G Model TCA-76331; No.

of Pages 6

ARTICLE IN PRESS
Thermochimica Acta xxx (2013) xxxxxx

Contents lists available at SciVerse ScienceDirect

Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca

Modulation of the acidity of niobic acid by ion-doping: Effects of nature and amount of the dopant ions
Paolo Carniti a , Antonella Gervasini a, , Matteo Marzo a , Aline Auroux b
a b

Dipartimento di Chimica, Universit degli Studi di Milano (UNIMI), Milano, Italy Universit Lyon 1, CNRS, UMR 5256, (IRCELYON), Villeurbanne, France

a r t i c l e
Article history: Available online xxx

i n f o

a b s t r a c t
The acidity of niobic acid (NBO) has been successfully mitigated and tuned by addition of K+ , Ba2+ and Nd3+ dopant species in amounts from 1 to 15 atom nm2 . The characterization of the intrinsic acid properties of the samples was performed by adsorption of NH3 in a volumetricmicrocalorimetric coupled line and by temperature programmed desorption (TPD) of 2-phenylethylamine in a thermogravimetric apparatus. The K-dopant was more effective in decreasing the acidity of niobic acid than the Ba- and Nd-dopants. Complementary measurements of the effective acidity of the samples in water by base titrations with 2phenylethylamine completed the study and revealed a different picture of the effect of the three dopants on the NBO acidity in water. All the results indicated that the K-dopant targeted more selectively the Brnsted acid sites, acting as an ion-exchanger, while Ba- and Nd-species predominantly acted on the Lewis acid sites of the NBO surface. 2013 Elsevier B.V. All rights reserved.

Keywords: Niobic acid catalyst Ion doping Intrinsic and effective acidity Adsorption microcalorimetry Thermal programmed desorption

1. Introduction The surface acidity is the most important characteristic of niobic acid when employed as catalyst [1,2]. For this feature, it has found great success in heterogeneous catalysis for various reactions of industrial chemistry both in gas-phase and liquid-phase [3,4]. In the last decade, the development of processes for the catalytic conversion of biomass to chemicals and fuels has required the use of water-tolerant acid catalysts; bulk, and supported niobic acid catalysts have found new applications [5,6]. Indeed, a notable feature of the acid sites of niobic acid is their tolerance to water [6,7], so it can be used efciently as acid catalyst for reactions occurring in protic and polar liquids [810], such as water and alcohols, as well as in vapour rich atmospheres. Even when calcined at moderate temperatures, niobium oxide (NBO) can retain a sufcient amount of water to act as a strong solid acid of Brnsted type; besides, Lewis acid sites in association with tetrahedral niobium-containing centers are also present [11]. The relative proportion between the Brnsted and Lewis acid sites depends on the temperature at which NBO has been treated. For catalytic purposes, the tuning of the acidity of the NBO surface might be aimed to a modication of the acid site density as well as

Corresponding author at: Universit degli Studi di Milano (UNIMI), Dipartimento di Chimica, via Camillo Golgi 19, I-20133 Milano, Italy. Tel.: +39 02 50314254; fax: +39 02 50314300. E-mail address: antonella.gervasini@unimi.it (A. Gervasini). 0040-6031/$ see front matter 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.tca.2013.01.021

to a modication of the prevalent nature, Brnsted or Lewis type, of the surface acidity, so as to optimize the catalytic activity of NBO for different types of reactions. For this purpose the surface of NBO can be chemically modied by ion doping. The possibility of modifying the acidbase properties of niobic acid by addition of alkali metals has already been reported in the literature; no signicant differences among the different alkali metal elements (from Li to Cs) were observed [12]. There is less information on the doping effect of other metal elements on the acidity of the niobic acid surface. This was the reason why beside potassium, two different basic metal elements, barium and neodymium [13], have been selected for this study. These three dopant species with different electronic and basic properties have been added to the NBO surface in different amounts. The effect on the activity and stability of such doped catalysts has been already studied in reactions involving biomass conversion to chemicals in water solvent, like sucrose hydrolysis and fructose dehydration [14,15]. A decrease of activity due to the lowering of the surface acidity has been evidenced on all the doped samples, if compared to bare NBO, with clear differences due to the amount and nature of the dopant ion. In parallel, the decrease of surface acidity was benecial in terms of catalyst deactivation and led to an increase of the catalyst stability in the fructose dehydration. We present here a detailed study of the acidic characteristics of the three series of NBO-doped samples performed with calorimetric and thermal techniques of study, paying attention to the amount, strength, and strength distribution of

