CN115814832A - Defect-modified graphite-phase carbon nitride titanium dioxide heterojunction composite material and application thereof in photo-thermal catalytic reduction of carbon dioxide - Google Patents
Defect-modified graphite-phase carbon nitride titanium dioxide heterojunction composite material and application thereof in photo-thermal catalytic reduction of carbon dioxide Download PDFInfo
- Publication number
- CN115814832A CN115814832A CN202211400247.3A CN202211400247A CN115814832A CN 115814832 A CN115814832 A CN 115814832A CN 202211400247 A CN202211400247 A CN 202211400247A CN 115814832 A CN115814832 A CN 115814832A
- Authority
- CN
- China
- Prior art keywords
- titanium sheet
- composite material
- defect
- tio
- modified graphite
- 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.)
- Pending
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 19
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 15
- 238000010531 catalytic reduction reaction Methods 0.000 title claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 51
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000007547 defect Effects 0.000 claims abstract description 17
- 238000011065 in-situ storage Methods 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006722 reduction reaction Methods 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 11
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000001228 spectrum Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 27
- 230000001699 photocatalysis Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 11
- 229910052724 xenon Inorganic materials 0.000 description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000013032 photocatalytic reaction Methods 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000002336 sorption--desorption measurement Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 238000004445 quantitative analysis Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000004435 EPR spectroscopy Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001055 reflectance spectroscopy Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a defect modified graphite-phase carbon nitride titanium dioxide heterojunction composite material and application thereof in photo-thermal catalytic reduction of carbon dioxide. The preparation method of the composite material comprises the following steps: in-situ growth of TiO on the surface of a metal titanium sheet by adopting a hydrothermal method 2 Then with urea and NaBH 4 And carrying out thermal reduction reaction to obtain the defect modified graphite phase carbon nitride titanium dioxide heterojunction composite material. The invention combines three strategies of doping, defect and heterojunction into the material through one-step calcination, so that the material has full-spectrum absorption and short carrier diffusion distance, can effectively promote the separation of light-excited carriers, has high photo-thermal effect,thereby remarkably improving CO 2 The conversion efficiency. The raw materials used in the invention are low in price and easy to obtain, the experimental operation is simple and convenient, the period is short, the materials are easy to recover and recycle, and the materials are used for photo-thermal catalytic reduction of carbon dioxide, so that the global energy shortage and artificial climate change can be relieved.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a defect-modified graphite-phase carbon nitride titanium dioxide heterojunction composite material and application thereof in photo-thermal catalytic reduction of carbon dioxide.
Background
The large consumption of fossil fuels leads to serious environmental problems and large carbon emissions, causing a serious greenhouse effect. Through a photocatalysis technology, the carbon dioxide can be converted into fuel and industrial chemicals with high added values by utilizing solar energy, and the energy crisis is relieved while the greenhouse effect is inhibited. Although semiconductor photocatalytic technology has been widely studied, to date, weak absorption in the visible and infrared regions has prevented large-scale application of photocatalytic technology.
In recent years, with the development of semiconductor photocatalytic technology, photothermal catalytic technology has become an emerging research field. Photothermal catalysis has attracted considerable interest as a new approach to carbon dioxide reduction using light rather than heat input. In fact, the photothermal catalysis technology can simultaneously utilize the advantages of both thermal catalysis and photocatalysis, and thus can exhibit excellent catalytic performance even under mild conditions. In some cases, the introduction of light can alter the reaction pathway, providing a simple and novel approach to tailoring product selectivity, and localized photothermal effects have been shown to increase carrier mobility and reactant and product mobility, thereby increasing photocatalytic efficiency. The photothermal effect is based on light and heat Yang Nengde, so that the photothermal effect can effectively utilize wide solar energy to drive the gas-solid catalytic system to convert carbon dioxide. Therefore, it is very necessary to develop a novel photo-thermal catalyst having high efficiency and full spectral photoresponse.
Disclosure of Invention
The invention aims to provide a defect modified graphite-phase carbon nitride titanium dioxide heterojunction composite material and a preparation method thereof, and the defect modified graphite-phase carbon nitride titanium dioxide heterojunction composite material is applied to a reaction of photo-thermal catalytic reduction of carbon dioxide.
The preparation method of the defect modified graphite phase carbon nitride titanium dioxide heterojunction composite material comprises the following steps: in-situ growth of TiO on the surface of a metal titanium sheet by adopting a hydrothermal method 2 Then with urea and NaBH 4 And carrying out thermal reduction reaction to obtain the defect modified graphite phase carbon nitride titanium dioxide heterojunction composite material.
