J Porous Mater (2016) 23:475–487

DOI 10.1007/s10934-015-0101-z

Synthesis and characterization of silica doped alumina catalyst

support with superior thermal stability and unique pore
properties
Maryam Khosravi Mardkhe1 • Baiyu Huang1 • Calvin H. Bartholomew2 •

Todd M. Alam3 • Brian F. Woodfield1

Published online: 21 November 2015

Ó Springer Science+Business Media New York 2015

Abstract A facile, solvent-deficient, one-pot synthesis of structure of alumina without moving Al from tetrahedral
a thermally stable silica-doped alumina, having high sur- positions and forms a silica–alumina interface.
face area, large pore volume and uniquely large pores, has
been developed. Silica-doped alumina (SDA) was synthe- Keywords Silica-doped alumina
Thermally stable

sized by adding 5 wt% silica from tetraethyl orthosilicate Large pore size
High surface area
(TEOS) to aluminum isoproxide (AIP), a 1:5 mol ratio AIP
to water, and a 1:2 mol ratio TEOS to water in the absence
of a template. The structure of silica-doped alumina was 1 Introduction
studied by in situ high-temperature powder XRD, nitrogen
adsorption, thermogravimetric analysis, solid-state NMR, Gamma alumina (c-Al2O3) is one of the most widely used
and TEM. The addition of silica significantly increases the commercial catalyst supports because of its moderately
stability of c-Al2O3 phase to 1200 °C while maintaining a high surface area, meso- and macro-porosity and relatively
high surface area, a large pore volume and a large pore high thermal and hydrothermal stabilities. It is an effective
diameter. After calcination at 1100 °C for 2 h, a surface catalyst support for both base and noble metals in many
area of 160 m2/g, pore volume of 0.99 cm3/g, and a different applications: e.g., Pt/Pd catalytic converters [1],
bimodal pore size distribution of 23 and 52 nm are Ni catalyst in hydrogenation [2], Co(Ni)–Mo(W) sulfide
observed. Compared to a commercial silica-doped alumina, catalysts for hydrotreating of petroleum feed stocks [3],
after calcination for 24 h at 1100 °C, the surface area, pore and Co catalyst for Fischer–Tropsch synthesis (FTS) [4, 5].
volume, and pore diameter SDA are higher by 46, 155, and Since each of these applications typically requires a unique
94 %, respectively. Results reveal that Si stabilizes the range of surface area, pore volume and pore diameter,
porous structure of c-Al2O3 up to 1200 °C, while unstabi- commercial aluminas are supplied with a wide range of
lized alumina is stable to only 900 °C. From our data, we surface areas and porosities [6–8]. Therefore, the ability to
infer that Si enters tetrahedral vacancies in the defect spinel optimize c-Al2O3 porosity is vital in the manufacture of
these materials [4, 9–11].
While c-Al2O3 is stable during long term use at
500–600 °C, at higher reaction temperatures
& Brian F. Woodfield (650–1100 °C) and especially in the presence of water
[email protected] vapor, the porous structure collapses due to sintering and
1
Department of Chemistry and Biochemistry, Brigham Young
structural transformations to other forms of alumina (a-
University, Provo, UT 84602, USA Al2O3), resulting in lower porosity of the supports, and in
2 some cases, deactivation of the catalyst. Thus, in a number
Department of Chemical Engineering, Brigham Young
University, Provo, UT 84602, USA of catalytic reactions taking place at elevated temperatures
3 and high steam concentrations, e.g. auto emissions control
Department of Electronic, Optical and Nanostructured
Materials, Sandia National Laboratories, Albuquerque, and steam reforming [12–17], the thermal and hydrother-
NM 87185, USA mal stability of c-Al2O3 is inadequate. Nevertheless, c-

