Single-Layer MoS 2 -MoO 3-x Heterojunction Nanosheets with Simultaneous Photoluminescence and Co-Photocatalytic Features

: Single-layer MoS 2 -MoO 3-x heterojunction nanosheets with visible-light-sensitive band gap energy and average lateral dimensions of ~70 nm were synthesized by using a two-step combined exfoliation method. The exfoliation was initiated from pristine MoS 2 , while some sulfur sites in expanded MoS 2 sheets during exfoliating were substituted by ambient non-thermal oxygen, resulting in formation of α -MoO 3-x crystalline domains. The morphological features, crystalline structure, phase formation, number of layers, and optical properties of the MoS 2 -MoO 3-x nanosheets were determined by atomic force microscopy; X-ray diffraction; ﬁeld emission electron microscopy; transmission electron microscopy; and Raman, UV–visible–NIR, diffuse transmittance, and photoluminescence spectroscopies. The produced α -MoO 3-x domains displayed a narrower indirect band gap energy (~1.95 eV) than that of stoichiometric MoO 3 (~3 eV), and a broad light absorption range from visible to near-infrared region can act as a plasmonic material facilitating the separation of the photoinduced carriers and enhancing the photocatalytic activity of the MoS 2 domain, having ~1.75(2.16) eV indirect (direct) band gap energy. In this regard, the MoS 2 -MoO 3-x heterojunction nanosheets showed single-layer-based excitation-dependent luminescence emissions and visible-light-induced photocatalytic features, at the same time. This study can contribute to promising applications of sheet-like nanomaterials for purposes requiring simultaneous photoluminescence and photocatalytic features, such as in-vivo monitoring and targeting.


Introduction
Photocatalytic materials have attracted increasing attention in various scientific fields [1] and for various technological applications [2,3] since 1972 [4].In response to the growth of environmental pollutants and infections, photocatalysts can be widely used in environmental remediation processes such as organic pollutants decomposition [4,5]; inorganic pollutant treatment [5]; photocatalytic disinfection of bacteria [5,6], viruses [7], and parasitic organisms [8]; and photocatalytic hydrogen production for replacing fossil fuels [9][10][11].TiO 2 [12] and ZnO [13], as efficient photocatalysts, are mostly applicable in common processes, but TiO 2 's wide band gap in pure state (~3.2 eV) is considered a barrier to its use due to having an excitation wavelength in the UV region [5].This problem can be overcome by addition and/or cooperation of metallic [14] or carbon-based [15] nanomaterials.Recently, MoS 2 nanosheets have been applied as effective photocatalysts (the fewer layers, the higher the photocatalytic activity [5]), because of their excellent optical and chemical properties [5,16,17] and having a more suitable and direct band gap energy of about 1.9 eV in single-layer MoS 2 for harvesting visible light than the bulk MoS 2 , which has a small and insufficient indirect band gap (1.2 eV) [5], large surface area [18], and high in-plane carrier mobility (200-500 cm 2 /V s) in single-layer MoS 2 [16,19].MoS 2 is earth-abundant and nontoxic for environmental application [4,5].In photocatalytic processes, the existence of MoS 2 single layers results in a very high and fast absorption capacity in the visible light region due to direct band gap energy, which is greater than that of MoS 2 multilayers with indirect band gap energy [20].On the other hand, the ultrathin MoS 2 nanosheets show higher electron mobility and catalytic activity than bulk MoS 2 , which is beneficial to transferring photogenerated charges [21][22][23].The high catalytic activity of ultrathin MoS 2 nanosheets (especially 1T-MoS 2 ) is due to the number of active edge sites for catalysis [22,23].
Among various exfoliation methods for bulk MoS 2 , liquid-phase chemical exfoliation approaches for the production of MoS 2 single layers (as the nanosheets with the highest photocatalytic activity [5]) are highly attractive due to very good control of the amount of intercalated atoms [24], the high yield of MoS 2 single layers, cost-effectiveness, and mass scalability [16,19,25].The liquid-phase chemical exfoliation based on the intercalation of alkali metals such as Li and Na results in the partial loss of semiconducting 2H-MoS 2 phase [26] due to structural deformation and the change from trigonal prismatic (2H-MoS 2 , stable semiconductor phase) to octahedral (1T-MoS 2 , metastable metal phase [16,19,27].However, 1T-MoS 2 phase is unstable, so a heat treatment converts 1Tphase to 2H-phase [16].It is worth noting, though, that the existence of 1T-MoS 2 domains as co-catalyst enhances charge mobility in the material, which causes higher electrochemical and photocatalytic performances [28].In this regard, Fan et al. [29] prepared 1T@2H-MoS 2 /black-TiO 2 core-shell structures, which were applied as an effective photocatalyst for the degradation of RhB under visible light irradiation. In pure MoS 2 single layers, insufficient photocatalyst separation induces a fast photogenerated electron-hole recombination, causes a low photocatalytic activity, and finally, hinders practical application of pure MoS 2 as an efficient photocatalyst [4,30].Hence, incorporation of other photocatalyst species with appropriate properties is known as one of the effective ways to reduce the recombination efficiency of photoexcited e − h+ pairs [11,29].In this regard, MoO 3-x substoichiometric nanosheets with orthorhombic phase (α-MoO 3-x ) in corporation with MoS 2 single layers can be considered as effective co-photocatalysts, due to their excellent electrochemical, photochemical, and catalytic properties [31][32][33], which arise from the possibility of having a wide range of oxidation states ranging from +2 to +6 owing to the presence of delocalized 4d electrons [32].The α-MoO 3-x possesses a higher photocatalytic activity with narrower band gap energy than stoichiometric MoO 3 (with band gap energy of ~2.8-3.6 eV) [10,31,34].The presence of MoO 3-x domains with broad light absorption range inhibits the undesirable electron-hole recombination and promotes the electron-hole separation.Interestingly, the α-MoO 3-x phase shows a highly reactive nonmetallic plasmonic property with a strong absorption and localized surface plasmon resonance (LSPR) across the visible to near-infrared region [35][36][37][38].MoO 3-x domains with a large amount of Mo 5+ oxidation states enable easy charge carrier generation due to plasmonic effect, so that the integration of MoO 3-x as a LSPR material with MoS 2 ultrathin nanosheets provides a considerable number of active edge sites for catalysis and enhances the catalytic and light-harvesting performances [22,23,39].
In this regard, Patra et al. [39] prepared a MoS 2 /MoO 3-x /RGO nanocomposite from a MoS 2 /GO composite by a hydrothermal synthesis followed by calcination under N 2 atmosphere, since they could more greatly enhance the photocatalytic activity of MoS 2 /MoO 3-x /RGO nanocomposite than the pristine MoS 2 /GO composite.Li [30] et al. prepared the α-MoO 3 @MoS 2 hybrid rod-sphere structure via a hydrothermal method and applied it as a photocatalyst with synergistic effects for degradation of organics.Chen et al. [20] synthesized the porous MoO 3 @MoS 2 core-shell nanorods by hydrothermal method using MoO 3 nanorod as the precursor for RhB photodegradation.They reported that at a low concentration of RhB, the MoO 3 @MoS 2 sample exhibited photocatalytic degradation ability.However, few studies have been conducted on synthesis, characterization, and photocatalytic activity of MoS 2 -MoO 3-x heterojunction as photocatalyst.
In this study, single-layer MoS 2 -MoO 3-x heterojunction nanosheets were synthesized by using a two-step combined liquid-phase chemical self-exfoliation technique at room temperature.The morphological features, crystalline structure, photoluminescent properties, and optical band gap energy of the separate MoS 2 and MoO 3-x regions of the heterojunction sheets were examined.The capability of MoS 2 -MoO 3-x heterojunction nanosheets for presenting single-layer-based excitation-dependent luminescence emissions and visible-light-induced photocatalytic features at the same time was investigated.Finally, the mechanism involved in the simultaneous photoluminescence and photocatalytic activity is discussed.It should be clarified that the main goal of this work is indicating the ability to form 2D MoS 2 -MoO 3-x heterojunctions working as a photocatalyst, without any attempt at optimization.However, optimization can be considered in the future works.

