(19)
(11)EP 3 708 535 A1

(12)EUROPEAN PATENT APPLICATION

(43)Date of publication:
16.09.2020 Bulletin 2020/38

(21)Application number: 19215770.9

(22)Date of filing:  12.12.2019
(51)International Patent Classification (IPC): 
C01B 17/20(2006.01)
D01F 1/00(2006.01)
C01G 39/06(2006.01)
(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR
Designated Extension States:
BA ME
Designated Validation States:
KH MA MD TN

(30)Priority: 13.03.2019 KR 20190028798

(71)Applicant: Seoul National University R & DB Foundation
Seoul 08826 (KR)

(72)Inventors:
  • JOO, Young Chang
    06289 Seoul (KR)
  • JOO, Won Hyo
    08814 Seoul (KR)
  • NAM, Dae Hyun
    51426 Gyeongsangnam-do (KR)
  • KIM, Ji Yong
    07070 Seoul (KR)

(74)Representative: Shearman, James Ward 
Marks & Clerk LLP 15 Fetter Lane
London EC4A 1BW
London EC4A 1BW (GB)

  


(54)METHOD OF MANUFACTURING MOS2 HAVING 1T CRYSTAL STRUCTURE


(57) Provided is a method of manufacturing MoS2 having a 1T crystal structure. The method includes performing phase transition from a 2H crystal structure of MoS2 to the 1T crystal structure by reacting MoS2 having the 2H crystal structure with CO gas. The phase transition includes annealing the MoS2 having the 2H crystal structure in an atmosphere including CO gas.




Description

CROSS-REFERENCE TO RELATED APPLICATION



[0001] This application claims the benefit of Korean Patent Application No. 10-2019-0028798, filed on March 13, 2019, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein in its entirety by reference.

BACKGROUND


1. Field



[0002] The present invention relates to a method of manufacturing MoS2 having a 1T crystal structure. More particularly, the present invention relates to a method of performing phase transition of MoS2 having a 2H crystal structure (2H-MoS2) as a stable phase to MoS2 having the 1T crystal structure (1T-MoS2) via reaction with CO gas.

2. Description of the Related Art



[0003] MoS2 has a two-dimensional (2D) planar structure. With the development of techniques of separating single layers from a bulk material, various physical properties thereof may be induced, e.g., bandgaps may be changed, by adjusting a structural factor such as the number of stacked layers. Therefore, MoS2 has drawn attention in various application fields such as electrochemical, electrical, and optical application fields.

[0004] Particularly, depending on the arrangement of sulfur atoms, MoS2 is found in two distinct phases: 1T phase and 2H phase. Since the 1T phase is a metastable phase that is thermodynamically unstable compared to the 2H phase, MoS2 is mostly formed to have a 2H crystal structure in nature. The 2H phase has a hexagonal structure exhibiting electrical properties of semiconductors. In terms of hydrogen-generating catalytic characteristics, the 2H phase has no activity at the bottom surface due to symmetrical alignment of sulfur atoms about a Mo atom, and thus it is important to develop a technique for inducing a single-layered structure (vertically aligned structure) of MoS2 to maximize exposure of edges of the structure for excellent catalytic performance.

[0005] On the other hand, the 1T phase has an octahedral structure exhibiting electrical properties of metals. In terms of hydrogen-generating catalytic characteristics, the 1T phase has a very high activity to the bottom surface, and thus extensive research has been conducted to develop a method of inducing the 1T phase.

[0006] As methods of inducing the 1T-MoS2 structure developed to data, a method of supplying electrons by substitutional doping of Re, Tc, Mn, and the like, a method of supplying electrons by intercalating alkali metal such as Li or a ligand, a method of inducing a pressure in a layer, and a method of forming empty spaces at S sites using plasma have been reported. However, impurities are inevitably included therein according to these methods, thereby deteriorate physical properties thereof. Although the impurities are removed by performing an additional process after conversion to the 1T phase, the 1T phase tends to easily return to the 2H phase due to very low stability thereof. Also, these methods require a very long processing time over 48 hours to obtain the 1T-MoS2 structure, are not suitable for mass production, and entail considerable production costs.

