Multi-channel direct-deposit assembly method to high-throughput synthesize three-dimensional macroporous/mesoporous material array

Abstract

A multi-channel direct-deposit assembly method is disclosed to high-throughput synthesize three-dimensional macroporous/mesoporous (3DMM) material array with precisely controlled composition, pore size, and pore structure. The macropore size of the synthesized 3DMM material is in the range of 50-1000 nm; the mesopore size of the synthesized 3DMM material is in the range of 1-50 nm. The surface area of the 3DMM material is in the range of 20-1000 m.sup.2/g. The 3DMM material array can be used for rapid synthesis, screening and manufacture of catalysts and nanosensors.

Claims

1. A method of forming porous structured material array, comprising: preparing pore-forming template agent solutions, wherein the pore-forming agent solutions comprising one kind or a mixture of two or more kinds selected from polymer nanospheres, carbon blacks, carbon nanotubes, carbon nanofibers, carbon nanospheres, and poly(methyl methacrylate) (PMMA) microspheres, polystyrene nanosphere, latex spheres, and inorganic nanoparticles, silica nanoparticles, carbon nanoparticles, carbon dots, carbon nanocells, polymer, and amphoteric solvent; preparing precursor solutions to generate a target product, wherein the precursor solution comprising one kind or a mixture of two or more kinds of metal species, graphene oxide, MXene, carbon nanotubes, metal nanoparticles, organosilicate, polymer, and amphoteric solvent; depositing at least one of precursor solutions and at least one of pore-forming template agent solutions as dots onto a substrate to generate an as-synthesized array, wherein each of the dots has independent compositions of said at least one of precursor solutions and said at least one of pore-forming template agent solutions.

2. The method of claim 1, further comprising: prior to the depositing, imputing said at least one of precursor solutions into at least one of a first set of channels and imputing said at least one of pore-forming template agent solutions into at least one of a second set of solution channels.

3. The method of claim 1, further comprising: evaporating the as-synthesized array at 20-500 C. to remove amphoteric solvent in the pore-forming template agent solutions and precursor solutions and form an as-synthesized film array.

4. The method of claim 3, further comprising: generating the porous structured material array with heating the as-synthesized array at 100-1000 C. to remove organic pore-forming templates, removing silica pore-forming template with NaOH or HF aqueous solution, or both the heating and the removing.

5. The method of claim 4, wherein the porous structured material array is a three-dimensional macroporous/mesoporous material array.

6. The method of claim 1, wherein said depositing further comprising: dispensing pore-forming template solutions and precursor solutions of target product into the each channel of a multi-channel direct deposition apparatus individually, wherein software programs dispense droplets of each channel with a certain volume onto the substrate to create a patterned as-synthesized thin film array with controlled compositions and combinations.

7. The method of claim 1, wherein said amphoteric solvent may be one kind or a mixture of two or more kinds selected from water, alcohol, acid, alkali, and acetone.

8. The method of claim 7, wherein said alcohol may be one kind or a mixture of two or more kinds selected from methanol, ethanol, propanol, butanol and glycerol.

9. The method of claim 7, wherein said acid may be one kind or a mixture of two or more kinds selected from formic acid, acetic acid, nitric acid, hydrochloric acid, sulfuric acid, and citric acid.

10. The method of claim 7, wherein said alkali may be one kind or a mixture of two or more kinds selected from ammonia, sodium hydroxide, potassium hydroxide.

11. The method of claim 1, wherein said metal species precursors may be one kind or a mixture of two or more kinds selected from main group, transition, lanthanide, or actinide metal.

12. The method of claim 1, wherein said metal species precursors selected from nitrate, carbonate, acetate, chlorate, and alkoxide.

13. The method of claim 1, wherein said solution is deposited by a process selected from inkjet printing, spin coating, gravure, micro-pen, nano-fountain pen, dip-pen, screen printing, spray coating, slide coating, slot coating, curtain coating, dip coating, and combinations thereof.

14. The method of claim 1, wherein said deposited substrates selected from paper, membrane, glass, corundum, ceramic, silicon wafer, steel, wood, quartz, circuit board, conductive materials, and combinations thereof.