Please cite this article in press as: P. Carniti, et al., Modulation of the acidity of niobic acid by ion-doping: Effects of nature and amount of the dopant ions, Thermochim. Acta (2013), http://dx.doi.org/10.1016/j.tca.2013.01.021

G Model TCA-76331; No. of Pages 6 2

ARTICLE IN PRESS
P. Carniti et al. / Thermochimica Acta xxx (2013) xxxxxx

BET surface area / m2g-1

the acid sites. Microcalorimetry of ammonia adsorption and temperature-programmed desorption of 2-phenylethylamine have been used to measure the intrinsic acid properties of the samples, while adsorption of 2-phenylethylamine in water has been used as measurement of the effective acid properties of the samples. The observed differences between the intrinsic and effective acidities of each series of samples have been related to the different nature of the acid sites blocked by each dopant species.

100

75

50

25

2. Experimental Niobic acid (Nb2 O5 nH2 O) was kindly furnished by Companhia Brasileira de Metalurgia e Minerc o (CBMM); it was calcined at 400 C for 5 h before any use (hereafter called NBO). All the doped samples with variable amounts of K+ , Ba2+ , and 3+ Nd were prepared starting from NBO by incipient wetnessimpregnation with water solutions of acetate salts, respectively potassium acetate, CH3 CO2 K (Fluka, purity 99.0%), barium acetate, (CH3 CO2 )2 Ba (Fluka, purity 99.0%), and neodymium acetate, (CH3 CO2 )3 Nd, (Sigma Aldrich, purity 99.9%). After impregnation, the samples were dried at 120 C for 16 h and calcined at 400 C for 5 h. The doped NBO samples were labeled as MX/NBO, where M is the dopant-ion (K, Ba, or Nd) and X the dopant-ion concentration (115 atom nm2 ). Details on the preparation can be found in Ref. [15]. Morphologic properties (surface area, pore volume, and pore size distribution) have been determined from the isotherms of N2 adsorption and desorption measured at the temperature of liquid nitrogen in a Sorptomatic 1900 instrument (Carlo Erba Instruments). The standard deviation for the BET values obtained is ca. 2 m2 /g. The microcalorimetric measurements of NH3 adsorption have been performed at 80 C in a heat-ow calorimeter of the TianCalvet type (C80 from Setaram) linked to a conventional volumetric apparatus equipped with a capacitance manometer for the pressure measurements (Datametrics) (see Refs. [16,17]). Ammonia was dried on sodium wires and puried by successive freezethaw pumping cycles before use. About 0.1 g of each sample was outgassed at 400 C for 16 h before any measurement. A 1:1 stoichiometry for the NH3 adsorption on the acid site was assumed. The number of acid sites titrated has been evaluated at the intersection point between the straight line of the isotherm at the low NH3 pressure and the asymptotic part of the adsorption isotherm. The standard deviations for the experimental determinations, heat evolved and moles adsorbed are 3%. The temperature programmed desorption measurements of 2-phenylethylamine (PEA, Fluka, purity 99.0%) from the saturated powders have been performed in a thermogravimetric analyzer (TGA 7, from PerkinElmer). The temperature in the range 150800 C was calibrated by measuring the Curie transitions of high-purity reference materials (alumel, nickel, perkalloy, and iron). Prior to the desorption analysis, the powders were activated in vacuum for 16 h at 350 C and successively saturated by liquid PEA (see Refs. [18,19]). The saturated powder was loaded on the pan of the TGA apparatus (1015 mg) and a two-step analysis was performed under N2 ow (30 ml min1 ). The rst isothermal step was carried out at 200 C (boiling point of PEA = 195 C) to remove all the excess of PEA from the surface, while in the second step, a temperature increase from 200 up to 800 C at a constant heating rate of 10 C min1 was carried out. The high temperature attained at the end of the desorption experiment (800 C) ensured the complete removal of PEA from the strongest acid sites of the sample surfaces. Blank tests performed on bare NBO and selected samples with K-, Ba-, and Nd-dopants (all calcined at 400 C) showed that
0 0