SUMMARY



[0007] The present invention has been proposed to solve various problems including the above problems, and an object of the present invention is to provide a method for quickly and uniformly converting a structure of MoS2 to a 1T crystal structure regardless of the shape of MoS2.

[0008] Another object of the present invention is to provide a method for quickly and uniformly converting a structure of MoS2 hybridized with other materials such as carbon nanofiber to a 1T crystal structure.

[0009] However, these problems to be solved are illustrative and the scope of the present invention is not limited thereby.

[0010] Additional aspects will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the presented embodiments.

[0011] According to an aspect of the present invention to achieve the object, provided is a method of manufacturing molybdenum disulfide (MoS2) having a 1T crystal structure. The method includes performing phase transition from a 2H crystal structure of MoS2 to the 1T crystal structure by reacting MoS2 having the 2H crystal structure with CO gas.

[0012] According to an embodiment, the performing of phase transition may include annealing the MoS2 having the 2H crystal structure in an atmosphere including CO gas.

[0013] According to an embodiment, the performing of phase transition may include annealing the MoS2 having the 2H crystal structure in an atmosphere including CO gas and CO2 gas.

[0014] According to an embodiment, the MoS2 may be in the form of at least one of bulk, powder, film, wire, and fiber.

[0015] According to another aspect of the present invention, provided is a method of manufacturing MoS2 having a 1T crystal structure. The method may include forming a MoS2-carbon composite by reacting an MoS2 precursor-organic material composite with CO gas. In this regard, at least one portion of MoS2 included in the MoS2-carbon composite has the 1T crystal structure.

[0016] According to an embodiment, the MoS2 precursor-organic material composite may be in the form of fiber.

[0017] According to an embodiment, the MoS2 precursor-organic material composite may be prepared by electrospinning.

[0018] According to an embodiment, the MoS2 included in the MoS2-carbon composite may have a single-layered or a multi-layered structure.

[0019] According to an embodiment, the forming of the MoS2-carbon composite may include annealing the MoS2 precursor-organic material composite in an atmosphere including CO gas.

[0020] According to an embodiment, the forming of the MoS2-carbon composite may include annealing the MoS2 precursor-organic material composite in an atmosphere including CO gas CO2 gas.

[0021] According to an embodiment, the forming of the MoS2-carbon composite may include annealing performed at a temperature in the range of 700°C to 1000°C.

[0022] According to another aspect of the present invention, provided is a catalyst for generating hydrogen prepared according to the above-described method.

[0023] According to another aspect of the present invention, provided is a MoS2-carbon composite.

[0024] The MoS2-carbon composite includes a carbon structure in the form of fibers and MoS2 distributed in the carbon structure.

[0025] According to an embodiment, the MoS2 included in the MoS2-carbon composite may have a single-layered or a multi-layered structure.

[0026] According to an embodiment, at least one portion of the MoS2 may have a 1T crystal structure.

BRIEF DESCRIPTION OF THE DRAWINGS



[0027] These and/or other aspects will become apparent and more readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings in which:

FIGS. 1A to 1C show graphs illustrating free energy of formation of S-vacancies formed in MoS2 via reaction with CO gas and calculated according to DFT and 1T phase stability according to S-vacancy concentration and particle size of MoS2;

FIG. 2 is a graph illustrating equilibrium oxygen partial pressures according to CO:CO2 flow ratio;

FIGS. 3A to 3C show graphs illustrating amounts of generated MoS2, MoO2, Mo2C, and MoC in a three-component phase diagram of CO-CO2-MoS2 at 800°C at 1 atm;

FIGS. 4 and 5 are graphs showing X-ray photoelectron spectroscopy (XPS) results to measure formation of a 1T structure in MoS2 powder and a MoS2 precursor according to experimental examples of the present invention;

FIGS. 6A to 6C show high-resolution transmission electron microscope images obtained to identify formation of 1T of MoS2 powder;

FIG. 7 shows graphs illustrating XPS measurement results of MoS2/C nanofibers manufactured according to experimental examples of the present invention;

FIG. 8 is a graph illustrating Raman spectrum measurement results of MoS2/C nanofibers manufactured according to experimental examples of the present invention;

FIGS. 9A and 9B show graphs illustrating extended X-ray absorption fine structure (EXAFS) measurement results of Mo in the MoS2/C nanofibers according to experimental examples of the present invention;

FIGS. 10A to 10F show transmission electron microscope images of microstructures of MoS2/C nanofibers according to experimental examples of the present invention;

FIG. 11 shows graphs illustrating XPS measurement results of MoS2/C nanofibers annealed in an oxygen atmosphere according to experimental examples of the present invention; and

FIGS. 12A and 12B show graphs illustrating hydrogen-generating catalytic characteristics of MoS2/C nanofibers according to experimental examples of the present invention.


