Catal Lett (2009) 130:318326 DOI 10.

1007/s10562-009-9934-x

Synthesis and Characterization of Hexamethylenediammonium Thiometallates as Precursors of MoS2 and WS2 Catalysts: In situ Activation During HDS of DBT
n ez R. Huirache-Acun a F. Paraguay-Delgado G. Alonso-Nu a-Alamilla A. Castillo-Mares J. A. Lumbreras R. Garc R. Romero R. Somanathan R. R. Chianelli

Received: 27 January 2009 / Accepted: 13 March 2009 / Published online: 28 March 2009 Springer Science+Business Media, LLC 2009

Abstract Hexamethylenediammonium thiometallate (HeDaT) of molybdenum and tungsten were synthesized using the aqueous solution method. This method improved signicantly the yield of the catalysts. The HeDaT precursors were in situ activated during the hydrodesulfurization (HDS) of dibenzothiophene (DBT) generating MoS2 and WS2 catalysts. To characterize the precursors Fourier Transform Infra Red (FTIR), Ultraviolet (UVVis) and Nuclear Magnetic Resonance (1H NMR) spectroscopy techniques were used to determine their chemical structures. In addition, thermal analysis (TGA-DTA) were performed to study the fragmentation and decomposition behavior of their molecular structures. Catalysts were studied by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) which showed the shapes of the particles and the characteristic fringes of the layered MoS2 and WS2

phases, respectively. Specic surface areas were determined by the BET method with values of 5 and 19 m2/g with type I and IV adsorptiondesorption nitrogen isotherms for both catalysts. The X-ray diffraction study showed poorly crystalline catalysts with weak (002) intensity for the MoS2 and a better-dened (002) reection for the WS2. Keywords Aqueous solution Hexamethylenediammonium thiometallates In situ-activated MoS2 WS2 catalysts

1 Introduction Thiometallates are widely used as biological systems [13] and also as catalyst precursors to produce transition metal

n ez (&) G. Alonso-Nu noma de Me xico, Universidad Nacional Auto a, Centro de Nanociencias y Nanotecnolog C.P. 22800, Ensenada, BC, Mexico e-mail: galonso@cnyn.unam.mx a R. Huirache-Acun CFATA-UNAM, Boulevard Juriquilla 3001, taro, Mexico C.P. 76230, Juriquilla Quere F. Paraguay-Delgado n en Materiales Avanzados S. C., Centro de Investigacio C.P. 31109, Chihuahua, Mexico F. Paraguay-Delgado National Institute for Nanotechnology, 11421 Saskatchewan Drive, Edmonton, AB T6G 2M9, Canada J. A. Lumbreras Universidad del Istmo Campus Tehuantepec, C.P. 70760, Sto. Domingo Tehuantepec, Oaxaca, Mexico

a-Alamilla A. Castillo-Mares R. Garc gico de Ciudad Madero, Instituto Tecnolo C.P. 89440, Cd. Madero, Tamps., Mexico R. Romero micas, UABC, C.P. 22390, Tijuana, Facultad de Ciencias Qu BC, Mexico R. Somanathan n del ITT, C.P. 22000, Centro de Graduados e Investigacio Tijuana, BC, Mexico R. R. Chianelli MRTI, University of Texas at El Paso, El Paso, TX, USA