15. The method of claim 5, (a) wherein said the three-dimensional macroporous/mesoporous material array comprises metal oxide composites, metal/metal oxides composites, metal/reduced graphene oxide (rGO) composites, metal oxide/rGO composites, metal/carbon nanotube (CNT) composites, metal oxide/CNT composites, metal/Mxene composite, and metal oxide/Mxene composite and (b) wherein the macropore size of the synthesized three-dimensional macroporous/mesoporous material is in the range of 50-1000 nm; the mesopore size of the synthesized three-dimensional macroporous/mesoporous material is in the range of 1-50 nm, (c) wherein the surface area of the three-dimensional macroporous/mesoporous material is in the range of 20-1000 m.sup.2/g.

16. The method of claim 2, further: wherein in said preparing pore-forming template agent solutions, preparing pore-forming template agent solutions, wherein the pore-forming agent solutions comprising one kind or a mixture of two or more kinds selected from polymer nanospheres, carbon blacks, carbon nanotubes, carbon nanofibers, carbon nanospheres, and poly(methyl methacrylate) (PMMA) microspheres, polystyrene nanosphere, latex spheres, and inorganic nanoparticles, silica nanoparticles, carbon nanoparticles, carbon dots, carbon nanocells, polymer, and amphoteric solvent; wherein said preparing precursor solutions, preparing precursor solutions to generate a target product, wherein the precursor solution comprising one kind or a mixture of two or more kinds of metal species, graphene oxide, MXene, carbon nanotubes, metal nanoparticles, organosilicate, polymer, and amphoteric solvent to control growth and condensation kinetics for forming stable nanoparticle precursor solution; wherein in said depositing, depositing at least one of the precursor solutions and at least one of the pore-forming template agent solutions as dots onto a substrate to generate an as-synthesized array, wherein each dot has independent compositions of said at least one of the precursor solutions and said at least one of the pore-forming template agent solutions.

17. The method of claim 16, further comprising: evaporating the as-synthesized array at 20-500 C. to remove amphoteric solvent in the pore-forming template agent solutions and precursor solutions and form an as-synthesized film array.

18. The method of claim 17, further comprising: generating a three-dimensional macroporous/mesoporous material array with heating the as-synthesized array at 100-1000 C. to remove organic pore-forming templates, removing silica pore-forming template with NaOH or HF aqueous solution, or both the heating and the removing.

19. The method of claim 16, wherein said depositing further comprising: dispensing pore-forming template solutions and precursor solutions of target product into the each channel of a multi-channel direct deposition apparatus individually, wherein software programs dispense droplets of each channel with a certain volume onto the substrate to create a patterned as-synthesized thin film array with controlled compositions and combinations.

20. The method of claim 16, wherein said amphoteric solvent may be one kind or a mixture of two or more kinds selected from water, alcohol, acid, alkali, and acetone.

21. The method of claim 20, wherein said alcohol may be one kind or a mixture of two or more kinds selected from methanol, ethanol, propanol, butanol and glycerol.

22. The method of claim 20, wherein said acid may be one kind or a mixture of two or more kinds selected from formic acid, acetic acid, nitric acid, hydrochloric acid, sulfuric acid, and citric acid.

23. The method of claim 20, wherein said alkali may be one kind or a mixture of two or more kinds selected from ammonia, sodium hydroxide, potassium hydroxide.

24. The method of claim 16, wherein said metal species precursors may be one kind or a mixture of two or more kinds selected from main group, transition, lanthanide, or actinide metal.

25. The method of claim 16, wherein said metal species precursors selected from nitrate, carbonate, acetate, chlorate, and alkoxide.

26. The method of claim 16, wherein said solution is deposited by a process selected from inkjet printing, spin coating, gravure, micro-pen, nano-fountain pen, dip-pen, screen printing, spray coating, slide coating, slot coating, curtain coating, dip coating, and combinations thereof.

27. The method of claim 16, wherein said deposited substrates selected from paper, membrane, glass, corundum, ceramic, silicon wafer, steel, wood, quartz, circuit board, conductive materials, and combinations thereof.

28. The method of claim 18, (a) wherein said the three-dimensional macroporous/mesoporous material array comprises metal oxide composites, metal/metal oxides composites, metal/reduced graphene oxide (rGO) composites, metal oxide/rGO composites, metal/carbon nanotube (CNT) composites, metal oxide/CNT composites, metal/Mxene composite, and metal oxide/Mxene composite and (b) wherein the macropore size of the synthesized three-dimensional macroporous/mesoporous material is in the range of 50-1000 nm; the mesopore size of the synthesized three-dimensional macroporous/mesoporous material is in the range of 1-50 nm, (c) wherein the surface area of the three-dimensional macroporous/mesoporous material is in the range of 20-1000 m.sup.2/g.

