A CONTINUOUS FLOW PROCESS FOR THE SYNTHESIS OF METAL NANOWIRES USING BUBBLE COLUMN REACTOR

Abstract

A continuous flow process for the synthesis of metal nanowires using a bubble column reactor. Also disclosed are different types of multiphase bubble column reactors for synthesizing metal nanowires in high yields and purity through a continuous process. The continuous process provides tunability for the aspect ratio of the nanowires.

Claims

1. A continuous flow process for the synthesis of metal nanowires, wherein the said process employs at least one bubble column reactor, and wherein the said process comprises the steps of: a) dissolving a metal salt in ethylene glycol to obtain a solution A; b) preheating ethylene glycol and dissolving poly (vinyl pyrrolidone) (PVP 40,000-360,000) to obtain a solution B; c) continuously feeding a blend of the solution A, solution B and a solution of FeCl.sub.3 in ethylene glycol to the bubble column reactor from a bottom inlet; d) maintaining the temperature in each reactor at 130-190° C., with a cumulative residence time of 25-80 min; and e) allowing the growth of nanowires of the metal to the desired dimensions, wherein the aspect ratio of said nanowire is tunable in the range of 300 to 1200 with 100% purity, and the conversion of metal salt is in the range of 85% to 95%.

2. The process as claimed in claim 1, wherein it employs at least two bubble column reactors.

3. The process as claimed in claim 1, wherein the bubble column reactors are connected in series.

4. The process as claimed in claim 1, wherein 2-10 bubble column reactors are connected in series.

5. The process as claimed in claim 1, wherein the metal salt of step (a) is silver nitrate.

6. The process as claimed in claim 1, wherein solution A is 0.25 to 0.65 M solution of silver nitrate in ethylene glycol.

7. The process as claimed in claim 1, wherein solution B is 0.077 M solution of poly vinyl pyrrolidone in ethylene glycol.

8. The process as claimed in claim 1, wherein the continuous flow process for the synthesis of metal nanowires comprises the steps of: a) dissolving a metal salt into ethylene glycol to obtain 0.25 to 0.65 M solution of metal salt; b) preheating ethylene glycol to 110° C. and dissolving poly (vinyl pyrrolidone) (PVP 360,000) to obtain a 0.077 M solution of poly (vinyl pyrrolidone); c) continuously feeding the blend of 0.25 to 0.65 M metal salt, 0.077 M poly (vinyl pyrrolidone) (MW˜40,000-360,000), 800 μM FeCl.sub.3 in ethylene glycol solution to the first multiphase unstirred reactor from the bottom inlet; d) maintaining the temperature in each reactor at 130-190° C., with a cumulative residence time of 25-80 min; and e) allowing the growth of nanowires of the metal to the desired dimensions.

9. The process as claimed in claim 1, wherein the said bubble column reactor comprises: a column alone or in series with at least one more column optionally comprising at least one external or one internal air loop or said column comprising one or at least two sections, the diameter of each section being same, the sections connected by a narrower section, wherein the ratio of diameter of narrow section: diameter of section is in the range 0.2 to 0.5 and the ratio of the length of section: diameter of section is always 1 to 2; a sintered plate sparger or a ring sparger wherein the diameter of the sparger is equal to or greater than the diameter of the narrow section, with a superficial air velocity of 0.01-0.06 m/s and at least two air jets of 1 mm diameter and a velocity >1 meter/second.

10. The process as claimed in claim 1, wherein the said bubble column reactor further comprises one or more multiphase unstirred reactors wherein said reactor further comprises a simple bubble column reactor or a sectionalized bubble column reactor with perforated plates or sectionalized bubble column with plurality of compartments having no perforated plates or an internal air-lift loop reactor or external air-lift loop reactor with draft tube having diameter of 0.1-0.4 times the column diameter and the ratio of the reactor height to diameter in the range 6-20 and a sparger (ring sparger or sintered sparger) with at least one air jet periodically operated at 0.5 mm to 2 mm diameter with a jet air velocity >1 meter/second, wherein the diameter of the sparger is equal to the diameter of the column.