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sulde catalysts [46]. Ammonium thiometallates (mainly thiomolybdates and thiotungstates) are well known precursors for Mo and W disulde catalysts used in hydrodesulfurization and hydrodenitrogenation processes [710]. One major achievement would be to reach an electronic structural understanding toward the nature of these chemical activities [11, 12]. In this regard, extensive theoretical work has recently been carried out on several MoS complexes [13], and transition metal sulde materials [11]. Active sulde catalysts are conventionally prepared by converting the respective oxides to suldes in a reductive atmosphere such as hydrogen sulde. Reductive sulding of the oxides is usually difcult and does not proceed in a regular manner [14]. Some alternative methods include the thermal decomposition of the corresponding salts [15] and low temperature precipitation from solutions [16]. Materials obtained by these routes have an amorphous or poorly crystallized structure; it is a function of the preparation temperature. On the other hand, the decomposition of tetraalkylammonium thiometallates at 400 C and after 2 h in a owing gas mixture of 10% H2S/H2 yield transition metal sulde catalysts [17]. Alonso et al. [18, 19] and Chianelli et al. [20] have recently reported that ammonium thiosalts as catalytic precursors can be decomposed in situ, during the hydrotreating reaction at high pressure and temperature conditions to produce MoS2 and WS2 catalysts with high activity and high surface area, as well. Some HeDaT such as [(Et)4 N]2MS4 where (M = Mo or W) were prepared by McDonald et al. [21], who synthesized the materials by stoichiometric reaction of ammonium thiomolybdate (ATM) and ammonium thiotungstate (ATT) with tetraalkylammonium hydroxide (R4NOH) or chloride (R4NCl) in methanol or acetonitrile solution. Pan et al. [22] and Liang et al. [23] also prepared alkylthiomolybdate and alkylthiotungstate sulde complexes such as [(Et)4N]2M3S9 (M = Mo, W) by heating (NH4)2MS4 (M = Mo, W) in dimethyl formamide at 358 K for Mo or 403 K for W under anaerobic conditions. Recently, Alonso et al. [24] have reported a simple aqueous solution method that signicantly improved the yield of tetraalkylammonium compounds compared to previous studies. This aqueous solution method involved a one-step rapid substitution of [NH4]? ions from ammonium thiomolybdate (ATM) and/or ammonium thiotungstate (ATT) with the respective ions of the desired salts. In this work, an aqueous solution method was used for the preparation of two new catalyst precursors. The two prepared diammonium thiometallates were namely hexamethylenediammonium thiomolybdate (NH3(CH2)6NH3 MoS4, HeDaTM) and hexamethylenediammonium thiotungstate (NH3(CH2)6NH3WS4, HeDaTT).

The chemical structures of the two HeDaTs were characterized by using spectroscopic techniques such as Fourier Transform Infra Red (FT-IR), Ultra Violet (UV) and Nuclear Magnetic Resonance (1H-NMR). Thermal analyses (TGA-DTA) were performed to study the fragmentation of their molecular structures and to determine their decomposition behavior. Upon proper decomposition, as shown by the thermogravimetric analysis, these thiometallates produced the transition metal suldes MoS2 and WS2. The X-ray diffraction of the catalysts in situ activated during the HDS of DBT showed poor crystalline structures of Mo and W suldes.

2 Experimental Procedure 2.1 Synthesis of Hexamethylenediammonium Thiometallates Precursors Hexamethylenediamine (NH2(CH2)6NH2, HeDa), (Aldrich), 99% pure was used. The ATM and ATT compounds were prepared following methods reported elsewhere [25, 26]. 2.2 Synthesis of NH3(CH2)6NH3MoS4 (HeDaTM) Ammonium thiomolybdate (NH4)2MoS4 (2.0 g, 7.7 mmol) was dissolved in water (30 mL). This solution was added to hexamethylenediamine NH2CH2)6NH2 (0.89 g, 7.7 mmol) previously dissolved in water (10 mL) at room temperature; immediately after that, a precipitate of red HeDaTM crystals was formed. 2.3 Synthesis of NH3(CH2)6NH3WS4 (HeDaTT) Ammonium thiotungstate (NH4)2WS4 (2.0 g, 5.7 mmol) was dissolved in water (30 mL). This solution was added to hexamethylenediamine NH2(CH2)6NH2 (0.66 g, 5.7 mmol) previously dissolved in water (10 mL) at room temperature; immediately after that, a yellow HeDaTT precipitate was formed. Crystals were washed and dried a room temperature. 2.4 Characterization of Precursors The FT-IR spectra were obtained using a Nicolet MagnaIR 750 Fourier Transform spectrophotometer. Electronic (UVVis) spectra were recorded on a Perkin-Elmer Lambda-10 UV spectrometer. The thermogravimetric analysis were performed on a TA Instrument SDT 2960 DTA-TGA. The 1H-NMR spectra were recorded in DMSO-d6 solutions using a Gemini 200 Varian spectrometer, and were referenced to SiMe4 (1H).

