Method for creating nanopores in MOS.SUB.2 .nanosheets by chemical drilling for disinfection of water under visible light
11351508 · 2022-06-07
Assignee
Inventors
- Pradeep Thalappil (Chennai, IN)
- Depanjan Sarkar (Chennai, IN)
- Anirban Som (Chennai, IN)
- Biswajit Mondal (Chennai, IN)
- Swathy Jakka Ravindran (Chennai, IN)
Cpc classification
C02F2305/023
CHEMISTRY; METALLURGY
B01D67/006
PERFORMING OPERATIONS; TRANSPORTING
B82Y40/00
PERFORMING OPERATIONS; TRANSPORTING
B01J37/348
PERFORMING OPERATIONS; TRANSPORTING
B01D69/145
PERFORMING OPERATIONS; TRANSPORTING
B01D69/10
PERFORMING OPERATIONS; TRANSPORTING
B01D67/0069
PERFORMING OPERATIONS; TRANSPORTING
C01P2004/24
CHEMISTRY; METALLURGY
International classification
B01D67/00
PERFORMING OPERATIONS; TRANSPORTING
B01D61/02
PERFORMING OPERATIONS; TRANSPORTING
B01J37/34
PERFORMING OPERATIONS; TRANSPORTING
B01J35/00
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The present invention relates to a new method for creating nanopores in single layer molybdenum disulfide (MoS.sub.2) nanosheets (NSs) by the electrospray deposition (ESD) of silver ions on a water suspension of the former. Electrospray deposited silver ions react with the MoS.sub.2 NSs at the liquid-air interface resulting in Ag.sub.2S nanoparticles (NPs) which goes into the solution leaving the NSs with holes of 3-5 nm diameter. Specific reaction with the S of MoS.sub.2 NSs leads to Mo-rich edges. Such Mo-rich defects are highly efficient for the generation of active oxygen species such as H.sub.2O.sub.2, under visible light, which causes efficient disinfection of water. The holey MoS.sub.2 NSs shows 10.sup.5 times higher efficiency in disinfection compared to normal MoS.sub.2 NSs. Developed a conceptual prototype and tested with multiple bacterial strains and a viral strain, demonstrating the utility of the method for practical applications.
Claims
1. A method of making nanoscale holes in two dimensional MoS.sub.2 nanosheets, the method comprising: electrospraying deposition of reactive Ag.sup.+ ions onto the two dimensional MoS.sub.2 nanosheet, wherein the Ag.sup.+ ions react with the MoS.sub.2 nanosheet forming Ag.sub.2S and a defect-rich MoS.sub.2 nanosheet; generating H.sub.2O.sub.2 under visible light using the nanoscale holes in the MoS.sub.2 nanosheet; and exposing contaminated water to the H.sub.2O.sub.2 for disinfection.
2. The method of making nanoscale holes in two dimensional MoS.sub.2 nanosheets as claimed in claim 1, wherein the Ag.sup.+ ions are selected from various salts of Ag comprising silver acetate, silver nitrate, and silver perchlorate.
3. The method of making nanoscale holes in two dimensional MoS.sub.2 nanosheets as claimed in claim 1, wherein the nanoscale holes have dimensions below 20 nm.
4. The method of making nanoscale holes in two dimensional MoS.sub.2 nanosheets as claimed in claim 1, wherein the reaction between electrosprayed AG+ ions and MoS.sub.2 nanosheets makes nanoporous MoS.sub.2 nanosheets with Mo-rich edges.
5. The method of making nanoscale holes in two dimensional MoS.sub.2 nanosheets as claimed in claim 1, further comprising metal ions including monovalent ions Ag.sup.+, Cu.sup.+, and divalent ions, Hg.sup.2+, Cu.sup.2+, Zn.sup.2+, Ni.sup.2+.
6. The method of making nanoscale holes in two dimensional MoS.sub.2 nanosheets as claimed in claim 5, further comprising electrospraying the metal ions in water, acetonitrile, methanol, ethanol, dimethyl formamide, tetrahydrofuran, and combination thereof at different proportions.