DETAILED DESCRIPTION



[0028] In the following detailed description, reference is made to the accompanying drawings that show, by way of illustration, specific embodiments in which the invention may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention. It is to be understood that the various embodiments of the invention, although different, are not necessarily mutually exclusive. For example, a particular feature, structure, or characteristic described herein, in connection with one embodiment, may be implemented within other embodiments without departing from the spirit and scope of the invention. In addition, it is to be understood that the location or arrangement of individual elements within each disclosed embodiment may be modified without departing from the spirit and scope of the invention. The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention is defined only by the appended claims, appropriately interpreted, along with the full range of equivalents to which the claims are entitled. In the drawings, like numerals refer to the same or similar functionality throughout the several views and length, areas, thicknesses, and shapes of elements in the drawings may be exaggerated for descriptive convenience.

[0029] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that these embodiments may be readily implemented by those skilled in the art.

[0030] The present invention provides a method of converting a crystal structure of MoS2 by reacting MoS2 or a MoS2 precursor with carbon monoxide (CO) gas. CO is one of the representative reductive gases and the present inventors have found that CO reacts with sulfur (S) contained in MoS2 to induce S-vacancies therein as shown in Reaction Scheme1 below, resulting in formation of MoS2 having a 1T crystal structure via atomic diffusion and rearrangement by the S-vacancies. The S-vacancy refers to an empty lattice point of a crystal lattice of MoS2 from which an S atom is removed.

         Reaction Scheme 1     MoS2+δ·CO(g)=MoS2-δ+δ·COS(g)

(where, MOS2-δ refers to a state in which δ S-vacancies are present in MoS2 and a stoichiometric value of S is reduced by δ from 2.)

[0031] FIG. 1A shows free energy of S-vacancy formation (ΔEf) calculated according to Density Functional Theory (DFT) using S-vacancy concentration as a variable under typical implementation conditions. The typical implementation conditions were set based on results measured in experiments and include a temperature of 800°C, a CO partial pressure of 0.5 atm, a CO2 partial pressure of 0.5 atm, and a COS partial pressure of 10-5 atm. Meanwhile, (b) of FIG. 1 shows differences between crystal structure energy (E1T') of 1T'-MoS2 and crystal structure energy (E2H) of 2H-MoS2 according to S-vacancy concentrations. Here, the 1T' structure is a distorted structure of the 1T structure and calculation results show that the 1T' structure is more stable than the 1T structure. In general, the 1T' structure and the 1T structure have similar properties and it is difficult to distinguish one from the other by experiments, and thus the 1T structure may be used as a generic name for both. (C) of FIG. 1 shows E1T'-E2H values calculated according to particles sizes of MoS2, in the absence of S-vacancy (Cv=0%) and at an equilibrium S-vacancy concentration (Cv=17%).

[0032] Referring to FIG. 1A, a free energy of S-vacancy formation (ΔEf) is an almost constant value of about -1 eV, when the S-vacancy concentration is low (below 9%) under the typical implementation conditions. In this regard, an ΔEf value less than 0 indicates that S-vacancy formation reaction occurs spontaneously. When the S-vacancy concentration exceeds 9%, the ΔEf value begins to increase. The ΔEf value is zero, when the S-vacancy concentration reaches about 17% and the ΔEf value exceeds 0, when the S-vacancy concentration is greater than 17%. This means that an equilibrium S-vacancy concentration is about 17%, and thus the S-vacancy concentration in the MoS2 may be expected to be about 17% under the typical implementation conditions.