The hydrothermal method is used for growing TiO on the surface of the metal titanium sheet in situ 2 The specific operation of the method is as follows: cleaning a metal titanium sheet, putting the metal titanium sheet into an alkaline solution, carrying out a hydrothermal reaction in a polytetrafluoroethylene reaction kettle for 12-24h at 160-200 ℃, cooling the reaction kettle to room temperature, taking out the titanium sheet, rinsing the titanium sheet with deionized water, soaking the titanium sheet in an acidic solution for 5-24h, taking out the titanium sheet, washing the titanium sheet to be neutral, and finally calcining the titanium sheet at 300-700 ℃ for 2-4h to obtain TiO 2 Growing on the surface of the metallic titanium sheet in situ.
The specific operation of the thermal reduction reaction is as follows: growing TiO on the surface in situ 2 Titanium sheet of (2) inserting into urea and NaBH 4 Then placing the titanium substrate in a tube furnace, calcining for 2-4h at 400-600 ℃ in nitrogen or inert atmosphere to obtain the defect modified graphite phase carbon nitride titanium dioxide heterojunction composite material loaded on the titanium sheet.
The alkaline solution is one or more of NaOH, KOH and LiOH solutions.
The concentration of the alkaline solution is 1-7mol/L.
The acid solution is one or more of nitric acid, hydrochloric acid and sulfuric acid.
The concentration of the acid solution is 0.1-0.5mol/L.
The urea and NaBH 4 The mass ratio of (A) to (B) is 6-14.
The prepared defect-modified graphite-phase carbon nitride titanium dioxide heterojunction composite material is applied to photo-thermal catalytic reduction carbon dioxide reaction.
The specific operation of the photo-thermal catalytic reduction carbon dioxide reaction is as follows: placing the defect modified graphite phase carbon nitride titanium dioxide heterojunction composite material into a reactor, introducing carbon dioxide mixed steam into the reactor, removing air, and performing illumination reaction at room temperature to 70 ℃.
The invention has the following beneficial effects:
1) The raw materials used in the invention are low in price and easy to obtain, and the method is simple and convenient in experimental operation, short in period and easy to recover and recycle.
2) The prepared composite material combines three strategies (dopant, defect and heterojunction) into the material through one-step calcination, so that the material has full-spectrum absorption and short carrier diffusion distance, can effectively promote the separation of light-excited carriers, and has certain photothermal effect, thereby obviously improving CO 2 The conversion efficiency. The catalytic performance reaches the optimum when the reduction temperature reaches 500 ℃, and the maximum total CO yield of the BCT-500 catalyst within 5 hours is 1326.1 mu mol g -1 . Meanwhile, the average CO yield of BCT-500 reaches 265.2 mu mol g -1 h -1 Is respectively pure TiO 2 (35.3μmol g -1 h -1 ) And g-C 3 N 4 Powder (29.7. Mu. Mol g) -1 h -1 ) 7.5 and 8.9 times.
3) The prepared composite material has a certain photo-thermal effect, the temperature of the catalyst is rapidly increased after illumination, and the highest temperature is reached within 8 minutes. In particular, the introduction of OV and B dopants imparts a more effective thermal effect to the BCT-500 catalyst, which rapidly increases in temperature from room temperature to 140.5 ℃. So that the BCT catalyst shows obvious CO generation rate and can be further improved to 345.1 mu mol g -1 h -1 。
4) Photocatalytic CO of the present invention 2 The reduction rate is high, and the composite material provides a new strategy for designing an effective solar energy utilization scheme, and can be used for relieving global energy shortage and artificial climate change.
Drawings
FIG. 1 is an SEM image of BCT-500;
FIG. 2 shows TiO 2 XRD profiles of BCT-400, BCT-500 and BCT-600;
FIG. 3 shows TiO 2 And the EPR map of BCT-500;
FIG. 4 is TiO 2 And a high resolution B1s plot of BCT-500;
FIG. 5 is TiO 2 BCT-400, BCT-500 and BCT-600;
FIG. 6 (a) shows g-C 3 N 4 、TiO 2 powder、TiO 2 CO of BCT-400, BCT-500 and BCT-600 2 The rate of CO formation by photo-reduction, and (b) is TiO 2 And the CO generation rate of the BCT-500 catalyst at different temperatures;
FIG. 7 lower TiO of xenon lamp 2 BCT-400, BCT-500, and BCT-600 for (a) photothermal images and (b) temperature profiles.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
In-situ growth of TiO on surface of metal titanium sheet by hydrothermal method 2 : 2X 5cm 2 Washing a rectangular metal titanium sheet with distilled water and absolute ethyl alcohol, putting the washed rectangular metal titanium sheet into a 50mL polytetrafluoroethylene reaction kettle containing 35mL of 3mol/L NaOH solution, carrying out hydrothermal reaction at 180 ℃ for 20h, cooling the reaction kettle to room temperature, taking out the titanium sheet, rinsing the titanium sheet with deionized water, soaking the titanium sheet in 0.1M HCl solution for 24h, taking out the titanium sheet, washing the titanium sheet to be neutral, and finally heating the titanium sheet to 500 ℃ at the speed of 3 ℃/min and calcining the titanium sheet for 2h to obtain TiO 2 The nano-sheet grows on the surface of the metal titanium sheet in situ.