Description

BRIEF DESCRIPTION OF THE DRAWING

[0015] The inventive concepts will become more apparent in view of the attached drawings and accompanying detailed description.

[0016] FIG. 1 shows a flow chart of multi-channel direct-deposit assembly method for high-throughput synthesizing a three-dimensional macroporous/mesoporous material array.

[0017] FIG. 2 shows an example schematic diagram for generating 3DMM material array.

[0018] FIG. 3 shows Scanning Electron Microscope (SEM) image of silica nanospheres.

[0019] FIG. 4 shows the as-synthesized 3DMM NiCoFePbO.sub.x material array on filter paper based on multi-channel direct-deposit assembly method (ink-jet printing assembly method).

[0020] FIG. 5 X-ray diffraction (XRD) of the synthesized CoFe.sub.2O.sub.x in 3D MM NiCoFePbO.sub.x array based on multi-channel direct-deposit assembly method (inkjet printing assembly method).

[0021] FIG. 6 SEM of the synthesized 3DMM AgCoNiO.sub.x material based on multi-channel direct-deposit assembly method (spin coating assembly method)

[0022] FIG. 7 Synthesized 3DMM CuCoMnWO.sub.x material array on a glass slide based on multi-channel direct-deposit assembly method (ink-jet printing assembly method).

[0023] FIG. 8 SEM images and XRD analysis of the synthesized 3DMM CuCoMnWO.sub.x material array based on ink-jet printing assembly method. (a) SEM image of CuCoMnO.sub.4; (b) SEM image of W.sub.0.7Mo.sub.0.3O.sub.3; (c) SEM image of Cu.sub.1.5Mn.sub.1.5O.sub.4 material; (d) XRD of CuCoMnO.sub.4; (e) XRD of W.sub.0.7Mo.sub.0.3O.sub.3; (f) XRD of Cu.sub.1.5Mn.sub.1.5O.sub.4 material

DETAILED DESCRIPTION OF THE INVENTION

[0024] A high-throughput method for forming a three-dimensional macroporous/mesoporous material array is discussed below. FIG. 1 shows a flow chart of the process. In step 1, the pore-forming template agent solutions are prepared by using one kind or a mixture of two or more kinds of polymer nanospheres, carbon blacks, carbon nanotubes, carbon nanofibers, carbon nanospheres, and poly(methyl methacrylate (PMMA) microspheres, polystyrene nanosphere, latex spheres, and inorganic nanoparticles, silica nanoparticles, carbon nanoparticles, carbon dots, carbon nanocells, polymer with amphoteric solvent. In step 2, the precursors solutions are prepared to generate a target product by using one kind or a mixture of two or more kinds of metal species, graphene oxide, MXene, carbon nanotubes, metal nanoparticles, oligomeric organosilicate (1,4-bis (triethoxysilyl) benzene, 1,2-Bis(triethoxysilyl)ethane, Bis[(3-trimethoxysilyl)propyl]amine (amine), Ethyltriethoxysilane) with amphoteric solvent. In step 3, each of the precursor solutions and the pore-forming template agent solutions are inputted into an individual one of channels of a deposition apparatus as an independent solution. In step 4, different proportions of each independent solution are deposited onto a substrate to generate different combinations and compositions of as-synthesized film on a spot of an array; Each dot has independent compositions of at least one of the precursor solutions and at least one of the pore-forming template agent solutions. In step 5, evaporating the amphoteric solvent, the composite meso/macrostructures can be formed into as-synthesized film array. And finally in step 6, heating the as-synthesized film array to remove the organic pore-forming template, and/or treating the film array by NaOH or HF aqueous solution to remove silica template, to generate a 3D macroporous and mesoporous structured material array.

[0025] FIG. 2 shows an example schematic diagram for generating 3DMM material array, the pore-forming template agent solutions 10, the precursor solutions 20, at each element of an array with independently controlled composition and combination. The pore-forming template agent solutions 10 and the precursor solutions 20 are inputted to each of channels 30 of a deposition apparatus. Different proportions of solutions from each channel are deposited onto a substrate 40. Software 50 controls different combinations and compositions of the solutions deposited on a spot of an array. The array is then evaporated 60 and calcined 70 to remove the organic pore-forming template, and treating 80 the film array by NaOH or HF aqueous solution to remove silica template, to generate a 3D macroporous and mesoporous structured material array.