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Al2O3 can be stabilized against sintering and phase trans- were available. Horiuchi et al. [17] used supercritical
formations through the incorporation of suitable dopants drying to synthesize silica-doped alumina with a surface
(i.e. alkaline earth oxides, transition, and rare-earth ele- area of 110 m2/g, pore volume of 0.9 cm3/g and pore
ments, as well as SiO2). Previous studies have demon- diameter of 18.6 nm at 1200 °C. Later, Horiuchi et al. [35]
strated that thermal and hydrothermal stabilities of alumina reported silica doped alumina with even higher surface area
are substantially improved by the addition of 1–20 wt% (150 m2/g) after calcination at 1200 °C. However, their
silica [15–21], titania [22, 23], zirconia [19, 24, 25], and method involved a multi-step preparation, such as peptiz-
rare earth elements such as lanthanum [1, 13, 26], mag- ing, refluxing, gelation, solvent exchanging, and super-
nesium [25, 27], and ceria [12, 28, 29]. critical drying, which was relatively complex and time
Of particular pertinence to the present work is the use of consuming.
silica at 1–10 wt% as a stabilizer for c-Al2O3. A number of From this previous work, it is evident that the addition
previous papers and patents address the preparation of of silica to alumina produces alumina support materials
stable silica-doped alumina. In an early patent, a multi-step with substantially higher porosity at high temperatures
co-gel preparation method was reported to produce silica– (relative to pure alumina). Such materials having thermal
alumina with high porosity: the alumina sample contained and hydrothermal stabilities facilitate higher catalyst
7 % silica, with a surface area of 150 m2/g, and a pore loadings and increase catalyst lifetime, activity, and pro-
volume of 0.9 cm3/g at 1100 °C (no pore diameter was ductivity at high operating temperatures [5]. However,
reported) [30]. This method involves the reaction of an most of the previous preparation methods involve complex,
alkali metal aluminate and silicate, followed by filtration, multi-step procedures and hence higher manufacturing
washing, and drying. Preparation of silica-modified-alu- costs. Therefore, it would be desirable to devise simple,
mina with 2–10 % silica using a different co-gel method low-cost methods that produce such materials.
has also been reported: after calcination at 648 °C, the 5 % In the present work, we report a simple, one-pot, sol-
silica sample was reported to have a moderately high sur- vent-deficient preparation method for silica-doped c-Al2O3
face area of 318 m2/g and relatively low pore volume of supports with high surface area, large pore volume,
0.46 cm3/g [31]. This method uses acid in the sol prepa- uniquely large pores having a bimodal distribution, and
ration and base in the gelation step. Wan et al. [32]. high thermal stability. The results indicate that in 5 %
reported a stabilized 5.5 % silica–alumina support pro- SDA, Si ions are incorporated into vacant tetrahedral sites
duced by impregnating alumina with polyorgano silane; of the alumina spinel and retard the phase transformation
after calcination at 1100 and 1200 °C, the surface area was from c to a, and therefore stabilize the alumina structure at
158.2 and 93 m2/g, respectively; however, neither pore elevated temperatures.
volume nor pore diameter data were reported. Other
complex methods involving solvents and pH adjustment
techniques have also been used to make stable silica-doped 2 Experimental
alumina [12, 16, 18, 33]. However, these particular sup-
ports do not maintain high surface areas and pore volumes 2.1 Material
at higher temperatures. For example, Shutilov et al. [16]
used an impregnation method to make a stable silica-doped Aluminum isopropoxide (C9H21O3Al) (granular, 98? %)
alumina but reported low values for both surface area and tetraethyl orthosilicate (SiC8H20O4) (liquid, 99.9 %)
(68 m2/g) and pore volume (0.34 cm3/g) and a moderately (TEOS) were purchased from Alfa-Aeser. Commercial 5 %
large pore diameter (15 nm) at 1100 °C. Zhao et al. [34] silica-doped alumina (Siral-5) was purchased from Sasol
studied the effect of dopants, including silica, on the alu- for comparison.
mina supports for Rh catalysts. However, the surface area
of the silica doped alumina after calcination at 1200 °C, i.e. 2.2 Synthesis method
55 m2/g, was still relatively low. Silica-doped aluminas
having high surface area and pore volume at high tem- Silica-doped aluminas (100 g batches) (SDAs) were pre-
peratures have also been synthesized using aerogel and pared via a patented method [36] that involves mixing
crygol methods, but they are costly and time consuming aluminum isopropoxide (AIP) and water at a 5:1 mol ratio
[15, 17, 20]. For example, Miller et al. [15] produced a of water to AIP, then 5 wt% silica from tetraethyl
stable silica-doped alumina containing 10 % silica by the orthosilicate (TEOS) and water at a 2:1 water to TEOS
multi-step aerogel method and using supercritical drying to mole ratio. These starting materials were mixed for 30 min
remove the solvent. At 1200 °C, it has a surface area of with a Bosch Universal Mixer at a RPM of 300. The
150 m2/g and pore volume of 0.65 cm3/g, which are resulted intermediate, or precursor, was then calcined at
unusually high for this temperature; no pore diameter data 700, 900, 1100, 1200 °C for 2 h each with 5-h ramps.

