG-1). Nickel filtered CuK, was Used at Xeray radiation source. Results and Discussion Single Oxides and Binary Oxides Containing Titanium Oxide. The acidity distribution of single oxides which are component oxides of binary oxides are shown in Table 2, together with the surface areas. SiO, gave no X-ray diffraction lines indicating its amorphous form. Al,O, gave only weak diffraction lines indicating its partial crystal and TiO,, ZO,, CaO, SnO,, ZnO, SP,Os and PbO gave strong ditt fraction lines indicating ‘each crystal. We sce that the acid strengths of the single oxides are generally weak (Hy> +15), TiO, and ZnO weaker than those observed previously.®” This is considered to be due to the difference in the mode of preparation.2906 K, Sumara, T. Krvouna, J. Kracawa, T. Susavostt, and K, Taxane (Vol. 46, No. 10 ‘Tame 2. Acmrry pisrRBunoN oF soe oxDes ‘Surface ‘Acid amount (wmol/g) at diferent pKy= Oxides ‘ea ee mis +he +40 433) OLS 308 TiO, 38.5 0.057 0.057 ° - Z20 T4 0.006 ° ALO, 190 — 0.285 0.075, ° Si, 289 0.264 0.109 0.066, ° 2:0, 72.0 — 0.280 0.060 0,060 ° MgO 49.1 ° Bi,0, 6.5 0.210 0.250 ° $b,0, 7.0 — 0.055 0.055 ° PLO 0.7 0.065 cao 22 0.209 S00, 27 0.133 ‘Tante 3. Acprry pisrunevton oF mINARY oxiDES Surface ‘Reid amount (wmollg) at diferent pRys mig 448 HO $931 0 56 BR aor 0.422 —~—«0.4—~—~O.3BT—~—~O.NSR-——0.2D~—~—~O.OBDS~SC« 22 0.565 0.565 0.565 0.865 0.565 0.480.083 230 — 0.475 0.389 0.350 0.375 0.150.050 13.6 0.009 0.009 0.022 Ti0,-B,0, 35.6 0.099 0.019 0.025 0.025 ° Ti0,-Gdo 35.0 0.193 0.136 «0.136— 0.090 .06t Ti;-Sn0, 121 0.154 0.108 0.046 0.030.018 Zn0-Al,0, 117 0.582 0,352 0.270 0,166 0 Z0-Si0, 77.0 0.216 0.175 0.175 0.175002 200-210, 24 Ol OLE OE OL 2n0-MgO 6.0 0.0250 Zn0-Sb,0, 8.3 0.01 oI ° 240-Bi,0, 1.0 0.175 0.015015 ° Z10-PDO” 5.5 ° R020, 320 = 0.500.205 ——~0.205—~—~« 0S SSC ALO,-Sb,0, 3.1 0.079 0.079 0.0790 {AL,0,-BiO, 21.2 0.087 0.083 «0.088 0.070 20,-C40 102 = 0.399 0.391 0.84306 '8) Color of the indicator (pRy=+6.8) changed. The acid amounts and strengths of the binary oxides containing TiO, (molar ratio=1) are shown in Table 3. ‘The X-ray diffraction diagrams of TiO,-SiO, and TiO,-ZrO, showed only diffused or weak diffraction fines and were assumed to be amorphous. TiO, ‘Al,O, gave only the diffraction lines of TiO... ‘Thedif- fraction lines of TIO; MgO, TiO,-Bi,0,, ‘TiO,-CdO and TiO,-SnO, were those of the component oxides. The resulls indicate the binary oxides are not mechani cally mixed oxides. The acid strengths of TiO, SiO, and TiO,-ZrO,, found to be surprisingly high, were HyS—82 and. those of TiO,-Al,0, and TiO, Gd, also high, —5.6 and —3, respectively. Since SiO,- ZrO, is known to have very high acid strength (Hy .2),9 it can be said that the combinations "of oxides’ of metals (Si, Ti and Zx) which belong to the 2) V. A. Daitho, Proc. Intern. Congr. Catalysis, Srd, Amster dam, 1, No. 19 (1964). same fourth group in the peri highest acid strength. All the ing TiO, showed higher acid strength than each com- ponent oxide. ‘The acid amount at a certain acid strength per unit surface area of any larger than the sum of the acid amounts di the sum of the surface areas of the component oxides. ‘The results indicate that the new acidic sites which differ from those of single oxides are created on the surface of binary oxides. The acidity change with variation of composition was examined in the case of TiO,-Al,O,. As shown in Fig. 1, the acidity maximum was observed when the molar ratio of TiO,-AlO, is about 1:9. Te is interesting to note that the acidity maximum of SiO,~ Al,O, appears when the molar ratio is about 8 : 2,0 despite the fact that both TiO, and SiO, are oxides 8) see Feb I), ps 126,October, 1973) a8) z 2 as 3 i 3 2 oa " 240 «60 B00 smol% of TO, Fig, 1. Acid amount at various acd strengths of TiOy- ‘ALO, vr, mol% of Ti O-}: cach He ~82 Acid amount, mmollg #8 100 mol% of Z20 Fig. 2. Acid amounts at various acid strengths of Z20-AlOs ts. mol% of ZnO. ys 4.8, 2 Hy 3.0, ( MS 1.5, of metals of the same fourth group in the periodic table and that the acidity maximum of TiO,-ZnO® appears when the molar ratio is 1 :9 as in the case of TiO,-Al,Os. Recently, TiO,-AlO, was reported to show high catalytic activity for the synthesis of aniline from phenol and ammonia.” ‘The high ac- tivity can be now understood to be due to its high acid strength. SiO,-TiO, shows higher activity than SiO,-Al,O, for the aniline synthesis. Binary. Oxides Containing Zine Oxide or Alumina and Other Binary Oxides. The acidity distribution of the binary oxides containing ZnO or Al,O, and other 9) RS. Parker, Japanese Pat, Sho 42-23571. 