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NH 2(CH 3)6NH 2 (HeDa)

2.5 Synthesis of MoS2 and WS2 Catalysts The MoS2 and WS2 catalysts were obtained by in situ decomposition during the HDS of DBT. The reaction was carried out in a Parr model 4522 high-pressure batch reactor. The proper amount of HeDaT precursors to yield 0.5 g of MoS2 and WS2 catalysts was placed in the reactor with the reactant mixture (3.3 g DBT in 150 ml of decaline; [DBT]0 = 0.119 mol/L). The reactor was pressurized to 3.1 MPa with hydrogen and heated to 350 C at a rate of 10 C/min. Reaction run time averaged was 5 h. The catalysts prepared in situ were separated from the reaction mixture by ltration, washed with isopropanol to remove hydrocarbons and dried at room temperature. 2.6 Characterization of Catalysts Catalysts were characterized by using a scanning electron microscope (JEOL JSM5800-LV) coupled with an electron dispersive X-ray (EDX) to perform morphological and elemental analysis. Specic BET surface area and BJH method for pore size distribution were determined with a Quantachrome AUTOSORB-1 model by nitrogen adsorption. Samples were rst subjected to an Argon ow before degassing under vacuum at 200 C for 2 h. The X-ray diffraction studies were carried out in a Phillips X-Pert MPD diffractometer, equipped with a curved graphite ) monochromator using Cu Ka radiation (k = 1.54056 A operating at 43 kV and 30 mA. Transmission electron micrographs were obtained in a Philips CM-200 transmission electron microscope operated at 200 kV with a LaB6 lament as a source of electrons.

HeDaTM
Transmitance (a. u.)

HeDaATT

464

445
4000 3500 3000 2500 2000 1500 1000 500

cm -1
Fig. 1 FT-IR spectra for NH2(CH2)6NH2, HeDaTM and HeDaTT

3.2 Fourier Transform Infra Red The FT-IR spectra for both molybdenum and tungsten thiosalts HeDaTM and HeDaTT, are shown in Fig. 1, using HeDa as a reference. The spectra of HeDaTM and HeDaTT are very similar, showing bands corresponding to the MoS and WS stretching mode at 464 and 445 cm-1, respectively. This difference in wave numbers could be explained according to MoS bond strength which is relatively high compared to the one of WS [27]. On the other hand, from 3,200 to 2,750 cm-1 the conversion of the amine groups (NH2) of the HeDa to ammonium groups (NH3) for HeDaTM and HeDaTT, is very clear, as shown in reaction (1). 3.3 UVVis The electronic spectra as shown in Fig. 2: (a) HeDaTM and (b) HeDaTT. Both materials used water as solvent. Three main transition bands corresponding to tetrahedral groups (MS)2 4 (M = Mo or W) were detected with a shift to lower wavelengths for W complexes compared to the Mo ones. The Mo and W complexes exhibited absorption bands in both the visible and the UV spectral regions. In the case of HeDaTM, the wavelength maxima appeared at 470, 330 and 250 nm, while for HeDaTT the bands appeared at lower positions: 400, 280 and 210 nm. This displacement of the maximum wave lengths demostrates that the molecular structure of HeDaTM was excited at a higher wave length, that is, at low energy it was possible to carry out the electronic transitions of p to p* and r to r* which is the case of the HeDaTT structure. The FT-IR and UVVis results are in agreement with previously reported results by: McDonald et al. [21] for other similar tetraethylammonium thiometallates, Pan et al. [22] for molybdenum and tungsten sulde-complexes and, ller et al. [28, 29] for tetrathio-bimetallate compounds. Mu

3 Results and Discussion 3.1 Precursors Characterization In this work, a high-yield method for the easy preparation of HeDaTM and HeDaTT is described. This preparation involves the reaction in aqueous solution of (NH4)2MoS4 (ATM) and (NH4)2WS4 (ATT) with stoichiometric amounts of hexamethylenediamine. The reaction involves an acidbase process between the amine groups of the diamine, and the ammonium ions in ATM or ATT producing ammonia and the corresponding HeDaTs, while water acts as an electrolyte for the reaction. For the hexamethylenediammonium thiometallates formation, we propose that the process occurs according to reaction (1): NH4 2 MS4 NH2 CH2 6 NH2 ! NH3 CH2 6 NH3 MS4 2NH3 where M = Mo or W. 1

