Catalytic Oxidative / Extractive Desulfurization of Model Oil using Transition Metal Substituted Phosphomolybdates-Based Ionic Liquids

Polyoxometalates based ionic liquids (POM-ILs) exhibit a high catalytic activity in oxidative desulfurization. In this paper, four new POM-IL hybrids based on transition metal mono-substituted Keggin-type phosphomolybdates, [Bmim]5[PMo11M(H2O)O39] (Bmim = 1-butyl 3-methyl imidazolium; M = Co2+, Ni2+, Zn2+, and Mn2+), have been synthesized and used as catalysts for the oxidation/extractive desulfurization of model oil, in which ILs are used as the extraction solvent and H2O2 as an oxidant under very mild conditions. The factors that affected the desulfurization efficiency were studied and the optimal reaction conditions were obtained. The results showed that the [Bmim]5[PMo11Co(H2O)O39] catalyst demonstrated the best catalytic activity, with sulfur-removal of 99.8%, 85%, and 63% for dibenzothiophene (DBT), 4,6-dimethyldibenzothiophene (4,6-DMDBT), and benzothiophene (BT), respectively, in the case of extraction combining with a oxidative desulfurization system under optimal reaction conditions (5 mL model oil (S content 500 ppm), n(catalyst) = 4 μmol, n(H2O2)/n(Substrate) = 5, T = 50 ◦C for 60 min with [Omim]BF4 (1 mL) as the extractant). The catalyst can be recycled at least 8 times, and still has stability and high catalytic activity for consecutive desulfurization. Probable reaction mechanisms have been proposed for catalytic oxidative/extractive desulfurization.