NBO
4

K/NBO

Ba/NBO
8

Nd/NBO
12

Dopant concentration / atomnm-2

Fig. 1. Trend of the surface area values of all the samples in comparison with bare NBO as a function of the dopant concentration.

only a small amount of water was evolved in the 400800 C temperature interval, due to OH condensation without any signicant modication of the surfaces. Total and intermediate PEA mass losses have been determined by subtracting the nal mass determined at 800 C (for determining the total PEA removed) or at denite intermediate temperatures of analysis (for determining PEA removed from acid sites of denite acid strength) from the mass measured at the end of the rst isothermal step. For the acid sites calculation, a 1:1 stoichiometry for the PEA adsorption on the acid site was assumed. The standard deviation for the experimental determination of the amount of acid sites is around 1%. The acidity of the samples in water solvent has been performed by collecting isotherms of PEA adsorption in water at 30 C. For the measurements, a HPLC adsorption line working in total recirculation and comprising a pump (Waters 515) and a UV detector (Waters, model 2487, = 254 nm) has been used [10]. The sample (about 0.1 g) was placed in a stainless steel sample holder between two sand pillows. Prior to the measurement, the sample was activated at 350 C for 4 h in owing air (8 ml min1 ) and then lled with water (HPLC grade). Successive dosed amounts of PEA (50 l, 0.10 M) were injected into the line in which water continuously circulated, until adsorption equilibrium was achieved. For the acid site calculation, a 1:1 stoichiometry for the PEA adsorption on the acid sites has been assumed. The standard deviation for the experimental determination of the amount of acid sites is around 3%. 3. Results and discussion All the doped NBO catalysts were prepared by wetness impregnation from different amounts of K-, Ba-, and Nd-acetate salts; their preparation and characterization have been detailed elsewhere (Refs. [14,15]). The K-doped and the Ba-doped samples showed a regular increase of the dopant enrichment with the amount used in the preparation (from 1.53 to 11.8 atom nm2 and from 1.13 to 8.65 atom nm2 respectively for the K/NBO and Ba/NBO sample series), while for the Nd-doped samples, severe differences between the measured Nd content (from 1.80 to 3.02 atom nm2 ) and the amount used in the preparation have been observed (Table 1). This can be explained by a low Nd-dispersion obtained in the NBO doping [14]. The samples, and NBO as well, were calcined at 400 C, a temperature chosen in order to reach a good compromise between obtaining clean oxide surfaces and maintaining a suitable acidity. All three samples series showed a regular decrease of the surface area values with increasing amount of doping ion (Fig. 1). If the surface area has a clear correlation with the amount of doping

Please cite this article in press as: P. Carniti, et al., Modulation of the acidity of niobic acid by ion-doping: Effects of nature and amount of the dopant ions, Thermochim. Acta (2013), http://dx.doi.org/10.1016/j.tca.2013.01.021

G Model TCA-76331; No. of Pages 6

ARTICLE IN PRESS
P. Carniti et al. / Thermochimica Acta xxx (2013) xxxxxx 3 Dopant concentrationa Atom nm2 Intrinsic acid sites equiv. g1 wt.% 1.04 2.98 5.02 8.04 2.70 4.19 7.85 12.4 20.7 2.50 4.53 5.00 7.60 NH3 -calorimetryb 250 120 71 41 29 224 179 184 155 115 239 211 228 219 PEATPDc 238 155 122 117 80 214 155.5 202 193 216 218 235 230 192 132 122 85 65 50 46 23 16 64 33 48 27 Effective acids sitesd equiv. g1

Table 1 Samples and main characteristics. Sample code

NBO K2/NBO K6/NBO K10/NBO K15/NBO Ba1/NBO Ba2/NBO Ba4/NBO Ba6/NBO Ba10/NBO Nd1/NBO Nd2/NBO Nd3/NBO Nd6/NBO
a b c d

1.53 4.37 7.37 11.8 1.13 1.75 3.28 5.17 8.65 0.99 1.80 1.99 3.02

Measured by EDX analysis [14]. Measured by NH3 adsorption. Measured by PEATPD. Measured by PEA adsorption in water.

