Ultrathin TiO2(B) Nanosheets as the Inductive Agent for Transfrering

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Ultrathin TiO2(B) Nanosheets as the Inductive Agent for Transfering H2O2 into Superoxide Radicals Zhen Wei, Di Liu, Weiqin Wei, Xianjie Chen, Qiang Han, Wenqing Yao, Xinguo Ma, and Yongfa Zhu ACS Appl. Mater. Interfaces, Just Accepted Manuscript • Publication Date (Web): 24 Apr 2017 Downloaded from http://pubs.acs.org on April 25, 2017

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ACS Applied Materials & Interfaces

Ultrathin TiO2(B) Nanosheets as the Inductive Agent for Transfering H2O2 into Superoxide Radicals Zhen Wei,a Di Liu,c Weiqin Wei,a Xianjie Chen,a Qiang Han,a Wenqing Yao,a Xinguo Ma*b and Yongfa Zhu*a a Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China. b School of Science, Hubei University of Technology, Wuhan 430068, P. R. China. c School of Chemical & Environmental Engineering, China University of Mining and Technology, Beijing 100084, P.R.China KEYWORDS: TiO2(B); ultrathin nanosheets; superoxide radicals; selective oxidation; catalysis

ABSTRACT

Reflux method to synthesis ultrathin polycrystalline TiO2(B) nanosheets (NS) which is assembled by single crystals, and further stacked into nanoflowers structure. Based on the theoretical calculations and experiments, H2O2 can easily substitute the ethylene glycol adsorded on the surface of TiO2(B) NS, forming H2O2-NS due to the lower adsorption energy and the unique structural features of ultrathin TiO2(B) nanosheets. TiO2(B) NS and H2O2 system can be

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accelerated to generat superoxide radicals under heat or light and thus exhibits a great degradation property on dye molecules, the total organic carbon (TOC) removal rate was 6 times higher than H2O2 alone. Meanwhile, TiO2(B) NS and H2O2 system has a good application on the selective oxidation due to the reactive specie of superoxide radicals avoiding over-oxidized of benzyl alcohol. The conversion of benzyl alcohol oxidized to benzaldehyde in water solution under low temperature and atmospheric pressure was 51.13%, while the selectivity was close to 100%. We believe that the present findings will provide valuable methods for highly efficient generation of superoxide radicals and broadening their applications in catalysis.

1. INTRODUCTION

Titanium dioxide (TiO2) nanomaterials are known for their numerous and diverse applications, such as photovoltaic cells,1-2 catalytic degradation of pollutants,3-4 water splitting,5 lithium ion batteries6 and biosensing,7 due to its low cost, non-toxicity, abundance, and outstanding chemical stability. The metastable polymorph of TiO2(B) was observed in the 1980s with monoclinic phase, which is different from other crystal structures such as anatase, rutile, and brookite.8 It possesses favorable open channels, which facilitate lithiation/delithiation in an interesting pseudocapacitive manner, rather than the solidstate diffusion process observed in anatase titanium dioxide. Therefore, most of the researches of TiO2(B) focused on the lithium ion battery. There are two main synthesis methods of TiO2(B), one is hydrothermal method with concentrated sodium hydroxide, following by acid washing and high temperature calcination, the product was TiO2(B) nanowires (NW).9-10 The other is solvothermal method with ethylene glycol and titanium trichloride to obtain TiO2(B) nanosheets (NS),11 among which the adsorption of


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ethylene glycol on the surface of TiO2(B) guaranteed the existence of this metastable polymorph.12 But both the two methods need large energy consumption and cause great pollution to environment. In the past, most researches of TiO2(B) were focused on its applications in lithium ion batteries due to its excellent performance.13 However, some researchers found that TiO2(B) NS also have excellent performance not only in lithium ion batteries but also in catalytic reactions recently. As we all know, ultrathin two-dimensional materials with atomic thickness can be homogeneously dispersed without the assistance of capping ligand, while their atomic thickness favors building clear atomic structure, defect, and electronic structure variations on its physicochemical properties.14-17 Zheng et al. fabricated a stable atomically dispersed palladium– ultrathin TiO2(B) NS catalyst (Pd1/TiO2) assisted with ethylene glycolate (EG) using a photochemical strategy and the product exhibited high catalytic activity in hydrogenation of C=C bonds.18 Lin et al. controlled epitaxial growth the ultrathin TiO2(B) NS to one-dimensional TiO2(B) hierarchitectures, presenting outstanding photocatalytic and photoelectrochemical capabilities.19 In the presence of H2O2, the -OOH groups of H2O2 would substitute for the -OH groups in the basic ≡TiOH forming yellow surface complexes, it has a visible light absorption compared to TiO2.20-21 H2O2 and TiO2 can react together like Fenton reaction to produce hydroxyl radicals under ultraviolet or visible light, accelerate the degradation of pollutants, and are widely used in the degradation of pollutants.22-24 We synthesized a large amount of ultrathin TiO2(B) NS with a high surface area through a simple refluxing method which has potential in practical production. H2O2 could substitute the ethylene glycol adsorbed on the surface of TiO2(B) NS, forming H2O2-