Structural Analysis
The surface morphology of the synthesized MoS 2 -MoO 3-x heterojunctions were characterized by FESEM and TEM, as presented in Figure 1.In this regard, Figure 1A shows some sheet-like features with large lateral size of ~500 nm, which are often features indicating multi-layers, due to aggregation of the layers during SEM sample preparation.The presence of some structural edge defects and disorder (as marked with yellow rectangular in FESEM image) are distinguishable in the image.It should be noted that our SEM experiences showed that imaging as well as distinguishing the single-and/or multi-layer sheets were very hard.Therefore, for obtaining a SEM image with distinguishable sheetlike features, we selected the aggregated samples (in contrast to the sample preparations considered for AFM and TEM).This means that any condition resulting in aggregation of the sheets can result in the morphologies presented in the SEM image.
In Figure 1B, a better presentation for the unaggregated sheets is given.The more transparent regions can be assigned to the presence of single-layer sheets, and the dark regions are attributed to overlapping of the sheets.The light-brown transparent solution shown in Figure 1C also demonstrated high uniform dispersion and solubility of the sheets in water without any sedimentation.
The morphology, thickness and the lateral dimensions of the sheets were investigated by AFM, as shown in Figure 2. The thickness of single-layer MoS 2 or MoO 3-x is almost the same at about 0.6-0.7 nm [34,40,41].In this work, the thickness of the sheets obtained through the height profile analysis was found to be ~0.6-1.0 nm, indicating the presence of single layers in the synthesized samples.The height profiles along the randomly selected colored cross-lines in Figure 2A exhibit single-and bi-layers of the sheets with lateral sizes ~200 nm.The histograms B and C present statistical data of the layer number and lateral size distribution of the sheets, respectively.The average lateral dimension of MoS 2 -MoO 3-x single layers is ~70 nm (histogram C).The MoS 2 -MoO 3-x heterojunctions with lateral size below 100 nm are often single-layer.It should be noted that although the lateral dimension of ~70 nm is not distinguished as a critical size in our work, we tried to reduce the lateral dimension down to values lower than 100 nm, in order to obtain intensive as well as sharp PL peaks.In addition, further reduction in the lateral dimension corresponds to higher metallic edge defects and therefore better catalytic features for layered materials [42,43].The crystal structure and phase formation of the samples were determined by XRD characterization technique, as shown in Figure 3.In XRD pattern (Figure 3a), the (002) peak of pristine MoS 2 related to the hexagonal 2H-MoS 2 was separated into two diffraction peaks of (001) 1T-MoS2 and (002) 2H-MoS2 in MoS 2 -MoO 3-x heterojunction, indicating the interlayer expansion along the c-axis [19,27,44] and a successful exfoliation as well as the presence of two-phase MoS 2 (1T-and 2H-MoS 2 ) [44].The interlayer spacing of (002) basal planes of the hexagonal 2H-MoS 2 structure were enlarged from 6.1 A • in the pristine MoS 2 to 12.11 A • in the prepared heterojunction, due to effective exfoliation by sodium naphthalenide.In fact, the use of Na with ionic radius several times larger than that of Li, the use of sodium naphthalenide (Na + C 10 H 8 − ) as an effective intercalant [19], and the persistence of a water double layer in the interlayer region due to the insertion of one or two water molecules per intercalated metal atom [24,27] resulted in much change in the interlayer.The peaks related to MoS 2 significantly weakened in the heterojunction sample due to exfoliating to single layers [45].As observed in Figure 3a, a weak hump (broadband) appeared between 20 and 40 • , attributed to MoO 3-x structure in the prepared heterojunction.The appearance of (0k0) preferred orientations (k = 2, 4, and 6) in XRD pattern were ascribed to MoO 3-x orthorhombic structure [11,38,46].It should be noted that the XRD pattern of the layered MoS 2 -MoO 3-x sample is not perfect, due to the low thickness of the layers and low crystallization of the nonstoichiometric composition.On the other hand, the XRD pattern related to MoS 2 is sharp, because it is in a bulk state.Raman spectroscopy is also utilized to determine the structure as well as the layer numbers of the MoS 2 -based sheets [18,26,47,48].In Raman spectrum of MoS 2 -MoO 3-x heterojunction (Figure 3b), the appearance of E 1g , E 1 2g , and A 1g longitudinal acoustic phonon modes verified the existence of 2H-MoS 2 phase after the liquid-phase chemical exfoliation [18,44].Two characteristic Raman peaks at 379.89 and 397.89 cm −1 were ascribed to E 1 2g and A 1g active modes, respectively [18,47,48].The frequency difference in thickness dependency between E 1 2g and A 1g phonon modes indicates the number of layers of MoS 2 [49], as this frequency difference decreases with a reduction in the number of layers [49,50].The frequency differences of 18, 22.4, 23.7, 24.3, and 25.1 cm −1 are attributed to 1, 2, 3, and 4 L and bulk MoS 2 , respectively [48,49,51,52].In fact, the reducing of the layer numbers of MoS 2 and, subsequently, the decreasing of the interlayer Van der Waals force result in the absent influence of neighboring layers on the effective restoring forces on atoms, lacking suppression of atomic vibrations, a decrease in long-range Coulomb interactions, and eventually, a decrease in the space between the Raman modes of E 1 2g and A 1g compared to bulk MoS 2 [48,51].In this work, the difference of 18 cm −1 confirmed the successful exfoliation of pristine MoS 2 to single-layer MoS 2 -MoO 3-x heterojunction sheets.Moreover, the J 1 and J 2 modes are attributed to the 1T-MoS 2 unstable phase [16,26,27] due to the sodium intercalation.The peaks located at 166, 185, and 198 cm −1 are related to MoO 3-x .0.5 H 2 O [53].In addition, the peaks at 116 cm −1 (transitional mode), 129 cm −1 (transitional mode), 243 cm −1 (τ O=Mo=O twist mode), 286 cm −1 (δ O=M=O wagging), and 298 cm −1 (δ O=M=O wagging) indicate the formation of MoO 3-x domains in the samples [54].