7. The method of making nanoscale holes in two dimensional MoS.sub.2 nanosheets as claimed in claim 1, the two dimensional materials comprising MoS.sub.2, MoSe.sub.2, WS.sub.2, WSe.sub.2.
8. The method of making nanoscale holes in two dimensional MoS.sub.2 nanosheets as claimed in claim 1, wherein the two dimensional nanosheets are supported on substrates including water, ITO-coated glass, copper, silicon using an adsorption process.
9. The method of making nanoscale holes in two dimensional MoS.sub.2 nanosheets as claimed in claim 5, wherein the metal ions are deposited on the nanosheet substrate using nanoelectrospray ionization.
10. The method of making nanoscale holes in two dimensional MoS.sub.2 nanosheets as claimed in claim 1, wherein the chemical reaction of MoS.sub.2 nanosheets with the metal ions is photocatalytically more active which increases the generation of reactive oxygen species and disinfection efficiency.
11. The method of making nanoscale holes in two dimensional MoS.sub.2 nanosheets as claimed in claim 1, wherein the nanoporous MoS.sub.2 nanosheets supported on silica or alumina are used as a device for filtration.
12. The method of making nanoscale holes in two dimensional MoS.sub.2 nanosheets as claimed in claim 5, wherein the metal ions for chemical etching are supplied as droplets in the gas phase onto the two dimensional nanosheet supported on a substrate.
13. The method of making nanoscale holes in two dimensional MoS.sub.2 nanosheets as claimed in claim 5, wherein the metal ions for chemical etching are supplied in solution containing the two dimensional nanosheets.
14. The method of making nanoscale holes in two dimensional MoS.sub.2 nanosheets as claimed in claim 1, wherein the nanoporous MoS.sub.2 nanosheets act as a membrane for desalination of water.
15. The method of making nanoscale holes in two dimensional MoS.sub.2 nanosheets as claimed in claim 1, further comprising using molecular ions to extract sulphur.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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(13) Referring to the drawings, the embodiments of the present invention are further described. The figures are not necessarily drawn to scale, and in some instances the drawings have been exaggerated or simplified for illustrative purposes only. One of ordinary skill in the art may appreciate the many possible applications and variations of the present invention based on the following examples of possible embodiments of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
(14) The following description is presented to enable any person skilled in the art to make and use the embodiments, and is provided in the context of a particular application and its requirements. Various modifications to the disclosed embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the present disclosure. Thus, the present invention is not limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and features disclosed herein.
(15) The present invention relates to a new method for creating nanopores in single layer MoS.sub.2 NSs. More specifically relates to creating nanoscale holes in chemically synthesized MoS.sub.2 NSs by electrospraying Ag ions.
(16) The present invention provides an easy, cost-effective, ambient, solution-based method to create nanopores in single layer MoS.sub.2 nanosheets. The nanoholes are created by electrospraying Ag ions on a water suspension of chemically synthesized MoS.sub.2 NSs, wherein the Ag ions react with the nanosheets and forms Ag.sub.2S, leaving them with defects. This reaction process will make the MoS.sub.2 NSs porous, with Mo-rich edges.
(17) The present invention illustrates electrospray deposition of reactive ions on a substrate which can make interesting new materials. For example, an electrospray deposition of Ag ions on MoS.sub.2 NSs creates nanoscale holes by reacting it with charged droplets of silver acetate. Wherein, the Ag ions are from various salts of silver including silver acetate, silver nitrate and silver perchlorate.
(18) The present invention provides a new material used for effective disinfection and desalination of water. Electrospray deposition of silver acetate on chemically synthesized MoS.sub.2 nanosheets reacts and forms Ag.sub.2S which creates holes in the nanosheets. This reaction process will make the MoS.sub.2 NSs porous, with Mo-rich edges. These nanoporous MoS.sub.2 NSs will be highly effective in both water desalination and disinfection. The high reactivity of the porous NSs is due to the increase in effective surface area. The edges of MoS.sub.2 NSs are responsible for their unusual reactivity. Mo enriched pores may lead to larger flux of filtered water, much larger than graphene. These NSs, with tiny holes in it, will have more reactive edges to show enhanced reactivity. Moreover chemical drilling with metal ions like Ag.sup.+ make the MoS.sub.2 nanosheets photo catalytically more active which increase the ROS generation and disinfection efficiency.