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NS compounds which can produce superoxide radicals to get the dyes degraded. The degradation rate could be greatly accelerated by the visible light or heat. In addition, ultrathin TiO2(B) NS and H2O2 system can selectively oxidate benzyl alcohol to benzaldehyde at low temperature and normal pressure in water system with good selectivity and conversion rate.

Scheme 1. Schematic illustration of the growth mechanism of TiO2(B) NS nanoflowers.

2. RESULTS AND DISCUSSION

TiO2(B) NS was prepared by a simple refluxing method using tetrabutyl titanate, glycol and hydrochloric acid as the reactants described in the Experimental Section and Scheme 1. The Xray diffraction (XRD) pattern of TiO2(B) NS was shown in Figure 1a, which well matches the JCPDS No. 74-1940. The diffraction peak near (003) of TiO2(B) NS were significantly lower than TiO2(B) NW (detailed synthetic method and morphology structure can be seen in the Experimental Section and Figure S2a and S2b). The morphology of TiO2(B) NS was nanoflowers assembled by nanosheets from observations of TEM (Figure 1d and 1e) and SEM (Figure 1f and 1g). From the HRTEM (Figure 1h and 1i) picture of TiO2(B) NS, it can be seen that TiO2(B) NS exhibit layer structures with nano single crystal with a scale of 5 nm, indicating that it was polycrystalline. The nanocrystals assembled to the ultrathin polycrystalline TiO2(B) NS and further stacked into nanoflowers structure. The thickness of one nanosheet of TiO2(B)


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NS was only 4.2 nm as revealed by AFM (Figure 1b and 1c). TiO2(B) NS have a large Brunauer–Emmett–Teller (BET) specific surface area with 328.2 m2/g and the pore width was 3.8 nm (Figure S1). When TiO2(B) NS was fabricated through hydrothermal treatment at 180 °C for 24 h, it becomes the phase of anatase (denoted as TiO2(A), detailed synthetic method seen in the Experimental Section), and the XRD peak is obviously enhanced (Figure 1a), indicating an increased crystallinity. The morphology of TiO2(A) was a small irregularity nanosheet with the size of around 20 nm (Figure S2c and S2d), indicating TiO2(B) NS was decomposed into small pieces under hydrothermal conditions. However, the product H2O2-NS formed by the reaction of TiO2(B) NS and H2O2 had no obvious diffraction peak (Figure 1a), indicating that it was amorphous (detailed synthetic method seen in the Experimental Section). As can be seen from the HRTEM (Figure 1j and 1k) picture, H2O2-NS maintains the shape of nanosheet，but it have no obvious lattice fringes compared to TiO2(B) NS, also indicating it was amorphous. The absorption band of TiO2(B) NS was about 370 nm by diffuse reflectance spectroscopy, while H2O2-NS extended to about 550 nm (Figure S3), which can absorb visible light.