Optical Analysis
The optical absorption in the UV-visible and NIR regions is a characteristic related to the band structure of a semiconductor [55].In order to study the optical properties of the MoS 2 -MoO 3-x heterojunction sheets, the optical spectrum of the heterojunction sheets and the pristine MoS 2 were studied, as shown in Figure 4.The peaks related to the MoS 2 and MoO 3-x phases were marked by (•) and (*) signs, respectively.No characteristic absorption peaks appeared in the pristine MoS 2 spectrum (Figure 4a), because it has an indirect band gap [45,55].The electronic, optical, and electrochemical properties of nano-scale semiconductors are size-dependent due to quantum confinement [56].Concerning this, the absorption peaks located at 352 and 396 nm in Figure 4b can be assigned to the presence of MoS 2 nanosheets with small sizes due to the quantum confinement effect [17,56,57].Meanwhile, the absorption peaks observed at 244 and 270 nm of the UV region can be ascribed to the excitonic characteristics of MoS 2 QDs [17,18,47].It is worth noting that the single-layer 2H-MoS 2 has the two low-energy absorption peaks of A and B between 600 and 700 nm as the excitonic peaks [17,58,59].The valence band (VB) is split at the K-point of the Brillouin zone due to spin-orbit coupling (SOC), which results in the generation of two separate exciton bands (A and B excitonic bands) and the direct gap transitions [17,[58][59][60].In this work, MoS 2 -MoO 3-x single layers with average lateral dimensions of ~70 nm possess the excitonic absorption peaks of A and B between 600 and 700 nm.There are two pairs of excitonic peaks of single-layer MoS 2 , i.e., (A 1 , B 1 ) and (A 2 , B 2 ) peaks (see the inset of Figure 4b), because of the existence of dispersity in the lateral size of single layers.The position and photon energy of excitonic peaks related to the single-layer MoS 2 domains in single-layer heterojunctions are evaluated and presented in Figure 4c using the equation E g = hc /λ (E g , h, c, and λ are energy gap, Planck's constant, light speed, and wavelength of absorption peak, respectively) [45].The splitting energy difference of 0.14 and 0.15 eV between exciton peaks A and B (Figure 4c) confirmed the existence of MoS 2 single layers in our sample, while it increased with increasing MoS 2 film thickness, reaching 0.16 eV in the bilayer and 0.19 eV in the bulk [17,58].The high-energy exciton peak C at 498 nm (2.48 eV) originates from inter-band transitions with high state density from the deep valence band to the conduction of MoS 2 nanosheets [17,56,58,59].The peak C at 2.48 eV can be associated with the optical absorption of 2H-MoS 2 small-sized nanosheets due to the quantum effects [17,58].
In the absorption spectrum of the MoS 2 -MoO 3-x heterojunction sheets, the optical absorption peak at 316 nm was attributed to the MoO 3-x QDs [10,33,46,54,61].The peaks located at 731 and 963 nm in the visible and NIR regions were related to the LSPR optical absorption of plasmonic MoO 3-x domains [10,35,37,38,54] which are highly effective for photocatalytic activities [9,37].In fact, the appearance of LSPR peaks confirmed the existence of oxygen-vacancy-rich MoO 3-x domains with strong reducing capacity [35].The presence of MoO 3-x phase in the nanosheets is expected to replace or complement the noble metals in a wide range of photonic applications [37].Figure 4d,e show optical microscopic images of the MoS 2 -MoO 3-x heterojunction sheets with magnification of 400× and 1000×, respectively.The difference in color observed is due to the difference in the number of layers of nanosheets.
The absorption spectrum is sufficient to investigate the energy levels of MoS 2 -MoO 3-x heterojunction.However, some specific signatures in PL emission spectra strongly confirm the presence of single layers and MoS 2 phase domain in heterojunction [17,49,58].Hence, PL spectroscopy was carried out for further examination of heterojunction.The PL spectra are also helpful to investigate optical properties such as the separation and recombination of electron-hole pairs as the primary processes in the field of photocatalysis [62].The photoluminescence emission (PLE) spectra of heterojunction sheets were recorded at excitation wavelengths of 250, 300, 370, 400, 450, 485, 500, and 532 nm, at room temperature (Figure 5).The MoS 2 -MoO 3-x heterojunction sheets showed the excitation-dependent luminescence emissions, because both MoS 2 and MoO 3-x nanosheets possess excitation-dependent PL emissions [17,36,46,47].In Figure 5, the emission peaks related to the MoS 2 and MoO 3-x phases were marked with • and * signs, respectively.In the wavelength range between 600 and 700 nm, the PL peaks of A ex , B ex and A ex , B ex were attributed to excitations of single-layer MoS 2 domains of MoS 2 -MoO 3-x heterojunction nanosheets [47,49,58,60].The peaks of A ex , A ex and B ex ,B ex are associated with the direct gap transitions at K A K A (K B K B ) points, the Brillouin zone, and the energy difference between the A ex and B ex peaks or A ex and B ex peaks, corresponding to the valence-band splitting due to the strong spin−orbital interaction [43,49].The existence of the two pair PL emission peaks is due to the dispersion in lateral size of single-layer MoS 2 domains of heterojunctions.The direct gap transitions of the B ex and B ex peaks happen between the conduction band and a lower-lying valence band [43].The weak intensity of excitation peaks of (A ex , B ex ) and (A ex , B ex ) indicates the low recombination of photoexcited charge carriers due to the effective separation of the photoexcited charge carriers [11].The PLE peaks located at 684 nm (spectrum f) and 679 nm (spectrum of h) are attributed to the MoS 2 bound excitons formed by localized excitons at defect sites [26], and these emission peaks can also be related to the direct band gap emissions [63].Generally, the MoS 2 nanosheets (depending on their size and the excitation wavelength) possess emission around 450-600 nm due to quantum confinement [17].Hence, in this work, the obvious emission maxima located at 564, 563, 575, 579, 564, 575, 578 [64], 569 [17,64], 524, 546 [57], 530, 531, and 544 nm [17,57] can be attributed to surface recombination in quantum-confined MoS 2 regions [64].MoS 2 QDs with excitation-dependent characteristic emission spectra emit a distinct blue PL under UV excitation wavelengths [47].In spectra of Figure 5, the obvious emissions located at 424, 423 [18,47], 339 [48], 392 [18], 415 [47,57], 442, and 446 nm [65] excited by the wavelengths of 250, 300, 350, 370, and 400 nm were attributed to the MoS 2 nanoscale regions.
The PL analysis for MoO 3-x nanostructures is an important characteristic that offers extraordinary optical properties owing to the wide range of nonstoichiometric MoO 3-x [36].The optical band gap energies and PL emissions of MoO 3-x nanostructures are also excitationdependent [36,46] due to oxygen vacancies and defects [46].The PLE peaks observed at 720, 722, 723, 726, and 721 nm (see the spectra of e-i of Figure 5) were ascribed to the MoO 3-x nanoscale domains [66].The PLE peaks that were excited with the different wavelengths located at 466, 460, 463 [36,46], 485, 482, 487 [46,61,67], 589 [46,66], 487 [46], 508, and 507 nm [46] correspond to the presence of MoO 3-x QDs in the samples.The PLE peaks at 466, 460, and 463 nm can also be related to the band-to-band radiative recombination of photo-excited electrons and holes [36], and the PLE peaks at 485, 482, and 487 nm can be related to recombination between the conduction bands and the valence bands in MoO 3-x [66].As a basic feature, the generated hole-electron pairs in plasmonic MoO 3-x nanomaterials under irradiation of LSPR excitation can activate chemical reactions (such as water splitting, methylene blue reduction) on their surface [35,37].
To estimate the optical band gap energy (E g ) of the MoS 2 -MoO 3-x heterojunction sheets, the optical transmittance spectrum of the samples was recorded by DTS.Then, the Tauc plot was used to determine the band gap of the samples using Tauc's relation where hν is the incident photon energy, C is the proportionality constant, E g is the band gap energy, and n = 1 /2 and 2 for direct and indirect band gap, respectively [60,68,69].In this regard, the curves of (αhν) 2 and (αhν) 1/2 versus photon energy (hν), derived from the transmittance spectra, were fitted to the Tauc model [34,60] (see Figure 6).The band gap energy of 2.16 and 2.36 eV (Figure 6a) can be ascribed to the direct band gap energies of single-layer MoS 2 domains of the heterojunctions, and the value of 1.75 eV (Figure 6b) can be assigned to the indirect band gap energy of the part of MoS 2 nanosheets of heterojunctions.The up-shift of MoS 2 indirect band gap energy from 1.2 eV in pristine to 1.75 eV in nanosheets indicates effective exfoliation and induced quantum confinement [59,70].Moreover, the values of 1.95 and 2.25 eV can be ascribed to the indirect band gap energies of MoO 3-x domains (Figure 6b).The existence of two direct band gap energies is owing to the dispersion in lateral sizes of single-layer MoS 2 domains of heterojunctions, and the existence of two indirect band gap energies related to MoO 3-x domains is due to the presence of oxygen vacancies in MoO 3-x .The narrower indirect band gap energy of MoO 3-x domains of the heterojunction nanosheets (~1.95 and 2.25 eV) than that of MoO 3 (~3 eV) is due to the existence of oxygen vacancies, which improve the carriers' mobility and enhance photocatalytic activity [10,30,71].The simultaneous presence of direct and indirect band gap energies in the MoS 2 -MoO 3-x heterojunction sheets, especially the smaller indirect band gap energies as compared to the larger direct band gap ones, provides a more efficient photocatalyst under visible as well as solar light irradiation [69].

