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HomeChemistryExcessive-temperature stability in air of Ti3C2Tx MXene-based composite with extracted bentonite

Excessive-temperature stability in air of Ti3C2Tx MXene-based composite with extracted bentonite

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Fabrication and characterization of MEB

Ti3C2Tx was obtained by selectively etching the Ti3AlC2 MAX section (see particulars in Strategies). EB was achieved by extracting and delaminating sodium bentonite powder (see particulars in Strategies). The profitable synthesis of these two supplies was confirmed by X-ray diffraction (XRD) patterns (Fig. S1), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) photographs (Fig. S2), which present typical nanosheet morphology with lateral dimension of 8 μm for Ti3C2Tx and a pair of–5 μm for EB, respectively1,26,27. As proven in Fig. S3a, the blended aqueous dispersions of Ti3C2Tx/EB are aggregated when the mass share of EB is greater than 50 wt%. With the Zeta potential of −42 mV (Fig. S3b) near sole Ti3C2Tx or EB, the homogeneously blended dispersion (Fig. S3c) with an EB mass ratio of fifty wt% is chosen to manufacture Ti3C2Tx/EB composite movie for the next examine and be denoted as MEB. MEB maintains an analogous lamellar construction and adaptability in comparison with the restacked Ti3C2Tx and EB movies (Fig. S4), which is additional confirmed by the photographs of scanning transmission electron microscopy (STEM). As proven in Fig. 2a, layered and homogeneous distributions of Si and Ti components point out the stacking of EB and Ti3C2Tx.

Fig. 2: Characterization of pristine Ti3C2Tx and MEB beneath high-temperature annealing with the presence of oxygen.
figure 2

a Cross-sectional STEM photographs of MEB with EDX mapping. b Optical picture of pristine Ti3C2Tx movie and MEB movie earlier than and after annealing at 400 °C for two h in artificial air. c The tensile stress-strain curves of MEB-RT and MEB-Air-400C-2. Cross-sectional SEM photographs of the annealed Ti3C2Tx movies (d) and MEB movies (e). f Raman spectra of Ti3C2Tx movies earlier than and after therapy beneath artificial air at 400 °C for two, 4, and 6 h. g Raman spectra of MEB movies earlier than and after therapy beneath artificial air at 400 °C for two, 4, and 6 h. Supply knowledge are offered as a Supply Knowledge file.

As talked about beforehand, O2 contributes to the oxidation of Ti3C2Tx within the air, which might be accelerated at elevated temperatures. Subsequently, we take the annealing time and temperature as variables to analyze the antioxidation of MEB beneath artificial air (with quantity fractions of 21% O2 and 79% N2). The samples handled at totally different circumstances are denoted as sample-air-T-t, the place the pattern is Ti3C2Tx, EB, or MEB, T is annealing temperature, and t is annealing time. The pristine Ti3C2Tx and MEB at room temperature are the management samples denoted as Ti3C2Tx-RT and MEB-RT.

As proven in Fig. 2b, MEB-Air-400C-2 reserves the flexibleness of contemporary MEB and retains its integrity after ultrasonication for 1 min in DI water (Fig. S5b). Against this, Ti3C2Tx-Air-400C-2 tends to be fragile (Fig. 2b and Fig. S5a). In line with the tensile stress-strain take a look at (Fig. 2c and Fig. S6), MEB-Air-400C-2 reveals a ten.6% lower in tensile stress and a 1.0% lower in pressure. Against this, Ti3C2Tx-Air-400C-2 reveals a 57.7% lower in tensile stress and a 5.5% lower in pressure, which is attributable to the degradation of Ti3C2Tx in high-temperature therapy. The cross-sectional SEM photographs (Fig. second, e) present good retention of layered construction for MEB-Air-400C-2 and partial transformation from nanosheets to particles in Ti3C2Tx-Air-400C-2, demonstrating that the presence of EB nanosheets can delay the oxidation of Ti3C2Tx. Additional measurements are utilized to analyze the high-temperature stability of MEB beneath the ambiance of artificial air. Raman spectra (Fig. 2f, g) show that typical Eg (Ti, C) mode at 289, 369 cm−1 and A1g (Ti, C) mode at 201, 599, and 722 cm−1 of Ti3C2Tx28,29 stay excessive power in MEB-Air-400C-2 and A1g peak (201 cm−1) remains to be apparent in MEB-Air-400C-6. In sharp distinction, no typical peaks of Ti3C2Tx stay, whereas the peaks of TiO2 at 145, 400, 519, and 637 cm−1 seem in Ti3C2Tx-Air-400C-2, exhibiting the transformation of Ti-C bonding to Ti-O bonding to the good extent30,31. Apparently, the morphology of MEB stays the lamellar construction even after therapy at 400 °C for six h within the air, as proven in cross-sectional SEM photographs (Fig. S7c), whereas pristine Ti3C2Tx flakes remodel into thicker chunk beneath the identical therapy situation (Fig. S8c). The crystalline construction analyses of annealed MEB (Fig. S9b) and Ti3C2Tx (Fig. S9a) additional verify the suppression of oxidation for MEB at excessive temperatures within the air, even for a protracted therapy time.