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Figure 1. a) Experimental XRD pattern of TiO2 (A), TiO2(B) NS, TiO2(B) NW and H2O2NS; b) AFM images of TiO2(B) NS, and c) the corresponding height profiles; d-e) TEM of TiO2(B) NS; f-g) SEM of TiO2(B) NS; h-i) HRTEM of TiO2(B) NS; j-k) HRTEM of H2O2-NS. The absorption at 2943 and 2872 cm-1 from the FTIR spectrum (Figure 2a) of TiO2(B) NS corresponds to the methyl and methylene groups,25-26 indicating that the solvent ethylene glycol was adsorbed on TiO2(B) NS. However, H2O2-NS does not have a significant absorption there, indicating that ethylene glycol has been removed. From the thermogravimetry of TiO2(B) NS under an oxygen atmosphere is shown in Figure S4, the weight loss was about 6.33% in the whole process due to the adsorbed ethylene glycol. The Raman spectroscopy of TiO2(B) NS (Figure 2b) confirmed that it was the typical B-type structure of titanium dioxide as described in the literature12. The H2O2-NS formed by TiO2(B) NS and H2O2 had strong absorption at 521, 685 and 905 cm-1, among which the 685 cm-1 can be assigned to the symmetric Ti-O2 stretching vibration27-29, indicating that H2O2 have changed the surface structure of TiO2(B) NS.


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Figure 2. a) FT-IR spectra of TiO2(B) NS and H2O2-NS; b) Raman spectra of TiO2(B) NS and H2O2-NS. As is known that, H2O2 peforms a certain oxidation capacity, but it can only oxidize 6 % of RhB in 360 min under the condition of darkness at 30 °C and TiO2(B) NS alone had no degradation activity (Figure 3a). TiO2(B) NS could degrade RhB (2×10-5 mol/L) with 40 mM of H2O2 completely in 300 min. However, degradation efficiency on RhB of TiO2(B) NW, TiO2(A) and Degussa P25 under the same condition was only 18%, 23% and 22%, respectively (Figure 3a). The degradation rate increased with increasing H2O2 concentration in the range of 2-40 mM, and the degradation was not obvious at 2 mM (Figure S5a). The total organic carbon (TOC) removal rate of RhB was 60.0% in TiO2(B) NS and H2O2 system for reaction 7 days, and only 8.6% in H2O2 alone under the same conditions (see Figure S6 for experimental conditions). After one round of degradation experiment, adding new RhB and H2O2 to reach the initial value, continue to react for another 7 days and the TOC removal rate was 57%, indicating that TiO2(B) NS and H2O2 system can maintain long-term degradation performance by adding new H2O2. In addition, the elevated temperature will significantly increase the degradation rate, it need 300 min degradation RhB completely at 35 °C, however, it only need 180 min at 40 °C. The


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relationship between the temperature and degradation time can be calculated: k=e-11074.83/T+34.74. Besides, visible light can also greatly promote the degradation rate, it need more than 360 min to complete degradation at 30 °C, while it only need 150 min under the visible light (Figure 3b). At the same time, the RhB degradation rate and H2O2 consumption rate was positively related, the concentration of H2O2 could be dropt rapidly when the RhB degraded completely under the visible light (Figure S5b).

Figure 3. a) Different materials degrade RhB (2×10-5 mol/L) in 40mM H2O2 under darkness at 30 °C; b) TiO2(B) NS degradation of RhB (2×10-5 mol/L) in 20mM H2O2 at different temperatures and visible light effects; c) HPLC of different reaction products of TiO2(B) NS degradation of 20 ppm phenol in 40 mM H2O2 degradation. (The reaction was at 30 °C without


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light); d) Different conditions in aqueous solution of selective oxidation of benzyl alcohol, benzyl alcohol: 0.5mmol; TiO2(B) NS or P25: 16 mg; H2O2:3 mmol. The TiO2(B) NS and H2O2 system was also tried to degrade phenol, it is found that this system can not mineralize phenol, the phenol was converted into p-benzoquinone after the reaction from the analysis of HPLC (Figure 3c). This indicates that the TiO2(B) NS and H2O2 system have a certain extent oxidative capacity which is not strong to mineralize phenol. Selective oxidation of alcohols to aldehydes is one of the most important functional group transformations in organic synthesis due to carbonyl compounds widely used as the intermediates for drugs.30-32 Nevertheless, the traditional method for alcohols synthesis aldehydes were not only need toxic oxidants (such as ClO− and Cr4+), but also consume lots of energy to provide high temperature and pressure of the reactions.33-34 Besides, water is a desirable solvent for chemical reactions due to the environmental concerns and cost, hence the organic syntheses in water is currently drawing much attention.35-37


