# US 10,441,945 B2 · Composite material used for catalyzing and degrading nitrogen oxide and preparation method and application thereof

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- Number: US 10,441,945 B2
- Document ID: US10441945B2
- Status: Granted
- Kind: B2
- Application number: 15/382,630
- Filed: 2016-12-17
- Published: 2017-06-22
- Granted: 2019-10-15
- Earliest claimed: 2015-12-17
- Assignees: Soochow University
- Applicants: Soochow University
- Inventors: Jianmei Lu; Dongyun Chen
- Web page: https://patentgrep.com/patent/US10441945B2

## CPC

- B01J 31/069: {Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups (nitrogen containing groups on mineral substrates B01J31/0254; organometallic polymers B01J31/123; coordination complexes immobilised on an inorganic support B01J31/1616; coordination polymers, e.g. metal-organic frameworks B01J31/1691)}
- B01D 53/8628: {Processes characterised by a specific catalyst}
- B01J 19/127: {Sunlight; Visible light}
- B01J 21/18: Carbon
- B01J 27/24: Nitrogen compounds
- B01J 35/19: {Catalysts containing parts with different compositions}
- B01J 35/39: Photocatalytic properties
- B01J 35/52: Hollow spheres
- B01J 35/58: Fabrics or filaments
- B01J 37/0018: {Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)}
- B01J 37/0072: {Preparation of particles, e.g. dispersion of droplets in an oil bath}
- B01J 37/0221: {of particles}
- B01J 37/04: Mixing {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/084: {Decomposition of carbon-containing compounds into carbon}
- C01B 21/0605: {Binary compounds of nitrogen with carbon}
- B01D 2255/70: Non-metallic catalysts, additives or dopants
- B01D 2255/702: Carbon
- B01D 2255/802: Photocatalytic
- B01D 2257/404: Nitrogen oxides other than dinitrogen oxide
- B01D 2259/802: Visible light
- B01J 2231/005: General concepts, e.g. reviews, relating to methods of using catalyst systems, the concept being defined by a common method or theory, e.g. microwave heating or multiple stereoselectivity
- B01J 2531/002: Materials
- B01J 2531/008: Methods or theories
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}

## Abstract

The invention discloses a composite material used for catalyzing and degrading nitrogen oxide and its preparation method and application thereof. The invention of the hollow g-C3N4 nanospheres/reduced graphene oxide composite-polymer carbonized nanofiber material is prepared as follow: 1) the preparation of silica nanospheres; 2) the preparation of hollow g-C3N4 nanospheres; 3) the preparation of graphene oxide; 4) the preparation of surface modified hollow g-C3N4 nanoparticles preparation; 5) the preparation of composites; 6) the preparation of composite-polymer carbon nanofiber material. The raw materials used in the process is low cost and easy to get; the operation of the invention is simple and convenient without the use of expensive equipment in the whole process; the composite has high adsorption efficiency of ppb level nitrogen oxide with good repeatability.

