CN114452998B - Preparation method and application of multiwall carbon nanotube and graphitized carbon nitride composite material - Google Patents

Preparation method and application of multiwall carbon nanotube and graphitized carbon nitride composite material Download PDF

Info

Publication number
CN114452998B
CN114452998B CN202210093637.4A CN202210093637A CN114452998B CN 114452998 B CN114452998 B CN 114452998B CN 202210093637 A CN202210093637 A CN 202210093637A CN 114452998 B CN114452998 B CN 114452998B
Authority
CN
China
Prior art keywords
composite material
cnn
reaction kettle
preparation
carbon nanotube
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210093637.4A
Other languages
Chinese (zh)
Other versions
CN114452998A (en
Inventor
史彦涛
辛存存
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian University of Technology
Original Assignee
Dalian University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian University of Technology filed Critical Dalian University of Technology
Priority to CN202210093637.4A priority Critical patent/CN114452998B/en
Publication of CN114452998A publication Critical patent/CN114452998A/en
Application granted granted Critical
Publication of CN114452998B publication Critical patent/CN114452998B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B01J21/185—Carbon nanotubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention belongs to the field of new materials, and provides a preparation method and application of a multiwall carbon nanotube and graphitized carbon nitride composite material. The CNN composite material is prepared from graphitized carbon nitride g-C 3 N 4 And carboxylated carbon nanotube CNTs are calcined in an inert atmosphere. In the calcination process, a soft template is added as a pore-forming agent, so that the specific surface area of the composite material is improved. The composite CNN material prepared by the invention is used for photocatalysis of CO by infrared light 2 Excellent activity was demonstrated in the conversion to CO reaction. The composite material is different from other photocatalytic materials, and can be catalyzed by utilizing spectral energy below 800 nm. The CNN material greatly expands the range of the absorbable and utilizable spectrum of the semiconductor material and improves the utilization rate of solar energy. At the same time, can effectively convert greenhouse gas CO 2 Is converted into CO with higher utilization value.