Mechanism of high-temperature resistant property in MEB

The mechanism of high-temperature resistant property in MEB is investigated experimentally and theoretically. The thermogravimetry-mass spectrum (TG − MS) was used to disclose detailed perception into the thermal stability of Ti3C2Tx, EB, and MEB in artificial air or argon (Ar). As proven in Fig. 3a, Ti3C2Tx reveals 4 phases of weight change at 100, 360, 480, and 600 °C, respectively. At 100 °C, the elimination of intercalated water results in the looks of the primary H2O peak and weight reduction. The second weak H2O peak is noticed at 360 °C as a result of gradual dissociation of hydroxyl floor terminations32. The burden loss at 100–360 °C is in settlement with the TG − MS of Ti3C2Tx in Ar (Fig. S10a), which signifies that the degradation of Ti3C2Tx in artificial air begins at~360 °C. That is additionally the rationale why we set the temperature variable above 400 °C on this work. Round 480 °C, the burden of Ti3C2Tx shortly will increase as a result of interplay with O2, which evolves into TiO2 accompanied by the technology of CO233. The oxidation course of accelerates with the rise of annealing temperature and approaches completion at 600 °C. For EB, as proven in Fig. 3b and S10b, solely H2O is detected from the mass spectrum within the heating course of beneath air and Ar atmospheres, suggesting the excessive thermal stability of EB with additional confirmed by XRD and SEM analyses in Figs. S11–S13. The degradation of EB begins at 700 °C due to the dissociation of -OH and =O terminations26. Notably, EB reveals a weight lack of 3.7% at 700–1040 °C in air, bigger than that in Ar (2.5%). We assume that EB might interaction with O2, thereby inducing the change in weight reduction throughout the O2 adsorption and desorption. That is evident that the speed of weight lack of EB in artificial air adjustments at round 200 °C (Fig. 3b), whereas a negligible change within the fee of weight reduction may be noticed from the TG curve in Ar (Fig. S10b). Apparently, as proven in Fig. 3c, MEB reveals significantly better resistance to oxidation than pure Ti3C2Tx, as demonstrated by (i) the burden of MEB begins to extend at 650 °C with the looks of CO2, which is way increased than pure Ti3C2Tx of 480 °C; (ii) Ti3C2Tx in MEB transforms into TiO2 utterly at 920 °C with the strongest sign of CO2, whereas 600 °C is sufficient for Ti3C2Tx. Since EB is thermally secure in artificial air throughout annealing, and the interplay between the floor of Ti3C2Tx and O2 performs a key position within the oxidation course of, we moderately speculate that the induction of EB might have an effect on the interplay between adsorbed O2 and Ti3C2Tx by the Ti3C2Tx/EB interface coupling.

Fig. 3: Mechanism of high-temperature resistance in MEB.
figure 3

Thermal gravimetric (TG) curves within the air with mass spectrometry evaluation (MS) for the atomic mass unit (amu) of 18/H2O and 44/CO2 for (a) Ti3C2Tx, (b) EB, and c MEB. d The cost density distinction plots for the secure configurations of 1 O2 adsorbed on Ti3C2O2, EB, and Ti3C2O2/EB heterostructure. Within the heterostructure, EB is topic to saturated oxygen adsorption. The isosurface degree is about to be 0.0002 e/Å3 apart from O2 adsorbed on EB with a price of 0.0006 e/Å3. The yellow space signifies cost accumulation, and the inexperienced area represents cost depletion. e X-ray photoelectron spectroscopy (XPS) of O 1 s of Ti3C2Tx-RT and MEB-RT. Supply knowledge are offered as a Supply Knowledge file.