Photocatalytic Activity Test
The MoS 2 -MoO 3-x heterojunction can be employed as a novel and efficient photocatalyst for harvesting the visible light due to superior adsorption capacity, tunable band structure of MoS 2 and MoO 3-x , and the effective separation of electron-hole pairs [4,11,35,37,54].The simultaneous presence of considerable open metal edges, ultrathin nanosheets, 1T-MoS 2 structural phase, sheet-like morphology, and high surface area in MoS 2 -MoO 3-x heterojunctions result in extraordinary catalytic activity [22,23,72].The MoO 3-x domains also enhance the photocatalytic activity by broadening the light absorption range from 200 to 1000 nm, due to the oxygen vacancies facilitating the separation of photoexcited electron-hole pairs and preventing their fast recombination [11,30,41].In this work, the photocatalytic performance of MoS 2 -MoO 3-x heterojunction nanosheets was examined by photocatalytic degradation of methylene blue (MB) dye under visible light irradiation.The emission spectrum of the LED lamp applied in the photocatalytic test (which is located at 449 nm (2.76 eV) and 553 nm (2.32 eV) visible light range) is shown in Figure 7A (in the inset).This source would be suitable for exciting the electron-hole pairs of MoS 2 -MoO 3-x heterojunctions due to values of the direct and indirect band gap energies including 2.16, 2.36, 1.75, 1.95, and 2.25 eV determined by the DTS analysis (see, Figure 6).The characteristic absorption of MB at 665 nm [33] was chosen as the parameter to be monitored for the photocatalytic degradation process.The CB and VB edge positions of MoS 2 and MoO 3-x can be calculated by the DTS spectra and Mott-Schottky (MS) plots as reported by Huang et al. [11].In this regard, the band gap energies of MoS 2 and MoO 3-x were calculated by DTS analysis (Figure 6), and then the approximate positions of their conduction band (CB) and valence band (VB) were estimated using References [11,20,21].There are two approaches to describing the mechanism of the photocatalytic process: (1) Under light excitation, the excited electron can easily transfer from the MoS 2 CB (conduction band) to the MoO 3-x CB, and the holes in the MoO 3-x VB (valance band) can easily transfer to the MoS 2 VB [30].However, according to the literature, the CB potential of MoO 3-x (0.34 V) is more positive than that of O 2 / • O 2 − (−0.33 V), and thus the superoxide anions ( • O 2 − ) could not be generated [11], while the • O 2 − is the major active species in dye degradation.Therefore, another approach would be considered for the photocatalytic activity of the MoS 2 -MoO 3-x heterojunction.(2) The excited electrons of MoS 2 and MoO 3-x can separately jump from their VB to CB, at step 1 (see Figure 7B).The 1T-MoS 2 phase as a co-catalyst with special metal properties is a good electron acceptor, which can facilitate and accelerate the electron transfer to participate in the redox reaction and eventually enhances photocatalytic activity [29,39].Hence, the excited-state electrons in the 2H-MoS 2 and α-MoO 3-x tend to transfer onto 1T-MoS 2 [29].Meanwhile, oxygen vacancies (O v ) in MoO 3-x with broad light absorption range can serve as a recombination center to keep the charge balance [11].Oxygen vacancies can receive the electrons from the 1T-MoS 2 (electrons transferred from α-MoO 3-x to 1T-MoS 2 ) and holes from MoS 2 VB (step 2) [11].Thus, oxygen vacancies (O v ) of the MoO 3-x cause the promotion of the separation efficiency of photoexcited charge carriers and eventually enhance photocatalytic activity of MoS 2 -MoO 3-x heterojunction [11].The effective separation of the electron-hole pairs may contribute to producing a high amount of active radicals from the harvested photons according to the following reactions in step 3 [29,30,62,66,69]:

