# US 9,517,460 B2 · Method for fabricating hollow metal nano particles supported on carrier > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,517,460 B2 - Document ID: US9517460B2 - Status: Granted - Kind: B2 - Application number: 14/649,446 - Filed: 2013-12-27 - Published: 2015-11-19 - Granted: 2016-12-13 - Earliest claimed: 2012-12-27 - Assignees: LG Chem, Ltd. - Applicants: LG Chem, Ltd. - Inventors: Jun Yeon Cho; Sang Hoon Kim; Gyo Hyun Hwang; Kwanghyun Kim - Web page: https://patentgrep.com/patent/US9517460B2 ## CPC - B22F 1/0549: {Hollow particles, including tubes and shells} - B01J 23/892: {Nickel and noble metals} - B01J 35/45: Nanoparticles - B01J 37/0072: {Preparation of particles, e.g. dispersion of droplets in an oil bath} - B01J 37/16: Reducing - B22F 9/24: starting from liquid metal compounds, e.g. solutions - B82B 3/00: Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units - B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy - B82Y 40/00: Manufacture or treatment of nanostructures - B22F: WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER (making alloys by powder metallurgy C22C); APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - B82B: NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF - B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES ## Abstract The present application relates to a method for fabricating hollow nano particles supported on carrier. ## Claims ### Claim 1 A method for fabricating catalyst comprising hollow metal nano particles supported on a carrier, the method comprising: forming a solution by adding a first metal salt, a second metal salt, and a surfactant to a solvent which consists of water; forming hollow metal nano particles having an average particle diameter of 30 nm or less by adding a reducing agent to the solution; and supporting the hollow metal nano particles on a carrier, wherein the forming of the solution comprises forming a micelle by the surfactant, and surrounding the outside of the micelle by the first metal salt and the second metal salt, the forming of the hollow metal nano particles comprises forming the micelle region to a hollow form, and a concentration of the surfactant in the solution is 0.2 time to 5 times a critical micelle concentration (CMC) to water. ### Claim 2 (depends on 1) The method of claim 1, wherein the supporting of the hollow metal nano particles on a carrier comprises adding the carrier after the forming of the hollow metal nano particles. ### Claim 3 (depends on 1) The method of claim 1, wherein the carrier is a carbon-based material or an inorganic fine particle. ### Claim 4 (depends on 1) The method of claim 1, wherein a carbon number of the chains of the surfactant is 15 or less. ### Claim 5 (depends on 1) The method of claim 1, wherein the surfactant is an anionic surfactant. ### Claim 6 (depends on 5) The method of claim 5, wherein the anionic surfactant comprises NH4+, K+, Na+, or Li+ as a counter ion. ### Claim 7 (depends on 1) The method of claim 1, wherein the surfactant is a cationic surfactant. ### Claim 8 (depends on 7) The method of claim 7, wherein the cationic surfactant comprises I−, Br−, or Cl− as a counter ion. ### Claim 9 (depends on 1) The method of claim 1, wherein the forming of the solution comprises further adding a non-ionic surfactant. ### Claim 10 (depends on 1) The method of claim 1, wherein the forming of the solution comprises further adding a stabilizer. ### Claim 11 (depends on 1) The method of claim 1, wherein the first metal of the first metal salt and the second metal of the second metal salt are each independently selected from the group consisting of metals belonging to Group 3 to Group 15 of the periodic table, metalloids, lanthanide metals, and actinide metals. ### Claim 12 (depends on 1) The method of claim 1, wherein the first metal of the first metal salt and the second metal of the second metal salt are each independently selected from the group consisting of platinum (Pt), ruthenium (Ru), rhodium (Rh), molybdenum (Mo), osmium (Os), iridium (Ir), rhenium (Re), palladium (Pd), vanadium (V), tungsten (W)), cobalt (Co), iron (Fe), selenium (Se), nickel (Ni), bismuth (Bi), tin (Sn), chromium (Cr), titanium (Ti), gold (Au), cerium (Ce), silver (Ag), and copper (Cu). ### Claim 13 (depends on 1) The method of claim 1, wherein each of the first metal salt and the second metal salt is nitrate, halide, hydroxide, or sulfate of the first metal and the second metal. ### Claim 14 (depends on 1) The method of claim 1, wherein a molar ratio of the first metal salt to the second metal salt in the solution is 1:5 to 10:1. ### Claim 15 (depends on 1) The method of claim 1, wherein the fabrication method is carried out at room temperature. ### Claim 16 (depends on 1) The method of claim 1, wherein the reducing agent has a standard reduction potential of −0.23 V or less. ### Claim 17 (depends on 1) The method of claim 1, wherein a particle diameter of the hollow metal nano particles is within a range from 80% to 120% of an average particle diameter of the hollow metal nano particles. ### Claim 18 (depends on 1) The method of claim 1, further comprising: after the forming of the hollow metal nano particles, removing the surfactant inside the hollow metal nano particles. ### Claim 19 (depends on 1) The method of claim 1, wherein the hollow metal nano particles have an average particle diameter of 20 nm or less. ### Claim 20 (depends on 1) The method of claim 1, wherein the hollow metal nano particles have a spherical shape. ### Claim 21 (depends on 1) The method of claim 1, wherein a volume of the hollow portion is 50% by volume or more of a total volume of the hollow metal nano particle. ### Claim 22 (depends on 1) The method of claim 1, wherein the hollow metal nano particle comprises: a hollow