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1 Layered Sulfur Nanosheets Prepared by Assembly of Sulfur

2 Quantum Dots: Implications for Wide Optical Absorption and

3 Multiwavelength Photoluminescence

4 Zhuangwei Bai, Lihua Shen,* Jianhang Wei, Yuangang Li, Azhar Abbas, Yinyan Li, Mengnan Qu,
5 Dongdong Zhang,* and Chengxiao Zhang*

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sı Supporting Information

6 ABSTRACT: Preparation, characterization, and optical properties of layered

7 sulfur nanosheets (S-NSs) from natural sublimed sulfur were reported in this
8 work. Few-layered S-NSs were prepared by a developed liquid-phase method
9 including three steps: (1) forming sulfur quantum dots from natural sublimed
10 sulfur; (2) forming multilayered nanosheets by assembling sulfur quantum
11 dots through the hydrothermal method; and (3) sonication exfoliation of the
12 multilayered S-NSs. The thinnest S-NSs (sulfurene) with a 0.84 nm thickness
13 were obtained by the developed method. The obtained S-NSs showed wide-
14 range absorption from ultraviolet to the visible region, multiwavelength
15 photoluminescence, and superb water dispersibility and stability over two months in air. A reduction current peak was observed at
16 −1.2 V (vs Ag/AgCl, Sat. KCl) on a fluorine-doped tin oxide electrode in 0.010 M HCl containing S-NSs, which is attributed to the
17 reduction from S0 to S2− of the S-NSs. These alternative two-dimensional (2D) nanosheets of S-NSs with good stability and water
18 dispersibility will provide opportunities for the research fields of visible-light-active photocatalysis and optical sensing.
19 KEYWORDS: sulfur nanosheets, sulfurene, hydrothermal assembly, optical absorption, photoluminescence

1. INTRODUCTION are difficult to be obtained; (2) some lamellar materials 45

The two-dimensional (2D) layered nanomaterials of graphene obtained have inferior dispersibility and stability. Thus, 2D 46
20
have brought a revolutionary development in chemistry.1−3 materials that are easily prepared and have good stability are 47
21
However, layered graphene materials have zero band gap, highly desirable. 48
22
which limits their further applications in the semiconductor Based on the above research and some limitations, in this 49
23
field. Therefore, much effort has been made on searching work, we selected sublimed sulfur as a raw material to prepare 50
24
layered graphene analogues such as boron nitride layer layered sulfur nanosheets (S-NSs). Sublimed sulfur is 51
25
material,4,5 transition metal layer material (e.g., MoS2),6,7 abundant, low-cost, environmentally friendly, and possesses 52
26
black phosphorene,8 and other 2D nanomaterials such as remarkable optical stability.23 With excellent theoretical 53
27
germanene,9 tellurene,10 and selenene.11 Li et al. first fabricated specific capacitance, sulfur has also been widely used in the 54
28
boron nitride nanosheets from boron nitride powder by the research of Li−S batteries.23,24 Moreover, sulfur nanoparticles 55
29
wet ball milling method.4 Layered boron nitride (BN) have unique bactericidal and anti-inflammatory properties.25 56
30
nanomaterials are electrically insulating (a band gap of ∼5−6 Recently, the emergence of sulfur quantum dots26−29 has 57
31
aroused an upsurge in the research on sulfur nanomaterials. 58
32 eV), have profound chemical and thermal stability, and at the
same time are equally thermally conductive and mechanically Our group has successfully prepared sulfur quantum dots, 59
33
robust as their C counterparts, which can be used for sensors which have excellent optical properties (fluorescence, electro- 60
34
chemiluminescence, and chemiluminescence) and good 61
35 and detectors.12−14 Nevertheless, it is a fact that the well-
defined synthesis of BN-based nanostructures is a much more aqueous dispersibility.26 Up to now, only Jin et al. used S- 62
36
NSs as cathode active materials in Li−sulfur batteries,24 which 63
37 challenging task compared to the case of C. Accordingly, the
38 study of MoS2 and black phosphorus has drawn tremendous
39 attention due to their tunable band gap. However, multiple Received: July 25, 2020
40 layered molybdenum disulfide belongs to indirect band gap Accepted: November 1, 2020
41 materials and15,16 black phosphorus is unstable and is easy to
42 be oxidized.17−22 The existing 2D materials have the following
43 disadvantages: (1) the preparation method is tedious and
44 difficult to operate, in particular, monolayered nanomaterials

© XXXX American Chemical Society https://dx.doi.org/10.1021/acsanm.0c02024

A ACS Appl. Nano Mater. XXXX, XXX, XXX−XXX
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Scheme 1. Schematic Illustration of the Preparation of Multilayer S-NSs (a) and Sulfur Nanorods (b)

64 were obtained by the ball milling of commercial sulfur in the

65 presence of dopamine. The important and closely related
66 optical properties of S-NSs have not been of concern so far.
67 Herein, the S-NSs with monolayer or atomic layer
68 thicknesses are prepared by a simple liquid-phase hydrothermal
69 method through the assembly of sulfur quantum dots.
70 Monolayered sulfur nanosheets (sulfurene) with a thickness
71 of 0.84 nm were observed by further sonication exfoliation of
72 the obtained multilayer S-NSs. Their distinct optical properties
73 including wide-range optical absorption and multiwavelength
74 photoluminescence (PL) emission with satisfactory stability
75 have been investigated. The as-obtained S-NSs have excellent
76 water dispersibility, and their eletrochemical properties in an
77 aqueous medium have been investigated. The distinct wide-
78 range optical absorption properties from ultraviolet to the
79 visible region may find potential applications in photochemical
80 sensing or photocatalysis field.