. (Degradation or oxidation of MB)
Upon light excitation, the generated electron-hole pairs are trapped on the surface of the photocatalyst, while water and hydroxyl groups are subsequently adsorbed on it.The generated electron-hole pairs initiate redox reactions; the holes in MoO 3-x may react with absorbed water or hydroxide ions as hole scavengers (hole acceptor) to form strong oxidizing hydroxyl radicals (OH • ) [29,30,66].In addition, the excited electrons in the 2H-MoS 2 , which can transfer into the 1T-MoS 2 as a co-catalyst, can react with adsorbed oxygen, as electron scavengers (electron acceptor) can produce the oxidizing radicals ( • O 2 − and H 2 O 2 ) and eventually the hydroxyl radicals (OH • ) [29,30].Meanwhile, the oxidizing radicals of • O 2 − and H 2 O 2 prevent the recombination of the photoinduced e − h+ pairs and enhance quantum efficiency and photocatalytic activity [30,73].During photocatalytic degradation, the generated active radical species such as OH • and HO 2 • first break the N-CH 3 bond, and then -CH 3 is oxidized to form HCHO or HCOOH [74].The free radicals (OH • and HO 2 • ) then break the C-S and C-N bonds of thionine molecules to produce relatively unstable smaller organic byproducts.These oxidization reactions continue until the MB degrades completely to produce smaller inorganic molecules, such as H 2 O, Cl − , CO 2 , SO 4 2− , and NO 3 [74].Here, the main characteristics of MoS 2 -MoO 3-x single-layer heterojunction are compared with the corresponding heterojunction samples in Table 1.The extraordinary photocatalytic activity of MoS 2 -MoO 3-x heterojunction under visible light can be ascribed to following factors: (1) the existence of MoS 2 single layers with a very high and fast absorption capacity in the visible light region due to direct band gap energy and larger value than the indirect band gap energies; (2) the presence of the ultrathin 1T-and 2H-MoS 2 nanosheets with high electron mobility and catalytic activity; (3) the presence of MoO 3-x domains as plasmonic photocatalyst with narrow band gap energy and broad light absorption range, which facilitate charge carrier generation, inhibit the undesirable electron-hole recombination, and promote the electron-hole separation; and (4) the synergistic effect of the 1T/2H-MoS 2 and MoO 3-x heterojunction sheets in the promotion of the separation of the photoelectron-hole pairs.