(19) The following description details the method and application of the new material and explains the experimental parts for creating a hole in a chemically synthesized substrate by chemical drilling.
(20) All the commercially available chemicals were used as is, without any further purification. Silver acetate (AgOAc), molybdenum disulfide (MoS.sub.2), 1.6 M n-butyllithium in hexane and solvent hexane were purchased from Sigma Aldrich, India.
(21) Synthesis of MoS.sub.2 NS:
(22) Chemical exfoliation method was used to synthesize MoS.sub.2 NSs, from MoS.sub.2 powder. 300 mg of MoS.sub.2 powder was taken under an argon atmosphere and 3 mL of 1.6 M n-butyllithium was added to it. The resulting solution was stirred for 2 days under the same atmosphere. Then the resulting lithium intercalated product was washed repeatedly with hexane to remove unreacted reactants followed by addition of 80 mL of distilled water. The resulting solution was sonicated in a bath sonicator for 1 h. Then the aqueous dispersion of MoS.sub.2 NSs was centrifuged at a speed of 10000 rpm to remove bulk, un-exfoliated MoS.sub.2. The quality of the synthesized MoS.sub.2 NSs was checked using electron microscopy, UV-Vis and Raman spectroscopy. The concentration of MoS.sub.2 dispersion was determined using inductively coupled plasma mass spectrometry (ICP MS).
(23) Electrospray deposition on MoS.sub.2 NSs:
(24) For electrospray deposition, a home built nanoelectrospray ionization (nESI) source was made. The nESI tip was made by pulling a borosilicate glass capillary into two, using a micropipette puller (Sutter Instruments, U.S.A.). Each tip, after pulling, was checked using a microscope to ensure the size and quality of the cut. Tips with an opening of 10-15 μm were used for all deposition experiment. 10 mM aqueous solution of AgOAc was filled in the nESI tips using a microinjector pipette tip and it was connected to a platinum electrode, for high voltage connection. For deposition on MoS.sub.2 NSs, an aqueous suspension of 3.7 mM (in terms of Mo) MoS.sub.2 NS was taken in a properly shaped Eppendorf vial and deposition was performed. The water suspension of MoS.sub.2 was connected to ground through a picoammeter. The deposition current was varied from 20-100 nA for different experiments.
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(26) To prove that the deposition of ions followed by the reaction is the only reason for the defects in MoS.sub.2 NSs, a detailed characterization of synthesized NSs were done.
(27) From the high-resolution TEM (HRTEM) image (
(28) With these MoS.sub.2 NSs, the electrospray deposition experiments were done. The deposition time and rate were optimized by trial and error based method. In a typical experiment, Ag.sup.+ ions were electrosprayed on MoS.sub.2 NSs suspension (3.7 mM with respect to Mo) for 30 min at a deposition current of 60 nA. After the deposition, a portion of the NSs was seen floating on the water surface and rest of it was still in the bulk. Both of these categories of NSs were taken on a carbon coated TEM grid for imaging.
(29) Disinfection of Water:
(30) The photocatalytic disinfection performance of nanoporous MoS.sub.2 sheets was then checked under visible light and the disinfection efficiency was then compared with the controls; namely as synthesized MoS.sub.2 NSs under visible light at the same concentration of Ag.sup.+ used for chemical drilling and an equal mass of bulk MoS.sub.2 under same experimental conditions.