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6 5

(a)
250 330

HeDaTM

4 3 2 1 0 200 300 400 500 600 700

470

which are beside to the N atom. The next two signals at 1.55 and 1.30 ppm are due to the 8 protons and may be attributed to the continuing CH2 groups, respectively as their positions become farther from the N atom. Figure 3b shows the NMR spectrum for HeDaTT which consists of the four signals coming from four different types of protons. The rst signal corresponds to a broad singlet at 7.30 ppm due to the 6 protons in the NH3 groups. The second signal is a triplet at 2.50 ppm (j = 8 MHz). This triplet should be the 4 protons corresponding to the CH2 groups which are beside to the N atom. The next two signals at 1.24 and 0.98 ppm are due to the 8 protons and may be attributed to the continuing CH2 groups, respectively as their positions become farther from the N atom. 3.5 Thermal Analysis

Absorbance (a. u)

(nm)
6 5

(b)
210 280

HeDaTT

4 3 2 1 0 200 300 400 500 600 700

400

(nm)
Fig. 2 UVVis Spectra of a HeDaTM and b HeDaTT

For the case of electronic spectra, it is important to show the three characteristic transitions corresponding to the (MS4)-2 group. This is in agreement with reported data [24] on similar compounds. 3.4 Nuclear Magnetic Resonance H-NMR spectroscopy should show the four types of protons that are present in the chemical structures. The results of this study precisely reect the existence of the four groups of protons from their respective HeDaTM and HeDaTT salts. Figure 3a shows the NMR spectrum for HeDaTM which consists of four signals due to the four different types of protons. The rst signal corresponds to a broad singlet at 7.64 ppm due to 6 protons in the NH3 groups. The second signal is a triplet at 2.80 ppm (j = 7.4 MHz). This triplet should be the 4 protons corresponding to the CH2 groups
1

The resulting TGA-DTA curves for HeDaTM and HeDaTT were compared to previous studies made recently by Alonso et al. [18, 19], Brito et al. [30] and Poisot et al. [31] to obtain MoS2 and WS2 catalyst materials. In this work, it is proposed the fragmentation of the chemical structures according with the experimental results by thermogravimetric analysis. The fragmentation occurs mainly between the interaction of the sulfurnitrogen and nitrogencarbon bonds. The thermal decomposition of the various tetraalkylammonium thiometallates in nitrogen follows a different pattern to previously reported works for ATM and ATT [19, 30]. In fact, the most noticeable difference is the absence of the exothermic peak corresponding to the trisuldedisulde transition. In the thermal decomposition of ATM and/or ATT, NH3 and H2S were rst removed at 150218 C to form MoS3. The second decomposition step is notably exothermic and is characterized by the simultaneous reduction of Mo(VI) to Mo(IV) while, S2- is oxydized to S0 at 403 C. However, it is important to indicate that the nal composition of MoS2 depends on the type of atmosphere used during the thermal decomposition of the thiosalts. Indeed, Brito et al. [30] showed that in hydrogen atmosphere the decomposition of ATM yields MoS2-x, whereas in air atmosphere MoS2O was observed. In this work, according to thermogravimetric data reported in Table 1 and Fig. 4, the thermal decomposition of HeDaTM under nitrogen atmosphere (Fig. 4a), occured in three endothermic steps. The rst step, suggests that one molecule of C6H14 (hexane) was removed at 200 C while, in the second and third steps, two molecules of sulfur-amine (SNH2) were removed at 400, and at 800 C, respectively. Accordingly, the nal product of the thermal decomposition corresponds to nearly stoichiometric MoS2.The weight losses as indicated in Table 1 and the Fig. 4a, were consistent with the decomposition reactions (24):

Absorbance (a. u.)

123

322 Fig. 3 200 MHz 1H NMR spectra of a HeDaTM and b HeDaTT

n ez et al. G. Alonso-Nu

Table 1 DTATGA results for HeDaTM and HeDaTT precursors in nitrogen atmosphere

HeDaTM T1 (C) Dwexp, %wt loss Dwtheor, %wt loss Assuming loss of T2 (C) Dwexp, %wt loss Dwtheor, %wt loss Assuming loss of T3 (C) Dwexp, %wt loss Dwtheor, %wt loss Assuming loss of RDwexp, %wt loss (Final product)exp, %wt remaining (Final product)theor, %wt remaining assuming nal product MS2 200 26.0 25.0 C6H14 (2) 400 14.5 14.0 SNH2 (3) 800 14.5 14.0 SNH2 (4) 55.0 45.0 47.0

HeDaTT 250 24.5 23.6 C6H15N (3) 560 6.5 7.4 S (6) 800 13.0 11.4 SNH3 (7) 44.0 56.0 57.6

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323

(a)
100 90

NH3(CH2)6NH3MoS4 (HeDaTM)

C6H14
26% exp.