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During the calcination, Al(OH)3 precursor decomposes The 27Al chemical shift was referenced to the external
leading to the formation of water and nano crystalline c- secondary standard 1 M Al(H2O)? 6 d = 0.0 ppm, and the
29
Al2O3 at high temperatures and all of the byproducts were Si chemical shift was referenced to the secondary stan-
released as gases. Pure alumina [37] and samples with 15 dard Q8M8 d = ?12.6 ppm with respect to neat TMS
and 27 wt% of silica were prepared for comparison. (d = 0 ppm). Spectral simulations and deconvolutions
were performed using DMFIT [40, 41]. The Czejeck dis-
2.3 Characterization tribution [42] of the 27Al electrical field gradient (EFG)
tensor was used in the analysis of the 27Al NMR, and gives
The alumina phase was identified by powder x-ray rise to the asymmetric line shapes. In some instances it was
diffraction (XRD) using a PANalytical X’Pert Pro necessary to include multiple distributions for a given Al
diffractometer with a Cu Ka x-ray source (k = 1.5418 Å) environment to reproduce the experimental line shape.
operated at 45 kV and 40 mA. Scans were performed
between 10° and 90° 2h with a step size of 0.0167° at a rate
of 0.013°s-1. The Scherrer formula was used to estimate 3 Results
crystallite size [38]. In situ high-temperature XRD
(HTXRD) experiments were performed using this same 3.1 X-ray diffraction
instrument equipped with an Anton Paar HTK 1200N
stage. Scans were collected using the same parameters just Figure 1 shows XRD patterns for pure alumina and three
described as the samples were heated in purified air from silica-doped alumina samples after calcination at 700, 900,
400 to 1200 °C. 1100, 1200 and 1300 °C. Only characteristic broad peaks
Nitrogen adsorption measurements were carried out for c-Al2O3 at 45.7° and 66.6° are observed at 700–900 °C
using a Micromerictics Tristar 3020 for the determination for all samples; the broad lines indicate that samples con-
of surface properties at -196 °C. Surface area was calcu- sist of small crystallites of small diameter. For the pure
lated using the Brunauner–Emmett–Teller (BET) model in alumina sample only a-Al2O3 is observed at 1200 °C
the P/P0 range from 0.05 to 0.20. Pore volumes were (Fig. 1a). In contrast, mostly the c-Al2O3 phase is observed
determined at a single point of P/P0 equal to 0.990. Pore for 5, 15, 27 % silica samples, respectively (Fig. 1b–d).
size distributions were calculated using an improved slit Figure 1b shows XRD patterns of 5 % silica-doped
pore geometry (SPG) model for large pore sizes [39]. alumina (5 % SDA), calcined from 700 to 1300 °C for 2 h.
Samples were degassed at 200 °C under N2 flow overnight Characteristic peaks of c-Al2O3, along with traces of h-
before each measurement. Al2O3 are observed for 5 % SDA after calcination at
Microscopic images of samples were obtained with an 1200 °C, suggesting that the c phase is largely stable and
FEI Philips Tecani F30 transmission electron microscope the transition to the a phase has not yet occurred at this
(TEM) at a voltage of 200 kV. TEM samples were pre- temperature. The peaks attributed to a-Al2O3 are not
pared by placing a drop of silica-doped alumina (1 % observed until 1300 °C. A comparison of these results with
dispersed in ethanol) on a carbon film with a copper mesh other published SDA materials is given below.
grid (Ted-Pella Inc.). Figure 2 shows in situ high-temperature XRD patterns
Thermo-gravimetric (TG) and differential-temperature for 5 % SDA in flowing purified air. It is evident that the c-
(DT) analyses were performed using a NETZSCH STA Al2O3 phase in 5 % SDA is stable to 1200 °C without
409PC instrument (NETZSCH, Germany) in the tempera- transforming to either h- or a-Al2O3, since no h- or a-
ture range of 25–1400 °C under 20 mL/min He gas flow Al2O3 peaks are detected at 1200 °C. The in situ results are
with a heating rate of 3 °C/min. A sample weight of 30 mg largely consistent with those for the ex situ furnace-cal-
was used in a platinum pan. cined samples (Fig. 1b).
Solid state MASNMR spectra were obtained on a Bru-
ker Avance I 400 (9.6 T) instrument using a 7 mm (29Si) or
a 4 mm (27Al) broadband MAS probe. All spectra were 3.2 Nitrogen adsorption
obtained at room temperature, and a spinning speed of
12.5 kHz for 27Al or 4 kHz for 29Si. The 1D 29Si MAS Table 1 shows surface areas, pore volumes, and pore
NMR spectra used a single pulse direct polarization (DP) diameters for pure alumina and three silica-doped alumina
Block decay with a 240 s recycle delay to assure complete samples, calcined at 700, 900, 1100 and 1200 °C. Pore size
relaxation, while the 1H–29Si cross polarization (CP) MAS distributions for 5 % silica-doped alumina (SDA) calcined
NMR spectra was obtained using a 5 ms contact time and a at different temperatures are shown in Fig. 3. The surface
10 s recycle delay. The 27Al MAS spectra were also area and pore volume of the pure alumina sharply
obtained using a DP Bloch decay, and a p/6 pulse length. decreases with increasing calcination temperatures from