ion, no effect was observed with the nature of the dopant species (K, Ba, or Nd). 3.1. Intrinsic acidity by microcalorimetry of NH3 adsorption The results obtained from the adsorption of NH3 by microcalorimetry experiments, that is the amount and strength of the intrinsic acid sites, are reported in Table 1 while in Fig. 2 are reported the differential heat curves (qdiff ) as a function of the amount of NH3 adsorbed. The following general considerations can be made. As expected, NBO had the highest total number of acid sites (250 equiv. g1 of acid sites); on each sample obtained by ion-doping, a lower number of acid sites has been measured. The decrease in the amount of acid sites of the samples doped with the K-species was proportional to the amount of K-doping. The sample containing the highest amount of K-dopant (K15/NBO) displayed only 29 equiv. g1 of acid sites (corresponding to a 88% decrease in acid sites compared with NBO). Ba- and Nd-doping led to less pronounced decreases in the NBO acidity. With the highest amount of Ba-dopant used (Ba10/NBO), the measured amount of acid sites was 115 equiv. g1 , corresponding only to a 54% acidity decrease compared to NBO. The same trend was observed for the samples doped with Nd-species, where a very limited decrease of the amount of acid sites (12%) was observed on the sample with the highest amount of Nd (Nd6/NBO). The distributions of the acid site strengths of the doped samples compared with that of the bare NBO are well evidenced by the curves of the differential heats of NH3 adsorption (qdiff ) as a function of NH3 coverage, reported in Fig. 2 for the K-, Ba-, and Nd-doped samples. The increase of the concentration of K in the samples led to a pronounced modication of the qdiff -curves from a quantitative point of view as well as for the shapes of the different curves. The qdiff curves progressively achieved the lowest measured values (around 25 kJ/mol) at even lower ammonia coverage (Fig. 2A). This behavior clearly indicated the progressive reduction of the acidity of NBO in terms of both amount and acid-strength of the sites. The clear tuning effect of the K-species in the reduction of the acidity of NBO was less evident for the Ba- and Nd-dopant species (Fig. 2B and C). The differential heat curves of the Ba/NBO and Nd/NBO samples are grouped in a wide band with only a slight modication of the curve shape. Thus, Ba- or Nd-doping resulted in only a slight modication of the amount of acid sites and of the acid-site distribution strength.

To provide a comparative view of the effect of the nature and amount of the dopant species on the acidity of NBO, Figs. 3 and 4 show the average heats of ammonia adsorption (Qav , which is related to the average acid strength of the doped NBO-surfaces) as a function of the dopant concentration (expressed as atom nm2 ) (Fig. 3) and as a function of the amount of acid sites measured on each doped sample (Fig. 4). For all three dopant species Fig. 3 shows a decreasing trend of Qav with the dopant concentration, which indicates the effectiveness of the doping action of all the three dopant species. The effect of the K-species is visibly more pronounced than that of Ba and Nd-species. An order of effectiveness can be clearly deduced: K/NBO Ba/NBO = Nd/NBO. In Fig. 4, a similar distinction among the three dopant-species in terms of ability to decrease the acidity of NBO emerges, too. The Ba- and Nd-series samples (which are more acidic than the K-series samples) lie on a single line regardless to their nature, while K-series samples (which are less acidic than Ba- and Nd-samples) lie on a more sloping line. This proves the better effectiveness of K-species compared to Ba- and Nd-species in modulating and tuning the NBO acidity. 3.2. Intrinsic acidity by temperature programmed desorption of 2-phenylethylamine (PEA) The temperature programmed desorption experiments, PEATPD, were performed in a thermal analyzer which allows to monitor the mass loss of the sample saturated with PEA as a function of time/temperature. For all the doped samples and bare NBO, decreasing curves with more or less apparent inection points corresponding to desorption of PEA from acid sites of given acid strength have been observed (Fig. 5). At the highest attained temperature (800 C), the basic probe was completely desorbed from all samples; from the total loss of mass recorded, the amount of PEA desorbed can be calculated, as reported in Fig. 5AC for the K-, Ba-, and Nd-doped samples, respectively. The PEATPD curves of the samples displayed different shapes with respect to NBO and they differ between the K-, Ba-, and Nd-dopant species. The TPD curves of the K-doped samples (Fig. 5A) showed great differences in terms of amount of PEA desorbed in comparison with that of NBO up to ca. 400 C. A marked and progressive decrease of acidity with the increase in doping ion concentration was evidenced on the K/NBO samples, while the TPD curves of samples with higher K-concentration lay below those at lower K-concentration, thus