Description

Preparation method and application of multiwall carbon nanotube and graphitized carbon nitride composite material
Technical Field
The invention belongs to the field of new materials, and relates to a novel graphitized carbon nitride composite material (CNN). Firstly, carboxylated multiwall carbon nanotubes are dispersed by ultrasonic, and then added into a solution containing dicyandiamide and ammonium chloride to be thoroughly and uniformly mixed. And (3) evaporating the water, calcining the mixture in an inert gas atmosphere to obtain the composite material CNN of the carbon nano tube and the carbon nitride, wherein the composite material can effectively utilize solar energy in an infrared light region. The invention also relates to application of the composite material in the field of photocatalytic carbon dioxide reduction.
Background
The continuous consumption of fossil energy not only brings about energy crisis, but also releases CO during combustion 2 The greenhouse effect caused by the method also seriously affects the living environment of human beings. How to develop and utilize clean renewable energy sources is therefore the most interesting issue. Photocatalytic CO 2 The solar energy can be utilized to convert greenhouse gases into formic acid, carbon monoxide, methane and the like which are valuable to human beings. How to use solar energy for CO 2 Reduction is a hot problem. There have been many studies demonstrating that certain semiconductor materials can efficiently absorb light energy to catalyze CO 2 And (3) transformation. However, there is still much room for attention and improvement in this area of research.
The light energy is used as a renewable energy source with rich reserves, and has the advantages of simple and convenient acquisition, high energy, wide coverage range and the like. The solar radiation reaches the earth with light energy up to 173,000 TW/s, which is equivalent to the energy provided by burning 500 ten thousand tons of coal. In the current photocatalytic reaction, the photocatalystThe solar energy absorbed by the chemical agent is determined by its own band gap. Typically, the bandgap of the semiconductor is such that it is capable of catalyzing CO 2 The size is determined in the case of transformation. The size of the band gap in turn determines the spectral range that can be utilized by the semiconductor catalyst. To use g-C most widely 3 N 4 For example, the band gap is around 2.7eV, and only the ultraviolet region of the solar spectrum is often used. The ultraviolet light in the sunlight radiated to the earth has the proportion of about 3 percent, and the rest is visible light and infrared light. How to extend the range of available solar spectrum as much as possible while ensuring the catalytic activity of the catalyst is the most interesting issue.
Cheng et al (adv. Mater.2015,27, 4572-4577) developed an amorphous C with an in-plane highly disordered structure 3 N 4 The existence of disordered structure makes the photo-generated exciton capable of being separated fast and the life of photo-generated electron is greatly prolonged. In addition, the structure can reduce C 3 N 4 The band gap of the solar energy collector expands the absorption spectrum and improves the utilization rate of the solar energy. Under 300wXe lamp irradiation, the catalytic material exhibits marked photocatalytic hydrogen production activity; li et al (adv. Mater.2021,33,2102690) prepared three-dimensional ordered macroporous N-doped carbon (NC) -supported CdS quantum dot (3 DOM CdSQD/NC) photocatalyst by in-situ conversion method for photocatalytic CO 2 RR. The catalyst can effectively utilize solar energy in ultraviolet and partial visible light regions and exhibits an apparent quantum efficiency of 2.9% at 450 nm. Under the condition of not adding any sacrificial agent, the generation rate of CO reaches 5210umol/g/h at the highest; xie et al (Joule, 2018,2,1004-1016) prepared WO3 materials having different defect numbers by hydrogen reduction, WO3 materials having increasing defect numbers 3 Gradually darkening in color. The intermediate band gap caused by the defects enables the catalytic material to have ultraviolet absorption in the infrared region, and infrared light with lower photon energy and higher quantity can be utilized. As described above, although there are many semiconductor photocatalysts at present, most of the catalysts can use only ultraviolet and part of visible light. In the solar spectrum, the energy in the infrared region accounts for more than 55%, and how to use the energy becomes important for efficiently using solar energyProblems. Although some cases of catalysis are carried out by infrared light, the quantity is far insufficient, and the effect is still to be improved.