Conclusions
In summary, single-layer MoS 2 -MoO 3-x heterojunction nanosheets (with lateral average dimensions of ~70 nm) were synthesized through a two-step combined method.The nanosheets showed an excitation-dependent PL behavior along with visible-light-induced photocatalytic activity.The existence of plasmonic MoO 3-x domains with a broad light absorption due to the oxygen vacancies promoted the essential photocatalytic activity of single-layer MoS 2 sheets by facilitating separation of photoexcited electron-hole pairs and preventing their fast recombination.Moreover, formation of the co-catalyst 1T-MoS 2 phase with special metallic properties (such as working as an electron acceptor) resulted in facilitating and accelerating the electron transfer for participation in the redox reaction and eventually enhancing the photocatalytic activity.This research can drive further works on fabrication of 2D materials having domains with various chemical compositions in a single sheet, i.e., 2D heterojunctions.The unique characteristics of the synthesized MoS 2 -MoO 3-x heterojunction nanosheets can result in promising applications in upcoming nanotechnology-based medicine, which highly requires biocompatible nanomaterials with simultaneous photoluminescence and photocatalytic features, such as tumor targeting, imaging, and phototherapy.In the first step, 100 mL anhydrous tetrahydrofuran (THF) was poured into a 500 mL laboratory glass bottle followed by adding 8 g naphthalene.The mixture was continuously stirred using a magnetic bar (500 rpm) to allow mass transfer.Then, to prepare alkali naphthalenide solution, 1.4 g sodium metal was added to the mixture.In order to prevent sodium oxidation, sodium was stored in paraffin oil.It was washed with N-hexane before being used to remove paraffin oil, completely.In order to enhance the reaction kinetics and to prevent sodium oxidation, sodium metal was wired and added to the mixture at a very high speed.After complete dissolution of sodium by vigorous stirring for 2 h, a dark-blue mixture was obtained.Then, for intercalating sodium naphthalenide into the pristine MoS 2 , 2.0 g powder of pristine MoS 2 was dispersed in the reaction mixture and stirred for 12 h.