Please cite this article in press as: P. Carniti, et al., Modulation of the acidity of niobic acid by ion-doping: Effects of nature and amount of the dopant ions, Thermochim. Acta (2013), http://dx.doi.org/10.1016/j.tca.2013.01.021

G Model TCA-76331; No. of Pages 6 4

ARTICLE IN PRESS
P. Carniti et al. / Thermochimica Acta xxx (2013) xxxxxx

200 NBO K2/NBO K6/NBO K10/NBO K15/NBO

100

Qav / kJmol-1

150

qdiff / kJmol

75

-1

100

50

50

25

NBO

K/NBO
4

Ba/NBO
8

Nd/NBO
12

0 0 100 200
-1

300

NH3 adsorbed / molg

Dopant concentration / atomnm-2

Fig. 3. Trends of the average heats (Qav ) of NH3 adsorption on bare NBO and K-, Ba-, and Nd-doped samples as a function of the dopant concentration (Qav has been calculated from the ratio between total heat released from the NH3 adsorption and the relevant titrated acid sites), reported in Table 1, 4th column.

B
-1

200 NBO Ba1/NBO Ba2/NBO Ba4/NBO Ba6/NBO Ba10/NBO

150

100

50

0 0 100 200
-1

300

similar results, as can be revealed by an inspection of Fig. 6. The same amounts of acid sites were measured on the Ba- and Ndsample series by NH3 adsorption and PEA-desorption, while a higher amount of acid sites was measured by PEA-desorption than by NH3 adsorption on the K-sample series. This might be explained by the different acid strengths of the surface sites still present on the three series of doped samples. The lower acidity of the surface sites of the K-containing samples required saturation by the basic probe, while in the adsorption, the low coverage of the surface with NH3 did not allow for titration of all the weak acid sites. 3.3. Effective acidity by adsorption of 2-phenylethylamine (PEA) in water

qdiff / kJmol

NH3 adsorbed / molg

200 NBO Nd1/NBO Nd2/NBO Nd3/NBO Nd6/NBO

150

100

50

0 0 100 200 300

The surface acidity of the samples has also been determined in liquid phase, by a method set up by the authors and already presented in the literature [10]. This method, consisting in a liquidsolid titration in equilibrium conditions, permits the determination of the effective acidity of the surface sites in any chosen liquid medium. In this case, we have chosen to realize the determination of the effective acidity of the doped-NBO samples in water, in order to establish more reliable relations with their catalytic activity, which has been previously measured in reactions of saccharide transformation in water (e.g., disaccharide hydrolysis and fructose dehydration [9,10,15]).
120

qdiff / kJmol-1

NH3 adsorbed / molg-1

Fig. 2. Microcalorimetric curves of the differential heats, qdiff , of NH3 adsorption as a function of surface coverage on NBO and K- (A), Ba- (B), and Nd- (C) doped samples (Tads = 80 C).

90

showing the decrease of acidity with the increase of the K-dopant. For the Ba/NBO and Nd/NBO samples, the loss of acidity with the doping increase was lower. The TPD curves of the Ba- and Nd-doped samples (Fig. 5B and C) are more similar to the TPD curve of NBO in the rst part (up to 400 C), while the curves differ more at higher temperatures. In this case, PEA was more tightly bound to the acid sites of the Ba- and Nd-doped samples than on the acid sites of NBO, indicating that new acid sites could be created following the Ba and Nd doping (as already observed from the ammonia adsorption microcalorimetry). For each sample, the total number of acid sites determined by PEATPD has been reported in Table 1. We attempted to compare the intrinsic acidities determined by the two methods: adsorption of NH3 and desorption of PEA. In general, both methods gave

Qav / kJmol-1

60

30

NBO K/NBO Ba/NBO Nd/NBO

0 0 100 200 300

Intrinsic acid sites (from NH3 ads) / molg-1

Fig. 4. Trends of the average heats (Qav ) of NH3 adsorption on NBO and K-, Ba-, and Nd-doped samples as a function of the amount of intrinsic acid sites (Qav has been calculated from the ratio between total heat released from the NH3 adsorption and the relevant titrated acid sites), reported in Table 1, 4th column.