In conclusion, the method can efficiently utilize the energy of the solar infrared region to perform photocatalysis and treat greenhouse gas CO 2 Catalytic conversion is an important topic for CO products with higher utility value. The invention utilizes carboxylated multiwall carbon nanotubes with narrow band gap and common photocatalytic semiconductor g-C 3 N 4 And (5) compounding. Ammonium chloride was used as a pore former and a soft master. During the heat calcination process, the ammonium chloride decomposes and escapes to make the composite material more porous and porous, and the specific surface area is larger, thereby exposing more reactive sites. By using the surface functional groups of CNTs and g-C 3 N 4 Chemical bonding is formed between the two components, so that photo-generated charges can be transferred and separated more quickly, and the reaction is facilitated. By means of the unique energy band structure of CNTs, the composite CNN can effectively utilize the energy in the infrared region to carry out photocatalysis CO 2 And (3) transformation. Under the illumination of 600-750nm and 850-1100nm, the CNN material can make CO 2 Converted into CO. And g-C 3 N 4 But only energy in the ultraviolet and part of the visible region. CNN material catalyzes CO in infrared region 2 The highest efficiency of the CO conversion can reach 1.7umol/g/h, and the material can greatly expand the spectrum range of the available land and improve the solar energy utilization rate.
Disclosure of Invention
The invention aims to prepare a catalyst capable of exposing more active sites by utilizing the soft template effect of ammonium chloride. Simultaneously, CNTs and g-C are combined by utilizing the functional groups on the surface of the carboxylated carbon nano tube 3 N 4 Coupling is performed. Due to unique photoelectric characteristics of CNTs, the obtained CNN composite sample has the characteristic of being capable of absorbing and utilizing photon energy in an infrared light region. The invention can greatly expand the utilization rate of the photocatalyst to solar energy.
The technical scheme of the invention is as follows:
a multi-wall carbon nano tube and graphitized carbon nitride composite material is prepared from graphitized carbon nitride g-C 3 N 4 And carboxylated carbon nanotube CNTs are calcined in an inert atmosphere. In the calcination process, a soft template is added as a pore-forming agent, so that the specific surface area of the composite material is improved. Carboxyl groups and g-C on CNTs surface 3 N 4 Bonding between them. The composite material can effectively utilize the energy of the infrared light region of sunlight.
XRD test shows that the composite sample still retains g-C 3 N 4 Is that the addition of CNTs does not alter g-C 3 N 4 Is a crystal structure of (a).
A preparation method of a multi-wall carbon nano tube and graphitized carbon nitride composite material comprises the following steps:
step (1): thorough mixing of the precursors:
(1) dicyandiamide, ammonium chloride and carbon nano tubes are mixed according to the mass ratio of 10:10:1, mixing and dispersing in deionized water, and carrying out ultrasonic treatment to ensure that the dispersion is uniform to obtain a mixed solution; wherein the mass concentration of dicyandiamide is 3g/L;
(2) stirring and heating the mixed solution obtained in the step (1) in a water bath kettle at 60-80 ℃, and evaporating water in the mixed solution to dryness to obtain gray black solid with the surface of the carbon nano tube coated with recrystallized dicyandiamide and ammonium chloride;
(3) grinding the obtained gray black solid balls into uniform gray black powder;
step (2): preparation of CNN composite material:
and (3) transferring the gray-black powder obtained in the step (1) into a tube furnace, introducing inert gas, evacuating for 1h, heating at a speed of 2-5 ℃/min, calcining at 550 ℃ for 1-2h, cooling to room temperature, and grinding the black solid obtained by calcining to obtain the composite material.
The composite material obtained by the preparation method is used for photocatalysis of CO 2 Application in conversion, using CNN composite material according to photocatalysis CO 2 The test step of conversion is operated and the CO product is detected by gas chromatography as follows:
(1) dispersing the composite material in deionized water, wherein the concentration of the composite material in the deionized water is 0.1g/L; ultrasonic dispersing, transferring to stainless steel reaction kettle, and packagingAfter finishing, start to feed CO 2 The reaction kettle is thoroughly ventilated for 1 to 2 hours to empty other gases;
(2) the reaction kettle is illuminated by using a 300WXe lamp, and a 600nm optical filter or a 800nm optical filter is used during illumination, so that the wavelength of light injected into the reaction kettle is respectively 600-750nm and 800-1100nm, and the temperature of the reaction kettle is kept constant by condensed water at 25 ℃;
(3) after reacting for a certain time, the gas in the reaction kettle is injected into the gas chromatograph by using an injector for detection.
The invention has the beneficial effects that: the composite CNN material prepared by the invention is used for photocatalysis of CO by infrared light 2 Excellent activity was demonstrated in the conversion to CO reaction. The composite material is different from other photocatalytic materials, and can be catalyzed by utilizing spectral energy below 800 nm. The CNN material greatly expands the range of the absorbable and utilizable spectrum of the semiconductor material and improves the utilization rate of solar energy. At the same time, can effectively convert greenhouse gas CO 2 Is converted into CO with higher utilization value.