2. RESULTS AND DISCUSSION

81 2.1. Preparation of Multilayer S-NSs. A schematic
82 diagram for the preparation of multilayer S-NSs by the
83 hydrothermal assembling of sulfur quantum dots is shown in
s1 84 Scheme 1.26 The first step aims to dissolve sublimed sulfur. Figure 1. TEM of the multilayer S-NSs without dialysis (a), sulfur
85 The sublimed sulfur powder (1.4 g) was first treated with nitric quantum dots (inset of (a)), sulfur nanorods (b), multilayer S-NSs
86 acid at 70 °C for 48 h. The suspension of the sulfur powder after dialysis (c), selected area electron diffraction (SEAD) pattern of
the multilayer S-NSs (inset of (c)), and high-resolution TEM
87 was centrifuged and the sediment was washed with ultrapure (HRTEM) image of the multilayer S-NSs (d).
88 water. Then, the ultrapure water (50 mL) and poly(ethylene
89 glycol) (PEG)-400 (3 mL) were added and stirred with the
90 above-obtained sulfur for 0.5 h in a round-bottom flask at NSs obtained were dialyzed to remove redundant sulfur 107
91 room temperature. Further, NaOH (4 g) was added to the quantum dots and small molecules. Sonication exfoliation of 108
92 round-bottom flask and the mixture was continuously stirred at the above-obtained multilayer S-NSs indicate that S-NSs have 109
93 70 °C for 24 h. The sublimed sulfur powder started dissolving different thicknesses. The thinnest S-NS that has ever been 110
94 gradually on heating, and the suspension of sulfur turned into a observed referred to as a monolayer sulfur nanosheet or 111
95 red transparent solution.26 Second, after the dissolution of sulfurene. 112
96 sublimed sulfur, 30% H2O2 (2.1 mL) was added into the Besides, it is found that sulfur nanorods can also be prepared 113
97 mixture (15 mL, the final concentration of H2O2 is 3.7%) using a similar procedure except that 0.35 mL of 30% H2O2 114
98 under vigorous stirring, resulting in the formation of a light was added to the mixture (final concentration of H2O2 is 115
99 yellow transparent sulfur quantum dot colloid. The morphol- 0.68%) instead of 2.1 mL. The details are given in Section 1 of 116
100 ogies of the sulfur quantum dots were observed by trans- the Supporting Information (SI). It was supposed that the 117
101 mission electron microscopy (TEM), as shown in Figure S1 hydrothermal process was the crucial step for assembling and 118
f1 102 and the inset of Figure 1a. Finally, the obtained sulfur quantum forming S-NSs or sulfur nanorods from sulfur quantum dots. 119
103 dots were then transferred into a 100 mL Teflon-lined 2.2. Characterization of S-NSs. In the synthesis process, 120
104 autoclave and were maintained at 180 °C for 24 h in an before the step of hydrothermal assembling in the Teflon-lined 121
105 oven. In this step, the sulfur quantum dots were subjected to autoclave, the obtained sulfur materials were typical sulfur 122
106 assembling and forming multilayer S-NSs. The multilayer S- quantum dot particles as observed by TEM (inset of Figure 123

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Figure 2. XPS S2p spectra of the multilayer S-NSs (a), cyclic voltammograms (b) of the fluorine-doped tin oxide (FTO) electrode in a solution of
0.010 M HCl + multilayer S-NS solution (red line) and a suspension solution of 0.010 M HCl + sublimed sulfur (blue line) at a scan rate of 100
mV/s, XRD pattern (c), Raman spectrum (d) of the multilayer S-NSs dispersed in water, SEM (e), and energy-dispersive spectrometry (EDS)
elemental mapping data (f−h) throughout the multilayer S-NSs.