Introduction
Problems of environmental pollution caused by exhaust emissions are receiving more and more attention worldwide with the development of society.Sulfur-containing compounds can be converted to sulfur oxides during the combustion process, causing serious harm to the environment.Many countries have adopted more stringent environmental regulations to restrict the sulfur level of fuels, limiting the sulfur level to less than 10 ppm [1,2].Accordingly, deep desulfurization of fuels has become a crucial subject in environmental catalysis study.Conventionally, the hydrodesulfurization process (HDS) has been applied to remove aliphatic and alicyclic sulfur-containing compounds from fuels in a refinery [3,4].However, the HDS process is less efficient for polyaromatic sulfur-containing compounds, such as dibenzothiophene (DBT) and its derivatives [5,6].Additionally, the HDS process is carried out under severe operation conditions.Therefore, developing more efficient desulfurization processes is paramount.Some alternative or supplementary processes have been studied, such as extractive desulfurization (EDS) [7,8], biodesulfurization [9], oxidative desulfurization (ODS) [10][11][12][13][14], adsorptive desulfurization [15], ultrasound desulfurization [16], and others [17][18][19].Among all these processes, ODS has been highlighted with special interest as one of the most promising processes, because it can proceed under mild reaction conditions, and oxidized products can be easily removed by extraction with organic extractants, owing to oxidized compounds being more polar than hydrocarbon molecules [20][21][22][23][24].Although conventional organic extractants, including acetonitrile, methanol, dimethylsulfoxide (DMSO), dimethylformamide (DMF), sulfolane, and dichloromethane, reveal good extraction, their flammable and toxic properties limit their development and application in industries.
Ionic liquids (ILs), as a class of green solvents, have numerous advantages over conventional organic solvents [25,26].In 2001, Wasserscheid et al. first reported desulfurization of diesel fuel by extraction with ionic liquids [27].The results demonstrated that ILs have the potential to play an important role in achieving clean fuel oil.Subsequently, significant literature has become available about desulfurization systems by extraction with various ILs, such as imidazolium-based ionic liquids [28][29][30][31], pyridiniuim-based ionic liquids [32], Lewis and Brösted acidic ionic liquids, and redox ionic liquids [7,33].However, sulfur removal using only ILs as the extractant is insufficient and hardly meets stringent environmental regulations.
Thus, researchers turned towards the addition of catalysts, combining peroxides with the ILs to achieve enhancement in efficiency.H 2 O 2 is often chosen as an oxidant in oxidative desulfurization, because it only produces water as a byproduct and is environmentally benign.Polyoxometalates (POMs) have received increasing attention as oxidative catalysts, due to their characteristic structures and various functionalities [34][35][36][37].In particular, Keggin type POMs have received enormous interest as catalysts, due to their good stability, adjustable composition at the atomic level, and unique acidic and redox properties [38][39][40].In recent years, Keggin type and transition metal substituted POMs-IL phase-separation catalysts have emerged as one of the most promising catalysts in the ODS process [36,[41][42][43][44].However, little work has been reported on the study of transition metal substituted phosphomolybdates for oxidative desulfurization.Recently, our group reported catalytic oxidation desulfurization using cesium salts of the transition metal mono-substituted phosphomolybdates as heterogeneous catalysts, with H 2 O 2 as the oxidant and acetonitrile as the extractant.The results showed that the transition metal mono-substituted phosphomolybdates exhibited higher catalytic activity than their parent (Cs 3 PMo 12 O 40 ), and Cs 5 [PCo(H 2 O)Mo 11 O 39 ] was found to be the best catalyst, with the removal of nearly all DBT at optimal reaction conditions [45].For more effective catalysts of desulfurization under very mild conditions, herein four new POM-IL hybrid materials, [Bmim] 5 [PMo 11 M(H 2 O)O 39 ] (M = Co 2+ , Ni 2+ , Zn 2+ , and Mn 2+ ), have been used as catalysts for the extractive and catalytic oxidation desulfurization (ECODS) of model oil, with ILs used as an extraction solvent and H 2 O 2 as an oxidant.[46].The bands observed between 3200 and 2820 cm −1 , and between 1660 and 1350 cm −1 , are attributed to the IL cation (alkyl and imidazole ring C-H stretching).When the transition metal was introduced into the framework, the P-O band stretching at 1062 cm  O 39 ] (M = Co 2+ , Ni 2+ , Zn 2+ , and Mn 2+ ), respectively [46].Mo-O d band stretching at 959 cm −1 shifted to 941, 943, 939, and 937 cm −1 for those of [Bmim]    The thermal gravity-derivative thermogravimetric (TG-DTG) curves of four POM-IL hybrid materials (see Figure S1) are very similar.Their thermal decomposition process is approximately   The thermal gravity-derivative thermogravimetric (TG-DTG) curves of four POM-IL hybrid materials (see Figure S1) are very similar.Their thermal decomposition process is approximately The thermal gravity-derivative thermogravimetric (TG-DTG) curves of four POM-IL hybrid materials (see Figure S1) are very similar.Their thermal decomposition process is approximately divided into three steps.A first weight loss of 0.8% occurs before 150 • C and is in accord with the loss of one coordinated water molecule (calcd.0.73%).The second weight loss is 28.0-29.0%,occurring from 310 to 500 • C, and is assigned to the loss of all five Bmim molecules (calcd.28.5%).The last weight loss occurs after about 500 • C, and is attributed to the framework decomposition of polyanions.

Characterization of the Catalysts
The phosphorus-31 nuclear magnetic resonance ( 31 P NMR) spectra of the parent compound   [48].These results further confirmed the successful preparation of the substituted Keggin-type phosphomolybdates associated to 1-butyl 3-methyl imidazolium.