[0033] Meanwhile, referring to FIG. 1B, it may be confirmed that a difference between the crystal structure energy of 2H-MoS2 as a stable phase and the crystal structure energy of 1T'-MoS2 decreases as the S-vacancy concentration increases in MoS2. This indicates that thermodynamic stability of the 1T'-MoS2 crystal structure relatively increases as the S-vacancy concentration increases in the crystal lattice of MoS2.

[0034] Meanwhile, referring to FIG. 1C, the difference between the crystal structure energy of 2H-MoS2 and the crystal structure energy of 1T'-MoS2 is considerably affected by the particle size of MoS2. As the particle size decreases, the 1T' structure becomes more stable. When the S-vacancy concentration is 0% and the particle size is about 2 nm or less, it may be confirmed that the 1T' structure is more stable than the 2H structure. When the S-vacancy concentration reaches an equilibrium concentration under the conditions according to an embodiment of the present invention, the 1T' structure becomes more stable at a particle size below 7 nm (Cv=17%).

[0035] Based thereon, it may be inferred that once S-vacancies are formed in MoS2 by CO gas via the reaction represented by Reaction Scheme 1 above, thermodynamic stability of the 1T' crystal structure tends to be improved with an increased S-vacancy concentration caused by the reaction with the CO gas. A decrease in the difference of thermodynamic energy between the 2H and 1T' crystal structures may be understood as an increase in the probability of phase transition from the 2H crystal structure to the 1T' crystal structure. Also, the 1T' crystal structure tends to be more stable as the particle size of MoS2 decreases. In this case, especially in the absence of S-vacancy, the 1T' crystal structure becomes more stable than the 2H crystal structure when the particle size is 2 nm or less. When the S-vacancy concentration reaches the equilibrium concentration of 17% via reaction with CO gas and the particle size is 7 nm or less, the 1T' crystal structure becomes more stable, causing spontaneous phase transition.

[0036] Annealing MoS2 in a CO atmosphere may be performed for reaction between CO and MoS2. For example, after MoS2 is placed in an annealing furnace, CO gas may be introduced into the annealing furnace while heating the annealing furnace at a predetermined temperature. The annealing furnace may be used in the atmosphere and may create a vacuum.

[0037] In the present invention, the MoS2, a target of reaction with CO gas, may be in various forms such as in the form of bulk, powder, film, wire, and fiber, without being limited to a particular form. Alternatively, pure MoS2 may be present alone or may be mixed or combined with other materials. This may be possible because the reactant that reacts with MoS2 to induce the 1T crystal structure is CO in a gaseous state.

[0038] Alternatively, a MoS2 precursor used to chemically synthesize MoS2 may also be a target of reaction with CO. For example, the MoS2 precursor may include ammonium tetrathiomolybdate (ATTM).

[0039] As another example, a composite of a MoS2 precursor and an organic material may be a target of reaction with CO. For example, the MoS2 precursor may include ammonium tetrathiomolybdate (ATTM, (NH4)2MoS4), and the organic material may include polyacrylonitrile (PAN) forming a hydrogen bond with the ammonium tetrathiomolybdate. The composite may be in the form of fiber, for example, prepared by electrospinning that is a method of producing fiber by applying electrostatic repulsive force. In electrospinning, a thickness of nanofiber may easily be adjusted according to a magnitude of voltage of several tens of kV applied to a solution and a length of fiber over 100 µm may be realized.

[0040] The MoS2 precursor-organic material composite in the form of nanofiber may be converted into MoS2-carbon nanofiber via reaction with CO gas, and at least one portion of MoS2 included in the MoS2-carbon nanofiber may have the 1T crystal structure.

[0041] Annealing temperature for reaction between MoS2 and CO may be adjusted according to a partial pressure of CO gas in the annealing furnace, for example, may be in the range of 700°C to 1000°C.

[0042] CO gas alone may be added to the annealing furnace or CO gas diluted in an inert gas such as N2 or Ar may be added to the annealing furnace. Alternatively, a mixed gas of CO and CO2 may be added thereto. When the CO/CO2 gas mixture is added, oxygen may be generated in an small amount corresponding to an equilibrium pressure of the reaction represented by Reaction Scheme 2 during the annealing process. By precisely measuring a partial pressure of the small amount of oxygen using an oxygen sensor and controlling the oxygen partial pressure, the partial pressure of CO gas may be precisely controlled in the annealing furnace.