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Figure 4. a) Trapping experiments of reactive species in the system of degradation of RhB by using TiO2(B) NS and H2O2 system under visible light at 30 °C; b) The production of •O2by different materials detected by NBT method under visible light at 30 °C; c) in situ EPR spectra of TiO2(B) NS and H2O2-NS at 103 K; d) The high-resolution XPS spectrum of O1s in H2O2-NS. TiO2(B) NS and H2O2 system was used to study the selective oxidation of aldehyde to alcohol, and it was found that benzyl alcohol was oxidized to benzaldehyde at low temperature and atmospheric pressure in water. Only 2.23% benzyl alcohol was oxidized to benzaldehyde in H2O2 alone at 55 °C for 4 hours, while only 3.84% benzyl alcohol was oxidized to benzaldehyde by H2O2 and P25 system. However, when TiO2(B) NS and H2O2 system reacted for 2 hours, 51.13% of benzyl alcohol was oxidized to benzaldehyde, the selectivity was close to 100%, and


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the conversion rate could increase gradually with the reaction time was prolonged, but the selectivity decreased slightly. When the reaction time was 8 hours, the conversion ratio of the benzyl alcohol increased to 75.14% and the selectivity decreased to 84.32% (Figure 3d). The conversion rate increased to 89.56% and the selectivity decreased to 65.32% after reaction 12 hours, continue to prolong the reaction time, the conversion rate was slightly changed and the selectivity

would

continue

to

decrease.

If

phase

transfer

catalyst

(PTC)

of

cetyltrimethylammonium bromide was not added, the conversion rate declined to 21.51% reacted for 4 hours due to water phase reaction, PTC could greatly promote the reaction. In order to study the active species in TiO2(B) NS and H2O2 system, EDTA-2Na as the hole scavenger38, p-benzoquinone as the superoxide radical scavenger39 and tertiary butanol as the •OH scavenger40 were added to the system (Figure 4a). It is found that adding the capture agent of p-benzoquinone decreased the rate significantly compared to others, indicating that the main active specie was superoxide radicals. In order to further capture the superoxide radicals, we added nitro blue tetrazolium (NBT) as superoxide radicals scavenger. NBT can be reduced by superoxide radicals formed purple formazan, which was insoluble in water.41 The ultraviolet absorption spectrum at 259 nm gradually weakened with the reaction time increacing (Figure S7), indicating that the system did exist in the superoxide radicals.42-43 The production of superoxide radicals of H2O2 alone was the least, TiO2(B) NS and H2O2 system was 6, 5 and 7 times higher than P25, TiO2(A) and TiO2(B) NW, respectively (Figure 4b). The production of superoxide radicals by TiO2(B) NS under irradiation with different band-pass filters was shown in Figure S8, the production of superoxide radicals were reduced with the wavelength increasing and 435nm was more useful for the production judging from Figure S8. In order to further confirm this result， TiO2(B) NS and H2O2 system was conducted EPR using 5,5՛ -dimethyl-1-pirroline-N-oxide


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(DMPO) as the spin-trap reagent (Figure S9), showing that there was no signal of hydroxyl radicals in dark or visible light conditions. The active specie of TiO2(B) NS and H2O2 system was superoxide radicals, of which the oxidization ability was much weaker than the hydroxyl radicals, which may explains why it cannot mineralize phenol.44 The mechanism of superoxide radicals selective oxidation of benzyl alcohol has been reported previously45. The superoxide radicals can effectively avoid the benzyl alcohol over-oxidized to benzoic acid. TiO2(B) NS and H2O2 system reaction product yellow powder H2O2-NS was measured the in-situ electron paramagnetic resonance (EPR) at 103 K in liquid N2 (Figure 4c). There was no obvious paramagnetic signal in the original TiO2(B) NS, and the obvious paramagnetic resonance signal appeared in H2O2-NS, gz = 2.024, gy = 2.008 and gx = 2.002 were very significant signal for superoxide radicals, indicating the formation of superoxide radicals on the H2O2-NS surface.46-47 TiO2(B) NS O 1s has an XPS absorption peak at 530.8 eV (Figure S10), which corresponds to the Ti-O bond.48 The O1s spectrum of the H2O2-NS is ftted to two peaks at 530.8 and 532.9 eV (Figure 4d), and 532.9 V corresponds to the O-O bond.49 Based on the active species trapping experiments and in situ EPR and XPS data, it can be inferred that TiO2(B) NS can induce the transformation of H2O2 into superoxide radicals.


