Porous copper sulfide nano/micro hollow sphere and method for preparing the same

Abstract

The present invention relates to a porous copper sulfide nano/micro hollow sphere and a method for preparing the same. The porous copper sulfide nano/micro hollow sphere of the present invention has plural through holes and a hollow structure so as to increase the reactive area thereof. In particular, the porous copper sulfide nano/micro hollow sphere can be applied in a solar cell to enhance a photoelectric effect.

1 . A porous copper sulfide Cu x S nano/micrometer hollow sphere having a diameter in a range of 300 nm to 700 nm and a plurality of through holes, wherein x is in a range of 1 to 2. 
   
   
       2 . The porous copper sulfide Cu x S nano/micrometer hollow sphere as claimed in  claim 1 , wherein the average distance between adjacent through holes is in a range of 5 nm to 30 nm. 
   
   
       3 . The porous copper sulfide Cu x S nano/micrometer hollow sphere as claimed in  claim 1 , wherein the average diameter of the through holes is in a range of 80 nm to 130 nm. 
   
   
       4 . The porous copper sulfide Cu x S nano/micrometer hollow sphere as claimed in  claim 1 , wherein the through holes have polygon-like cross sections. 
   
   
       5 . The porous copper sulfide Cu x S nano/micrometer hollow sphere as claimed in  claim 1 , wherein the through holes have pentagon and hexagon cross sections. 
   
   
       6 . A method for preparing a porous copper sulfide Cu x S nano/micrometer hollow sphere, comprising:
 mixing a copper source solution and a chelating agent to form a mixture solution; and   adding a first sulfur-based reducing agent and a second sulfur-based reducing agent into the mixture solution in sequence to perform reaction for a period in a range of 5 to 600 seconds at a temperature in a range of 60° C. to 100° C.,   wherein x is in a range of 1 to 2 and the reducing power of the first sulfur-based reducing agent is larger than that of the second sulfur-based reducing agent.   
   
   
       7 . The method as claimed in  claim 6 , further comprising a step for filtrating, washing and drying after the reaction is accomplished. 
   
   
       8 . The method as claimed in  claim 6 , wherein the copper source solution is a copper salt solution or a cuprous salt solution. 
   
   
       9 . The method as claimed in  claim 6 , wherein the chelating agent is a bidentate chelating agent, a tridentate chelating agent, a tetradentate chelating agent or a hexadentate chelating agent. 
   
   
       10 . The method as claimed in  claim 9 , wherein the bidentate chelating agent is HOOC—(CR 1 R 2 ) n —COOH or R 3 R 4 N—(CR 1 R 2 ) n —NR 3 ′R 4 ′, R 1 , R 2 , R 3 , R 3 ′, R 4  and R 4 ′ each independently are hydrogen or C1-6 alkyl, and n is an integer between 1 to 6. 
   
   
       11 . The method as claimed in  claim 9 , wherein the bidentate chelating agent is ethylmalonic acid, N,N-dimethylethylenediamine, trimethylenediamine or ethylenediamine. 
   
   
       12 . The method as claimed in  claim 9 , wherein the tridentate chelating agent is NR 3 R 4 —(CR 1 R 2 ) n —NR 5 R 6 —(CR 1 ′R 2 ′) m —NR 3 ′R 4 ′, R 3 N((CR 1 R 2 ) n COOH) 2  or R 3 N((CR 1 R 2 ) n OH) 2 , R 1 , R 1 ′, R 2 , R 2 ′, R 3 , R 3 ′, R 4 , R 4 ′, R 5  and R 6  each independently are hydrogen or C1-6 alkyl, and m and n each independently are an integer between 1 to 6. 
   
   
       13 . The method as claimed in  claim 9 , wherein the tridentate chelating agent is diethanolamine, diethylenetriamine or aminodiacetic acid. 
   
   
       14 . The method as claimed in  claim 9 , wherein the tetradentate chelating agent is N((CR 1 R 2 ) n COOH) 3  or N((CR 1 R 2 ) n OH) 3 , R 1  and R 2  each independently are hydrogen or C1-6 alkyl, and n is an integer between 1 to 6. 
   
   
       15 . The method as claimed in  claim 9 , wherein the tetradentate chelating agent is triethanolamine or ammoniatriacetic acid. 
   
   
       16 . The method as claimed in  claim 9 , wherein the hexadentate chelating agent is  2 (HOOC—(CR 3 R 4 ) n )N—(CR 1 R 2 ) m —N((CR 3 ′R 4 ′) r COOH) 2 , R 1 , R 2 , R 3 , R 3 ′, R 4  and R 4 ′ each independently are hydrogen or C1-6 alkyl, and m, n and r each independently are an integer between 1 to 6. 
   
   
       17 . The method as claimed in  claim 9 , wherein the hexadentate chelating agent is ethylenediamine tetraacetic acid or ethylenediaminetetrapropionic acid. 
   
   
       18 . The method as claimed in  claim 6 , wherein the chelating agent is a bidentate chelating agent. 
   
   
       19 . The method as claimed in  claim 6 , wherein the chelating agent is R 3 R 4 N—(CR 1 R 2 ) n —NR 3 ′R 4 ′, R 1 , R 2 , R 3 , R 3 ′, R 4  and R 4 ′ each independently are hydrogen or C1-6 alkyl, and n is an integer between 1 to 6. 
   
   
       20 . The method as claimed in  claim 6 , wherein the first sulfur-based reducing agent is sodium hydrogen sulfite or sodium sulfide, and the second sulfur-based reducing agent is sodium sulfide or sodium thiosulfate. 
   
   
       21 . The method as claimed in  claim 6 , wherein the concentration of the copper source solution is in a range of 0.05M to 1.00M. 
   
   
       22 . The method as claimed in  claim 6 , wherein the concentration of the chelating agent in the mixture solution is in a range of 0.05M to 1.00M. 
   
   
       23 . The method as claimed in  claim 6 , wherein the concentration of the first sulfur-based reducing agent in the mixture solution is in a range of 0.05M to 1.00M. 
   
   
       24 . The method as claimed in  claim 6 , wherein the concentration of the second sulfur-based reducing agent in the mixture solution is in a range of 0.05M to 1.00M. 
   
   
       25 . The method as claimed in  claim 6 , wherein the porous copper sulfide Cu x S nano/micrometer hollow sphere has a diameter in a range of 300 nm to 700 nm and a plurality of through holes, the average distance between adjacent through holes is in a range of 5 nm to 30 nm, and the average diameter of the through holes is in a range of 80 nm to 130 nm.