Description

BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS

[0035] FIG. 1A: Bubble column reactor (1—reactor inlet where the reactants are introduced into the column, 2—the inlet provided for gas/air, 3—sparger, 4—outlet for reactant mixture and 5—outlet for air)

[0036] FIG. 1B: Bubble column with ring sparger. (1—reactor inlet where the reactants are introduced into the column, 2—the inlet provided for gas/air, 3—sparger, 4—outlet for reactant mixture and 5—outlet for air)

[0037] FIG. 1C: Sectionalized bubble column reactor with perforated sections. (1—reactor inlet where the reactants are introduced into the column, 2—the inlet provided for gas/air, 3—sparger, 4—outlet for reactant mixture and 5—outlet for air)

[0038] FIG. 1D: Modified sectionalized bubble column reactor. (1—reactor inlet where the reactants are introduced into the column, 2—the inlet provided for gas/air, 3—sparger, 4—outlet for reactant mixture and 5—outlet for air)

[0039] FIG. 1E: External loop air lift reactor. (1—reactor inlet where the reactants are introduced into the column, 2—the inlet provided for gas/air, 3—sparger, 4—outlet for reactant mixture and 5—outlet for air)

[0040] FIG. 1F: Internal loop air lift reactor. (1—reactor inlet where the reactants are introduced into the column, 2—the inlet provided for gas/air, 3—sparger, 4—outlet for reactant mixture and 5—outlet for air)

[0041] FIG. 2: FESEM images of Silver Nanowires produced using 2 CSTRs followed by bubble column reactor set up.

[0042] FIG. 3: FESEM images of Silver Nanowires produced using 2 CSTRs followed by bubble column with attached condenser set up.

[0043] FIG. 4: FESEM images of Silver Nanowires produced using 2 CSTRs followed by bubble column with sectional plates.

[0044] FIG. 5: FESEM images of Silver Nanowires produced in single bubble column.

[0045] FIG. 6: FESEM images of Silver Nanowires produced in single bubble column with converging-diverging sections.

[0046] FIG. 7: FESEM images of Silver Nanowires produced in a single bubble column with modified sparger and air compressor was used for gas sparging.

[0047] FIG. 8: FESEM images of Silver Nanowires produced using two bubble columns in series set up.

[0048] FIG. 9: FESEM images of Silver Nanowires produced using two bubble columns in series set up.

[0049] FIG. 10: FESEM images of Silver Nanowires produced using two bubble columns in series set up (simple bubble column followed by air lift bubble column)

DETAILED DESCRIPTION OF THE INVENTION

[0050] The invention will now be described in detail in connection with certain preferred and optional embodiments, so that various aspects thereof may be more fully understood and appreciated.

[0051] In an aspect, the present invention provides a continuous flow process for the synthesis of metal nanowires by using a bubble column reactor comprising the steps of: [0052] a) dissolving a metal salt into ethylene glycol to obtain a solution A; [0053] b) preheating ethylene glycol and dissolving poly (vinyl pyrrolidone) (PVP 40,000-360,000) to obtain a solution B; [0054] c) continuously feeding the blend of the solution A of metal salt, the solution B of poly (vinyl pyrrolidone) (MW˜40,000-360,000), FeCl.sub.3 in ethylene glycol solution to the bubble column reactor from the bottom inlet; [0055] d) maintaining the temperature in each reactor at 130-190° C., with a cumulative residence time of 25-80 min; and [0056] e) allowing the growth of nano wires of the metal to the desired dimensions.

[0057] In another aspect, the present invention provides a continuous flow process for the synthesis of metal nanowires by using a bubble column reactor comprising the steps of: [0058] a) dissolving a metal salt into ethylene glycol to obtain 0.25 to 0.65 M solution of metal salt; [0059] b) preheating ethylene glycol to 110° C. and dissolving poly (vinyl pyrrolidone) (PVP 360,000) to obtain a 0.077 M solution of poly (vinyl pyrrolidone); [0060] c) continuously feeding the blend of 0.25 to 0.65 M metal salt, 0.077 M poly (vinyl pyrrolidone) (MW˜40,000-360,000), 800 μM FeCl.sub.3 in ethylene glycol solution to the first multiphase unstirred reactor from the bottom inlet; [0061] d) maintaining the temperature in each reactor at 130-190° C., with a cumulative residence time of 25-80 min; and [0062] e) allowing the growth of nanowires of the metal to the desired dimensions.