To additional reveal the mechanism of the high-temperature resistant property of MEB, theoretical calculations have been carried out based mostly on density practical idea (DFT). The adsorption power (Eadvert) and Bader cost states of O2 molecule adsorbed on Ti3C2O2 and EB substrates are listed in Desk 1. Ti3C2O2 was chosen because the prototype mannequin as a result of O-termination is the dominant method in experimentally synthesized Ti3C2Tx MXene (as proven in Fig. 4d). The extra unfavorable Eadvert for the oxygen adsorbed on EB signifies the stronger coupling when put next with that on Ti3C2O2. In the meantime, the Bader cost evaluation34 was carried out with a view to quantitatively assess the quantity of cost switch inside the adsorbed techniques, as proven in Fig. 3d and S14a, b. The adsorbed O2 obtains 0.421 electrons on EB, a lot bigger than that on Ti3C2O2 (0.068 electrons), additional confirming the stronger binding skill between O2 and EB.

Desk 1 The calculated adsorption power Eadvert and Bader cost state that transferred from substrates to adsorbed O2 molecules
Fig. 4: Completely different termination ratios of MILD-Ti3C2Tx and HF-Ti3C2Tx, and high-temperature resistant property of MILD MEB with the presence of oxygen.
figure 4

ac XPS of O 1s, F 1s, and Cl 2p alerts, respectively, for the pristine HF-Ti3C2Tx and MILD-Ti3C2Tx movies. d The termination ratio of HF-Ti3C2Tx and MILD-Ti3C2Tx was measured by XPS with a desk record (inserted). e Raman spectra of MILD Ti3C2Tx earlier than and after therapy beneath artificial air at 400 °C for two, 4, and 6 h. f Raman spectra of MILD MEB earlier than and after therapy beneath artificial air at 400 °C for two, 4, and 6 h. Supply knowledge are offered as a Supply Knowledge file.

Moreover, we calculated the Eadvert of oxygen adsorbed on Ti3C2O2 that’s interfaced with EB (denoted as Ti3C2O2/EB heterojunction). Contemplating that EB would firstly couple with oxygen, 4 O2 molecules have been firstly positioned on the floor of EB to imitate the saturated adsorption of O2 after which EB was interfaced with Ti3C2O2 within the heterojunction mannequin (Fig. S14c). The Eadvert of 1 O2 molecule on Ti3C2O2/EB heterojunction (Fig. 3d) is −0.126 eV, which is much less unfavorable than that of pure Ti3C2O2 (−0.254 eV) (Desk 1). This means a big lower within the interplay of Ti3C2O2 with oxygen in Ti3C2O2/EB heterojunction. The Bader costs of adsorbed O2 on heterostructure is 0.056 electrons, smaller than that on pure Ti3C2O2 (0.068 electrons), consistent with the cost density distinction plot (Fig. 3d). As well as, the cost density distinction plot exhibits that the adsorbed O2 on freestanding Ti3C2O2 primarily obtains electrons from the nearest-neighbor Ti-O sub-layer of Ti3C2O2. Upon Ti3C2O2 is interfaced with EB (O2 molecules saturatedly adsorbed), the existence of the interface produces a clean channel for cost switch via the entire heterostructure alongside the c path (Fig. S14c). This results in a cost accumulation across the saturated O2 layer (4 O2 molecules) and a poor area of electron states within the higher Ti3C2O2 layer. When another O2 is adsorbed on the outermost Ti3C2O2 layer of Ti3C2O2/EB heterostructure, the quantity of electron loss within the intermediate area is drastically decreased, thus weakening the coupling of O2 with the Ti3C2O2 layer. That is related to the weakened hybridization of O-p orbitals of adsorbed O2 molecules and Ti-d orbitals. All of those point out that the formation of the Ti3C2O2/EB interface drastically inhibits the additional adsorption of O2 and thus enhances environmental stability.