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Fig. 1 XRD patterns of different aluminas calcined at different temperatures for 2 h. a Pure alumina, b 5 % SDA, c 15 % SDA, d 27 % SDA.
Standards: (1) gamma alumina, (2) alpha alumina, (3) theta alumina, (4) mullite

10 20 30 40 50 60 70 80 90

SDA_1200C

SDA_1180C

SDA_1160C

SDA_1140C
Intensity

SDA_1100C

SDA_1000C

SDA_900C

SDA_820C

SDA_700C

10 20 30 40 50 60 70 80 90
Angle deg

Fig. 2 In situ high-temperature XRD patterns of 5 % SDA 700–1200 °C

1100 to 1200 °C; however, the addition of silica main- and larger pore diameter compared to other aluminas. The
tained the surface area and pore volume of the aluminas. In 5 % SDA has a surface area of 160 m2/g, a pore volume of
addition, 5 % SDA shows a bimodal pore size distribution 0.99 cm3/g, and a bimodal pore distribution of 22.5 and

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Table 1 BET results of 0–5–15–27 % SDAs calcined at different temperatures for 2 h

Silica % Calcination T (°C/2 h) BET surface area (m2/g)a Mesopore volume (cm3/g)a Pore diameter (nm)b SD (nm)

0% 700 291 1.56 19.8 1.1

900 208 1.12 25.5 1.2
1100 119 0.77 26.7 1.6
1200 15 0.05 0.00 –
5% 700 378 1.83 14.7 and 35.0 1.8
900 300 1.60 19.8 and 51.8 1.8
1100 160 0.99 22.5 and 52.0 1.8
1200 111 0.59 15.4 and 32.2 1.6
15 % 700 222 1.40 43.1 1.8
900 180 1.10 39.2 1.8
1100 146 0.96 33.6 1.6
1200 100 0.66 31.1 1.6
27 % 700 195 1.0 51.6 1.5
900 143 0.89 51.3 1.4
1100 100 0.57 45.4 1.8
1200 65 0.33 48.6 1.9
a
Determined by N2 adsorption at 77 K
b
Determined by an improved slit pore geometry (SPG) model for large pore sizes using the desorption branch

(a) (b)
0.45 0.35
Normalized dVp/ln(drpavg)
Normalized dVp/ln(drpavg)

0.40 0.30
0.35
0.25
0.30
0.25 0.20
0.20 0.15
0.15
0.10
0.10
0.05 0.05
0.00 0.00
0.0 1.0 2.0 3.0 4.0 5.0 0.0 1.0 2.0 3.0 4.0 5.0
ln(rpavg) ln(rpavg)
(c) (d)
0.25 0.14
Normalized dVp/ln(drpavg)
Normalized dVp/ln(drpavg)