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Figure 5. a) The optimized model of ethylene glycol adsorbed on the surface of TiO2(B) were obtained by GGA-TS method (side view); b) The optimized model of H2O2 adsorbed on the surface of TiO2(B) were obtained by GGA-TS method (side view); c) The initial configuration of the two hydroxyl groups adsorbed on the surface of TiO2(B) (side view); d) The structure of TiO2(B) surface adsorbed superoxide radicals by GGA-TS was optimized (side view); e) The mechanism of TiO2(B) NS inducing decomposition of H2O2 into superoxide radicals. In order to further elucidate the interaction mechanism of TiO2(B) NS and H2O2, plane ultrasoft pseudopotential method based on density functional theory (DFT) was used to calculate the different models.50 The adsorption energy of ethylene glycol (EG) on the (010) plane of TiO2(B) was calculated under different conditions(Figure 5a and S12). The calculated adsorption energies for the dissociative configurations (Figure S12c-d) are significantly more negative than those for molecular configurations (Figure S12a–b), indicating that the EG molecules are more favorable to adsorb onto TiO2(B) (010) facet through dissociative configurations. The dissociative


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adsorption energies are -1.46 eV (or -0.73 eV per Ti site) for the bidentate configuration and 1.07 eV for the monodentate configuration. This strong bidendate interaction can stabilize the metastable B-phase of TiO2.12 The calculated results show that H2O2 can form stable adsorption on the (010) surface of TiO2(B) with a larger adsorption energy of -2.42 eV (GGA-TS method), which is more negative than the adsorption ezlnergy of ethylene glycol (-1.46 eV) (Figure 5b and S13), indicating that H2O2 can substitute the ethylene glycol more stability adsorption on the surface of TiO2(B). The adsorption energy of single hydroxyl group on TiO2(B) (010) surface is 0.61eV. The distance from the hydroxyl group to the surface initial 5-coordinated Ti was 2.08 Å, the lateral distance of two hydroxyl groups (2 oxygen) on the surface was only 1.487 and 1.322 Å in the optimized model A and model B obtained by GGA-TS method (Figure 5c and S14), indicating that the two hydroxyl groups will be close to each other, the formation of H2O2 configuration, that is the surface easy to adsorbed H2O2, rather than form a separate hydroxyl. So hydroxyl groups can not be stable adsorption TiO2(B) surface. The distance between two oxygen atoms of superoxide radicals adsorbed on The surface of TiO2(B) was 1.26 Å obtained by GGATS optimized configuration (Figure 5d and S15), while the distance of the two oxygen atoms from the nearby 5-coordinated Ti atoms was 2.936 and 2.407 Å, respectively, indicating that there was a certain intermolecular force. The adsorption energy of superoxide radicals on the surface of TiO2 (B) is 0.73 eV, and the adsorption energy is relatively low. Thus, the adsorption of superoxide radicals on TiO2(B) surface is stable, confirming that the surface does exist superoxide radicals rather than hydroxyl radicals. It was also reported that the (010) plane of metastable TiO2(B) phase was stable due to the adsorption of ethylene glycol on the surface12. Comparisons of the adsorption energy of H2O2, hydroxyl and ethylene glycol on the surface of TiO2(B) NS (010) plane through theoretical calculation revealed that the former was the lowest.


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Therefore, it provided a favorable condition to substitute the ethylene glycol on TiO2 (B) NS (010) plane through H2O2, forming H2O2-NS, while TiO2(B) NW with less (010) plane exposed could not have this essential condition, and TiO2(B) NS and H2O2 system could enhance the production of superoxide radicals by heat or light (Figure 5e).

3. CONCLUSIONS

In conclusion, we used an easy reflux method to synthesis ultrathin polycrystalline TiO2(B) NS which is assembled by many single crystals, and further stacked into nanoflowers structure. TiO2(B) NS and H2O2 can react with each other to generat superoxide radicals and form H2O2NS due to the low adsorption energy between the surface of TiO2(B) NS and H2O2. TiO2(B) NS and H2O2 system has a great degradation property on dye molecules, visible light and heat can accelerate the reaction rate tremendously. Meanwhile, TiO2(B) NS and H2O2 system may has a good application on the selective oxidation in water solution under low temperature and atmospheric pressure. We believe that the present findings will provide valuable methods for highly efficient generation of superoxide radicals and broadening their applications in catalysis.