Extractive and Catalytic Oxidation Desulfurization (ECODS) of Model Sulfur Compounds
The studies of ECODS were performed using a model oil (500 ppm DBT in n-octane) with 30% H 2 O 2 as an oxidant and the traditional IL (1 mL) as the extraction solvent, in the presence of POM-ILs as catalysts.Model oil was immiscible with the traditional ILs, while the catalysts could dissolve in ILs and hardly dissolved in the model oil.Table 1 shows the results obtained for the desulfurization of DBT in different desulfurization systems.The sulfur removal of S-containing compounds with the ionic liquids is affected by the structure and size of the anion and cation of the ionic liquid [28,29].It can be seen from Table 1 that the ability of [Omim]BF 4 (31.5%) to remove DBT was better than that of [Omim]PF 6 (28.3%).The same trends were found in the other two systems.It is obvious that the system of extraction combining with catalytic oxidation is much more effective than the pure extraction and the extraction combining with chemical oxidation when the different desulfurization systems were in the same IL extraction.In the case of the extraction combining with the oxidative desulfurization system in [Omim]BF 4 , the removal of DBT reached 99.8%, higher than that of pure extraction (31.5%) and extraction combining with chemical oxidation (35.6%).Therefore, the catalyst played a very significant role in the desulfurization system.The catalytic activities of different transition metal substituted-phosphomolybdates were evaluated for oxidation desulfurization of sulfides.Plots of the conversion (%) and ln(C t /C 0 ) against the reaction time are constructed in Figure 3, where C 0 and C t correspond to the DBT concentration at the beginning and at time t, respectively.It can be seen from Figure 3 that the four kinds of transition metal substituted-phosphomolybdates as catalysts exhibited high catalytic efficiency in the ECODS of model oil, and the catalytic activity was found in the  39 , respectively.The catalytic system of the cobalt substituted-phosphomolybdate as the catalyst exhibits the highest catalytic efficiency for oxidation desulfurization of sulfide.Thus, the cobalt substituted-phosphomolybdate catalyst was selected to explore the various parameters, such as catalyst quantity, oxidant quantity, the reaction temperature, and reaction time.[Bmim]5PMo11Ni(H2O)O39, and [Bmim]5PMo11Mn(H2O)O39, respectively.The catalytic system of the cobalt substitutedphosphomolybdate as the catalyst exhibits the highest catalytic efficiency for oxidation desulfurization of sulfide.Thus, the cobalt substituted-phosphomolybdate catalyst was selected to explore the various parameters, such as catalyst quantity, oxidant quantity, the reaction temperature, and reaction time.

Influence of the Amount of Catalyst on Desulfurization
Different amounts of catalyst were added in the ECODS process by changing the molar ratio of DBT and the catalyst (Figure 4).It can be observed that as the molar ratio of DBT and the catalyst was changed from 100 to 20, the removal of DBT increased from 35.6% to 99.8%.With the increase in the amount of catalyst, more active species were produced, and therefore the conversion increased.When the molar ratio reached 20, the sulfur removal remained unchanged.

Influence of the Amount of Catalyst on Desulfurization
Different amounts of catalyst were added in the ECODS process by changing the molar ratio of DBT and the catalyst (Figure 4).It can be observed that as the molar ratio of DBT and the catalyst was changed from 100 to 20, the removal of DBT increased from 35.6% to 99.8%.With the increase in the amount of catalyst, more active species were produced, and therefore the conversion increased.When the molar ratio reached 20, the sulfur removal remained unchanged.[Bmim]5PMo11Ni(H2O)O39, and [Bmim]5PMo11Mn(H2O)O39, respectively.The catalytic system of the cobalt substitutedphosphomolybdate as the catalyst exhibits the highest catalytic efficiency for oxidation desulfurization of sulfide.Thus, the cobalt substituted-phosphomolybdate catalyst was selected to explore the various parameters, such as catalyst quantity, oxidant quantity, the reaction temperature, and reaction time.

Influence of the Amount of Catalyst on Desulfurization
Different amounts of catalyst were added in the ECODS process by changing the molar ratio of DBT and the catalyst (Figure 4).It can be observed that as the molar ratio of DBT and the catalyst was changed from 100 to 20, the removal of DBT increased from 35.6% to 99.8%.With the increase in the amount of catalyst, more active species were produced, and therefore the conversion increased.When the molar ratio reached 20, the sulfur removal remained unchanged.In the catalytic oxidative system, the amount of H 2 O 2 was one of the main factors.As shown in Figure 5, when the O/S molar ratio increased from 2:1 to 5:1, the removal of DBT from the model oil increased from 53.4% to 99.8%.However, with the molar ratio up to 8:1, the sulfur removal fell to 87.2%, because an excess amount of H 2 O 2 could be decomposed by the catalyst into water, which has a negative effect on the desulfurization systems.Therefore, we chose H 2 O 2 /DBT = 5:1 as the optimal ratio in the present research.

Influence of the H2O2/DBT Molar Ratio on Desulfurization
In the catalytic oxidative system, the amount of H2O2 was one of the main factors.As shown in Figure 5, when the O/S molar ratio increased from 2:1 to 5:1, the removal of DBT from the model oil increased from 53.4% to 99.8%.However, with the molar ratio up to 8:1, the sulfur removal fell to 87.2%, because an excess amount of H2O2 could be decomposed by the catalyst into water, which has a negative effect on the desulfurization systems.Therefore, we chose H2O2/DBT = 5:1 as the optimal ratio in the present research.