80 70 60
(NH2) 2MoS4

SNH 2
14.5% exp.

SNH 2
14.5% exp.

MoS 3NH 2
50 40 0 100 200 300 400 500

MoS 2
600 700 800 900

Temperature (C)
Deriv. Temperature Difference (`C/mg/`C)

(b)
100 90

NH3 (CH 2)6NH3WS 4 (HeDaTT)

24.5% exp.

Deriv. Temperature Difference (`C/mg/`C)

% Loss Weight

Fig. 5 XRD patterns for in situ activated MoS2 and WS2 catalysts

C6H15N
S

3.6 Catalysts Characterization The in situ activation of hexamethylenediammonium thiometallates during the HDS of DBT was used to generate MoS2 and WS2 non-promoted catalysts. This method leads to catalytic materials with low specic surface areas (SSA) and type I and IV adsorptiondesorption nitrogen isotherms, poorly crystalline structures and moderate catalytic activity in the HDS of DBT. 3.7 X-ray Diffraction Figure 5 shows the diffractograms of Mo and W suldes prepared in situ from HeDaTM and HeDaTT, respectively during the HDS of DBT reaction. It is observed poorly crystalline structures with a weak (002) signal at 2H & 14 for MoS2. On the other hand, the diffractogram of WS2 is very sharp [23] (JCPDS-ICDD 37-1492, 8-237). This means that WS2 has more stacking planes in this direction than MoS2. 3.8 Specic Surface Area Specic surface areas for the in situ activated samples were measured after the HDS reaction. Table 2 shows the specic surface area and total pore volume of the produced MoS2 and WS2 catalysts. The different composition of the catalysts inuenced the nal specic areas generated. As mentioned before, the catalysts were synthesized using hexamethylenediamine and thiometallates. The organic agent was used to increase the specic area of the catalyst and the second reagent to provide the active phase. The adsorptiondesorption curve of the WS2 corresponded to

% Loss Weight

80

WS4NH3
70 60 50 40 0 100 200 300 400 500

6.5% exp.

WS4NH3
13% exp.

SNH3
0

WS2

600

700

800

900

Temperature (C)

Fig. 4 DTA-TGA plot of a HeDaTM and b HeDaTT decomposition. Temperature in C and weight loss in %

NH3 CH2 6 NH3 MoS4 ! C6 H14 NH2 2 MoS4 NH2 2 MoS4 ! SNH2 MoS3 NH2 MoS3 NH2 ! SNH2 MoS2

2 3 4

The thermal decomposition of HeDaTT (Fig. 4b) was similar to the HeDaTM, it also occurred in three endothermic steps. In the rst step the removal of triethylamine (C6H15N) at 250 C took place, in a second step, it is proposed the removal of sulfur at approximately 560 C, and nally in the third step, the removal of SNH3 at 800 C. As shown in Table 1 and Fig. 4b, weight losses were consistent with the decomposition reactions (57): NH3 CH2 6 NH3 WS4 ! C6 H15 N WS4 NH3 WS4 NH3 ! S WS3 NH3 WS3 NH3 ! SNH3 WS2 5 6 7

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Table 2 Specic surface area, pore diameter, S/M atomic reaction rate constant (k) and selectivity (HYD/DDS) for MoS2 and WS2 HDS catalysts Catalysts MoS2 WS2 Specic surface area (m2/g) 5.5 19 ) Pore diameter (A 23 35 S/M atomic ratio 1.74 1.0 k (mol/g s) 4.7 9 10-7 3.7 9 10
-7

HYD/DDS 2.02 2.87

30

MoS 2
25

WS 2

Volume (cc / g)