[0043] Also, a microstructure of the composite including MoS2 may be controlled by using the oxygen partial pressure generated in a small amount. For example, the structure of the nanofiber and the particle size and structure of MoS2 contained in the nanofiber may be controlled by adjusting combustion reaction of the MoS2 composition in the form of nanofiber prepared by electrospinning.

         Reaction Scheme 2     CO(g) + 1/2 O2(g)=CO2(g)



[0044] An equilibrium constant of reaction represented by Reaction Scheme 2 with respect to temperature is well known. Based thereon, equilibrium oxygen partial pressures according to temperatures and CO:CO2 flow ratios are shown in FIG. 2. Here, lines indicate isobars each connecting points of equal oxygen partial pressure at an interval of 10 times of the oxygen partial pressure from 10-25 atm to 10-4 atm.

[0045] When a mixed gas of CO and CO2 reacts with MoS2 under the conditions including a temperature of 800°C and a pressure of 1 atm, amounts of reaction products according to a concentration of each component are shown in FIGS. 3A to 3C as three-component phase diagrams of CO-CO2-MoS2. FIG. 3A shows the amount of MoS2, FIG. 3B shows the amount of MoO2, and FIG. 3C shows a sum of the amounts of Mo2C and MoC. Referring to FIGS. 3A to 3C, although the MoS2 phase is maintained regardless of the CO:CO2 ratio, the reaction represented by Reaction Scheme 2 proceeds in the reverse direction at a CO2 fraction of 87.5% or greater to increase the oxygen partial pressure so that the MoO2 phase starts to form. On the contrary, when the CO fraction is 75% or greater, the reaction represented by Reaction Scheme 3 proceeds in the reverse direction to increase the concentration of C promoting generation of a carbide so that the Mo2C and MoC start to form. Based on such thermodynamic considerations, the CO:CO2 ratio may be appropriately determined to form a state without impurities such as MoO2, Mo2C, and MoC.

         Reaction Scheme 3     C + CO2(g) = 2CO(g)



[0046] Hereinafter, the present invention will be described in more detail with reference to the following experimental examples. However, these experimental examples are made only for illustrative purposes, and the present invention is not be construed as being limited to those experimental examples.

Experimental Example 1



[0047] MoS2 powder having a 2H crystal structure was prepared. The MoS2 powder was placed in an annealing furnace at ambient pressure and heated at a temperature of 800°C while simultaneously supplying CO gas into the annealing furnace at a flow rate of 80 sccm and CO2 gas thereinto at a flow rate of 120 sccm.

Experimental Example 2



[0048] Reaction was performed in the same manner as in Experimental Example 1, except that (NH4)2MoS4 (ATTM) that is a precursor of MoS2 was used as a target of reaction with CO gas.

XPS Analysis



[0049] X-ray photoelectron spectroscopy (XPS) was performed on products of Experimental Examples 1 and 2 to observe differences of crystal structures before and after CO gas annealing, and the results are shown in FIGS. 4 and 5. The XPS analysis was performed by using intensities of peaks corresponding to energy levels of Mo 3d3/2 and Mo 3d5/2 orbitals of MoS2 having the 2H and 1T crystal structures.

[0050] Referring to (a) of FIG. 4 and (a) of FIG. 5, no peak corresponding to the 1T crystal structure was observed before CO gas annealing both in the MoS2 powder and ATTM. On the contrary, referring to (b) of FIG. 4 and (b) of FIG. 5, peaks corresponding to the 1T crystal structure were observed after CO gas annealing. Thus, it was confirmed that MoS2 having the 2H crystal structure was converted into MoS2 having the 1T crystal structure by CO gas annealing.