Drawings
Fig. 1 is an XRD pattern of the CNN composite. It can be seen that the composite CNN still maintains g-C 3 N 4 Is a characteristic peak of (2). Indicating that the addition of CNTs does not alter g-C 3 N 4 Is a crystal structure of (a).
FIG. 2 (a) is g-C 3 N 4 N of (2) 2 Isothermal adsorption and desorption curves can be seen to obviously improve the specific surface area of the composite sample.
FIG. 2 (b) N of CNN composite 2 Isothermal adsorption and desorption curves can be seen to obviously improve the specific surface area of the composite sample.
FIG. 3 shows the photocatalytic properties of CNN composites over different wavelength ranges, from which it can be seen that the CO yield is significantly higher than for pure C when using composite CNN 3 N 4 Is a product of the above process. Notably, g-C when irradiated with infrared wavelengths 3 N 4 The material cannot catalyze CO 2 The conversion, however, CNN composites can be photocatalytically converted using infrared wavelengths.
Detailed Description
The invention will be further illustrated with reference to specific examples. The materials according to the present invention are not limited to the description in the following examples.
Example 1
Dispersing 100mg of CNTs,1g of dicyandiamide and 1g of ammonium chloride in 30mL of deionized water, uniformly dispersing by ultrasonic treatment, and evaporating the solution in a water bath kettle at 60-80 ℃ to obtain gray black powder for later use;
the gray black powder is put into a ball milling tank for ball milling, and ball milling is carried out for 30min by using a ball mill with the oscillating frequency of 50Hz, so as to ensure that evenly dispersed powder is obtained. Then transferring the powder into a tube furnace, introducing inert gas, and then heating to 550 ℃ for calcination. Cooling to room temperature, and grinding to obtain CNN composite material;
the mixture was warmed to 550 ℃ in a tube furnace at 2 ℃/min under an inert atmosphere, kept at constant temperature for 2 hours, and then cooled to room temperature at the same rate.
Example 2
The procedure was as in example 1. Except that carboxylated carbon nanotubes were not added to the dicyandiamide and ammonium chloride solution. In addition, all the operating steps and the amounts are identical. XRD and specific surface area measurements of the prepared samples were as described above with reference to FIGS. 1 and 2.
Example 3
The preparation procedure is as in example 1. Except that dicyandiamide was not added to the solution of CNTs and ammonium chloride. Obtaining g-C free at the same preparation temperature 3 N 4 Samples, except for all procedures and amounts, were identical. XRD of the prepared N-doped CNTs samples were as shown in FIG. 1 above.
Example 4
10mg of the composite material is dispersed in 100mL of deionized water, the mixture is transferred to a stainless steel reaction kettle after being uniformly dispersed by ultrasonic, CO2 is introduced after the encapsulation is finished, and other gases in the reaction kettle are thoroughly exhausted after 1 to 2 hours of ventilation. The reactor was illuminated with 300W Xe lamp, using a 600nm filter during illumination to ensure that the wavelength of light injected into the reactor was 600-750nm, the temperature of the reactor was kept constant by condensed water at 25 ℃. After 2h of reaction, the gas in the 1.5mL reactor was injected into the gas chromatograph for detection.
Example 5
Dispersing the composite material 10 in 100mL deionized water, transferring to a stainless steel reaction kettle after ultrasonic dispersion is uniform, and starting to introduce CO after encapsulation is completed 2 And (5) ventilation is carried out for 1-2h to thoroughly empty other gases in the reaction kettle. The reactor was illuminated with 300W Xe lamp, using an 800nm filter during illumination to ensure that the wavelength of light injected into the reactor was 800-1100nm, the temperature of the reactor being kept constant by condensed water at 25 ℃. After 2h of reaction, the gas in the 1.5mL reactor was injected into the gas chromatograph for detection.
The pair of yields of example 3 and example 4 are shown in figure 3.
The CNN composite material breaks through the defect of the traditional semiconductor used as a photocatalyst, and can fully utilize the energy of an infrared light region which is not utilized by the traditional semiconductor catalyst. Under the incident state of infrared light, the greenhouse gas CO can be generated 2 Effectively converts into CO, greatly expands the light absorption range of the semiconductor catalyst and improves the utilization rate of solar energy. Catalytic CO under irradiation of infrared light 2 The yield of the transformation is shown in FIG. 3. The CNN composite material becomes a novel photocatalytic material, greatly improves the solar energy utilization rate, and shows good application prospect.