124 1a). The morphology of the multilayer S-NS sample without The chemical composition of the multilayer S-NSs was 164
125 dialysis was shown using TEM, as shown in Figures 1a and S1. investigated by X-ray photoelectron spectroscopy (XPS), 165
126 It can be seen that the multilayer S-NSs have irregular shape which showed that the multilayer S-NSs mainly contained S, 166
127 with big size (>1 μm), and a few sulfur quantum dots adhered C, and O (Figure S7). Five peaks can be recognized in the 167
128 to on the sheet surface. The detailed TEM (Figure S2) showed high-resolution XPS S2p spectrum (Figure 2a). The peaks at 168 f2
129 that the multilayer S-NSs were stacked layer by layer and some 160.2 and 161.2 eV were assigned to S2−. The binding energies 169
130 were folded together with curling at the edges. After dialysis, at 164.5 eV were ascribed to zero-valent sulfur, which is similar 170
131 the multilayer S-NSs also exhibited an obvious layered to that in the sublimed sulfur (Figure S8). Other peaks at 166.1 171
132 structure with nosulfur quantum dots adhered (Figure 1c). and 167.3 eV were attributed to the sulfur of −SO and −SO2, 172
133 Scanning electron microscopy (SEM) of the multilayer S-NSs respectively,30,31 indicating the existence of the oxidized sulfur 173
134 also clearly showed their layered structure intersecting each species. In the high-resolution XPS C spectrum (Figure S7), 174
135 other (Figure S3). Some very specific rectangle-shaped the obvious higher peak at 286.2 eV than that at 284.8 eV 175
136 multilayer S-NSs were also observed occasionally (Figure S3). revealed most of the C−OH existed in the sample, which 176
137 Selected area electron diffraction (SEAD) revealed the originated from PEG.32,33 Three peaks located at 529.4, 531.2, 177
138 crystal planes of multilayer S-NSs. As shown in Figure 1c inset, and 533.9 eV in the XPS spectrum of O (Figure S7) are 178
139 the SEAD image showed clear diffraction spots, which can be recognized and belong to S−O, C−O, and CO, respectively, 179
140 indexed to the (044), (026), and (408) crystal planes of attributing to the adsorbing PEG or oxidized sulfur species.32,33 180
141 sublimed sulfur, indicating the well-synthesized crystalline Since the multilayer S-NSs have very high surface energy, PEG 181
142 multilayer S-NSs. The HRTEM (Figure 1d) presented a lattice played an important role in the passivation and stabilization of 182
143 spacing of 0.28 nm, which was well fitted with the sublimed the multilayer S-NSs. When a sample solution of the multilayer 183
144 sulfur crystal with (044) planes of the X-ray diffraction (XRD) S-NSs was dropcast onto the Si plate for XPS characterization, 184
145 standard card (No. 83-2285). Other SEAD pattern (Figure S4) PEG must exist on the surface of the multilayer S-NSs with 185
146 and HRTEM of the multilayer S-NSs (Figure S5) all confirmed obvious C and O signals. In addition, some chemical reactions 186
147 that the prepared S-NSs had good crystallinity. The obvious are involved in the synthesis process, producing SO42−, SO32−, 187
148 diffraction spots and the lattice of the HRTEM all matched and S2−, as shown in the following equations. Thus, zero-valent 188
149 with the “d” values of sublimed sulfur crystal planes, which sulfur existed in multilayer S-NSs, and sulfite and sulfonyl/ 189
150 means that the prepared S-NSs had a similar unit cell to the sulfonate species were adsorbed at some sites in the synthesis 190
151 sublimed sulfur, which is shown in Figure S5e,f. process, which is similar to the previous reports of sulfur 191
152 The TEM of the sulfur nanorods showed that the length was quantum dots.29,33 Besides, PEG as a stabilizer covered the 192

153 about 50−200 nm and the diameter was 2−5 nm (Figures 1b surface of the nanosheets. 193

154 and S6). Sulfur nanorods were needle-shaped and grafted S + 6HNO3 → H 2SO4 + 6NO2 + 2H 2O (1) 194
155 together forming a dendritic shape. The sulfur nanorods were
156 grown at the two sides of the branches, which provided 3S + 6NaOH = 2Na 2S + Na 2SO3 + 2H 2O (2) 195
157 evidence for further speculating the growth mechanism of the
158 sulfur nanomaterials. It is easy to controllably obtain sulfur (x − 1)S + Na 2S = Na 2Sx , x = 2 − 5 (3) 196
159 nanorods and the S-NSs by changing the volume of H2O2,
160 suggesting that the amount of H2O2 affected the surface state The electroreduction of sulfur in nonaqueous solvents 197
161 of the quantum dots, which resulted in assembling into (dimethylformamide (DMF), dimethyl sulfoxide (DMSO), 198
162 different morphologies. In the subsequent studies, we are etc.) has been studied by several authors over the past 40 199
163 presenting only the S-NSs in detail. years.34−36 However, there are few studies about the 200

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Figure 3. AFM images of the layered S-NSs after sonication for different times (a−e) and the edge height of the S-NSs under TEM (f).

Figure 4. TEM images of the exfoliated S-NSs after sonication for different times.

201 voltammetric behavior of sulfur in aqueous systems because The multilayer S-NSs dispersed in water were directly used 230
202 sulfur does not dissolve in water. Here, the redox character- as a sample for recording Raman spectra (Figure 2d) to 231
203 istics of the S-NSs were studied by recording cyclic monitor the sulfur species. Four obvious bands peaking at 472, 232
204 voltammogram (CV) at a fluorine-doped tin oxide (FTO) 552, 806, and 1100 cm−1 were observed. The peak at 472 cm−1 233
205 electrode (Figure 2b). Sublimed sulfur showed a reduction was assigned to the zero-valent sulfur atom, and the peak at 234
206 current peak at −1.2 V and an oxidation current peak at −0.3 806 cm−1 might be attributed to the stretching vibration of C− 235

207 V, which was similar to the electrochemical reduction behavior O,33 which originated from PEG. The sharp peak centered at 236

208 of sulfur in ionic liquids or organic solvents,34−36 which all 1100 cm−1 was attributed to the stretching vibration of S−O.33 237

209 experienced the reduction of S(0) to S2− during the cathodic The broad peak at 552 cm−1 was likely to originate from 238

210 scanning process, and then S2− ions were oxidized to S(0) in shorter chain polysulfides such as S4− and S5−, referring to the 239

211 the subsequent anodic scanning process. The only difference calculated Raman spectra by density functional theory 240