Influence of the H2O2/DBT Molar Ratio on Desulfurization
In the catalytic oxidative system, the amount of H2O2 was one of the main factors.As shown in Figure 5, when the O/S molar ratio increased from 2:1 to 5:1, the removal of DBT from the model oil increased from 53.4% to 99.8%.However, with the molar ratio up to 8:1, the sulfur removal fell to 87.2%, because an excess amount of H2O2 could be decomposed by the catalyst into water, which has a negative effect on the desulfurization systems.Therefore, we chose H2O2/DBT = 5:1 as the optimal ratio in the present research.

Catalytic Oxidation Results for 4,6-Dimethyldibenzothiophene (DMDBT) and Benzothiophene (BT)
The desulfurization of other sulfur-containing compounds involving 4,6-DMDBT and BT was also evaluated.As shown in Figure 7, the removal of 4,6-DMDBT and BT could reach 87% and 65%, respectively, at 50 • C after 80 min.Of the three sulfur-containing compounds, the reactivity was found in the order of DBT > 4,6-DMDBT > BT.The reason for this was that the reactivity of sulfur compounds is determined by steric hindrance and electron density around the sulfur atoms.With the increase of the electron density around the sulfur compounds (DBT (5.758), 4,6-DMDBT (5.760), and BT (5.739)), the reactivity is increased [51].The desulfurization of other sulfur-containing compounds involving 4,6-DMDBT and BT was also evaluated.As shown in Figure 7, the removal of 4,6-DMDBT and BT could reach 87% and 65%, respectively, at 50 °C after 80 min.Of the three sulfur-containing compounds, the reactivity was found in the order of DBT > 4,6-DMDBT > BT.The reason for this was that the reactivity of sulfur compounds is determined by steric hindrance and electron density around the sulfur atoms.With the increase of the electron density around the sulfur compounds (DBT (5.758), 4,6-DMDBT (5.760), and BT (5.739)), the reactivity is increased [51].

Recyclability of the Catalytic System
Recyclability is very important for industrial application.The ECODS processes were performed in an immiscible liquid-liquid phase system formed by the model oil phase and the traditional ILcatalyst phase.Model oil was decanted from the reactor after the reaction, and then fresh model oil and H2O2 were directly added into the original reactor for the next run.Though some white DBTO2 residue was produced in the system after every run, this had little influence on the sulfur removal ability of the IL-catalyst system.The obtained results are shown in Figure 8.It can be seen that oxidation desulfurization efficiency did not decline after the IL-catalyst system was run 8 times, and the sulfur removal could still reach 98.3%.

Recyclability of the Catalytic System
Recyclability is very important for industrial application.The ECODS processes were performed in an immiscible liquid-liquid phase system formed by the model oil phase and the traditional IL-catalyst phase.Model oil was decanted from the reactor after the reaction, and then fresh model oil and H 2 O 2 were directly added into the original reactor for the next run.Though some white DBTO 2 residue was produced in the system after every run, this had little influence on the sulfur removal ability of the IL-catalyst system.The obtained results are shown in Figure 8.It can be seen that oxidation desulfurization efficiency did not decline after the IL-catalyst system was run 8 times, and the sulfur removal could still reach 98.3%.
2.2.5.Catalytic Oxidation Results for 4,6-Dimethyldibenzothiophene (DMDBT) and Benzothiophene (BT) The desulfurization of other sulfur-containing compounds involving 4,6-DMDBT and BT was also evaluated.As shown in Figure 7, the removal of 4,6-DMDBT and BT could reach 87% and 65%, respectively, at 50 °C after 80 min.Of the three sulfur-containing compounds, the reactivity was found in the order of DBT > 4,6-DMDBT > BT.The reason for this was that the reactivity of sulfur compounds is determined by steric hindrance and electron density around the sulfur atoms.With the increase of the electron density around the sulfur compounds (DBT (5.758), 4,6-DMDBT (5.760), and BT (5.739)), the reactivity is increased [51].

Recyclability of the Catalytic System
Recyclability is very important for industrial application.The ECODS processes were performed in an immiscible liquid-liquid phase system formed by the model oil phase and the traditional ILcatalyst phase.Model oil was decanted from the reactor after the reaction, and then fresh model oil and H2O2 were directly added into the original reactor for the next run.Though some white DBTO2 residue was produced in the system after every run, this had little influence on the sulfur removal ability of the IL-catalyst system.The obtained results are shown in Figure 8.It can be seen that oxidation desulfurization efficiency did not decline after the IL-catalyst system was run 8 times, and the sulfur removal could still reach 98.3%.