HRTEM Analysis



[0051] To directly observe formation of the 1T crystal structure, a MoS2 single layer was separated from the MoS2 powder of Experimental Example 1 by sonication and a crystal structure thereof was analyzed by using a high-resolution transmission electron microscope (HRTEM). Referring to FIG. 6A and 6B, the MoS2 powder has the 2H crystal structure before CO gas annealing. However, after CO gas annealing, a mixed phase of the 1T structure and the 2T structure is observed. Here, two layers of the 1T crystal structures constitute a unit of the 2T structure and physical and chemical properties of the 2T crystal structure are known to be similar to those of the 1T crystal structure. Also, in the MoS2 powder after CO gas annealing, both the 2H crystal structure and the 1T+2H crystal structure are observed in a single layer as shown in FIG. 6C. This indicates that the crystal structure of the sample is being converted from the 2H crystal structure into the 1T+2T crystal structure.

Experimental Examples 3 to 10



[0052] MoS2-carbon nanofibers (hereinafter, referred to as "MoS2/C nanofibers") were prepared by electrospinning and calcination. First, 1.4 g of ammonium tetrathiomolybdate (ATTM) was dissolved in 5 g of N,N-dimethylformamide (DMF) at 120°C for 2 hours while stirring, and 0.7855 g of polyacrylonitrile (PAN, Mw=150,000 g/mol) was dissolved in 5 g of DMF at 120°C for 2 hours while stirring.

[0053] Then, the two solutions were mixed and stirred for 10 hours. After the stirring was completed, the mixed solution was added to a syringe of an electrospinning apparatus and a potential of 15 kV was set between a metal tip of the syringe and a collector, and then the mixed solution was sprayed at a rate of 0.3 ml/h using a syringe pump to produce ATTM-PAN nanofibers. The produced ATTM+PAN nanofibers were converted into MoS2/C nanofibers via chemical reactions such as thermal decomposition and oxidation during CO gas annealing.

[0054] Specifically, CO gas annealing was performed by using a tube furnace. The annealing was performed while flowing a CO/CO2 gas mixture at 800°C for 1 hour to 5 hours. In this case, the CO/CO2 gas mixture was prepared using CO and CO2 gases each having a purity of 99.9% by adjusting a ratio of CO:CO2 using a mass flow controller (MFC). Details of Experimental Examples 3 to 10 are shown in Table 1 below.
Table 1
Experimental ExampleCO flow rate (sccm)CO2 flow rate (sccm)CO flow ratioAnnealing time (h)
Experimental Example 3 50 150 25% 1
Experimental Example 4 60 140 30% 1
Experimental Example 5 80 120 40% 1
Experimental Example 6 120 80 60% 1
Experimental Example 7 50 150 25% 5
Experimental Example 8 60 140 30% 5
Experimental Example 9 80 120 40% 5
Experimental Example 10 120 80 60% 5

Analysis of Crystal Structure



[0055] The crystal structures of the manufactured MoS2/C nanofibers were identified by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy.

[0056] (a) to (h) of FIG. 7 are graphs illustrating XPS measurement results of the MoS2/C nanofibers manufactured according to the experimental examples of the present invention. (a) to (d) of FIG. 7 show XPS measurement results of the MoS2/C nanofibers according to Experimental Examples 3 to 6 after annealing for 1 hour according to the CO flow ratio. (e) to (h) of FIG. 7 show measurement results of the MoS2/C nanofibers according to Experimental Examples 7 to 10 after annealing for 5 hours according to the CO flow ratio.

[0057] Referring to FIG. 7, it may be confirmed that peaks of 1T-MoS2 are observed by CO gas annealing. Also, as the CO flow ratio and the annealing time increase, a peak intensity of 1T-MoS2 increases and an energy of a peak of 2H-MoS2 is relatively lowered. It may be understood that the higher the CO flow ratio and the longer the annealing time, the better the conversion from 2H-MoS2 to 1T-MoS2. In addition, according to quantitative analysis by deconvolution of XPS results, as the CO flow ratio increases, the ratio of the 1T phase tends to increase and it was confirmed that the 1T phase was formed up to about 70% in Experimental Example 6.

[0058] FIG. 8 shows Raman spectrum measurement results of MoS2/C nanofibers manufactured according to Experimental Examples 4 to 6 and Experimental Examples 8 to 10 according to the present invention. Referring to FIG. 8, J1, J2, and J3 peaks that were obtainable only in the 1T phase were identified regardless of the CO flow ratio and the annealing time, and thus it was confirmed that 1T-MoS2 was formed.