10) K. Tanabe, Bi. to, and M. Sato, Chem. Commun. in press Acidic Properties of Binary Metal Oxides 06 ‘Acid amount, mmole a0 69 60100 mol% of ZrOs Fig. 3. Acid amounts at various acid strengtht of ZrO ‘Al Os as. mol% of ZrOy CO: Cm is 40, HeS-3.0 My S3.3, (A): Hy S1-5, Highest acid strength, Hy a6 8 ee 8 ‘Averaged clectronegativity Fig. 4. Highest acid stength 2s. averaged electronegativity ‘of metal ions of binary oxides (molar ratio=). binary oxides (molar ratio=l) is shown in Table 3, According to X-ray diffraction, ZnO-SiO, and Al,O,- ZrO, were amorphous and "ZnO-MgO gave only the ‘diffraction lines of ZnO. ZnO-ALOy, ZnO~ Z10,, ZnO-Sb,0, and ZnO-PbO gave diffraction lines differing from those of the component oxides. The results indicate that these binary oxides are not mechanically mixed oxides. ‘The binary oxides which, showed high acid strength were ZnO-SiO,, Al,O,~ ZO, and ZrOy-CdO. “The acid strengths of binary oxides containing ZnO are relatively weak. The acidity changes of ZnO-AlO, and Al,O-ZrO, with composition are shown in Figs. 2 and 3, where the acidity maxima are found when the molar ratios are2988 approximately 1:9 and 3:2, respectively. Many binary oxides show higher acid amount and strength than each component oxide (Table 3). The acid strengths of ZnO-MgO and Al,0,-Sb,0, were the same as those of one of the component oxides, whereas their acid amounts per unit surface area were smaller. In the case of ZnO-Sb,O, and ZnO-PbO, both acid strength and amount were lower than those of the ‘component oxides. It was reported that both SiO, and ZnO are almost inactive for the isomerization of butenes, although the combination of both oxides is active.")‘The activity is considered to be due to the action of strong acid sites generated on the surface of SiO,-Zn0. Gorrelation between Acid Strengths of Binary Oxides and Electronegaivties of Metal Tons of Metal Oxides. The observed highest acid strengths of binary oxides (mo- lar ratio=1) are plotted against the algebraically averaged clectronegativities of metal ions in Fig. 4, where the data indicated by open circles were cited from the literature (Ref. 2 for TiO,-ZnO; Ref. 7 for 11) K, Tanabe, T. Sumiyoshi, and H. Hattori, Chem, Let, 1972, 723, K. Samara, T. Krvoura, J. Krracawa, T. Sumtvosin, and K. Taxane [Vol. 46, No. 10 SiOp-Z:0,; Ref 12 for SiOy-AhO,, Si0,-¥,0,, SiO;-La,0,). The clectronegativity values of ‘va- rious metal ions were cited from the work of Tanaka and Ozaki. ‘The highest acid strengths were found to increase with the increase of the algebraically averag- ed_clectronegativities. ‘The correlation between the acid strengths and the geometrically averaged values of electronegativities was slightly worse than but almost the same as that shown in Fig. 4. Since the clectronegativity of metal ion (Me**) is related to its acid strength (pX,) as shown in Me**-H,Oz[Me- (OH)]*@-)-.11, ‘the relation given in Fig. 4 seems to be reasonable. However, the reason why the alge- braically or geometrically averaged values of electro- negativities are correlated with the acid. strengths is not yet clear. Nevertheless, the correlation in Fig. 4 is useful for predicting the acid strengths of unknown Dinary oxides. 12) N.S. Kotareako, L. G. Karakchiew, and V, A. Dritko, Kinet, Kate, 9, 158 (1968). 13) K. Tanaka and A. Ozaki, J. Gata, 8, 1 (1967); K. Tanaka, wokubai Kogalss Koza," Vol. 10, ed. by A- Ozaki, K. Tamans, K. Tanabe, and 8. Nishimura, Chijishokan & Co. Ltd., Tokyo, (1967), p. 752.