0.12
0.20
0.10
0.15 0.08

0.10 0.06
0.04
0.05
0.02
0.00 0.00
0.0 1.0 2.0 3.0 4.0 5.0 0.0 1.0 2.0 3.0 4.0 5.0
ln(rpavg) ln(rpavg)

Fig. 3 Pore size distributions for 5 % SDA calcined at different temperatures for 2 h: a 700 °C, b 900 °C, c 1100 °C, and d 1200 °C

52 nm at 1100 °C. The surface area and pore volume were 3.3 TEM images
111 and 0.59 cm3/g, and a bimodal pore distribution of
15.4 and 32.2 nm is observed for the same sample at TEM images (Fig. 4a) show that primary particles of 5 %
1200 °C. SDA are slab-like, and have a length of ca. 20 nm and a

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Fig. 4 TEM micrograph of aluminas calcined at different temperatures: a 5 % SDA calcined at 700 °C, b pure alumina calcined at 700 °C,
c 5 % SDA calcined at 1100 °C

width of ca. 15 nm. Based on XRD using the Scherrer (Fig. 4b) has similar slab-like primary particles but less
formula [38], the thickness of the slabs was calculated to be order in the stacking, which is consistent with the nitrogen
ca. 5 nm. A random three- dimensional stacking of these adsorption results since the former possesses a larger pore
primary particles is also observed. The pure alumina volume than the latter. Consequently, at higher

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temperatures (i.e. 1100 °C, Fig. 4c), the shape and size of of 5 wt% of silica delays the c- to a-Al2O3 phase transition
the 5 % SDA primary particle remains relatively small; no by 100 °C, consistent with the XRD results.
significant grain growth is observed due to sintering from
the c- to a-Al2O3 phase transition, which is consistent with 3.5 Solid state NMR measurements
the XRD results.
Solid state 27Al MAS NMR spectra for pure and 5 % silica
3.4 TGA and DSC doped alumina and corresponding deconvolutions are
shown in Fig. 6. Three different major Al environments are
Figure 5a shows the TG (thermogravimetric analysis) and observed: an octahedral Al(VI) environment at
DSC (differential scanning calorimetry) curves of the 5 % d *?15 ppm, a five-coordinated Al(V) site at
SDA sample. From the data it is clear that the weight of d *?40 ppm and a tetrahedral site at ?75 ppm [43–45].
5 % SDA decreases by increasing the temperature to Pure alumina calcined at 700 °C has 18 % of the Al in the
1400 °C. This weight loss is associated with the octahedral Al(IV) environment; after adding 5 % silica, the
endothermic effect around 100 °C due to the evaporation percent of octahedral Al remains the same (18 %, 700 °C),
of alcohol and physically adsorbed water. There are also while there is an increase in the Al(V) environment. The
29
three exothermic effects: first, between 800 and 1000 °C Si MAS NMR and 29Si–1H CPMAS NMR spectra for
due to crystallization of the c-Al2O3 phase; second between 5 % SDA is shown in Fig. 7a. There is a broad overlapping
1000 and 1300 °C due to h-Al2O3 or silica–alumina phase resonance between (-) 81 and (-) 89 ppm. This broad
formation and collapsing of the 3D stack structure of c- resonance cross-polarizes (CP) with protons, and represents
Al2O3 (as shown in Fig. 4c); and third after 1300 °C due to a phase in this material containing proton species (hydroxyl
the h/c phases to a-Al2O3 phase transition. In contrast, the groups). (-) 81 ppm is assigned to Si(4Al), and (-)
c- to a-Al2O3 phase transition starts at 1200 °C for pure 89 ppm for Si(3Al) structures [45, 46]. The lack of the
alumina (Fig. 5b). These results confirm that the addition SiO4 species (d *-110 ppm) shows that Si incorporates
into Al rich coordination environments. This indicates that
no separate Si domain exists in the structure. 5 % SDA
(a) (Fig. 7a) is shifted to a less negative d in comparison to
27 % silica (Fig. 7b), most likely due to increased Al in the
pore collapsing & γ-θ
Si coordination sphere. For 27 % SDA (Fig. 7b) more
phase transition peaks are observed due to different Si and Al coordination
phase structures (e.g. Si(3Al), Si(2Al), Si(1Al), etc.) [4].
transition
to α