Claims (3)

1. The preparation method of the multi-wall carbon nano tube and graphitized carbon nitride composite material is characterized by comprising the following steps:
step (1): thorough mixing of the precursors:
(1) dicyandiamide, ammonium chloride and carboxylated multiwall carbon nanotubes are mixed according to the mass ratio of 10:10:1, mixing and dispersing in deionized water, and carrying out ultrasonic treatment to ensure that the dispersion is uniform to obtain a mixed solution; wherein the mass concentration of dicyandiamide is 3g/L;
(2) stirring and heating the mixed solution obtained in the step (1) in a water bath kettle at 60-80 ℃, and evaporating water in the mixed solution to dryness to obtain gray black solid coated with recrystallized dicyandiamide and ammonium chloride on the surface of the carboxylated multiwall carbon nanotube;
(3) grinding the obtained gray black solid balls into uniform gray black powder;
step (2): preparation of CNN composite material:
and (3) transferring the gray-black powder obtained in the step (1) into a tube furnace, introducing inert gas, evacuating for 1h, calcining for 1-2h at 550 ℃, cooling to room temperature, and grinding the black solid obtained by calcining to obtain the composite material.
2. The method according to claim 1, wherein the temperature rise rate during the calcination in the step (2) is 2 to 5 ℃/min.
3. The composite material obtained by the preparation method of claim 1 or 2 in photocatalysis of CO 2 The application in conversion is characterized in that CNN composite material is utilized to catalyze CO according to light 2 The test step of conversion is operated and the CO product is detected by gas chromatography as follows:
(1) dispersing the composite material in deionized water, wherein the concentration of the composite material in the deionized water is 0.1g/L; after being uniformly dispersed by ultrasonic, the mixture is transferred into a stainless steel reaction kettle, and CO is introduced after the encapsulation is finished 2 The reaction kettle is thoroughly ventilated for 1 to 2 hours to empty other gases;
(2) the reaction kettle is illuminated by using a 300WXe lamp, and a 600nm optical filter or a 800nm optical filter is used during illumination, so that the wavelength of light injected into the reaction kettle is respectively 600-750nm and 800-1100nm, and the temperature of the reaction kettle is kept constant by condensed water at 25 ℃;
(3) after reacting for a certain time, the gas in the reaction kettle is injected into the gas chromatograph by using an injector for detection.
CN202210093637.4A 2022-01-26 2022-01-26 Preparation method and application of multiwall carbon nanotube and graphitized carbon nitride composite material Active CN114452998B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210093637.4A CN114452998B (en) 2022-01-26 2022-01-26 Preparation method and application of multiwall carbon nanotube and graphitized carbon nitride composite material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210093637.4A CN114452998B (en) 2022-01-26 2022-01-26 Preparation method and application of multiwall carbon nanotube and graphitized carbon nitride composite material

Publications (2)

Publication Number Publication Date
CN114452998A CN114452998A (en) 2022-05-10
CN114452998B true CN114452998B (en) 2023-05-09

Family

ID=81412069

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210093637.4A Active CN114452998B (en) 2022-01-26 2022-01-26 Preparation method and application of multiwall carbon nanotube and graphitized carbon nitride composite material

Country Status (1)

Country Link
CN (1) CN114452998B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115318315B (en) * 2022-09-07 2023-08-04 东北师范大学 Magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109298049A (en) * 2018-11-22 2019-02-01 青岛大学 A kind of copper oxide/carbon nanotube/carbonitride electrochemical sensor and the preparation method and application thereof detecting paracetamol
CN111634893A (en) * 2020-05-21 2020-09-08 张家港市东大工业技术研究院 Synthesis method, product and application of carbon nitride nanotube with cross-linked structural characteristics

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110280788A1 (en) * 2010-05-14 2011-11-17 Perrotta Anthony J Method of Processing Carbon Dioxide Gas
JP2014169193A (en) * 2013-03-01 2014-09-18 Nec Corp Carbon material composed of nanocarbon and graphene or graphite compounded with each other, and method for producing the same
CN104923204B (en) * 2015-05-21 2017-10-17 大连理工大学 A kind of preparation method and applications of graphene coated catalyst with metal nanoparticles
CN107115880A (en) * 2017-04-24 2017-09-01 吉林师范大学 A kind of MoS2/CNTs/g C3N4 composite photo-catalysts and preparation method thereof
CN107537544B (en) * 2017-09-19 2020-02-14 江苏理工学院 g-C3N4-CNTs heterojunction photocatalyst and preparation method thereof
CN109046435A (en) * 2018-09-12 2018-12-21 华东理工大学 A kind of preparation method of nitrogen defect modification counter opal structure carbonitride
CN109126854B (en) * 2018-09-12 2020-09-04 华东理工大学 CdS/g-C3N4Preparation method of double nanosheet composite photocatalyst
CN109550516B (en) * 2018-12-19 2021-09-24 中国科学技术大学 Carbon/carbon nitrogen (C)xNy) Composite nanotube composite material and preparation method and application thereof
CN110787825A (en) * 2019-10-18 2020-02-14 王世扬 Carbon nanotube loaded CdSe-g-C3N4Photocatalytic material and method for producing the same
CN110732338B (en) * 2019-10-25 2022-08-09 湖北工业大学 Carbon nanowire/g-C 3 N 4 Composite visible light catalyst and preparation method thereof
US11299395B2 (en) * 2020-01-14 2022-04-12 Qatar University Porous one-dimensional polymeric graphitic carbon nitride-based nanosystems for catalytic conversion of carbon monoxide and carbon dioxide under ambient conditions
CN113289653A (en) * 2021-03-03 2021-08-24 大连理工大学 g-C of load metal monoatomic3N4Method for preparing photocatalyst
CN113042088A (en) * 2021-03-30 2021-06-29 华南师范大学 Preparation method of graphite phase carbon nitride nanotube and catalyst prepared by same
CN113198515B (en) * 2021-05-19 2023-07-28 上海城投原水有限公司 Ternary photocatalyst and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109298049A (en) * 2018-11-22 2019-02-01 青岛大学 A kind of copper oxide/carbon nanotube/carbonitride electrochemical sensor and the preparation method and application thereof detecting paracetamol
CN111634893A (en) * 2020-05-21 2020-09-08 张家港市东大工业技术研究院 Synthesis method, product and application of carbon nitride nanotube with cross-linked structural characteristics