[0063] In the processes described above, the metal salt is preferably silver nitrate. The ethylene glycol acts as solvent as well as reducing agent, and PVP acts as stabilizer and capping agent to guide the growth of nanowires. Further, the process may either employ at least one bubble column reactor or at least two bubble column reactors for the synthesis of metal nanowires. In an aspect, the process employs 2-10 bubble column reactors and the bubble column reactors are connected in series. The multiphase unstirred reactor of step (c) can be a bubble column reactor or a sectionalized bubble column reactor or an air-loop reactor.

[0064] The above process can be carried out in bubble column reactor alone or with continuous stirred tank reactors. The process of the invention employs a multiphase unstirred continuously operated reactor where the draft tube diameter is 0 to 0.15 times the reactor diameter and the height of the reactor is between 7-10 times the reactor diameter. The draft tube is a concentric tube inside an airlift reactor that facilitates an increase circulation of the contents of the reactor.

[0065] In another aspect, the present invention provides a bubble column reactor comprising: a column alone or in series with at least one more column or a continuously stirred reactor, optionally comprising at least one external (4) or one internal air loop (2) or said column comprising one or at least two sections, the diameter of each section being same, the sections connected by a narrower section, wherein the ratio of diameter of narrow section: diameter of section is in the range 0.2 to 0.5 and the ratio of the length of section: diameter of section is always 1 to 2; a sintered plate sparger (3) or a ring sparger (3) wherein the diameter of the sparger (3) is equal to or greater than the diameter of the narrow section, with a superficial air velocity of 0.01-0.06 m/s and at least two air jets (1 and 5) of 1 mm diameter and a velocity >1 meter/second.

[0066] In still another aspect, the present invention further provides one or more multiphase unstirred reactors wherein said reactor further comprises a simple bubble column reactor or a sectionalized bubble column reactor with perforated plates or sectionalized bubble column with many compartments having no perforated plates or an internal air-lift loop reactor or external air-lift loop reactor with draft tube having diameter of 0.1-0.4 times the column diameter and the ratio of the reactor height to diameter in the range 6-20 and a sparger (3)(ring sparger or sintered sparger) with at least one air jet periodically operated at 0.5 mm to 2 mm diameter with a jet air velocity >1 meter/second, wherein the diameter of the sparger is equal to the diameter of the column.

[0067] In a further aspect, a bubble column reactor is used having aspect ratio more than 8 in batch or continuous mode. Air was sparged continuously through a bottom sparger with the superficial gas velocity of 0.01-0.06 m/s. Air sparged in the bubble column was given a vent through a reflux condenser to condense acid vapors in the reactor and release the non-condensable.

[0068] In another aspect, an air-loop lift reactor having aspect ratio between 7 to 10 is used in continuous operation mode, wherein the draft tube diameter is 0.1-0.12 times the column diameter.

[0069] In still another aspect, the invention claims using at least one air jet periodically operated at 0.5 mm to 2 mm diameter with a jet air velocity>1 m/s, to create random flow field in the sparger area.

[0070] In yet another aspect, the final product is continuously mixed with acetone at 5 to 6 times in volume, in the outlet tubing for separation of silver nanowires in a still vessel. The aspect ratio of nanowires synthesized this way is in the range of 300 to 1200 with 100% purity. The purity of the metal was determined by EDAX/elemental analysis and the results indicated the metal to be 100% pure.

[0071] In a further aspect, the process provides metal nanowires with 85% to 95% conversion of metal salt taken initially and yield of >85% of nanowires.

[0072] The reactors and process conditions employed for the process of synthesis of metal nanowires as described herein result in a deposition free process of synthesis, wherein the aspect ratio of the nanowires is tunable in the range of 300-1200.

[0073] FIG. 1A represents Bubble column reactor , wherein 1—reactor inlet where the reactants are introduced into the column, 2—the inlet provided for gas/air, 3—sparger, 4—outlet for reactant mixture and 5—outlet for air.

[0074] FIG. 1B represent Bubble column with ring sparger, wherein 1—reactor inlet where the reactants are introduced into the column, 2—the inlet provided for gas/air, 3—sparger, 4—outlet for reactant mixture and 5—outlet for air.

[0075] FIG. 1C represent Sectionalized bubble column reactor with perforated sections, wherein 1—reactor inlet where the reactants are introduced into the column, 2—the inlet provided for gas/air, 3—sparger, 4—outlet for reactant mixture and 5—outlet for air.