[0026] One of examples of the preparation steps is as follows:

[0027] (1) For the pore-forming template agent solution preparation, the template agent and amphoteric solvent were uniformly mixed and stirred at 0-200 C. until a stable solution or dispersion was formed.

[0028] (2) For the precursor solutions, the precursors of a target product and amphoteric solvent were uniformly mixed and stirred at 0-200 C. until a stable solution or dispersion was formed.

[0029] (3) The pore-forming template solutions and the precursor solutions are dispensed into the each channel of the multi-channel direct deposition apparatus individually.

[0030] (4) Software programs may dispense droplets of each channel with a certain volume onto any kind of substrate to create a patterned as-synthesized thin film array with controlled compositions and combinations.

[0031] (5) The as-synthesized film array was placed at a certain temperature to evaporate solvent and form intermediate.

[0032] (6) The as-synthesized film array was calcined in a certain temperature to remove the organic pore-forming template, and/or treated by NaOH or HF aqueous solution to remove silica template, to generate a 3D macroporous and mesoporous structured material array.

[0033] The invention provides a multi-channel direct-deposit assembly method for high-throughput creating a patterned 3DMM material array comprises different combinations (e.g binary, ternary, quaternary, or more complex metal oxides, and metal/metal oxides composites, metal/reduced graphene oxide (rGO) composites, metal oxide/rGO composites, metal/CNT composites, metal oxide/CNT composites metal/Mxene composite, metal oxide/Mxene composite) and multi-digit precision compositions quickly and quantitatively.

[0034] In accordance with a further embodiment of this invention, the 3DMM material array high-throughput synthesized by multi-channel direct-deposit assembly method comprises metal oxide composites, metal/metal oxides composites, metal/reduced graphene oxide (rGO) composites, metal oxide/rGO composites, metal/carbon nanotube (CNT) composites, metal oxide/CNT composites, metal/Mxene composite, and metal oxide/Mxene composite. The 3DMM material array can be used for the rapid synthesis, screening and manufacture of catalysts and nanosensors. The macropore size of the synthesized 3DMM material is in the range of 50-1000 nm; the mesopore size of the synthesized 3DMM material is in the range of 1-50 nm. Both of the macropore and the mesopore are open pores and these pores are connected with each other to form a continuous 3D pore space. The surface area of the 3DMM material is in the range of 20-1000 m.sup.2/g.

[0035] The amphoteric solvent may be one kind or a mixture of two or more kinds selected from water, alcohol, acid, alkali, and acetone. The alcohol may be one kind or a mixture of two or more kinds selected from methanol, ethanol, propanol, butanol and glycerol. The acid may be one kind or a mixture of two or more kinds selected from formic acid, acetic acid, nitric acid, hydrochloric acid, sulfuric acid, and citric acid. The alkali may be one kind or a mixture of two or more kinds selected from ammonia, sodium hydroxide, potassium hydroxide. The metal species precursors may be one kind or a mixture of two or more kinds selected from main group, transition, lanthanide, or actinide metal. The metal species precursors selected from nitrate, carbonate, acetate, chlorate, and alkoxide.

[0036] The multi-channel direct-deposit process selected from inkjet printing, spin coating, gravure, micro-pen, nano-fountain pen, dip-pen, screen printing, spray coating, slide coating, slot coating, curtain coating, dip coating, pipette dropping, and combinations thereof. The deposited substrates selected from paper, membrane, glass, corundum, ceramic, silicon wafer, steel, wood, quartz, circuit board, conductive materials, and combinations thereof.

[0037] The evaporation temperature is 20-500 C. The heating treatment is 100-1000 C.

[0038] In addition, the invention provides a high-speed multiplex screening method to explore materials readily and rapidly by measuring the resistance change of materials after absorption or/and reaction with chemical vapors. More, the invention provides a sensor array based on 3D macroporous/mesoporous sensor materials that can be used for diseases detection from human exhaled breath.