4 Discussion

4.1 Silica–alumina structure

It is reported that alumina is a defect spinel structure, in

which vacancies are distributed in both octahedral and
(b) tetrahedral sites [46]. Silica content has been theoretically
calculated to be 13 %, if Si and Al fill all of the tetrahedral
phase
transition and octahedral sites [17, 47]. The results of this study show
to α
that ideal porosity and thermal stability of alumina are
achieved by adding 5 % silica.
It was shown from 27Al SSNMR data for 5 % SDA
pore collapsing & γ-θ
phase transition
(Fig. 6) that aluminum ions in tetrahedral sites are not
displaced from tetrahedral to octahedral sites by addition of
silicon ions, contrary to the conclusion of Horiuchi et al.
[17]; instead, Si enters the tetrahedral vacancies in the
defect spinel structure of alumina and forms a Si–Al spinel
phase since Al(IV) content is the same (18 %) in both pure
alumina and 5 % SDA.
The results of this study confirm those reported from
Fig. 5 Thermal analysis data for: a 5 % SDA, b pure alumina earlier papers [12, 15–17, 20, 21, 30–32, 48] that addition

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Fig. 6 The 1D 27Al MAS NMR

spectra for 5 and 27 % SDAs
and alumina calcined at 700 and
1200 °C for 2 h

Calcination
Sample ID Al (IV)% Al (V)% Al (VI)%
T °C / 2h
700 18 2 80
Pure alumina
1200 1 0 99
700 18 19 63
5% SDA
1200 22 2 76
700 14 29 57
27% SDA
1200 24 1 75
SDA: BYU silica doped alumina