20

15

10

0 0.0 0.2 0.4 0.6 0.8 1.0

Relative Pressure P/Po

Fig. 6 Adsorptiondesorption isotherms for MoS2 and WS2 catalysts

the type IV isotherm (Fig. 6) with a desorption curve characteristic to the mesoporous materials with an average . For MoS2 catalyst, a poorly pore diameter of 35 A developed porous system was observed with a lower specic surface area (5.5 m2/g), average pore diameter close and a type I adsorption isotherm (Fig. 6) characto 23 A teristic of the microporous material. However, the WS2 catalyst presented an intermediate situation with a small hysteresis loop. Its specic surface area (19 m2/g) was higher than that observed for the MoS2 catalysts, we suggest that the change in the surface area is due to the pore form produced during de decomposition of each precursor as it was discussed previously according to the type of isotherms. 3.9 Scanning Electron Microscopy and EDS Images of the catalysts after HDS reaction are reported in Fig. 7a and b. Catalysts show a disordered morphology with particles like rods with rough and smooth surface, as reported by Albiter et al. [32] and Paraguay-Delgado et al. [33]. In addition, different particle sizes were observed. Figure 7 shows particles ranging between 90 and 160 lm in length and 9 and 10 lm wide for MoS2 and WS2 catalysts. On the other hand, Table 2 shows the S/M atomic ratio measured for catalysts by using EDS (where M = Mo or W). For MoS2 catalyst it is observed a S/M atomic ratio

Fig. 7 Scanning electron microscopy images of catalysts after HDS reaction: a MoS2 and b WS2

very close to the theoretical value (S/M = 2) since this material presented a S/M = 1.74. In the case of WS2 a lower value for S/M atomic ratio was obtained (S/M = 1). These values should be due to the homogeneity of the materials because the analysis by EDS is from a microscopic area, not presenting good statistics. However, X-ray diffraction clearly reveals the MoS2 and WS2 phases. On the other hand, in this case it is important to mention that the amount of carbon was not measured by this analysis. 3.10 Transmission Electron Microscopy TEM eld micrographs for both synthesized catalysts are reported in Fig. 8. These images show characteristic

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HDS activity of catalysts. The HDS of DBT yielded biphenyl (BP) through the so-called direct desulfurization pathway (DDS) and cyclohexylbenzene (CHB) and tetrahydrodibenzothiophene (THDBT) through the hydrogenation pathway (HYD). Since these two pathways are parallel the selectivity (HYD/DDS) can be aproximated calculated by: HYD=DDS CHB THDBT=BP 8

Fig. 8 TEM micrographs of sulde catalysts before HDS reaction: a MoS2 and b WS2

Catalysts showed a moderate catalytic activity once the temperature of reaction was reached. The obtained values of catalytic activity are very close to those reported by Alonso et al. [5, 6, 19], for MoS2 and WS2 unsupported catalysts prepared under very similar conditions. The MoS2 catalyst exhibited a better performance in the HDS of DBT (k = 4.7 9 10-7 mol/g s), than the WS2 catalyst (k = 3.7 9 10-7 mol/g s). The behavior of the latter catalyst could be related to the lower S/M atomic ratio which is different to the theoretical expected value of 2. This can be due to the high hydrogen pressure during the HDS of DBT reaction which favors sulfur elimination through H2S, since the MoS bond strength is relatively high compared to the WS one [29]. In both cases the catalytic activity could be related to the structure of the catalysts which, in presence of hydrogen, favors the sulfur elimination and the subsequent sulfur vacancies formation. The MoS2 and WS2 catalysts synthesized in this work showed a marked tendency for the HYD pathway In relation to selectivity, it is very clear the preference of hydrogenation as in the case of WS2 (HYD/DDS = 2.8) versus MoS2 (HYD/DDS = 2.0), according with the Rimedge model [35]. In this case, WS2 presented more sites located at the exterior of the stacked layer which were more active toward hydrogenation than the MoS2 catalyst.

fringes of the layered MoS2 and WS2 materials. Fig. 8a shows a micrograph of a MoS2 sample. Even if fringes appear relatively stacked, their organization is largely disordered. Figure 8b image is from the WS2 material. It is better stacked, and its organization has slightly more order. The alkyl group of the precursor produced the appearance of this higher proportion of destacked layers, which is typical of a poorly crystalline (or rag) Mo (W)S2 structure, according to Chianelli et al. [34]. These differences in the stacking order reveal better X-ray diffraction; the (002) direction for WS2 has more intensity. 3.11 Catalytic Activity and Selectivity Results of DBT conversion as a function of time for HeDaTM and HeDaTT in situ activated catalysts are reported in Table 2. The concentration versus reaction time data were tted to a reaction rate expression of zero order and the reaction rate constants were used to compare the