Experimental Section
The sodium-intercalated materials were exfoliated by slowly adding 200 mL DI water.By adding DI water, the self-exfoliation process, along with oxidation and hydration reactions, proceeded much more intensively into the interlayer space, resulting in effective exfoliation.In this step, the hydrogen gas as a byproduct was generated in the form of a large number of bubbles due to the reaction of water with the intercalated sodium between the MoS 2 layers, which break and exfoliate the layered MoS 2 as the driving force of spatial separation of the layers (as previously applied for graphene exfoliation [75]).The mixture is post-sonicated in a low-power ice-water sonic bath for 1 h [19], in order to complete the exfoliating and to form a homogeneous suspension through a sonochemical cavitation phenomena [17].The resultant dark-blue dispersion with pH = 12 was produced and considered an initial dispersion (Figure 8).In the centrifugation cascades, the sediments were discarded, while the supernatants were applied for the next centrifugation.Finally, 11,000 rpm supernatant contained a large number of MoS 2 -MoO 3-x single-layer heterojunctions.For MB photocatalytic degradation, 11,000 rpm supernatant was used.The discarded sediment in each step is referred to as (DS).

The Centrifugation Cascades for Extracting MoS 2 -MoO 3-x Single-Layer Heterojunctions
The second step involves washing and extracting single-layer MoS 2 -MoO 3-x heterojunction nanosheets from the initial dispersion.In order to remove THF as solvent, excess sodium, NaOH, and access to neutral solution pH, the initial dispersion was washed 4 times with DI water by centrifuging dispersion in 21,000 rpm (41,415 g).The resultant sediments were redispersed in DI water by mild sonication every time.The earlier centrifuges were performed at a very low temperature to prevent the ignition of tetrahydrofuran.After the fourth washing, the sediment was redispersed and the obtained dispersion was considered as the washed dispersion (Figure 8).The dispersed single-layer heterojunctions can be separated from initial dispersion using controlled centrifugation cascades (Table 2) by sequentially increasing rotation speeds [76].This was performed by a short initial centrifugation at low rpm to eliminate thick and unexfoliated flakes in the sediment, and the obtained supernatant was centrifuged at a faster rpm in the next step.Thus, the resultant supernatant and sediment in each step of centrifugation included thinner and thick nanosheets, respectively.Finally, in the fifth centrifugation step, the 11,000 rpm supernatant (SN) included a large number of single-layer MoS 2 -MoO 3-x heterojunction nanosheets.All centrifugations were performed at room temperature, and all grey-black sediments were discarded.Finally, after consecutive centrifugation cascades, the obtained 11,000 rpm SN were washed with isopropyl alcohol (IPA) for removing organic material residues (ROMs) by centrifuging 11,000 rpm SN in 21,000 rpm for 10 min.The obtained sediment was redispersed in DI water again.A schematic of a two-step combined method for preparing MoS 2 -MoO 3-x single-layer heterojunctions dispersed into 11,000 rpm SN is presented in Figure 8.