[0059] In order to verify direct relationship between formation of the 1T-MoS2 crystal structure and the S-vacancy concentration, changes in coordination structures of Mo were identified by measuring an extended X-ray absorption fine structure (EXAFS). FIG. 9A shows Fourier transform results of the EXAFS measurement results of Experimental Examples 7 to 10. Referring to (a) of FIG. 9, it may be confirmed that the peak intensity corresponding to the Mo-S coordination number decreases as the CO flow ratio increases. Referring to FIG. 9B which illustrates quantitative analysis results of the Mo-S coordination number by fitting, the Mo-S coordination number was 5.34±0.49, close to 6 observed in a perfect crystal structure, at a CO flow ratio of 25% (Experimental Example 7), but the Mo-S coordination numbers gradually decreased to 4.83±0.49, 4.12±0.37, and 3.88±0.64 at the CO flow ratios of 30% (Experimental Example 8), 40% (Experimental Example 9), and 60% (Experimental Example 10), respectively, indicating that the number of S-vacancies tends to increase.

[0060] FIGS. 10A to 10F show transmission electron microscope images of microstructures of MoS2/C nanofibers according to experimental examples of the present invention. FIGS. 10A to 10C show results of Experimental Examples 4 to 6 and FIGS. 10D to 10F show results of Experimental Examples 8 to 10.

[0061] Referring to FIGS. 10A to 10F, it may be confirmed that the MoS2/C nanofibers according to the experimental examples of the present invention have a structure in which a single-layer of MoS2 is formed or multi-layers of MoS2 are stacked in the fibrous structure formed of carbon. In this regard, as the CO flow ratio decreases and the annealing increases, the number of stacked layers of MoS2 and the length of MoS2 increase. This is because the combustion amount of carbon increases as the CO flow ratio decreases and the annealing time increases.

[0062] First, in terms of the CO flow ratio, as the CO flow ratio decreases, the equilibrium moves to the left in the reaction represented by Reaction Scheme 2 to increase oxygen partial pressure. The increase in the oxygen partial pressure increases the combustion amount of carbon constituting the MoS2/C nanofiber, thereby enlarging empty space inside the MoS2/C nanofiber. When MoS2 units migrated through the empty space and gather, the growth of the MoS2 layer in the lengthwise direction is promoted and the number of stacked MoS2 layers increases. In terms of annealing, as the annealing time increases, the combustion amount of carbon increases, thereby increasing the length of the MoS2 layer and the number of stacked MoS2 layers.

Experimental Examples 11 to 12



[0063] As a control to verify the effect of the present invention, ATTM-PAN nanofibers prepared in the same manner as in Experimental Examples 3 to 10 were annealed at 800°C for 5 hours in an oxygen atmosphere instead of the CO atmosphere to prepare samples of Experimental Examples 11 and 12. Here, the oxygen partial pressures were 0.3 Torr and 0.4 Torr in Experimental Examples 11 and 12, respectively. XPS analysis results thereof are shown in FIG. 11.

[0064] Referring to FIG. 11, unlike the results of CO gas annealing, the products had a considerably low 1T structure ratio. According to quantitative analysis results by deconvolution, the ratios of the 1T structures according to Experimental Examples 11 and 12 were about 0% and 25%, respectively.

Measurement of Hydrogen-generating Catalytic Performance



[0065] Performance of the MoS2/C nanofibers prepared according to experimental examples as hydrogen-generating catalysts was measured. 8 mg of each of the MoS2/C nanofiber samples prepared according to Experimental Examples 9, 11, and 12, 800 µl of deionized water, 200 µl of ethanol, and a fluorine-based Nafion resin solution were mixed and sonicated for 30 minutes to prepare catalyst measurement inks.

[0066] 5 µl of the prepared ink was drop-cast on a glassy carbon electrode and dried to prepare an electrode and hydrogen-generating catalytic properties thereof were analyzed by using a 3 electrode H-cell. Here, 0.5 M sulfuric acid aqueous solution was used as an electrolyte, platinum was used as a counter electrode, and a saturated calomel electrode was used as a reference electrode. The activity of hydrogen generation was analyzed at room temperature at a rate of 2 mV/s from -0.6 V to 0 V with reference to a reversible hydrogen electrode. Measurement results were compensated by iR-compensation using a resistance of 5 Ω of the electrolyte.