[0076] FIG. 1D represent Modified sectionalized bubble column reactor, wherein 1—reactor inlet where the reactants are introduced into the column, 2—the inlet provided for gas/air, 3—sparger, 4—outlet for reactant mixture and 5—outlet for air.

[0077] FIG. 1E represent External loop air lift reactor-reactor inlet where the reactants are introduced into the column, 2—the inlet provided for gas/air, 3—sparger, 4—outlet for reactant mixture and 5—outlet for air)

[0078] FIG. 1F represent Internal loop air lift reactor, wherein 1—reactor inlet where the reactants are introduced into the column, 2—the inlet provided for gas/air, 3—sparger, 4—outlet for reactant mixture and 5—outlet for air.

[0079] FIG. 2 represent FESEM images of Silver Nanowires produced using 2 CSTRs followed by bubble column reactor set up.

[0080] FIG. 3 represent FESEM images of Silver Nanowires produced using 2 CSTRs followed by bubble column with attached condenser set up.

[0081] FIG. 4 represent FESEM images of Silver Nanowires produced using 2 CSTRs followed by bubble column with sectional plates.

[0082] FIG. 5 represent FESEM images of Silver Nanowires produced in single bubble column.

[0083] FIG. 6 represent FESEM images of Silver Nanowires produced in single bubble column with converging-diverging sections.

[0084] FIG. 7 represent FESEM images of Silver Nanowires produced in a single bubble column with modified sparger and air compressor was used for gas sparging.

[0085] FIG. 8 represent FESEM images of Silver Nanowires produced using two bubble columns in series set up.

[0086] FIG. 9 represent FESEM images of Silver Nanowires produced using two bubble columns in series set up.

[0087] FIG. 10 represent FESEM images of Silver Nanowires produced using two bubble columns in series set up (simple bubble column followed by air lift bubble column).

[0088] The comparative examples 1-5 employed continuous stirred tank reactors or bubble column reactors with different process parameters and this resulted in silver nanowires that did not possess the desired aspect ratio between 300-1200. The change in process parameters also affected the conversion of the silver nitrate to pure silver nanowires as evidenced in examples 1-5. Thus the process claimed is not a mere optimization of process parameters, but an unanticipated combination of the construct and configuration of the bubble column reactor and process parameters leading to 100% pure silver nanowires, with the aspect ratio tunable in the range of 300-1200, with 85-95% conversion of silver nitrate and >85% yield of silver nanowires.

EXAMPLES

[0089] The following examples are given by way of illustration only and therefore should not be construed to limit the scope of the present invention in any manner.

Comparative Examples—Examples 1-5

Example 1

[0090] Upon using two continuous stirred tank reactors (CSTRs 60 ml volume) followed by a bubble column reactor (FIG. 1A) (˜1200 mL) with inlet composition of the reactants as 0.25 M AgNO.sub.3, 600 μM FeCl.sub.3 and 0.077 M PVP (mol. wt. 360,000), to first CSTR and with temperature in each reactor maintained at 140° C., with a cumulative residence time of one hour, the analysis of outlet samples using Atomic Absorption Spectrophotometer (AAS) showed 73.6% conversion. Mixing in the bubble column was achieved with the aid of air sparging from the bottom at a superficial velocity of 0.0051 m/s. The average diameter and length of the nanowires (observed using Field Emission Scanning Electron Microscope) were 465±100 nm and 23±10 μm, respectively giving a low aspect ratio in the range of 50-70, refer FIG. 2.

[0091] The second CSTR allow more time for the reactants to react and form nuclei before entering the growth phase.

[0092] Example No. 2: Experimental set-up, reaction conditions as well as the procedure was followed as in Example 1 with the only addition of a reflux condenser at the top of the bubble column (using the reactor in FIG. 1A). The atomic absorption spectroscopy results revealed around 12% improvement in the conversion (˜85%), whilst a significant increase in the overall aspect ratio of nanowires in the range of 250-300 (average diameter 110±55 nm and length 26±15 μm) was observed, refer FIG. 3.

[0093] Example No. 3: The reaction was carried out keeping all the reaction parameters same as above (Example 1) using a sectionalized bubble column having 3 perforated plates with hole diameter 1 mm (FIG. 1C). The overall conversion in this experiment was 64% and significant decrease in the overall aspect ratio (150-180) of nanowires (average diameter 150±75 nm and length 10±5 μm) was observed. A lot of silver nanowires were found deposited on the perforated plates, refer FIG. 4.