was that the potential position slightly varied, since the (DFT).37,38 The EDS elemental mapping of multilayer S- 241
212
solvents and the electrode were different. Similar to the NSs was carried out (Figure 2e−h), which clearly showed the 242
213
presence of S, C, and O in the multilayer S-NSs. 243
214 electrochemical properties of sublimed sulfur, an obvious
Combining the characterization of XPS, Raman spectra, CV, 244
215 reduction current peak near −1.2 V and the oxidation current
and EDS, we feel that the prepared nanosheets were composed 245
216 peak near −0.3 V also appeared (red line, Figure 2b). The
of zero-valent sulfur forming a layered structure, which is 246
217 same reduction peak potential of the synthesized multilayer S- similar to the crystal unit cell structure of the sublimed sulfur, 247
218 NSs to that of sublimed sulfur was solid proof that zero-valent some ions or species such as SO42−, SO32− and S2− adsorbed at 248
219 sulfur existed in the sample. some sites, and PEG was indispensable as a stabilizer. 249
220 The XRD pattern of the multilayer S-NSs (Figure 2c) 2.3. Sulfurene or Few-Layered S-NSs Obtained by 250
221 showed fewer peaks than that of the sublimed sulfur (S8 phase) Sonication Exfoliation. To obtain mono- or few-layered S- 251
222 according to JCPDS file No. 83-2285 (Figure S9). The two NSs, the obtained multilayer S-NSs were exfoliated by 252
223 obvious peaks at 28.32 and 31.06° of the multilayer S-NSs also sonication for different times (0−192 h). They were then 253
224 existed as important strong peaks in the XRD pattern of the S8 characterized using atomic force microscopy (AFM) and 254
225 phase, which can be indexed to the (206) and (044) crystal TEM; the ultraviolet−visible (UV−vis) absorption spectra and 255
226 planes for sulfur (JCPDS file No. 83-2285). It is worth noting PL spectra of S-NSs at different sonication times (referred to as 256
227 that the diffraction peaks (044 planes) agreed with SEAD sample) were also recorded. 257
228 analysis. It can be speculated that the synthesized multilayer S- 2.3.1. AFM Observation. The AFM image (Figure 3) 258 f3
229 NSs were mostly related to the S8 phase. showed that S-NSs seemed to stack together forming a layered 259

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260 structure with varying layer thicknesses and morphologies, and

261 an increase in the sonication time trended an almost decrease
262 in the lateral height of the layers. The original multilayer S-NSs
263 (without sonication) were not monodisperse, and the lateral
264 height of the S-NS layers was about 6 nm (Figure 3a) with one
265 gradient. It was observed that the layer’s lateral height was 32.7
266 nm with four gradients in the 48 h sample, and the layer’s
267 lateral height was 27.7 nm with five gradients in the 72 h
268 sample (Figure 3b). After 96 h, the S-NSs seemed to have
269 more fragments with smaller size and with less stacking
270 phenomena. A layer lateral with a thickness of 3.44 nm can be
271 observed in the 96 h sample (Figure 3c), and a layer lateral
272 with a thickness of 1.11 nm was observed in the 120 h sample
273 (Figure 3d). The thinnest thickness of only 0.84 nm of S-NSs
274 was observed in the 144 h sample (Figure 3e). These S-NSs
275 with the thinnest thickness were supposed to be the monolayer
276 S-NSs, regarded as sulfurene, which seemed in close agreement
277 with those obtained from TEM observation, which was 0.71
278 nm at the edge of the S-NSs (Figure 3f). The detailed AFM of
279 the exfoliated S-NSs after different sonication times is shown in Figure 5. UV−vis absorption spectra of the multilayer S-NS sample
280 Figure S10. after sonication/exfoliation for different times (a). Inset of (a) is the
281 2.3.2. TEM Observation. The morphology of the exfoliated detailed UV−vis absorption spectra of the 144 h S-NS sample (b).
282 S-NSs under different sonication times was monitored by TEM UV−vis absorption spectra of the 144 h S-NS sample at different pH
f4 283 (Figure 4). From 0 to 96 h, the S-NSs had poor light values (c). PL spectra of the 144 h S-NS sample at different λex values
284 transmittance, due to multilayers stacking together, as shown (d). PL stability of the 144 h S-NS sample on the 66th day.
285 in the 72 h sample. The size of S-NSs was not monodisperse. It
286 was ∼4 μm2 in the 24 h sample, whereas it was less than 1 μm2
287 in the 48 h sample. With an increase in the sonication time view, the absorption behavior of S-NSs was also similar to the 323

288 from 96 to 192 h, TEM images showed better light absorption behaviors of other allotropes of elemental sulfur; for 324

289 transmittance, due to fewer layers stacking together; the size example, the absorption band of S6 had a maximum absorption 325

290 also gradually decreased with an increase in sonication time. peak at 234 nm and a shoulder at 269 nm.39 The particular 326

291 Many small fragments were observed in the 132 h sample, and absorption spectra of other allotropes showed the following 327

292 the area was less than 0.5 μm2 in the case of the 168 h sample. characteristic features in the region 190−340 nm. 328