[0067] FIGS. 12A and 12B show graphs illustrating measurement results of hydrogen-generating catalytic characteristics of the MoS2/C nanofibers manufactured according to Experimental Examples 9, 11, and 12.

[0068] Referring to FIG. 12A, it was confirmed that the MoS2/C nanofiber manufactured according to Experimental Example 9 annealed in the CO atmosphere had far better hydrogen-generating catalytic performance at an overvoltage than the MoS2/C nanofibers manufactured according to Experimental Examples 11 and 12 annealed in the oxygen atmosphere as a control and including very low ratio of the 1T crystal structures of 0% and 25% respectively.

[0069] FIG. 12B is a graph illustrating comparison results of hydrogen-generating catalytic characteristics of the MoS2-based materials with respect to overvoltage and Tafel slope. As a result, it was confirmed that the MoS2 according to the present invention had the best performance among the conventional MoS2-based hydrogen-generating catalysts reported so far in both conditions.

[0070] According to an embodiment as described above, the effect of quickly and uniformly converting the structure of MoS2 into the 1T-MoS2 structure regardless of the shape of MoS2 may be obtained.

[0071] Also, according to the present invention, the effect of quickly and uniformly converting the structure of MoS2 combined with other materials such as carbon nanofiber into the 1T-MoS2 structure may also be obtained.

[0072] However, the scope of the present invention is not limited by the effects described above.

[0073] While exemplary embodiments have been shown and described above, it will be apparent to those skilled in the art that modifications and variations could be made without departing from the scope of the present invention as defined by the appended claims.


Claims

1. A method of manufacturing molybdenum disulfide (MoS2) having a 1T crystal structure, the method comprising:
performing phase transition from a 2H crystal structure of MoS2 to the 1T crystal structure by reacting MoS2 having the 2H crystal structure with CO gas.
 
2. The method of claim 1,
wherein the performing of phase transition comprises annealing the MoS2 having the 2H crystal structure in an atmosphere including CO gas.
 
3. The method of claim 1,
wherein the performing of phase transition comprises annealing the MoS2 having the 2H crystal structure in an atmosphere including CO gas and CO2 gas.
 
4. The method of claim 2 or 3,
wherein the annealing is performed at a temperature in the range of about 700°C to about 1000°C.
 
5. The method of claim 1,
wherein the MoS2 is in the form of at least one of bulk, powder, film, wire, and fiber.
 
6. A method of manufacturing MoS2 having a 1T crystal structure, the method comprising:

forming a MoS2-carbon composite by reacting an MoS2 precursor-organic material composite with CO gas,

wherein at least one portion of MoS2 included in the MoS2-carbon composite has the 1T crystal structure.


 
7. The method of claim 6,
wherein the MoS2 precursor-organic material composite is in the form of fiber.
 
8. The method of claim 6,
wherein the MoS2 precursor-organic material composite is prepared by electrospinning.
 
9. The method of claim 6,
wherein MoS2 included in the MoS2-carbon composite has a single-layered or a multi-layered structure.
 
10. The method of claim 6,
wherein the forming of the MoS2-carbon composite comprises annealing the MoS2 precursor-organic material composite in an atmosphere including CO gas.
 
11. The method of claim 6,
wherein the forming of the MoS2-carbon composite comprises annealing the MoS2 precursor-organic material composite in an atmosphere including CO gas and CO2 gas.
 
12. The method of claim 10 or 11,
wherein the annealing is performed at a temperature in the range of 700°C to 1000°C.
 
13. A catalyst for generating hydrogen prepared according to the method of any one of claims 6 to 12.
 
14. A MoS2-carbon composite comprising:

a carbon structure in the form of fibers; and

MoS2 distributed in the carbon structure,

wherein the MoS2 included in the MoS2-carbon composite has a single-layered or a multi-layered structure, and

at least one portion of the MoS2 has a 1T crystal structure.


 




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Cited references

REFERENCES CITED IN THE DESCRIPTION



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Patent documents cited in the description