The Possible Mechanism
The ECODS process of the model oil occurred in two distinct stages: The initial extraction of the DBT from the oil phase to the IL phase, and then the catalytic oxidation.The initial extraction is favored by the formation of strong π-π interactions between aromatic sulfur compounds and the imidazolium rings of ILs [2].The subsequent catalytic oxidation process was always related with the formation of peroxometal intermediates, according to previous works [52][53][54][55].There were two possible catalytic oxidation mechanisms for the ODS process by H 2 O 2 in the presence of the transition metal mono-substituted phosphomolybdates as catalysts.One pathway was that the phosphomolybdate could be oxidized to peroxophosphomolybdates [56]  The ECODS process of the model oil occurred in two distinct stages: The initial extraction of the DBT from the oil phase to the IL phase, and then the catalytic oxidation.The initial extraction is favored by the formation of strong π-π interactions between aromatic sulfur compounds and the imidazolium rings of ILs [2].The subsequent catalytic oxidation process was always related with the formation of peroxometal intermediates, according to previous works [52][53][54][55].There were two possible catalytic oxidation mechanisms for the ODS process by H2O2 in the presence of the transition metal mono-substituted phosphomolybdates as catalysts.One pathway was that the phosphomolybdate could be oxidized to peroxophosphomolybdates [56] by H2O2, then the peroxophosphomolybdate could react with the S atom of DBT to form the intermediate, which could further react to form sulfone and [Bmim]5PMo11M (shown in Scheme 1).Alternatively, oxygen could be transferred from H2O2 to M II of [Bmim]5PMo11M(H2O)O39 (M = Mn 2+ , Co 2+ , or Ni 2+ ), leading to a higher valent transition metal-oxo site (M III = O).Then the Mperoxocomplex (M-O2) could be formed under the interaction with another H2O2.The M IIIperoxocomplex species could oxidize DBT to sulfone.Simultaneously, the M III -peroxocomplex could be reduced back to [Bmim]5PMo11M(H2O)O39 (shown in Scheme 2).The ECODS process of the model oil occurred in two distinct stages: The initial extraction of the DBT from the oil phase to the IL phase, and then the catalytic oxidation.The initial extraction is favored by the formation of strong π-π interactions between aromatic sulfur compounds and the imidazolium rings of ILs [2].The subsequent catalytic oxidation process was always related with the formation of peroxometal intermediates, according to previous works [52][53][54][55].There were two possible catalytic oxidation mechanisms for the ODS process by H2O2 in the presence of the transition metal mono-substituted phosphomolybdates as catalysts.One pathway was that the phosphomolybdate could be oxidized to peroxophosphomolybdates [56] by H2O2, then the peroxophosphomolybdate could react with the S atom of DBT to form the intermediate, which could further react to form sulfone and [Bmim]5PMo11M (shown in Scheme 1).Alternatively, oxygen could be transferred from H2O2 to M II of [Bmim]5PMo11M(H2O)O39 (M = Mn 2+ , Co 2+ , or Ni 2+ ), leading to a higher valent transition metal-oxo site (M III = O).Then the Mperoxocomplex (M-O2) could be formed under the interaction with another H2O2.The M IIIperoxocomplex species could oxidize DBT to sulfone.Simultaneously, the M III -peroxocomplex could be reduced back to [Bmim]5PMo11M(H2O)O39 (shown in Scheme 2).[36,41,43].Compared with the system using the corresponding cesium salts as catalysts [45], the ECODS process in this system shows higher desulfurization efficiency at lower temperature and in a shorter time.Therefore, it provides an alternative approach for more efficient deep desulfurization.[61].
Elemental analyses (C, H, and N) were performed on a Perkin-Elmer 2400 CHN elemental analyzer (PerkinElmer Inc., Waltham, MA, USA).FT-IR spectra were recorded in the range of 400-4000 cm −1 on an EQUINOX55 FT-IR spectrophotometer (Bruker, Billerica, MA, USA) using KBr pellets.The UV-Vis diffuse reflectance spectra were obtained using a Shimadzu UV-2550 UV-Vis spectrophotometer (Kyoto, Kyoto Prefecture, Japan), and BaSO 4 was used as a reflectance standard.TGA-DSC analyses were performed on a NETZSCH STA449C TGA instrument (Netzsch, Selb, Germany) in flowing N 2 with a heating rate of 10 • C/min.The 31 P NMR measurements were collected for liquid solutions (20 mg samples dissolved in 0.5 mL of DMSO) using a JEOL JNM-ECZ 600R spectrometer (Tokyo, Japan), and chemical shifts were given with respect to external 85% H 3 PO 4 .O (0.249 g, 1 mmol) was added and stirred at 80 • C for 1.5 h and filtered hot.Then, an aqueous solution of [Bmim]Br (1.096 g, 5 mmol) was added dropwise to the obtained filtrate, yielding a brown precipitate.The resulting suspension was stirred for 2 h at room temperature, and the solid product was separated by filtration, washed with deionized water, and then dried overnight at 60