Fig. 7 Direct 29Si MAS NMR

and 29Si–1H CPMAS spectra for
a 5 % SDA, b 27 % SDA
calcined at 700 °C for 2 h

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of a small amount of silica significantly enhances the in amorphous silica–alumina, Al(V) has been assigned to
thermal stability of the c-Al2O3 lattice structure up to very the interface between the alumina phase and a silica–alu-
high temperatures (1200 °C) without formation of a-Al2O3. mina phase [50]. This concept is consistent with an earlier
We suggest that Si doping may stabilize the oxygen lattice observation that addition of silica increases disordering of
and therewith retard the c to a phase transition (Fig. 1b). A alumina primary particles [51]. Moreover, it is also
similar conclusion has also been reported by Smith et al. reported that bridging Al atoms that stabilize stacking fault
[49] for the addition of lanthanum. defects in c-Al2O3 structure are Al(V) [49]. Another view
Thus, for the transformation of c- to a-Al2O3, more is that the interfacial silica–alumina phase disrupts the c-
energy is needed for oxygen atoms to undergo rotations to Al2O3 structure to form a new Si–Al spinel phase, con-
restructure the oxygen lattice from fcc (c-Al2O3) to hcp (a- sistent with data showing that alumina containing less than
Al2O3) and to suppress atomic diffusion of Al and O to the 28 % silica forms a Al–Si spinel structure [52]. However,
surface. It is known that the grain growth (a formation) and commercial 5 % silica doped alumina (Siral-5) has two
decrease in surface area are due to ionic diffusion [47]. distinct phases (SiO2 and Al2O3) [53].
Diffusion occurs in expanding neck regions and includes The postulate of a separate silica–alumina phase at the
dislocations and lattice defects where alpha nucleation interface of primary crystallites would suggest the possi-
occurs [14]. Alpha formation or grain growth formations bility of different pore size regimes, which is consistent
proceed at contacting points where defects and stresses with BET data of this study showing a bimodal pore size
exist [13, 17]. The NMR data in Fig. 5 confirm that pure distribution. The smaller pores in the 5 % SDA structure
alumina is in the hexagonal alpha phase at 1200 °C since are in the same range as for the pure alumina and are thus
4-coordinated and 5-coordinated Al essentially disappear, characteristic of those in the basic alumina structure in both
and the distribution (line width) of the Al(IV) is signifi- doped and pure samples. On the other hand, larger pores in
cantly reduced suggesting the formation of a-Al2O3, since 5 % SDA (i.e., 35–52 nm) can be assigned to the interfa-
only 6-coordinated Al exist in a-Al2O3 phase. However, for cial silica–alumina phase which apparently collapses at
5 % SDA calcined at 1200 °C, 4- and 6-coordinated Al are 1200 °C (note the absence of large pores in Table 1).
still present, confirming that the addition of silica to alu-
mina stabilizes spinel c-Al2O3 phase to 1200 °C, consistent 4.2 Comparison to other silica-doped alumina
with XRD and TGA-DSC results.
Evidence that the c to a transformations are minimized Table 2 shows the specific surface area, pore volume and
in the 5 % SDA structure compared to that of pure alumina pore diameter of lanthanum- and silica-doped aluminas
which is also shown in the TEM image (Fig. 4b) for this synthesized by different methods and of commercial doped
sample. The 5 % SDA samples have larger slab like pri- aluminas calcined at 700, 1100 and 1200 °C. After treat-
mary particles, more stacking and fewer neck regions than ment of 5 % SDA prepared by the method of this study at
pure alumina. This results in lower bulk density and less either 1100 or 1200 °C for 2 h, only the c phase is
contacting points between the alumina crystallites. In this observed; this was the case in only one previous study
study, the preparation involving a H2O/Al ratio of 5:1 using cryogel methods to prepare a 10 % silica/alumina.
involves relatively slow hydrolysis, formation of larger By contrast commercial and noncommercial lanthanum-
plates, and 3D stacking morphology, all of which result in and silica-doped aluminas synthesized by other methods
greater porosity [8]. This observation is consistent with the contain both c and a or h after treatment at 1100 and/or
nitrogen adsorption results, since 5 % SDA has a larger 1200 °C for 2 h. The surface and pore properties of the
pore volume than pure alumina (Table 1). 5 % SDA after treatment at 1100 °C for 2 h are remarkable
In addition to stabilizing the lattice structure of c-Al2O3, in comparison to the other silica-doped aluminas. The
Si addition may also affect the ordering and stability of surface area of 160 m2/g is the largest, the pore volume of
crystal agglomerates. From the NMR data (Fig. 6), the 0.99 cm3/g is 2nd largest, and the pore diameters of 22.5
increased Al(V) concentration for 5 % SiO2/Al2O3 treated and 52 nm are by far the largest. The bimodal pore size
at 700 °C relative to the undoped sample (0 % Al(V)) can distribution is also unique.
be attributed to the formation of an interfacial silica–alu- The 5 % SiO2/Al2O3 prepared by Horiuchi et al. [17]
mina phase in between primary crystallites in an agglom- using supercritical drying, is uniquely stable among those
erate. The 29Si SSNMR results also support this idea. prepared in previous studies. These workers reported a
Figure 6a show that the silica–alumina network originates highly thermally stable silica-doped alumina support that
in a structure consisting of Al–O–Si linkages and no sep- remains in the h phase after treatment at 1100 °C for 1 h
arate SiO2 phase is detected (no peak at d *-110 ppm) with the largest pore volume of 1.3 cm3/g compared to
suggesting that Si incorporates into alumina structure and 0.99 cm3/g for the 5 % SDA reported here, however the
forming silica–alumina phase in c-Al2O3 structure. Indeed,

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Table 2 Surface area, pore diameter, and mesopore volume for doped aluminas with different methods at different temperatures (°C)
Sample ID BET surface area Mesopore volume Pore diameter (nm) Alumina phase
(m2/g) (cm3/g)
700 1100 1200 700 1100 1200 700 1100 1200 1100 1200