core; and a shell portion comprising a first metal and a second metal. ### Claim 23 (depends on 22) The method of claim 22, wherein the shell portion comprises: at least one first shell comprising a first metal; and at least one second shell comprising a second metal. ### Claim 24 (depends on 22) The method of claim 22, wherein the shell portion comprises at least one shell comprising a first metal and a second metal. ### Claim 25 (depends on 22) The method of claim 22, wherein the shell portion has a thickness of 5 nm or less. ### Claim 26 A method for fabricating catalyst comprising hollow metal nano particles supported on a carrier, the method comprising: forming a composition by adding a carrier, a first metal salt, a second metal salt, and a surfactant to a solvent which consists of water; and forming hollow metal nano particles supported on the carrier by adding a reducing agent to the composition, wherein the forming of the solution comprises forming a micelle by the surfactant, and surrounding the outside of the micelle by the first metal salt and the second metal salt, the hollow metal nano particle comprises a hollow form formed by the micelle region, the hollow metal nano particles have an average particle diameter of 30 nm or less, and a concentration of the surfactant in the solution is 0.2 time to 5 times a critical micelle concentration (CMC) to water. ### Claim 27 (depends on 26) The method of claim 26, wherein the forming of the composition is mixing the carrier with a solution formed by adding the first metal salt, the second metal salt and the surfactant to the solvent which consists of water. ### Claim 28 (depends on 26) The method of claim 26, wherein the forming of the composition is adding the carrier to a solution formed by adding the first metal salt, the second metal salt and the surfactant to the solvent which consists of water and dispersing the composition. ### Claim 29 (depends on 26) The method of claim 26, wherein the carrier is a carbon-based material or an inorganic fine particle. ### Claim 30 (depends on 26) The method of claim 26, wherein the surfactant is an anionic surfactant. ### Claim 31 (depends on 30) The method of claim 30, wherein the anionic surfactant comprises NH4+, K+, Na+, or Li+ as a counter ion. ### Claim 32 (depends on 26) The method of claim 26, wherein the surfactant is a cationic surfactant. ### Claim 33 (depends on 32) The method of claim 32, wherein the cationic surfactant comprises I−, Br−, or Cl− as a counter ion. ### Claim 34 (depends on 26) The method of claim 26, wherein the forming of the solution comprises further adding a non-ionic surfactant. ### Claim 35 (depends on 26) The method of claim 26, wherein the forming of the solution comprises further adding a stabilizer. ### Claim 36 (depends on 26) The method of claim 26, wherein the first metal of the first metal salt and the second metal of the second metal salt are each independently selected from the group consisting of metals belonging to Group 3 to Group 15 of the periodic table, metalloids, lanthanide metals, and actinide metals. ### Claim 37 (depends on 26) The method of claim 26, wherein the first metal of the first metal salt and the second metal of the second metal salt are each independently selected from the group consisting of platinum (Pt), ruthenium (Ru), rhodium (Rh), molybdenum (Mo), osmium (Os), iridium (Ir), rhenium (Re), palladium (Pd), vanadium (V), tungsten (W)), cobalt (Co), iron (Fe), selenium (Se), nickel (Ni), bismuth (Bi), tin (Sn), chromium (Cr), titanium (Ti), gold (Au), cerium (Ce), silver (Ag), and copper (Cu). ### Claim 38 (depends on 26) The method of claim 26, wherein each of the first metal salt and the second metal salt is nitrate, halide, hydroxide, or sulfate of the first metal and the second metal. ### Claim 39 (depends on 26) The method of claim 26, wherein a molar ratio of the first metal salt to the second metal salt in the solution is 1:5 to 10:1. ### Claim 40 (depends on 26) The method of claim 26, wherein the fabrication method is carried out at room temperature. ### Claim 41 (depends on 26) The method of claim 26, wherein the reducing agent has a standard reduction potential of −0.23 V or less. ### Claim 42 (depends on 26) The method of claim 26, wherein a particle diameter of the hollow metal nano particles is within a range from 80% to 120% of an average particle diameter of the hollow metal nano particles. ### Claim 43 (depends on 26) The method of claim 26, further comprising: after the forming of the hollow metal nano particles, removing the surfactant inside the hollow metal nano particles. ### Claim 44 (depends on 26) The method of claim 26, wherein the hollow metal nano particles have an average particle diameter of 20 nm or less. ### Claim 45 (depends on 26) The method of claim 26, wherein the hollow metal nano particles have a spherical shape. ### Claim 46 (depends on 26) The method of claim 26, wherein a volume of the hollow portion is 50% by volume or more of a total volume of the hollow metal nano particle. ### Claim 47 (depends on 26) The method of claim 26, wherein the hollow metal nano particle comprises: a hollow core; and a shell portion comprising a first metal and a second metal. ### Claim 48 (depends on 47) The method of claim 47, wherein the shell portion comprises: at least one first shell comprising a first metal; and at least one second shell comprising a second metal. ### Claim 49 (depends on 47) The method of claim 47, wherein the shell portion comprises at least one shell comprising a first metal and a second metal. ### Claim 50 (depends on 47) The method of claim 47, wherein the shell portion has a thickness of 5 nm or less. ### Claim 51 (depends on 26) The method of claim 26, wherein a carbon number of the chains of the surfactant is 15 or less.