ECODS Process
The ECODS experiments were carried out in a closed Pyrex cell, equipped with a magnetic stirrer and a thermostatic oil bath.The model oil was prepared following the procedure described in the literature [45].ECODS experiments were performed in the presence of ILs as the extraction solvent.The catalysts, ILs, and 30% H 2 O 2 were added into the reactor, and then 5 mL of model oil was injected.The mixture was heated to the appropriate reaction temperature in the oil bath.Liquid samples from model oil (the upper) were taken from the reactor at an interval of 10 min and analyzed by microcoulometry (Jiangsu national innovation Instrument Co., Ltd.Jiangyan, China; detection limit, 0.2 ppm) to determine the concentration variation of the sulfur-compounds with time.

Conclusions
In this study, four POM-IL hybrid materials based on transition metal mono-substituted Keggin-type phosphomolybdates [Bmim]  )O 39 catalyst showed excellent catalytic activity for the oxidation of model oil in the immiscible liquid-liquid phase system formed by the model oil and traditional ILs as an extraction solvent, with H 2 O 2 as an oxidant under very mild conditions.Our reaction can achieve nearly 100% desulfurization efficiency at a relatively small amount of catalyst, shorter reaction time, and lower temperature, as compared to some reported systems with POMs catalyzed H 2 O 2 -based sulfoxidation reactions.Additionally, the oxidation desulfurization efficiency is not reduced after the IL-catalyst system has been recycled 8 times, and it is harmless to the environment.
Fourier transform-infrared spectroscopy (FT-IR) are useful to study the framework structure of Keggin anions and the organic cation in the POM-based IL hybrids.The FT-IR spectra of the parent [Bmim] 3 PMo 12 O 40 and the corresponding transition metal mono-substituted phosphomolybdates-based IL hybrids are compared in Figure 1.[Bmim] 3 PMo 12 O 40 shows the characteristic bands of the Keggin-type structure: P-O stretching mode at 1062 cm −1 , Mo-O t at 959 cm −1 , Mo-O b -Mo at 883 cm −1 , and Mo-O c -Mo at 798 cm −1 , which are in agreement with those of [Bmim] 3 PMo 12 O 40 reported in the literature

5
PMo 11 M(H 2 O)O 39 (M = Co 2+ , Ni 2+ , Zn 2+ , and Mn 2+ ), respectively.The shifts in these bands compared to [Bmim] 3 PMo 12 O 40 indicate that the transition metal was introduced into the framework of Keggin ions successfully.Catalysts 2018, 8, x FOR PEER REVIEW 3 of 13 compared to [Bmim]3PMo12O40 indicate that the transition metal was introduced into the framework of Keggin ions successfully.
by H 2 O 2 , then the peroxophosphomolybdate could react with the S atom of DBT to form the intermediate, which could further react to form sulfone and [Bmim] 5 PMo 11 M (shown in Scheme 1).Catalysts 2018, 8, x FOR PEER REVIEW 8 of 13

Scheme 1 .
Scheme 1.The possible mechanism of extractive and catalytic oxidation desulfurization (ECODS) via pathway one.

Scheme 1 .
Scheme 1.The possible mechanism of extractive and catalytic oxidation desulfurization (ECODS) via pathway one.

Scheme 2 .
Scheme 2. The possible mechanism of ECODS via pathway two.