293 The detailed TEM of the exfoliated S-NSs after different S6: 234 nm (maximum), 269 nm (shoulder) 329
294 sonication times is shown in Figure S11. S7: 222 nm (maximum), 255 nm (shoulder) 330
295 2.3.3. Wide-Range Light Absorption. The UV−vis S8: 222 nm (maximum), 264 nm (shoulder) 331
296 absorption spectra of the exfoliated S-NSs under different S10: 222 nm (maximum), 290 nm (broad shoulder) 332
f5 297 sonication times were recorded (Figure 5a). The exfoliated S- S12: 222 nm (maximum), 320 nm (broad shoulder) 333
298 NSs (e.g., the 144 h sample) clearly exhibited full band By comparing the UV−vis absorption spectra of S-NSs with 334
299 absorption (inset of Figure 2a) with two absorption bands those of different sulfur allotropic forms given above, it was 335
300 centered at 205 nm (maximum) and 285 nm (shoulder). Bulk found that all of these had a similar pattern of absorption 336
301 sulfur has intrinsic semiconductor-like absorption with a band spectra but with varying peak shifts. It can be speculated that 337
302 gap of 2.79 eV;40 the energy band gap (Eg) of the prepared S- the obtained S-NSs were also related to a kind of allotropic 338
303 NSs was estimated to be 3.21 eV from the absorption edge in sulfur, and their distinct structure endows them with wide- 339
304 the absorption spectrum. This is essentially different from range light absorption. 340
305 graphene, which has zero gap. This unique property of S-NSs The effect of sonication exfoliation on the UV−vis 341
306 will make it of great use in the research of the semiconductor. absorption spectra (Figure 5a) showed that the absorption 342
307 Since it is reported that α-S crystals have a visible-light intensity of the S-NSs quickly increased in the first 72 h and 343
308 elemental photocatalysis activity,40 with extremely improved then leveled off. Since the sonication lowered the layer 344
309 water dispersibility compared to α-S crystals,40 S-NSs with thickness of the S-NSs, as already indicated in AFM and TEM, 345
310 wide absorption in the visible light can find potential leading to the increase of the UV absorbance. The effect of pH 346
311 application in visible-light-active elemental photocatalysis. on the UV absorption was also investigated (Figure 5b). It was 347
312 These developments suggest that the semiconductors of the found that a weakly acidic medium and a weakly alkaline 348
313 S-NSs may represent a new class of photocatalysts for solar medium had inconspicuous influence. A strongly acidic 349
314 energy conversion. Compared with sulfur quantum dots26 that medium led to a blue shift of the absorption peak, while a 350
315 have three absorption bands centered at 222 nm (strong band strongly alkaline medium led to a red shift of the absorption 351
316 I), 303 nm (weak band II), and 370 nm (weaker band III), the peak. This phenomenon was similar to the effect of pH on a 352
317 first two absorption bands of the S-NSs (205 and 285 nm) are conjugate system.41 The S-NSs were supposed to contain the 353
318 similar in shape, except that the overall outline has a blue shift π-conjugation system and heteroatoms (O, S). In a strongly 354
319 of ∼20 nm. Generally, heteroatoms (S, O) contain non- acidic medium, a lone pair of sulfur or oxygen on the surface 355
320 bonding electrons and the transition of n−σ* usually has an was protonated and decreased the extended conjugation, 356
321 absorption in the range of 150−250 nm. Thus, the band at 205 leading to a blue shift. While in the strongly alkaline medium, 357
322 nm might arise from n−σ* transition. From another point of surface functional groups of the S-NSs were no more 358

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359 protonated and a lone pair of electrons was involved in the π− ASSOCIATED CONTENT 418
360 electron-conjugation system, causing a red shift. * Supporting Information
sı 419
361 2.3.4. Multiwavelength Photoluminescence and Stability. The Supporting Information is available free of charge at 420
362 The PL spectra of the S-NSs under different sonication times https://pubs.acs.org/doi/10.1021/acsanm.0c02024. 421
363 were recorded (Figure S12). The S-NSs (e.g., the 144 h
Experimental procedures; cyclic voltammetry; character- 422
364 sample) exhibited a multiwavelength emission PL property
ization methods; PL spectra; SEM images; TEM images; 423
365 (Figure 5c). The PL spectra of the S-NSs showed a unique electron diffraction pattern; XRD spectra; XPS survey; 424
366 emission pattern with five emission bands at 389, 412, 457, AFM images; and thermogravimetric analysis (PDF) 425

■
367 482, and 526 nm. These multiple emission wavelength (λem)
368 bands did not vary with excitation wavelengths (λex) from 260
369 to 340 nm. These multiwavelength emission bands might be AUTHOR INFORMATION 426

370 ascribed to the anisotropy of S-NSs or complicated band gap Corresponding Authors 427

371 structures, which provided an experimental basis for the future Lihua Shen − College of Chemistry and Chemical Engineering, 428

372 theoretical band gap calculation of the Brillouin curve. It was Xi’an University of Science and Technology, Xi’an 710054, P. 429

373 reported that the bulk α-S crystals had wide PL emission, R. China; Key Laboratory of Coal Resources Exploration and 430

374 which corresponds to direct band-to-band radiative recombi- Comprehensive Utilization, Xi’an 710021, P. R. China; 431

375 nation of photoexcited electrons and holes.40 So, it might be orcid.org/0000-0001-8882-8985; 432

376 speculated that the obtained S-NSs belong to the direct band Email: lihuashen1996@hotmail.com 433

377 gap materials.40 Compared with graphene, the S-NSs were Dongdong Zhang − School of Pharmacy, Health Science 434

