# US 2020/0391184 A1 · Oxygen and nitrogen functionalized carbonaceous supports with improved nanoparticle dispersion, and methods of making and uses of the same > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2020/0391184 A1 - Document ID: US20200391184A1 - Status: Published application - Kind: A1 - Application number: 16/903,992 - Filed: 2020-06-17 - Published: 2020-12-17 - Earliest claimed: 2019-06-17 - Assignees: The George Washington University - Applicants: The George Washington University - Inventors: Danmeng SHUAI; Tao YE - Web page: https://patentgrep.com/patent/US20200391184A1 ## CPC - B01J 21/18: Carbon - B01J 6/001: {Calcining} - B01J 23/44: Palladium - B01J 27/24: Nitrogen compounds - B01J 35/392: {Metal surface area} - B01J 35/393: {Metal or metal oxide crystallite size} - B01J 35/45: Nanoparticles - B01J 37/0045: {Drying a slurry, e.g. spray drying} - B01J 37/343: {of ultrasonic wave energy} - B01J 2235/00: Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties - B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS ## Abstract Metal nanoparticle-bearing carbonaceous supports, or solid-supported metal-catalysts, can be formed by incipient wetness, wet impregnation and ethylene glycol reduction methods. The solid-supported metal-catalysts can be used a heterogeneous catalysts in various catalytic reactions such as hydrodeoxygenation reactions, catalyze hydrodehalogenation reactions, N—N hydrogenolysis reactions and oxidation reactions. The solid-supported metal-catalysts are easy to handle, are easily separable from reaction media, are stable in various types of reaction media, and are recyclable. ## Claims ### Claim 1 A method of making a solid-supported metal-catalyst, the method comprising: providing a solution comprising one or more metal salts and a solvent; combining the solution with a carbonaceous support having one or both of nitrogen-containing functional groups and oxygen-containing functional groups to form a slurry; drying the slurry; and calcining the dried slurry at elevated temperature in a H2(g) atmosphere to form metal nanoparticles from metal ions in the one or more metal salts. ### Claim 2 (depends on 1) The method of claim 1, wherein the carbonaceous support is selected from the group consisting of activated carbon, graphite, graphite intercalation compounds, graphene, carbon black, charcoal, bone char, activated carbon fibers, single- or multi-walled carbon nanotubes, carbon-covered alumina, glassy carbon, pyrolytic carbon, polymer-derived carbon, fullerenes, amorphous carbon, carbon nanospheres, carbon microspheres, and cellulosic carbon. ### Claim 3 (depends on 1) The method of claim 1, wherein the one or more metal salts comprise one or more of Au, Ag, Cu, Co, Fe, Ir, In, Ni, Pd, Pt, Sn, Ru, Rh and Zn. ### Claim 4 (depends on 1) The method of claim 1, wherein the metal nanoparticles are selected from the group consisting of monometallic nanoparticles, bimetallic nanoparticles, and any combination thereof. ### Claim 5 (depends on 1) The method of claim 1, wherein the solution and the carbonaceous support are combined such that the resulting slurry has a metal ion to carbonaceous support, weight to weight, ratio ranging from about 0.1:100 to about 20:100. ### Claim 6 (depends on 1) The method of claim 1, wherein calcining comprises: raising the temperature of the dried slurry from a first temperature to a second temperature over a first period of time; and maintaining the dried slurry at the second temperature in the H2(g) atmosphere for a second period of time. ### Claim 7 (depends on 1) A solid-supported metal-catalyst prepared by a method according to claim 1. ### Claim 8 A method of making a solid-supported metal-catalyst, the method comprising: dispersing a carbonaceous support in water to form a suspension, the carbonaceous support having one or both of nitrogen-containing functional groups and oxygen-containing functional groups; mixing the suspension with one or more metal salts to form a metal salt-containing suspension; adding a solution comprising a reducing agent to the metal salt-containing suspension; and reducing, with the reducing agent, metal ions from the one or more metal salts to form metal nanoparticles. ### Claim 9 (depends on 8) The method of claim 8, wherein the carbonaceous support is selected from the group consisting of activated carbon, graphite, graphite intercalation compounds, graphene, carbon black, charcoal, bone char, activated carbon fibers, single- or multi-walled carbon nanotubes, carbon-covered alumina, glassy carbon, pyrolytic carbon, polymer-derived carbon, fullerenes, amorphous carbon, carbon nanospheres, carbon microspheres, and cellulosic carbon. ### Claim 10 (depends on 8) The method of claim 8, wherein the one or more metal salts comprise one or more of Au, Ag, Cu, Co, Fe, Ir, In, Ni, Pd, Pt, Sn, Ru, Rh and Zn. ### Claim 11 (depends on 8) The method of claim 8, wherein the metal nanoparticles are selected from the group consisting of monometallic nanoparticles, bimetallic nanoparticles, and any combination thereof. ### Claim 12 (depends on 8) The method of claim 8, wherein the suspension and the one or more metal salts are combined in relative amounts that result in a metal ion to carbonaceous support, weight to weight, ratio ranging from about 0.1:100 to about 20:100. ### Claim 13 (depends on 8) A solid-supported metal-catalyst prepared by a method according to claim 8. ### Claim 14 A method of making a solid-supported metal-catalyst, the method comprising: dispersing a carbonaceous support in ethylene glycol to form a dispersion for a first period of time, the carbonaceous support having one or both of nitrogen-containing functional groups and oxygen-containing functional groups; mixing the dispersion for a second period of time to form a suspension, the second period of time being longer than the first period of time; adding a solution to the suspension, the solution comprising one or more metal salts and a solvent to form a metal salt-containing suspension; mixing the metal salt-containing suspension for a third period of time; adding a strong base to the metal salt-containing suspension to increase the basicity of the metal salt-containing suspension; and mixing the metal salt-containing suspension for a fourth period of time under reflux conditions to form metal nanoparticles from metal ions in the one or more metal salts. ### Claim 15 (depends on 14) The method of claim 14, wherein the carbonaceous support is selected from the group consisting of activated carbon, graphite, graphite intercalation compounds, graphene, carbon black, charcoal, bone char, activated carbon fibers, single- or multi-walled carbon nanotubes, carbon-covered alumina, glassy carbon, pyrolytic carbon, polymer-derived carbon, fullerenes, amorphous carbon, carbon nanospheres, carbon microspheres, and cellulosic carbon. ### Claim 16 (depends on 14) The method of claim 14, wherein the one or more metal salts comprise one or more of Au, Ag, Cu, Co, Fe, Ir, In, Ni, Pd, Pt, Sn, Ru, Rh and Zn. ### Claim 17 (depends on 14) The method of claim 14, wherein the metal nanoparticles are selected from the group consisting of monometallic nanoparticles, bimetallic nanoparticles, and any combination thereof. ### Claim 18 (depends on 14) The method of claim 14, wherein the pH is adjusted to about 11. ### Claim 19 (depends on 14) The method of claim 14, wherein the suspension and solution comprising the one or more metal salts are combined in relative amounts that result in a metal ion to carbonaceous support, weight to weight, ratio ranging from about 0.1:100 to about 20:100. ### Claim 20 (depends on 14) A solid-supported metal-catalyst prepared by a method according to claim 14.