Please cite this article in press as: P. Carniti, et al., Modulation of the acidity of niobic acid by ion-doping: Effects of nature and amount of the dopant ions, Thermochim. Acta (2013), http://dx.doi.org/10.1016/j.tca.2013.01.021

G Model TCA-76331; No. of Pages 6

ARTICLE IN PRESS
P. Carniti et al. / Thermochimica Acta xxx (2013) xxxxxx 5

A
Intrinsic acidity decrease / %

0 NBO K/NBO Ba/NBO Nd/NBO

-25

-50

-75

-100 0 4 8 12

Dopant concentration / atomnm-2

B
Effective acidity decrease / %

0 NBO K/NBO Ba/NBO Nd/NBO

-25

-50

-75

-100 0 4 8 12

Dopant concentration / atomnm-2

Fig. 7. Percentage of acidity decrease of the doped NBO samples in comparison with bare NBO acidity, determined by NH3 adsorption (intrinsic acidity) (A) and by PEA adsorption in water (effective acidity) (B) as a function of the dopant concentration.

Fig. 5. Thermodesorption curves of PEA from NBO and K- (A), Ba- (B), and Nd- (C) doped samples collected in the TGA apparatus in nitrogen atmosphere; the mass loss of PEA was monitored as a function of time/temperature (10 C min1 ).

300

200

100

NBO K/NBO Ba/NBO Nd/NBO

0 100 200
-1

0 300

acid sites from NH3 ads-calo / molg

Fig. 6. Comparative view of the amount of acid sites determined by PEATPD and by NH3 adsorption microcalorimetry.

The results obtained show that the effective acidity of the dopedNBO samples is very different from their intrinsic acidity (Table 1). In this case too, the highest number of effective acid sites was determined for the bare NBO; the samples with lower K-concentration show a number of effective acid sites similar to the intrinsic ones, while the higher K-concentration samples display a larger amount of effective acid sites in comparison with the amount of intrinsic acid sites, as determined by NH3 adsorption. On the opposite, a pronounced decrease of effective acidity has been observed for the Baand Nd-doped samples, starting from the very low dopant concentration (a decrease of acidity of about 74% and 67% for Ba1/NBO and Nd1/NBO, respectively). Thus it appears that the K-doping is more successful in tuning the acidity of NBO, while Ba- and Nd-doping result in a markedly decreased acidity. In conclusion, ion-doping may be effective in modulating the surface acidity of NBO, with a clear inuence of the amount and of the nature of the doping ion. The intrinsic acidity of NBO was reduced following the order K Ba > Nd (Fig. 7A), while the opposite was observed for the effective acidity, with the following order: Ba Nd K (Fig. 7B). These observations can be related with the different interaction of the three dopant-ions with the acid surface sites of NBO. K-dopant is more selective toward the Brnsted acid sites of NBO, it acts like an ion-exchanger, while Ba- and Nd-dopant ions, due to their higher charge, likely modify the Lewis sites population of NBO. These considerations are supported by a successful correlation between the effective acidity and catalytic activity in water, already discussed in Refs. [14,15].

Please cite this article in press as: P. Carniti, et al., Modulation of the acidity of niobic acid by ion-doping: Effects of nature and amount of the dopant ions, Thermochim. Acta (2013), http://dx.doi.org/10.1016/j.tca.2013.01.021