The F-terminated MXene can be calculated as F termination accounts for a excessive proportion of Tx (Fig. 4d). The calculated Eadvert and Bader cost states of Ti3C2F2 earlier than and after adsorption of O2 present that Ti3C2F2 reveals extra inferior interplay with O2 in comparison with EB (Fig. S15), suggestive of comparable conduct to that of Ti3C2O2.

To additional verify the proposed mechanism, a 2D h-BN nanosheet with excessive thermal stability35 (Fig. S16) is chosen to composite with Ti3C2Tx. Theoretically, h-BN exhibits inferior adsorption of O2 to Ti3C2O2, which is proved by increased unfavorable Eadvert values (−0.143 eV) and fewer quantity of Bader cost transferred (0.055 electrons) of h-BN (Fig. S17 and Desk 1). The Ti3C2Tx/h-BN composite was ready by mixing two supplies with a mass ratio of 1/1 (denoted as MBN). After annealing at 400 °C for two h in artificial air, the layered construction of MBN transforms right into a nanoparticle@nanosheet construction, as proven in Fig. S18. The peaks of TiO2 at 145 cm−1 seem with excessive depth within the Raman spectrum (Fig. S19), indicating the oxidation of MBN. Since each of h-BN and EB exhibit good warmth retardant property, the totally different thermal stability efficiency of their composites with Ti3C2Tx excludes the likelihood that the high-temperature resistant property of MEB comes from the warmth retardant property of EB. Really, as MEB was handled at a excessive temperature for greater than 2 h, the warmth distribution round/in MEB needs to be extremely uniform. On this context, we imagine the high-temperature resistant property of MEB within the air needs to be attributed to the superior O2 adsorption on EB and the coupling between EB and Ti3C2Tx that largely weakens the additional adsorption of O2 on Ti3C2Tx.

As well as, we discovered one other phenomenon which may be useful for a high-temperature resistant property of MEB. As proven in X-ray photoelectron spectroscopy (XPS, Fig. 3e and S20), in comparison with pure Ti3C2Tx (44% Ti-O, 35% Ti-OH), the ratio of Ti-O species decreased to 21% whereas Ti-OH species elevated to 55% in MEB. It reveals that EB with plentiful hydroxy (confirmed by Fourier remodel infrared spectroscopy in Fig. S21) interacts with Ti-O terminations of Ti3C2Tx to type hydrogen-bond, inducing compact layered construction as confirmed by SEM (Fig. S4b) and XRD analyses with the shift of (002) peak from 2θ = 5.8° (Ti3C2Tx) to six.0° (MEB) (Fig. S9a, b). That is additional evidenced by the upper permeability of O2/H2O of Ti3C2Tx than MEB, as proven in Desk S1, which reveals the higher barrier property of MEB presumably benefitted by the compact layer construction. In consequence, the MEB composite may suppress the diffusion of O2 to some extent, reducing the quantity of O2/H2O round Ti3C2Tx.

As we talked about, H2O is one other issue for oxidizing Ti3C2Tx at elevated temperatures. Right here, we additionally examine the high-temperature resistant property of MEB within the H2O ambiance (argon with 90% relative humidity, denoted as RH 90%). The Raman spectra in Fig. S22 present that the intensities of Ti3C2Tx peaks in Ti3C2Tx-RH 90%-400C-2 develop into weak. Additional prolonging of annealing time leads to extra extreme oxidation which may be confirmed by the looks of TiO2 Eg peak at 145 cm−1 in pure Ti3C2Tx movie after annealing for 4 h. Nonetheless, negligible change of Ti3C2Tx fingerprints is detected in MEB-RH 90%-400C-4. Together with the outcomes of SEM (Figs. S23, S24) and XRD (Fig. S9c, d), it verifies the nice thermal stability of MEB within the H2O ambiance. As well as, the antioxidant functionality of MEB is detected at increased temperatures (500 and 600 °C) beneath RH 60% artificial air (simulated atmospheric atmosphere). The layered construction of MEB retains after annealing for two h at 600 °C; quite the opposite, the layered Ti3C2Tx transforms into amorphous TiO2 utterly, which is in settlement with the XRD evaluation (Fig. S25). All the outcomes verify that MEB demonstrates high-temperature resistant property even beneath long-time therapy with the presence of each oxygen and water molecules.