more likely to generate PL, which implies that the S-NSs will Center, Xi’an Jiaotong University, Xi’an 710061, P. R. 435
378
China; Email: ddzhang@xjtu.edu.cn 436
379 be more popular in optical sensing, photoelectronic devices,
Chengxiao Zhang − Key Laboratory of Analytical Chemistry 437
380 and photoelectric conversion.
for Life Science of Shaanxi Province, School of Chemistry and 438
381 The influence of the exfoliation time on the PL (Figure S12)
Chemical Engineering, Shaanxi Normal University, Xi’an 439
382 showed that the PL intensity (e.g., λem = 412 nm) increased 710062, P. R. China; orcid.org/0000-0003-2829-5122; 440
383 with the sonication time from 24 to 72 h, which was consistent Email: cxzhang@snnu.edu.cn 441
384 with the effect of sonication on UV spectra. It was because the
385 sonication affects the thickness of the S-NSs.42 Then, the PL Authors 442
386 emission maximum intensity was obtained at the 144 h sample. Zhuangwei Bai − College of Chemistry and Chemical 443
387 The exfoliated S-NSs (e.g., the 144 h sample) exhibited Engineering, Xi’an University of Science and Technology, 444
388 excellent PL stability (Figure 5d). The λem of the exfoliated S- Xi’an 710054, P. R. China; Key Laboratory of Coal 445
389 NSs dispersed in water remained almost unchanged with a Resources Exploration and Comprehensive Utilization, Xi’an 446
390 slight increase in the PL intensity after it was exposed to air at 710021, P. R. China 447
391 room temperature for two months. The excellent stability of S- Jianhang Wei − College of Chemistry and Chemical 448
392 NSs was much superior to the BP, which was most likely Engineering, Xi’an University of Science and Technology, 449
393 attributed to the effect of PEG and the innate property of S- Xi’an 710054, P. R. China 450
394 NSs. With excellent stability and unique optical properties, S- Yuangang Li − College of Chemistry and Chemical 451
395 NSs are believed to have potential applications in the fields of Engineering, Xi’an University of Science and Technology, 452
396 optical sensing. Xi’an 710054, P. R. China 453
Azhar Abbas − Ibn-e-sina Block, Institute of Chemistry, 454
University of Sargodha, Sargodha 40100, Pakistan 455
3. CONCLUSIONS Yinyan Li − College of Chemistry and Chemical Engineering, 456
397 (1) A kind of 2D layered nanomaterials, S-NSs, were prepared Xi’an University of Science and Technology, Xi’an 710054, P. 457
398 by a simple and versatile liquid-phase method of hydrothermal R. China 458
399 assembling of sulfur quantum dots, and monolayer sulfurene Mengnan Qu − College of Chemistry and Chemical 459
400 with a thickness of 0.84 nm was obtained by further sonication Engineering, Xi’an University of Science and Technology, 460
401 exfoliation of the multilayer S-NSs. (2) The electrochemical Xi’an 710054, P. R. China 461
402 behavior of the multilayer S-NSs in an aqueous medium Complete contact information is available at: 462
403 showed that the reduction of S(0) to S2− occurred at −1.2 V. https://pubs.acs.org/10.1021/acsanm.0c02024 463
404 (3) The optical properties of the S-NSs showed distinct wide-
405 range absorption from ultraviolet to the visible region and Notes 464
406 distinct multiwavelength PL with superb stability over two The authors declare no competing financial interest.

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465
407 months in air. (4) The wide absorption properties may find
408 potential applications in the field of visible-light-active ACKNOWLEDGMENTS 466
409 photocatalysis, and the unique PL is envisioned to have We especially thank Professor Xinrong Zhang for his support 467
410 promising prospects in the field of optical sensing. A more and valuable suggestions. This work was supported financially 468
411 attractive investigation of the S-NSs for photocatalysis or by the National Natural Science Foundation of China (Nos. 469
412 energy storage will be carried out in the future work, including 21505102, 21727813, and 22072113), the Youth Innovation 470
413 other potential photoelectric properties of S-NSs. We expect S- Team of Shaanxi Universities, and Shaanxi Key Research and 471
414 NSs to provide opportunities for the development of efficient Development Project (2020GY-250). The authors would like 472
415 visible-light-responsive photocatalysts and photoelectric con- to thank Dr. Jia Jiqiang from Advanced Material Analysis and 473
416 verting materials because of their intrinsic semiconductor Test Center of the Xi’an University of Technology for 474
417 properties. providing helpful assistance in TEM analysis. 475