[0039] Example 1 High-Throughput Synthesis of 3DMM Quaternary NiCoFePbO.sub.x Material Array

[0040] A typical high-throughput synthesis of 3DMM quaternary NiCoFePbO.sub.x material array is outlined below. We formulate six solutions respectively. Solution 1#, macropore pore-forming template solution, a silica nanosphere with diameter of 300 nm was synthesized by Stber process (FIG. 3). 5 g silica nanosphere was dispersed in 100 ml ethanol and stirred for 1 hour to obtain a stable dispersion. Solution 2#, mesopore pore-forming template agent solution, 1 g F127 (EO.sub.96PO.sub.70EO.sub.96, MW=12000 g/mol), 10 mmol of acetic acid, 6 mmol of HCl were dissolved in the 60 ml ethanol and stirred for 1 hour at 25-60 C. to obtain a clear homogeneous solution. Solution 3#, Ni precursor, 10 mmol Ni(NO.sub.3).sub.2 was dissolved in 60 ml anhydrous ethanol/isopropanol and stirred for 0.5 h. Solution 4#, Co precursor, 10 mmol Co(NO.sub.3).sub.2 was dissolved in 60 ml anhydrous ethanol/isopropanol and stirred for 0.5 h. Solution 5#, Fe precursor, 10 mmol FeCl3 was dissolved in 60 ml anhydrous ethanol/isopropanol and stirred for 0.5 h. Solution 6#, Pb precursor, 1 mmol Pb(NO.sub.3).sub.2, 0.5 mmol of acetic acid, 1 mmol of HCl and 0.8 g F127 (EO.sub.96PO.sub.70EO.sub.96, MW=12000 g/mol) were dissolved in the 60 ml ethanol and stirred for 1 hour at 25-60 C. to obtain a clear homogeneous solution.

[0041] Ink-jet printing technique was chosen to deposit six precursor and pore-forming template agent solutions in this example. Each solution was injected into the containers of the printer respectively. A software program of the printer will control the volume and position of the solutions delivered on the filter paper to generate as-synthesized thin film array with different combinations and compositions, as shown in FIG. 4. The motion-controlled stage of printer has x-y-z travel distance of 1 cm-100 cm with a resolution of 100 dpi-3600 dpi and travel speeds of 1 mm-1 m/sec.

[0042] The printed thin film array was then heated to 60 C. After the solvent was evaporated up, the sample was calcined in a muffle furnace in air at 300-800 C. for 2 hours with a ramp of 1-10 C./min. During this calcination process, the precursors were decomposed. The silica nanospheres and silica nanoparticles were removed by treating the sample with diluted HF aqueous solution with a concentration of 1-10 wt %. The final 3D MM NiFeCoPbO.sub.x material array was thus synthesized. FIG. 5 shows the XRD analysis of the synthesized CoFe.sub.2O.sub.x in 3D MM NiCoFePbO.sub.x array.

Example 2 High-Throughput Syntheses of 3DMM Ternary AgCoNiOx Material Array

[0043] A typical high-throughput synthesis of 3DMM ternary AgCoNiOx material array is outlined below. We formulate five solutions respectively. Solution 1#, pore-forming template solution, the silica nanoparticle aqueous solution with diameter of 300 nm was purchased from Sigma-Aldrich. 5 g silica nanosphere was dispersed in 100 ml ethanol, and stirred for 1 hour to obtain a stable dispersion. Solution 2#, pore-forming template agent solution, 2 g P123 (PEG-PPG-PEG, MW=5800 g/mol), 10 mmol of acetic acid, 6 mmol of HCl were dissolved in the 60 ml ethanol and stirred for 1 hour at 25-60 C. to obtain a clear homogeneous solution. Solution 3#, Ni precursor, 10 mmol Ni(NO.sub.3).sub.2 was dissolved in 60 ml anhydrous ethanol/isopropanol and stirred for 0.5 h. Solution 4#, Co precursor, 10 mmol Co(NO.sub.3).sub.2 was dissolved in 60 ml anhydrous ethanol/isopropanol and stirred for 0.5 h. Solution 5#, Ag precursor, 0.5 mmol AgNO3, 0.5 mmol of acetic acid, 1 mmol of HCl and 1.6 g P123 (PEG-PPG-PEG, MW=5800 g/mol) were dissolved in the 60 ml ethanol and stirred for 1 hour at 25-60 C. to obtain a clear homogeneous solution.

[0044] Glass substrates were cleaned by sonication in acetone, methanol, and deionized water for 10 min each. Then, the glass substrates were dried under 60 C. in the oven for 5 h.