The impact of termination ratio on the high-temperature resistant property of MEB

To detect the affect of terminations on the high-temperature resistant property of Ti3C2Tx, two approaches are adopted to synthesize Ti3C2Tx, that are minimally intensive layer delamination technique (denoted to MILD-Ti3C2Tx, Fig. S26) and HF etching technique (HF-Ti3C2Tx), respectively. By becoming the relative intensities of the O 1s, F 1s, Cl 2p peaks36,37 as proven in Fig. 4a–d and S27, we decide the termination of HF-Ti3C2Tx to be 38.7% = O, 31.6% -F, 7.7% -Cl, 22.0% -OH and MILD-Ti3C2Tx with 43.8% = O, 24.4% -F, 13.1% -Cl, 18.7% -OH, which reveals the totally different termination ratios for 2 samples. For clear description, a composite consisting of MILD-Ti3C2Tx and EB is denoted as MILD MEB with a view to differentiate with MEB (HF-Ti3C2Tx/EB). Following the identical thermal therapy of MEB, MILD MEB-Air-400C-2 exhibits high-intensive Eg (Ti, C) peaks at 289, 369 cm−1 and A1g (Ti, C) peaks at 201, 599, 722 cm−1 of Ti3C2Tx, and A1g peak (201 cm−1) remains to be apparent in MILD MEB-Air-400C-6 as proven in Fig. 4f. Against this, MILD Ti3C2Tx-Air-400C-2 (Fig. 4e) exhibits the transformation of Ti-C bonding to Ti-O bonding, which is indicated by the looks of TiO2 peaks at 145, 400, 519, 637 cm−1. Together with the SEM evaluation (Fig. S28), the outcomes verify the high-temperature resistant property for MILD MEB in air. The same conduct in MEB and MILD MEB reveals our technique for suppressing the oxidation of Ti3C2Tx is unbiased of the termination ratio of Ti3C2Tx.

The potential functions of MEB

Excessive-temperature resistant electromagnetic interference (EMI) shielding is of significance for the aerospace trade, for situations together with however not restricted to the EMI shielding of engine casing of plane (increased than 380 °C), and many others. Right here we examined the EMI shielding effectivity of MEB within the frequency vary of 0.2–1.3 THz after annealing at totally different temperatures for a very long time in RH 60% artificial air (simulated atmospheric atmosphere in a sensible state of affairs), that are denoted as MEB-Atmos-T-t (T is temperature, t is time) for various annealing circumstances. Pristine Ti3C2Tx is taken for comparability. As a way to actually replicate the efficiency comparability, MEB and Ti3C2Tx are managed to acquire the identical quantity of 11 mg Ti3C2Tx, because the EMI shielding originates from the excessive electrical conductivity of Ti3C2Tx and EB is noneffective for THz shielding (Fig. S29), which is additional defined by the proposed EMI shielding mechanism of MEB in Fig. S30. As proven in Fig. S31, the transmitted THz alerts of Ti3C2Tx-RT and MEB-RT are too weak to be detected as a result of wonderful THz shielding efficiency of Ti3C2Tx, and the typical THz shielding efficiencies (THz SEs) are obtained round 47 dB as proven in Fig. 5a–c. After annealing, MEB-Atmos-400C-6 have a superb shielding capability retention, even increased than pristine materials (50 dB). This may be attributed to the rise of {the electrical} conductivity from 850 to 1000 S cm−1, which is attributable to extra compact nanosheet stacking of MEB-Atmos-400C-6 with the elimination of intercalated water. The XRD evaluation validates the discount of the interlayer (d-) spacing, characterised by the height of (002) shifting from 2θ = 6.0° to ~8.2° after annealing (Fig. S9b). Against this, Ti3C2Tx-Atmos-400C-6 performs excessive transmittance and ultralow THz SE (method to zero) owing to its full degradation. Moreover, THz transmittance and shielding effectivity of MEB after annealing at a better temperature for two h are investigated, as proven in Fig. 5b, c. With the annealing temperature rising, the transmissions of THz waves via MEB-Atmos-500C-2 and MEB-Atmos-600C-2 stay at 0.001 and 0.0015%. In different phrases, the THz SE of the 2 samples can attain about 50 dB at 500 °C and 48 dB at 600 °C (Fig. 5b, c) due to good electrical conductivity (1090 S cm−1 for MEB-Atmos-500C-2h and 960 S cm−1 for MEB-Atmos-600C-2h), which is according to the XRD evaluation (Fig. S25d). Quite the opposite, THz SE of Ti3C2Tx decreases to~0 dB at 600 °C due to the oxidation of Ti3C2Tx. All the outcomes recommend that the introduction of EB can suppress the oxidation-induced deterioration of Ti3C2Tx, due to this fact making MEB promising high-temperature resistant THz shielding supplies. As well as, a complete literature assessment is summarized to check the efficiency of MEB with printed THz shielding supplies. Thus far, most THz shielding supplies are utilized at room temperature and few researchers give attention to their functions at excessive temperature or hash atmosphere, as proven in Fig. S32. Subsequently, MEB with high-temperature resistant property in air and humid atmosphere might meet the calls for of working in a harsh atmosphere (additional high-temperature THz take a look at is important to lastly consider the feasibility of MEB for the sensible state of affairs).