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476 REFERENCES (21) Abate, Y.; Akinwande, D.; Gamage, S.; Wang, H.; Snure, M.; 543
Nirakar, P.; Cronin, S. B. Recent Progress on Stability and Passivation 544
477 (1) Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, of Black Phosphorus. Adv. Mater. 2018, 30, No. 1704749. 545
478 Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Electric Field Effect (22) Kong, N.; Ji, X. Y.; Wang, J. Q.; Sun, X. N.; Chen, G. Q.; Fan, 546
479 in Atomically Thin Carbon Films. Science 2004, 306, 666−669. T. J.; Liang, W. Y.; Zhang, H.; Xie, A. Y.; Farokhzad, O. C.; Tao, W. 547
480 (2) Hu, H.; Yang, X. X.; Guo, X. D.; Khaliji, K.; Biswas, S. R.; Javier, ROS-Mediated Selective Killing Effect of Black Phosphorus: 548
481 F. G. A.; Low, T.; Sun, Z. P.; Dai, Q. Gas Identification with Mechanistic Understanding and Its Guidance for Safe Biomedical 549
482 Graphene Plasmons. Nat. Commun. 2019, 10, No. 1131. Applications. Nano Lett. 2020, 20, 3943−3955. 550
483 (3) Lee, J. H.; Tan, J. Y.; Toh, C. T.; Koenig, S. P.; Fedorov, V. E.; (23) Li, B.; Li, S. M.; Liu, J. H.; Wang, B.; Yang, S. B. Vertically 551
484 Castro Neto, A. H.; Ozyilmaz, B. Nanometer Thick Elastic Graphene Aligned Sulfur-Graphene Nanowalls on Substrates for Ultrafast 552
485 Engine. Nano Lett. 2014, 14, 2677−2680. Lithium-Sulfur Batteries. Nano Lett. 2015, 15, 3073−3079. 553
486 (4) Li, L. H.; Chen, Y.; Gavin, B.; Zhang, H. Z.; Petravic, P.; (24) Wang, L.; Dong, Z. H.; Wang, D.; Zhang, F. X.; Jin, J. Covalent 554
487 Glushenkov, A. M. Large-scale Mechanical Peeling of Boron Nitride Bond Glued Sulfur Nanosheet-Based Cathode Integration for Long- 555
488 Nanosheets by Low-energy Ball Milling. J. Mater. Chem. 2011, 21, Cycle-Life Li−S Batteries. Nano Lett. 2013, 13, 6244−6250. 556
489 11862. (25) Rao, K. J.; Paria, S. Use of Sulfur Nanoparticles as a Green 557
490 (5) Pakdel, A.; Bandoa, Y.; Golberg, D. Nano Boron Nitride Pesticide on Fusariumsolani and Venturia inaequalis Phytopathogens. 558
491 Flatland. Chem. Soc. Rev. 2014, 43, 934−959. RSC Adv. 2013, 3, 10471−10478. 559
492 (6) Radisavljevic, B.; Radenovic, A.; Brivio, J.; Giacometti, V.; Kis, A. (26) Shen, L. H.; Wang, H. N.; Bai, Z. W.; Zhang, S. C.; Zhang, X. 560
493 Single-layer MoS2 Transistors. Nat. Nanotechnol. 2011, 6, 147−150. R.; Zhang, C. X.; et al. Assembling of Sulfur Quantum Dots in Fission 561
494 (7) Splendiani, A.; Sun, L.; Zhang, Y. B.; Li, T. S.; Kim, J.; Chim, C. of Sublimed Sulfur. J. Am. Chem. Soc. 2018, 140, 7878−7884. 562
495 Y.; Galli, G.; Wang, F. Emerging Photoluminescence in Monolayer (27) Wang, H. G.; Wang, Z. G.; Xiong, Y.; Kershaw, S. V.; Li, T. Z.; 563
496 MoS2. Nano Lett. 2010, 10, 1271−1275. Wang, Y.; Zhai, Y. Q.; Rogach, A. L. Hydrogen Peroxide Assisted 564
497 (8) Liu, Z. F.; Sun, Y. L.; Cao, H. Q.; Xie, D.; Li, W.; Wang, J.; Synthesis of Highly Luminescent Sulfur Quantum Dots. Angew. 565
498 Cheetham, A. K. Unzipping of black phosphorus to form zigzag- Chem., Int. Ed. 2019, 58, 7040−7044. 566
499 phosphorene nanobelts. Nat. Commun. 2020, 11, No. 3917. (28) Wang, S.; Bao, X.; Gao, B.; Li, M. A Novel Sulfur Quantum Dot 567
500 (9) Ouyang, J.; Feng, C.; Ji, X. Y.; Li, L.; Gutti, H. K.; Kim, N. Y.; for the Detection of Cobalt ions and Norfloxacin as a Fluorescent 568
501 Artzi, D.; Xie, A.; Kong, N.; Liu, Y. N.; Tearney, G. J.; Sui, X. B.; Tao, “switch”. Dalton Trans. 2019, 48, 8288−8296. 569
502 W.; Farokhzad, O. C. 2D Monoelemental Germanene Quantum Dots: (29) Li, S. X.; Chen, D. J.; Zheng, F. Y.; Zhou, H. F.; Jiang, S. X.; 570
503 Synthesis as Robust Photothermal Agents for Photonic Cancer Wu, Y. Water-Soluble and Lowly Toxic Sulphur Quantum Dots. Adv. 571
504 Nanomedicine. Angew. Chem., Int. Ed. 2019, 58, 13405−13410. Funct. Mater. 2014, 24, 7133−7138. 572
505 (10) Wang, Y. X.; Qiu, G.; Wang, R. X.; Huang, S. Y.; Wang, Q. X.; (30) Kim, S. S.; Britcher, L.; Kumar, S.; Griesser, H. J. XPS Study of 573
506 Liu, Y. Y.; Du, Y. C.; Goddard, W. A., III; Kim, M. J.; Xu, X. F.; Ye, P. Sulfur and Phosphorus Compounds with Different Oxidation States. 574
507 D.; Wu, W. Z. Field-effect transistors made from solution-grown two- Sains Malays. 2018, 47, 1913−1922. 575
508 dimensional tellurene. Nat. Electron. 2018, 1, 228−236. (31) Smart, R. S. C.; Skinner, W. M.; Gerson, A. R. XPS of Sulphide 576
509 (11) Qin, J. K.; Qiu, G.; Jian, J.; Zhou, H.; Yang, L. M.; Charnas, A.; Mineral Surfaces: Metal-defificient, Polysulphides, Defects and 577
510 Zemlyanov, D. Y.; Xu, C. Y.; Xu, X. F.; Wu, W. Z.; Wang, H. Y.; Ye, P. Elemental Sulphur. Surf. Interface Anal. 1999, 28, 101−105. 578
511 D. Controlled Growth of a Large-Size 2D Selenium Nanosheet and Its (32) Thierry, B.; Lucie, Z.; Scott, M.; Kim, F.; Christophe, B.; Hans, 579

512 Electronic and Optoelectronic Applications. ACS Nano 2017, 11, J. G. Electrostatic Self-Assembly of PEG Copolymers onto Porous 580
513 10222−10229. Silica Nanoparticles. Langmuir 2008, 24, 8143−8150. 581

514 (12) Li, L. H.; Chen, Y. Atomically Thin Boron Nitride: Unique (33) Zhang, C. C.; Zhang, P.; Ji, X. J.; Wang, H. G.; Kuang, H. Z.; 582

515 Properties and Applications. Adv. Funct. Mater 2016, 26, 2594−2608. Cao, W. L.; Pan, M. Y.; Shi, Y.; Wang, Z. G. Ultrasonication- 583