4 Conclusions The HeDaTs, as new catalyst precursors to form MoS2 or WS2, can be synthesized by means of a simple reaction of ammonium thiometallates (ATM and/or ATT) with hexamethylenediamine in aqueous solution. This reaction involves an acidbase process between the ammonium [NH4]? from ATM and/or ATT and the amine groups in the diamine NH2(CH2)6NH2, producing HeDaT and/or thiotungstate, respectively. Evidence of the molecular structure of these compounds were obtained by FTIR, UVVis and 1H-NMR spectroscopic analyses and by DTATGA thermal decomposition. The proposed reactions from NH3(CH2)6NH3MoS4 and NH3(CH2)6NH3WS4 to generate MoS2 and WS2 catalysts materials respectively, are in agreement with the experimental TGA-DTA results at 800 C. The in situ activation of HeDaT during the

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n ez et al. G. Alonso-Nu 12. Liang KS, Hughes GJ, Chianelli RR (1984) J Vac Sci Technol A 2:991 13. Bernholc J, Stiefel EI (1985) Inorg Chem 24:1323 n MD, Vasudevan PT (1997) J Catal 14. Wilkinson K, Mercha 171:325 15. Muller A (1977) Coord Chem 432:127 16. Chianelli RR, Dines MB (1978) Inorg Chem 17:2758 17. Iwata Y, Sato K, Yoneda T, Miki Y, Sugimoto Y, Nishijima A (1998) Catal Today 45:353 18. Alonso G, Del Valle M, Cruz J, Petranovskii V, Licea-Claverie A, Fuentes S (1998) Catal Lett 52:55 19. Alonso G, Del Valle M, Cruz J, Petranovskii V, Licea-Claverie A, Fuentes S (1998) Catal Today 43:117 20. Chianelli RR, Berhault G (1999) Catal Today 53:357 21. McDonald WJW, Delbert Friesen G, Rosehein LD, Newton WE (1983) Inorg Chem Acta 72:205 22. Pan WH, Leonowics ME, Stiefel EI (1983) Inorg Chem 22:672 23. Liang KS, Chianelli RR, Chien FZ, Moss SC (1986) J Non-cryst Solids 79:251 24. Alonso G, Aguirre G, Rivero IA, Fuentes S (1998) Inorg Chem Acta 274:108 25. Kruss G (1884) Ann Chem 225:1 26. Corleis E (1886) Ann Chem 232:244 27. Pecoraro TA, Chianelli RR (1981) J Catal 67:430 ller A, Diemann E, Heinsen H-H (1971) Chem Ber 104:975 28. Mu ller A, Hellmann W, Schneider J, Schimanski U, Demmer U, 29. Mu Trautwein A, Bender U (1982) Inorg Chim Acta 65:41 30. Brito JL, Ilija M, Hernandez P (1995) Thermochim Acta 256:325 31. Poisot M, Bensch W, Fuentes S, Alonso G (2006) Thermochim Acta 444:35 n a R, Rico JL, Alonso-Nu ez G 32. Albiter MA, Huirache-Acun (2006) Nanotechnology 17(14):34733481 a R, Verde Y 33. Paraguay-Delgado F, Albiter MA, Huirache-Acun (2007) J Nanosci Nanotechnol 7(10):36773683 34. Chianelli RR, Prestidge EB, Pecoraro TA, Deneufville JP (1979) Science 203:1105 35. Daage M, Chianelli RR (1994) J Catal 149:414

hydrodesulfurization (HDS) of dibenzothiophene (DBT) produced MoS2 and WS2 catalysts with low SSA and type I and IV adsorptiondesorption nitrogen isotherms, poorly crystalline structures and moderate catalytic activity in the HDS of DBT.
Acknowledgments The authors appreciate the valuable technical nez, D. Lardizabal, C. Ornelas, assistance of F. Ruiz, W. Antu J. Saens, E. Flores and E. Torres.

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