acid sites from PEA-TPD / molg -1

G Model TCA-76331; No. of Pages 6 6

ARTICLE IN PRESS
P. Carniti et al. / Thermochimica Acta xxx (2013) xxxxxx [6] T. Okuhara, Water-tolerant solid acid catalysts, Chem. Rev. 102 (2002) 36413666. [7] G. Busca, Acid catalysts in industrial hydrocarbon chemistry, Chem. Rev. 107 (2007) 53665410. [8] R.M. West, D.J. Braden, J.A. Dumesic, Dehydration of butanol to butene over solid acid catalysts in high water environments, J. Catal. 262 (2009) 134143. [9] P. Carniti, A. Gervasini, S. Biella, A. Auroux, Niobic acid and niobium phosphate as highly acidic viable catalysts in aqueous medium: fructose dehydration reaction, Catal. Today 118 (2006) 373378. [10] P. Carniti, A. Gervasini, M. Marzo, Silicaniobia oxides as viable acid catalysts in water: effective vs. intrinsic acidity, Catal. Today 152 (2010) 4247. [11] K. Nakajima, Y. Baba, R. Noma, M. Kitano, J.N. Kondo, S. Hayashi, M. Hara, Nb2 O5 nH2 O as a heterogeneous catalyst with water-tolerant Lewis acid sites, J. Am. Chem. Soc. 133 (2011) 42244227. [12] V. Calvino-Casilda, R.M. Martn-Aranda, I. Sobczak, M. Ziolek, Modication of acidbase properties of alkali metals containing catalysts by the application of various supports, Appl. Catal. A 303 (2006) 12130. [13] A. Auroux, A. Gervasini, Microcalorimetric studies of the acidity and basicity of metal oxide surfaces, J. Phys. Chem. 94 (1990) 63716379. [14] A. Gervasini, P. Carniti, M. Marzo, A. Auroux, Effect of the K+ , Ba2+ , and Nd3+ addition to Nb2 O5 on intrinsic and effective acidity in relation to biomass reactions, J. Catal. (2012), http://dx.doi.org/10.1016/j.jcat.2012.09.014. [15] M. Marzo, A. Gervasini, P. Carniti, Improving stability of Nb2 O5 catalyst in fructose dehydration reaction in water solvent by ion-doping, Catal. Today 192 (2012) 8995. [16] A. Auroux, Acidity characterization by microcalorimetry and relationship with reactivity, Top. Catal. 4 (1997) 7189. [17] A. Auroux, Acidity and basicity: determination by adsorption microcalorimetry, Mol. Sieves 6 (2008) 45152. [18] A. Gervasini, P. Carniti, S. Bennici, C. Messi, Inuence of the chemical nature of the support (niobic acid and niobium phosphate) on the surface and catalytic properties of supported CuO, Chem. Mater. 19 (2007) 13191328. [19] A. Gervasini, P. Carniti, A. Auroux, Surface acidity of catalytic solids studied by base desorption: experimental and modelling approaches, Thermochim. Acta 434 (2005) 4249.

4. Conclusion Modulating the surface acidity of the niobic acid by ion-doping has been shown to be effectively possible. Depending on the nature and amount of the dopant-ions, it is possible to tune the surface toward a prevalent Brnsted- or Lewis-type acidity, and to modify the average acid strength as well. Low-valence ions, like K+ , can work as ion-exchangers with the protonic acid sites, while higher valence ions modify the Lewis population of the surface. Thermal techniques can be used in combination (like adsorption microcalorimetry and thermal desorption) to improve the information obtained on the amount, strength, and strength distribution of the acid sites of heterogeneous catalytic surfaces. Moreover, base adsorption in conditions more similar to those of catalyst operation (in liquid phase) can be used to determine the effective surface acidity for a better relationship with catalytic activity. References
[1] I. Novak, M. Ziolek, Niobium compounds: preparation, characterization, and application in heterogeneous catalysis, Chem. Rev. 99 (1999) 36033624. [2] M. Ziolek, Niobium-containing catalyststhe state of the art, Catal. Today 78 (2003) 4764. [3] K. Tanabe, S. Okazaki, Various reactions catalyzed by niobium compounds and materials, Appl. Catal. A 133 (1995) 191218. [4] K. Tanabe, Catalytic application of niobium compounds, Catal. Today 78 (2003) 6577. [5] A. Corma, S. Iborra, A. Velty, Chemical routes for the transformation of biomass into chemicals, Chem. Rev. 107 (2007) 24112502.

Please cite this article in press as: P. Carniti, et al., Modulation of the acidity of niobic acid by ion-doping: Effects of nature and amount of the dopant ions, Thermochim. Acta (2013), http://dx.doi.org/10.1016/j.tca.2013.01.021