(13) Grant, J. T.; Carrero, C. A.; Goeltl, F.; Venegas, J. M.; Mueller, promoted Synthesis of Luminescent Sulfur Nano-dots for Cellular 584
516
P.; Burt, S. P. B.; Specht, S. E.; Mcdermott, W. P.; Chieregato, A.; Imaging Applications. Chem. Commun. 2019, 55, 13004−13007. 585
517
(34) Manan, N. S. A.; Aldous, L.; Alias, Y.; Murray, P. R.; Yellowlees, 586
518 Hermans, I. Selective Oxidative Dehydrogenation of Propane to
L. J.; Lagunas, M. C.; Hardacre, C. Electrochemistry of Sulfur and 587
519 Propene Using Boron Nitride Catalysts. Science. 2016, 354, 1570−
Polysulfides in Ionic Liquids. J. Phys. Chem. B. 2011, 115, 13873− 588
520 1573.
13879. 589
521 (14) Li, L. H.; Cervenka, J. R.; Watanabe, K. J.; Taniguchi, T.; Chen,
(35) Evans, A.; Montenegro, M. I.; Pletcher, D. The Mechanism for 590
522 Y. Strong Oxidation Resistance of Atomically Thin Boron Nitride the Cathodic Reduction of Sulphur in Dimethylformamide: Low 591
523 Nanosheets. ACS Nano 2014, 8, 1457−1462. Temperature Voltammetry. Electrochem. Commun. 2001, 3, 514−518. 592
524 (15) Mak, K. F.; Lee, C.; Hone, J.; Shan, J.; Heinz, T. F. Atomically (36) Leghié, P.; Lelieur, J. P.; Levillain, E. Comments on the 593
525 thin MoS2: A New Direct-Gap Semiconductor. Phys. Rev. Lett. 2010, Mechanism of the Electrochemical Reduction of Sulphur in 594
526 105, 136805−136809. Dimethylformamide. Electrochem. Commun. 2002, 4, 406−411. 595
527 (16) Ganatra, R.; Zhang, Q. Few-Layer MoS2: A Promising Layered (37) Hagen, M.; Schiffels, P.; Hammer, M.; Dörfler, S.; Tübke, J.; 596
528 Semiconductor. ACS Nano 2014, 8, 4074−4099. Hoffmann, M. J.; Althues, H.; Kaskel, S. In-Situ Raman Investigation 597
529 (17) Najmaei, S.; Yuan, J. T.; Zhang, J.; Ajayan, P. M. A.; Lou, J. of Polysulfide Formation in Li-S Cells. J. Electrochem. Soc. 2013, 160, 598
530 Synthesis and Defect Investigation of Two-Dimensional Molybdenum A1205−A1214. 599
531 Disulfide Atomic Layers. Acc. Chem. Res. 2015, 48, 31−40. (38) Wu, H. L.; Huff, L. A.; Gewirth, A. A. In Situ Raman 600
532 (18) Zhang, Y.; Zheng, Y.; Rui, K.; Hng, H. H.; Hippalgaonkar, K.; Spectroscopy of Sulfur Speciation in Lithium−Sulfur Batteries. ACS. 601
533 Xu, J. W.; Sun, W. P.; Zhu, J. X.; Yan, Q. Y.; Huang, W. 2D Black Appl. Mater. Interfaces. 2015, 7, 1709−1719. 602
534 Phosphorus for Energy Storage and Thermoelectric Applications. (39) Steudel, R.; Jensen, D.; Petra, G.; Hugo, P. Optical Absorption 603
535 Small 2017, 13, 1700661−1700681. Spectra of the Homocyclic Sulfur Molecules S, (n = 6, 7, 8, 9, 10, 12, 604
536 (19) Hirsch, A.; Hauke, F. Post Graphene 2D Chemistry: The 15, 20) in Solution. Ber. Bunsenges. Phys. Chem. 1988, 92, 118−122. 605
537 Emerging Field of Molybdenum Disulfide and Black Phosphorus (40) Liu, G.; Niu, P.; Yin, L.; Cheng, H. M. α-sulfur Crystals as a 606
538 Functionalization. Angew. Chem., Int. Ed. 2017, 57, 4338−4354. Visible-Light-Active Photocatalyst. J. Am. Chem. Soc. 2012, 134, 607
539 (20) Buscema, M.; Groenendijk, D. J.; Blanter, S. I.; Steele, G. A.; 9070−9073. 608
540 Van, D. Z. H. S. J.; Castellanosgomez, A. Fast and Broadband (41) Shen, L. H.; Wang, C. X.; Abbas, A.; Yu, C. X.; Zhang, S. C.; 609
541 Photoresponse of Few-layer Black Phosphorus Field-effect Tran- Zhang, X. R.; Zhang, C. X. Switching Carbon Nanodots from Single 610
542 sistors. Nano Lett. 2014, 14, 3347−3352. Emission to Dual Emission by One-step Electrochemical Tailoring in 611

G https://dx.doi.org/10.1021/acsanm.0c02024
ACS Appl. Nano Mater. XXXX, XXX, XXX−XXX
 ACS Applied Nano Materials www.acsanm.org Article

612 Alkaline Alcohols: Implications for Sensing and Bioimaging. ACS

613 Appl. Nano Mater. 2019, 2, 2776−2784.
614 (42) Wang, Q. H.; Kalantar-Zadeh, K.; Kis, A.; Coleman, J. N.;
615 Strano, M. S. Electronics and Optoelectronics of Two-dimensional
616 Transition Metal Dichalcogenides. Nat. Nanotechnol. 2012, 7, 699−
617 712.

H https://dx.doi.org/10.1021/acsanm.0c02024
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