Also Published As

Publication number Publication date
CN114452998A (en) 2022-05-10

Similar Documents

Publication Publication Date Title
Li et al. Enhanced selective photocatalytic reduction of CO2 to CH4 over plasmonic Au modified g-C3N4 photocatalyst under UV–vis light irradiation
CN107686120B (en) Method for catalytically synthesizing ammonia by gathering solar energy and catalyst thereof
CN108067281B (en) Porous g-C3N4Photocatalyst and preparation method and application thereof
CN112076777B (en) For CO2Reduced photocatalyst and preparation method thereof
CN113634258B (en) Catalyst for generating ethylene by photocatalytic reduction of carbon dioxide and preparation method thereof
CN111330615B (en) Nano bismuth oxychloride/carbon nitride composite material and preparation method and application thereof
CN112774692B (en) Ru @ Ni2V2O7Efficient photo-thermal synergistic catalyst and preparation method and application thereof
CN111151285B (en) Nitrogen-doped porous carbon loaded ZnS nano composite material and preparation method and application thereof
CN109395749A (en) Oxyhalogen bismuth nano material, preparation method and application
CN113398970A (en) ZnO nanowire array/three-dimensional nitrogen-doped rGO nanotube composite material and preparation method and application thereof
CN113457657A (en) Carbon-based methanol hydrogen production catalyst and preparation method and application thereof
CN112973703A (en) Method for producing hydrogen by direct photo-thermal concerted catalysis of methanol
CN114452998B (en) Preparation method and application of multiwall carbon nanotube and graphitized carbon nitride composite material
Bai et al. Synergy of dopants and porous structures in graphitic carbon nitride for efficient photocatalytic H2 evolution
Qi et al. Synthesis of holey graphitic carbon nitride with highly enhanced photocatalytic reduction activity via melamine-cyanuric acid precursor route
CN114054036A (en) Preparation method and application of catalyst
CN109772423B (en) Phosphorus and bismuth co-doped porous graphite phase carbon nitride photocatalyst and application thereof
CN107537541B (en) Rapid preparation method of high visible light activity porous carbon nitride material
CN107662906B (en) A kind of preparation method of two selenizings W film and the application of photocatalytic reduction of carbon oxide
CN107442098B (en) Strontium titanate catalyst for preparing hydrogen by photolyzing water by adopting visible light and preparation method
CN110607576A (en) Delta-MnO with light-driven thermal degradation function2/SiO2Composite nanofiber and preparation and application thereof
CN113697783B (en) Porous g-C 3 N 4 Preparation method and application of nano-sheet
CN111013622B (en) Z-type graphitized carbon nitride/carbon/sulfur-doped graphitized carbon nitride composite material and preparation method thereof
CN115090318A (en) Preparation method and application of intermolecular heterojunction carbon nitride photocatalyst with high specific surface area
CN114570378A (en) CeO2Ni-coated nanotube photo-thermal composite catalyst, preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB03 Change of inventor or designer information

Inventor after: Shi Yantao

Inventor after: Xin Cuncun

Inventor before: Shi Yantao

Inventor before: Xin Cun

CB03 Change of inventor or designer information
GR01 Patent grant
GR01 Patent grant