5 % Si/Al2O3 (SDA)g,a 338 160 111 1.83 0.99 0.59 14.7 and 22.5 and 29.4 Gamma Gamma
35.0 52.0
5 % Si/Al2O3 (Siral-5)f,a 288 128 73 0.61 0.4 0.23 7.7 11.2 11.4 Gamma and Gamma and
alpha alpha
5 % Si/Al2O3 [17]b – 120 110 – 1.28 0.9 – 10.8 18.6 Theta Theta
5 % Si/Al2O35
3 – 200 150 – – – – 10.8 22.8 Delta Delta
10 % Si/Al2O3 [20]c – 100 47 – 0.2 0.1 – 3.5 3.5 Gamma Gamma
10 % Si/Al2O3 [15]a – – 150 – – 0.65 – – – – Alpha and
gamma
5 % Si/Al2O3 [16]d 187 68 – 0.57 0.35 – 7.4 15.0 – Alpha and theta –
3 % La/Al2O3 (BLDA)h 280 139 – 0.32 0.22 – 3.7 2.7 – Gamma –
e
3 % La/Al2O3 [26] 199 – – 0.50 – – 7.8 – – – –
3 % La/Al2O3 (Puralox- 174 140 – 0.50 0.5 – 11.4 16 – –
SCFa)f
Calcined for: a 2 h, b
1 h, c
5 h, d
4 h, e 6 h
f
Commercially available; results from this study (Puralox-SCFa: 3 % lanthanum doped alumina, and Siral5: 5 % silica doped alumina from
Sasol)
g
SDA: BYU silica-doped alumina
h
BLDA: BYU lanthanum-doped alumina

pore diameter of 10 nm for their support is much smaller SDA XRD shows peaks attributed to c and traces of h-
than the pore diameters of 5 % SDA of 22.5 and 52.0. Al2O3 at same temperatures (Fig. 8b). Thus the thermally
Table 3 shows the surface area and pore properties stable 5 % SDA is superior to other supports in term of
following very severe treatments at different temperatures maintaining a high surface area and a large porosity at
for 24 h for 5 % SDA and Siral-5 (5 % silica-doped alu- higher temperatures. Consequently, the increased thermal
mina from Sasol), the best commercial silica-doped sup- stability results in more control of the acid site properties of
port. The SDA reported here shows improvements of 46 % the SDA supports since it can be calcined at higher tem-
in surface area, 155 % in pore volume, and 94 % in pore perature to remove surface hydroxyl groups [54], which
diameter over Siral-5 after 24 h at 1100 °C. In addition, reduces interaction between active catalytic phase and
XRD data (Fig. 8a) shows that a-Al2O3 peaks are observed support and therefore offers better catalytic performance in
for Siral-5 calcine at 1100 °C for 24 h. In contrast, 5 % Fischer–Tropsch synthesis [55].

Table 3 BET results of 5 % SDA and Siral-5 calcine at different temperature for 24 h
Sample BET surface area (m2/g)a Mesopore volume (cm3/g)a Pore diameter (nm)b
ID
700 °C 900 °C 1100 °C 1200 °C 700 °C 900 °C 1100 °C 1200 °C 700 °C 900 °C 1100 °C 1200 °C

5% 349 270 131 61 1.06 1.11 0.84 0.24 14.7 and 19.8 and 22.5 and 15.4 and
SDAc 35.0 51.8 51.3 32.2
Siral-5- 262 203 90 28 0.61 0.56 0.33 0.13 8.8 10.5 12.4 18.6
Sasold
a
Determined by N2 adsorption at 77 K
b
Determined by an improved slit pore geometry (SPG) model for large pore sizes using the desorption branch
c
SDA: BYU silica doped alumina; Gamma and traces of theta alumina peaks are observed at 1100 and 1200 °C for 24 h
d
Siral-5: Commercially available 5 % silica doped alumina; alpha alumina peaks are observed at 1100 and 1200 °C for 24 h

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J Porous Mater (2016) 23:475–487 485

Fig. 8 XRD patterns of a Siral-5 calcined at different temperatures for 24 h, b 5 % SDA calcined at different temperatures for 24 h

5 Conclusions multi-program laboratory managed and operated by Sandia Corpo-

ration, a wholly owned subsidiary of Lockheed Martin Corporation,
for the U.S. Department of Energy’s National Nuclear Security
In summary, we have produced a thermally stable silica- Administration under contract DE-AC04-94AL85000. We also thank
doped alumina with a high surface area, a large pore vol- Dr. Jeff Farrer and the BYU microscopy lab for their assistance with
ume, and a large bimodal pore distribution via a facile, the TEM imaging.
one-pot, solvent deficient method. In this study, different
wt% of Si (0, 5, 15, 27) doped aluminas were synthesized
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