## Claims

### Claim 1

A preparation method of a hollow graphitic carbon nitride nanosphere/graphene composite and composite-carbonized polymer nano fiber material, comprising the following steps:
(1) preparation of silica nanospheres:
adding ethyl silicate into a mixture of ammonia, ethanol and water having a mass ratio of ammonia: ethanol: water: ethyl silicate=1:15˜20:1˜5:1˜2, the formed mixture standing for 1˜2 hours, adding a mixture of ethyl silicate and octadecyltrimethoxysilane having a mass ratio of ethyl silicate: octadecyltrimethoxysilane=1:1-2 to previously formed the mixture, mixing evenly and standing for 3˜5 hours, a resulted mixture being centrifugated, dried and calcined for 6˜8 hours at 55˜570° C., and then washed with 1M hydrochloric acid and dried, to obtain the silica nanospheres,
(2) preparation of hollow graphitic carbon nitride nanospheres:
using the silica nanospheres in the step (1) as a template and mixing with cyanamide in a mass ratio of 1:3˜7 and stirring for 3˜5 hours under vacuum, ultrasonic treating for 2˜3 hours, and then reacting at 60˜70° C. for 10˜12 hours and obtaining a solid by centrifugation, the obtained solid being heated to 55˜570° C. under inert gas atmosphere and calcined for 4˜5 hours producing a powder, then using 4M ammonium acid fluoride to etch the silica nanospheres template in the powder, after centrifuging, washing and drying, obtaining the hollow graphitic carbon nitride nanospheres,
(3) preparation of graphene oxide:
adding graphite to concentrated sulfuric acid in a ratio of graphite: concentrated sulfuric acid=1g: 20˜25mL with stirring in an ice water bath, after mixing evenly, adding potassium hypermanganate to the mixture of graphite and concentrated sulfuric acid in a mass ratio of graphite: potassium hypermanganate=1:5˜8, reacting at 35˜40° C. for 12h pouring the mixture of graphite, concentrated sulfuric acid, and potassium hypermanganate into ice water containing hydrogen peroxide, after centrifugation, washing and drying, obtaining the graphene oxide,
(4) preparation of surface modified hollow graphitic carbon nitride nanospheres:
adding 3-aminopropyltriethoxysilane to a suspension of the hollow graphitic carbon nitride nanospheres in methylbenzene in a mass ratio of the hollow graphitic carbon nitride nanospheres: 3-aminopropyltriethoxysilane=1g: 3˜5mL, after refluxing for 20˜24 hours, centrifuging, washing and drying, obtaining the surface modified hollow graphitic carbon nitride nanospheres,
(5) preparation of hollow graphitic carbon nitride nanospheres/graphene composite:
adding graphene oxide aqueous solution to the surface modified hollow graphitic carbon nitride nanospheres in step (4) dispersed in water with a pH value of 10 in a mass ratio of the surface modified hollow graphitic carbon nitride nanospheres: graphene oxide=1:0.1˜0.3, stirring the mixture of the surface modified hollow graphitic carbon nitride nanospheres and the graphene oxide at room temperature for 1˜2 hours, adding hydrazine hydrate into the mixture in a mass ratio of graphene oxide: hydrazine hydrate=1:1˜2, reacting for 1˜2 hours at 95° C., centrifuging, washing and drying, obtaining the hollow graphitic carbon nitride nanospheres/graphene composite,
(6) preparation of composite-carbonized polymer nanofiber material:
adding the composite obtained in step (5) to a DMF solution of a polymer with a mass ratio of composite: polymer=1:15˜20, stirring the mixture of the composite and polymer at room temperature for 5˜8 hours, preparing a nanofiber through electrostatic spinning, the nanofiber being heated to 500˜520° C. under inert gas atmosphere and calcined for 4˜5 hours, obtaining the composite-carbonized polymer nanofiber material.

### Claim 2 (depends on 1)

The preparation method according to claim 1, wherein:
the mass ratio of ammonia, ethanol, water, and ethyl silicate in step (1) is 1:18.7:3.2:1.8;
the mass percentage of the ammonia in step (1) is 22%˜25%;
the mass ratio of the ethyl silicate and the mixed liquid of ethyl silicate and octadecyltrimethoxysilane in step (1) is 1:1.5; and
the mass ratio of the ethyl silicate and octadecyltrimethoxysilane in the liquid mixture of the ethyl silicate and octadecyltrimethoxysilane in step (1) is 1:0.45.

### Claim 3 (depends on 1)

The preparation method according to claim 1, wherein:
the mass ratio of said silica nanospheres and cyanamide in step (2) is 1:5.

### Claim 4 (depends on 1)

The preparation method according to claim 1, wherein:
the ratio of graphite and concentrated sulfuric acid in step (3) is 1g: 23 mL;
the mass ratio of graphite and Potassium Permanganate in step (3) is 1:6; and
Potassium Permanganate is divided into two batches with the same mass in step (3).

### Claim 5 (depends on 1)

The preparation method according to claim 1, wherein:
the ratio of said hollow graphitic carbon nitride nanosphere and 3-aminopropyltriethoxysilane in step (4) is 1 g: 3 mL; and
the concentration of the hollow graphitic carbon nitride nanosphere in said suspension in step (4) is 1 mg/mL.

### Claim 6 (depends on 1)

The preparation method according to claim 1, wherein:
the mass ratio of said surface modified hollow graphitic carbon nitride nanospheres and the graphene oxide in step (5) is 1:0.1;
the concentration of surface modified hollow graphitic carbon nitride nanospheres in said suspension in step (5) is 1 mg/mL;
the concentration of graphene oxide in aqueous solution in step (5) is 0.1 mg/mL; and
the mass ratio of said graphene oxide and the hydrazine hydrate in step (5) is 1:1.

### Claim 7 (depends on 1)

The preparation method according to claim 1, wherein:
the mass ratio of the composite and the polymer in step (6) is 1:20;
said polymer in step (6) is selected from any one of PAN, polyvinyl alcohol and polyvinylpyrrolidone;
the mass percentage of the polymer in dimethylformamide in step (6) is 10%; and
the conditions of said electrostatic spinning in step (6) are as follows: negative voltage-9 kV, positive voltage 18 kV, speed 0.2 mm/min.