[0045] Each solution was deposited onto glass slides using pipette with a certain compositions and combinations. The spin coating of the films on the glass substrates was carried for 30 s at 2000 rpm. Then, the coated films were dried at 60 C. for 1 h. This procedure was repeated three times for generating a certain thickness films. After the solvent was evaporated up, the as-deposited film array was annealed for 2 h at 450 C. in an air furnace with a ramp of 2 C./min. Finally, the silica nanoparticles were removed by treating the sample with diluted HF aqueous solution with a concentration of 1-10 wt % in 10 min. The final 3D MM ternary AgCoNiOx material array was thus synthesized, according to the SEM images, as shown in FIG. 6.

Example 3 High-Throughput Syntheses of 3DMM Quaternary CuCoMnWO.SUB.x .Material Array

[0046] A typical high-throughput synthesis of 3DMM ternary AgCoNiOx material array is outlined below. We formulate six solutions respectively. Solution 1#, macropore pore-forming template solution, a silica nanosphere with diameter of 300 nm was synthesized by Stber process. 5 g silica nanosphere was dispersed in 100 ml ethanol, and stirred for 1 hour to obtain a stable dispersion. Solution 2#, mesopore pore-forming template agent solution, 1 g F127 (EO.sub.96PO.sub.70EO.sub.96, MW=12000 g/mol), 10 mmol of acetic acid, 6 mmol of HCl were dissolved in the 60 ml ethanol and stirred for 1 hour at 25-60 C. to obtain a clear homogeneous solution. Solution 3#, Cu precursor, 10 mmol Cu(NO.sub.3).sub.2 was dissolved in 60 ml anhydrous ethanol/isopropanol and stirred for 0.5 h. Solution 4#, Co precursor, 10 mmol Co(NO.sub.3).sub.2 was dissolved in 60 ml anhydrous ethanol/isopropanol and stirred for 0.5 h. Solution 5#, Mn precursor, 10 mmol MnCl2 was dissolved in 60 ml anhydrous ethanol/isopropanol and stirred for 0.5 h. Solution 6#, W precursor, 1 mmol WCl.sub.6, 0.5 mmol of acetic acid, 1 mmol of HCl and 0.8 g F127 (EO.sub.96PO.sub.70EO.sub.96, MW=12000 g/mol) were dissolved in the 60 ml ethanol and stirred for 1 hour at 25-60 C. to obtain a clear homogeneous solution.

[0047] Glass substrates were cleaned by sonication in acetone, methanol, and deionized water for 10 min each. Then, the glass substrates were dried under 60 C. in the oven for 5 h.

[0048] Ink-jet printing technique was chosen to deposit six precursor and pore-forming template agent solutions in this example. Each solution was injected into the containers of the printer respectively. A software program of the printer will control the volume and position of the solutions delivered on the glass slide to generate as-synthesized thin film array with different combinations and compositions, as shown in FIG. 7. The motion-controlled stage of printer has x-y-z travel distance of 1 cm-100 cm with a resolution of 100 dpi-3600 dpi and travel speeds of 1 mm-1 m/sec.

[0049] The printed thin film array was heated to 60 C. during printing. After the solvent was evaporated up, the sample was calcined in a muffle furnace in air at 300-800 C. for 2 hours with a ramp of 1-10 C./min. During this calcination process, the precursors were decomposed. The silica nanospheres and silica nanoparticles were removed by treating the sample with diluted NaOH aqueous solution with a concentration of 1-10 wt %. The final 3DMM single, binary, ternary and quaternary CuCoMnWO.sub.x material array was thus synthesized. FIG. 8 shows the SEM images and XRD analysis of the synthesized 3DMM CuCoMnWOx material array based on ink-jet printing assembly method. FIG. 8 (a, b, and c) shows the SEM image of CuCoMnO.sub.4, W.sub.0.7Mo.sub.0.3O.sub.3, and Cu.sub.1.5Mn.sub.1.5O.sub.4 material. We can find that both of the macropore and the mesopore are open pores and these pores are connected with each other to form a continuous 3D pore space. From the XRD of CuCoMnO.sub.4, W.sub.0.7Mo.sub.0.3O.sub.3 and Cu.sub.1.5Mn.sub.1.5O.sub.4 in FIG. 8, we can find that the binary and ternary materials generated by multi-channel direct-deposit assembly method.