The Application of MoS 2 -MoO 3-x Heterojunctions for MB Photocatalytic Degradation
In a typical degradation experiment, 5 mL methylene blue solution with a concentration of 10 − 5 mM and 10 mL of 11,000 rpm SN with a concentration of 0.14 mg/mL were added into a 30 mL Pyrex beaker, and then they were magnetically and continuously stirred in the dark for a few minutes to ensure establishment of an adsorption-desorption equilibrium on the surface of the photocatalyst.The equilibrium concentration of MB in contact with the dispersed photocatalytic heterojunctions was considered as the initial MB concentration before the start of irradiation, which is referred to as solution before irradiation (S 0 ).The Pyrex beaker containing solution of MB and photocatalyst was placed from 4 directions under 8 LED light irradiation of 1 W at a distance of approximately 10 cm from LED lamps (2 LEDs on each side).The solution after irradiation of a few hours was considered as the solution after irradiation (S t ).

Material Characterizations
The surface morphology of the samples was investigated by field-emission-scanning electron microscope (FESEM) using a MIRA3TESCAN-XMU (TESCAN, Brno, Czech Republic).The transmission electron microscopy (TEM) image of the nanosheets was accessed

Figure 2 .
Figure 2. Topographical characterization: (A) AFM image of MoS 2 -MoO 3-x heterojunction sheets, (a1,a2) height profiles of the indexed lines overlaid on the AFM image, and (B,C) statistical data of the layer number and lateral size distribution of the sheets, respectively.The inset of (C) presents a magnified view of the lateral size below 200 nm.

Figure 3 .
Figure 3. Structural characterization: (a) XRD patterns of pristine MoS 2 and MoS 2 -MoO 3-x heterojunction and (b) Raman spectrum of the MoS 2 -MoO 3-x heterojunction.The peaks related to MoS 2 and MoO 3-x of heterojunction were marked with • and * signs, respectively.The ID in (a) is the interlayer distance of (002) basal planes of MoS 2 in pristine and heterojunction samples.The black solid lines and short dash lines in (b) show the peaks related to 1T-MoS 2 and 2H-MoS 2 phase structures, respectively.

Figure 4 .
Figure 4. UV-Vis-NIR absorption spectra of pristine MoS 2 (a) and MoS 2 -MoO 3-x heterojunction sheets (b).The optical absorption peaks related to MoS 2 and MoO 3-x phases were marked with (•) and (*) signs, respectively.The inset of (b) shows a magnified view from 600 to 700 nm of the spectrum wavelength, in which the observed absorption peaks at A1, B1 and A2, B2 correspond to excitonic transitions of single-layer MoS 2 phase in single-layer heterojunctions.The positions and photon energy of excitonic peaks are given in (c), while the B-A shows the splitting energy difference between the exciton peaks due to spin-orbit coupling.Optical microscope images of the MoS 2 -MoO 3-x heterojunction sheets with magnifications of 400 (d) and 1000 (e).

Figure 5 .
Figure 5.The excitation-dependent PL emission spectra of the MoS 2 -MoO 3-x heterojunction sheets with different excitation wavelengths of (a) 250, (b) 300, (c) 350, (d) 370, (e) 400, (f) 450, (g) 485, (h) 500 and (i) 532 nm.The peaks related to MoS 2 and MoO 3-x were marked with • and * signs, respectively.The PL emission peaks of the single-layer MoS 2 domains of the heterojunctions corresponding to the A, B or A , B excitons are shown with A ex , B ex and A ex , B ex .

Figure 6 .
Figure 6.Tauc's plot for (a) direct and (b) indirect band gap energies of MoS 2 -MoO 3-x heterojunction sheets.The direct band gap was attributed to the MoS 2 domains.The indirect band gap can be originated from both MoS 2 and MoO 3-x domains in the heterojunction sheets.The intercept of red dash lines with the horizontal axis defines the value of the band gaps.

Figure 7 .
Figure 7. Photocatalytic degradation: (A) UV-visible absorbance spectra of the solution containing MB and MoS 2 -MoO 3-x nanosheets before irradiation (S 0 ) and after irradiation (S t ).(B) A schematic diagram describing the photocatalytic mechanism of the MoS 2 -MoO 3-x heterojunction in MB degradation.Inset of (a) shows the emission spectrum of the applied LED source applied in the photocatalytic tests.The oxygen vacancies of MoO 3-x domains in heterojunction were shown by O v .The CB and VB show the estimated approximate position of conduction band (CB) and valence band (VB).

Figure 8 .
Figure 8. Schematic illustration of the preparation of MoS 2 -MoO 3-x single-layer heterojunctions by a two-step combined method.In the centrifugation cascades, the sediments were discarded, while the supernatants were applied for the next centrifugation.Finally, 11,000 rpm supernatant contained a large number of MoS 2 -MoO 3-x single-layer heterojunctions.For MB photocatalytic degradation, 11,000 rpm supernatant was used.The discarded sediment in each step is referred to as (DS).

Table 1 .
Comparing some characteristics of similar MoS 2 -MoO 3 heterojunction nanomaterials used as photocatalysts.