[0094] Example No. 4: Modified design of bubble column using a bigger ring sparger (FIG. 1B), where the sparger diameter was kept same as the column diameter. Upon keeping all other parameters maintained as in Example 1, co-current flow of reactants and air (superficial velocity 0.0051 m/s) from the bottom of the column resulted in about 88.4% conversion of nanowires. The average diameter and length (analysed by FE-SEM and measured using ImageJ) was 65±10 nm and 33±15 μm respectively, refer FIG. 5.

[0095] Example No. 5: Using the reactor in FIG. 1D where the sections are achieved by reducing the cross-section of the reactor periodically, upon carrying out the reactions at conditions mentioned in Example 1, a lot of wall deposition as well as cluster formations on sparger were observed which led to the decrease in the overall conversion (61.5%). Also, the aspect ratio of the wires was very low (120-160) (average length 10±5 μm and diameter 200±55 nm), refer FIG. 6.

Experimental Examples Of The Invention Ex 6-13, Except 10

[0096] Example No. 6: Experiments were carried out in the setup (using only the reactor in FIG. 1C and without using any CSTR) and conditions of Example 3 such that the air sparging was done at an outlet pressure ˜1 bar. Analysis of samples showed a total overall conversion of 91.1%. The aspect ratio went beyond 1000 for an average diameter and length of 60±10 nm and 35±15 μm respectively, refer FIG. 7.

[0097] Example No. 7: Upon using only two bubble columns in series with same Hc/D ratio and sparger design (FIG. 1B and FIG. 1B), an overall residence time of 1 hour, the optimized reaction stoichiometry, and when the reactants were fed to the first bubble column at identical conditions as in Example 6, conversion increased to 91.7% and the nanowires produced in this example were longer by 50% when compared to the results in a single bubble column. The Average length and diameter of the Silver nanowires was 65±10 nm and 35±25 μm respectively, refer FIG. 8.

[0098] The second bubble column allow unidirectional growth of nanowires.

[0099] Example No. 8: Using only two bubble columns (FIG. 1B and FIG. 1B), with incorporation of jets for cleaning of surfaces and at a residence time of 15 min in each reactor and at 165° C. with the reaction stoichiometry as in Example 7, and with PVP having a combination of different molecular weights (mol. wt. 55,000:360,000) resulted in 96% conversion of silver nitrate and nanowires of 50 nm diameter and aspect ratio between 500 to 1000, refer FIG. 9.

[0100] Example No. 9: In the experimental set-up in Example 8, an internal air lift loop reactor was used after the first bubble column reactor (FIG. 1B and FIG. 1F). The temperature of the first reactor was maintained at 130° C. while the temperature of the second reactor was maintained at 160° C. It resulted in 97% conversion and wires having diameter of 55±10 nm and an aspect ratio was 600-1000, refer FIG. 10.

[0101] Example No. 10: Upon repeating the experiment in Example no. 3 (using the reactor in FIG. 1C), with sparging of air at a superficial velocity of 0.04 m/s, resulted in shorter nanowires and product was dominant with large number of silver nanoparticles. The conversion of silver ions into silver nanowires was up to 63.9%, while the aspect ratio was also significantly reduced in the range of 100-180 for an average diameter and length of 160±65 nm and 18±13 μm respectively.

[0102] Example No. 11: Upon repeating Example 9 by replacing the internal loop air lift reactor with an external loop air lift reactor, after a bubble column reactor (FIG. 1B and FIG. 1E), it resulted in 96% conversion and wires having diameter of 75±8 nm and an aspect ratio was 400-600.

[0103] Example No. 12: A sequence of two external air loop reactors (FIG. 1E and FIG. 1E) at 130° C. and 160° C. with the other parameters same as in Example 8, it resulted in 93% conversion and wires having diameter of 65±10 nm and an aspect ratio was 300-650.

[0104] Example No. 13: A sequence of two internal air loop reactors (FIG. 1F and FIG. 1F) at 130° C. and 160° C. with the other parameters same as in Example 8, it resulted in 96% conversion and wires having diameter of 60±10 nm and an aspect ratio was 500-650.

ADVANTAGES OF THE INVENTION

[0105] Continuous process of synthesis [0106] High yield providing process [0107] Easy to operate, since there are no moving parts [0108] Aspect ratio is tunable