(31) A Xenon lamp equipped with UV filter was used as a light source. In an aspect, 10 mL of synthetic water (typically containing Escherichia coli ATCC 25922 in a concentration of 1×10.sup.7 CFU/mL, unless otherwise mentioned) was used. A high concentration of the bacterial input was maintained considering the activity of the proposed material in the treatment of water from challenging environments. 1 mL of the diluted samples was plated along with nutrient agar on a sterile petridish using the pour plate method after 2 h reaction time. After 48 h of incubation at 37° C., the colonies were counted and recorded.
(32) Disinfection of bacteria: To check the efficiency of disinfection of holey MoS.sub.2 NSs, a series of experiments are performed along with several control experiments. The disinfection efficiency of the MoS.sub.2 NSs are tested using bacteria and virus-contaminated water.
(33) The following description shows that the holey MoS.sub.2 NSs are more efficient in generating at least one ROS species, namely H.sub.2O.sub.2. The disinfection efficiency of Ag.sup.+ alone was also examined under the same experimental conditions taking the same amount of Ag.sup.+ ions used for chemical drilling. Ag.sup.+ ions showed a negligible effect on E. coli inactivation because the concentration of Ag.sup.+ was 0.2 μM, much lower than the concentration needed for disinfection at a bacterial load of 10.sup.7 CFU/mL.
(34) Disinfection of viruses: Considering the fact that the major water purification techniques used for virus removal are the addition of chlorine which produces harmful disinfection byproducts, however the proposed holey MoS.sub.2 NSs could serve as an efficient method to reduce pathogenic viruses by a safer method. The bulk MoS.sub.2 with and without Ag.sup.+ and MoS.sub.2 NSs without holes are unable to affect the phage significantly, the porous MoS.sub.2 NSs are found to achieve a 7 log reduction by photocatalytic disinfection (
(35) From earlier reports, it is known that MoS.sub.2 in presence of visible light can generate active oxygen species like H.sub.2O.sub.2. Chong Liu et. al. has shown that the edges of MoS.sub.2 NSs are more active in this reaction. Thus the generation of H.sub.2O.sub.2, in presence of visible light is one of the reasons for the disinfection of water. To prove that the holey MoS.sub.2 is more efficient for the production of H.sub.2O.sub.2, a set of cyclic voltammetry (CV) experiments are performed. For all the CV experiments, a pre-cleaned gold electrode is used as the working electrode, Ag/AgCl is used as the reference electrode and Pt is used as the counter electrode. Prior to CV measurements of each sample, 5 mL of as-synthesized MoS.sub.2 suspension was dried at 55° C. in a glass bottle. Subsequently, CV experiments are performed by adding 5 mL of 1 M phosphate buffered saline (PBS, pH˜7.3) to the bottle having previously dried MoS.sub.2 and electrochemical experiment is performed after exposing the dispersion to visible light (for 1 or 2 h, depending on the experiment). CV of each sample was performed from 0 to +1 V with a fixed scan rate of 100 mV/s. CV profiles of Au, performed in blank solution (only PBS), as well as in PBS along with as synthesized MoS.sub.2 NSs and holey MoS.sub.2 NSs irradiated with visible light for 1 h and 2 h, respectively are shown in
(36) Imaging of Bacteria and Virus Before and After the Treatment with the Sample:
(37) SEM imaging establishes the damage of bacterial cells.
(38) The present invention provides a working prototype design for the disinfection of water developed using a commercially available low power LED strip.
(39) Thus the present invention provides a cheap ambient method for making nanometer size holes in a single crystalline NS. Electrospray deposition of reactive ions on a substrate can make interesting new materials. Resulting porous MoS.sub.2 NSs can act as a better membrane for desalination of water. In addition, Mo enriched pores will lead to the larger flux of water, predicted to be much larger than that of graphene [Heiranian, M. et al., Nature Communications 6, 8616 (2015)]. The edges of MoS.sub.2 NSs are responsible for their unusual reactivity. These NSs, with tiny holes in it, will have more reactive edges to show enhanced reactivity.
(40) It may be appreciated by those skilled in the art that the drawings, examples and detailed description herein are to be regarded in an illustrative rather than a restrictive manner.