Fig. 5: Potential functions of MEB.
figure 5

ac THz EMI shielding property of MEB. a EMI SE in 0.2–1.3 THz of Ti3C2Tx-RT, MEB-RT, Ti3C2Tx-Atmos-400C-6, MEB-Atmos-400C-6. b EMI SE in 0.2–1.3 THz of Ti3C2Tx-Atmos-500C-2, 600C-2, and MEB-Atmos-500C-2, 600C-2. c The common THz SE of the samples confirmed in Fig. 5a (left) and Fig. 5b (proper). d Lengthy-term Joule heating efficiency of MEB and Ti3C2Tx movies pushed by an utilized voltage of three.0 V. e The thermal biking efficiency of MEB movie, which is realized by switching the utilized voltage (3.0 V) on and off repeatedly. Supply knowledge are offered as a Supply Knowledge file.

To additional discover the potential software of MEB by advantage of the high-temperature resistant property, we additionally measure the Joule heating efficiency of MEB. Joule heating gadget is required to supply quick heating and high-temperature output (in some circumstances, tons of of levels are wanted). On the whole, the metallic conductivity and excessive thermal conductivity of Ti3C2Tx meet the demand for the Joule heating gadget. The Ti3C2Tx and MEB freestanding movies have been used to make the units of the Joule heater (Fig. S33). As proven in Fig. 5d, pristine Ti3C2Tx movie shortly reaches 190 °C beneath a driving voltage of three.0 V. Nonetheless, it’s secure for less than 0.57 h, then the temperature begins to say no as a result of oxidation of Ti3C2Tx. As a comparability, the heating fee of MEB movie may be 20 °C s−1, with a steady-state temperature of 198 °C with out massive temperature fluctuation for greater than 3.5 h, which displays the speedy thermal response and secure high-temperature electrothermal efficiency. As well as, the thermal biking efficiency of MEB is examined as proven in Fig. 5e. The steady-state temperatures of MEB beneath driving voltage being on/off is principally equivalent throughout 30 cycles, which reveals the secure thermal biking of MEB. The above outcomes recommend that the capabilities of quick thermal response and thermal biking stability make MEB probably appropriate for thermal/photothermal catalysis and past. As well as, a comparability of the regular temperature and heating fee for varied Joule heating supplies is listed in Desk S3.

In conclusion, we current a Ti3C2Tx-based composite that’s able to suppressing oxidation at excessive temperatures (increased than 400 °C) in air. We exhibit that oxygen is preferentially adsorbed on EB on account of superior oxygen adsorption. The saturated adsorption of oxygen on EB additional inhibits extra oxygen molecules to be absorbed on the floor of Ti3C2Tx as a result of weakened pd orbital hybridization between adsorbed O2 and Ti3C2Tx that’s induced by the Ti3C2Tx/EB interface coupling. As well as, our technique for suppressing the oxidation of Ti3C2Tx is unbiased of the termination ratio of Ti3C2Tx. Utilized as THz shielding materials, MEB exhibits a excessive THz EMI SE of 48 dB after annealing beneath 600 °C in an atmospheric atmosphere, which validates MEB as a promising candidate for THz shielding materials that works in a high-temperature state of affairs. Joule heating and thermal biking properties are additionally examined to increase the potential functions. The technique of designing high-temperature resistant MXene-based composite could also be relevant to different two-dimensional supplies and past.

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