4. EXPERIMENTAL SECTION

All chemicals were obtained from commercial suppliers and used without further purification. Synthesis of TiO2(B) NS: 1mL of concentrated hydrochloric acid was added to 6mL of ethylene glycol, and then 3ml of tetrabutyl titanate was added, heated to boiling with constant stirring under refluxing, at a temperature of approximately 180 °C for 12 h. The precipitate was collected by centrifugation and washed by ethanol for four times. Then, the TiO2(B) nanosheets were dried at 60 °C for 24 h.


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Synthesis of TiO2(A): 0.7 g TiO2(B) NS was added to 25 mL H2O with vigorously stirred for 30 min. Then the suspension was transferred into a 40 mL Teflon-lined stainless steel autoclave, which was then solvothermally treated at 180 °C for 12 h. The precipitate was collected by centrifugation and washed by ethanol for four times and drying at 60 °C for 24 h. Synthesis of H2O2-NS: 0.1 g TiO2(B) nanosheets was added to 10mL concentration of 30% H2O2 aqueous solution, the white suspension turned yellow immediately and stirred vigorously for 12 h without light irradiation. The yellow precipitate was collected by centrifugation and washed by ethanol for four times and drying at 60 °C for 24 h. Synthesis of TiO2(B) NW: 1 g TiO2 (Degussa P25) was added to a 10 M aqueous solution of NaOH. After stirring for 2h, the resulting suspension was transferred into a Teflon-lined stainless-steel autoclave and heated to 180 °C for 48h. The resulting products were filtered and acid-washed by stirring the sample in 0.1 M HCl solution for 24 h. Filtered again and washed with distilled water to pH 7 and dried at 60 °C for 24 h. The material was heating at 400 °C for 4 h in air at a heating rate of 5 °C min-1 obtaining TiO2(B) NW.12, 51 ASSOCIATED CONTENT The Supporting Information is available free of charge on the ACS Publications website at DOI: Description of detailed characterization methods, BET, UV-vis absorption spectra, UV–vis diffuse reflection spectra, X-ray photoemission spectroscopy (XPS) spectra and theoretical calculations. Corresponding Author a* Email: [email protected] b* Email: [email protected]


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Notes The author declares no competing financial interest. ACKNOWLEDGMENT This work was partly supported by National Basic Research Program of China (973 Program) (2013CB632403) and Chinese National Science Foundation (21437003，21673126，21621003) and Collaborative Innovation Center for Regional Environmental Quality. REFERENCES (1) Bai, Y.; Mora-Sero, I.; De Angelis, F.; Bisquert, J.; Wang, P., Titanium Dioxide Nanomaterials for Photovoltaic Applications. Chem. Rev. 2014, 114 (19), 10095-10130. (2) De Angelis, F.; Di Valentin, C.; Fantacci, S.; Vittadini, A.; Selloni, A., Theoretical Studies on Anatase and Less Common TiO2 Phases: Bulk, Surfaces, and Nanomaterials. Chem. Rev. 2014, 114 (19), 9708-9753. (3) Zhang, L.; Jing, D.; She, X.; Liu, H.; Yang, D.; Lu, Y.; Li, J.; Zheng, Z.; Guo, L., Heterojunctions in g-C3N4/TiO2(B) Nanofibres with Exposed (001) Plane and Enhanced VisibleLight Photoactivity. J. Mater. Chem. A 2014, 2 (7), 2071-2078. (4) Wei, Z.; Liang, F.; Liu, Y.; Luo, W.; Wang, J.; Yao, W.; Zhu, Y., Photoelectrocatalytic Degradation of Phenol-Containing Wastewater by TiO2/g-C3N4 Hybrid Heterostructure Thin Film. Appl. Catal. B 2017, 201, 600-606. (5) Cai, J.; Wang, Y.; Zhu, Y.; Wu, M.; Zhang, H.; Li, X.; Jiang, Z.; Meng, M., In Situ Formation of Disorder-Engineered TiO2(B)-Anatase Heterophase Junction for Enhanced Photocatalytic Hydrogen Evolution. ACS Appl. Mater. Interfaces 2015, 7 (45), 24987-24992.


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Table of Contents Graphic


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Ultrathin TiO2(B) Nanosheets as the Inductive Agent for Transfrering

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