Example 1:
5g of urea was mixed with 0.5g of NaBH 4 Mixing uniformly, growing TiO on the surface in situ 2 2 x 5cm 2 Titanium sheets are inserted into the furnace, then the furnace is put into a porcelain boat and put into a tube furnace, and the furnace is heated in N 2 Heating to 400 ℃ at the heating rate of 5 ℃/min in the atmosphere and calcining for 4h to obtain the defect modified graphite-phase carbon nitride titanium dioxide heterojunction composite material C loaded on the titanium sheet 3 N 4 /TiO 2-x the/Ti Foil, noted BCT-400.
One BCT-400 block was used as catalyst (1X 1 cm) 2 ) Placing on a quartz tripod in a photocatalytic reactor (200 mL) with high purity CO 2 Mixed with steam by a bubbler and introduced into the reactor for 1h to ensure CO of the catalyst 2 And (4) carrying out adsorption-desorption balance. Adopting a 300W xenon lamp as a light source for photocatalytic reaction to illuminate for 5hDuring the reaction, the reaction product was quantitatively analyzed by gas chromatography (Agilent 7890B). As shown in FIG. 6, the CO production rate of the BCT-400 composite was 139.33. Mu. Mol g -1 h -1 。
Example 2:
the calcination temperature is raised to 500 ℃, the rest conditions are the same as the example 1, and the obtained defect modified graphite phase carbon nitride titanium dioxide heterojunction composite material C loaded on the titanium sheet 3 N 4 /TiO 2-x the/Ti Foil is noted as BCT-500.
One BCT-500 block was used as catalyst (1X 1 cm) 2 ) Placing on a quartz tripod in a photocatalytic reactor (200 mL) with high purity CO 2 Mixed with steam by a bubbler and introduced into the reactor for 1h to ensure CO of the catalyst 2 And (4) carrying out adsorption-desorption balance. A300W xenon lamp is used as a light source for photocatalytic reaction to illuminate for 5h, and gas chromatography (Agilent 7890B) is used for carrying out quantitative analysis on reaction products in the whole reaction process. As shown in FIG. 6, the CO production rate of the BCT-500 composite was 265.23. Mu. Mol g -1 h -1 。
BCT-500 was used as a catalyst (1X 1 cm) 2 ) Placing on a quartz tripod in a photocatalytic reactor (200 mL) and treating with high purity CO 2 Mixed with water vapor by a bubbler and introduced into the reactor. The process was continued for 1h to ensure CO of the catalyst 2 And (4) carrying out adsorption-desorption balance. A300W xenon lamp is used as a light source for photocatalytic reaction to illuminate for 5 hours, three groups of parallel tests are carried out by respectively keeping circulating water of a reaction system at 30 ℃, 50 ℃ and 70 ℃ in the whole reaction process, a gas chromatography (Agilent 7890B) is used for carrying out quantitative analysis on reaction products, and meanwhile, no additional light source is used as a comparative example. As shown in FIG. 6 (b), the CO production rates of BCT-500 materials were 1413.30. Mu. Mol g, respectively -1 、1531.51μmol g -1 、1725.48μmol g -1 。
Example 3:
the calcination temperature is raised to 600 ℃, the rest conditions are the same as the example 1, and the defect modified graphite phase carbon nitride titanium dioxide heterojunction composite material C loaded on the titanium sheet is obtained 3 N 4 /TiO 2-x the/Ti Foil is noted as BCT-600.
One piece of BCT-600 was used as a catalyst (1X 1 cm) 2 ) Placing on a quartz tripod in a photocatalytic reactor (200 mL) with high purity CO 2 Mixed with water vapor by a bubbler and introduced into the reactor. The process was continued for 1h to ensure CO of the catalyst 2 And (4) carrying out adsorption-desorption balance. A300W xenon lamp is used as a light source for photocatalytic reaction to illuminate for 5h, and gas chromatography (Agilent 7890B) is used for carrying out quantitative analysis on reaction products in the whole reaction process. As shown in FIG. 6, the CO production rate of the BCT-600 composite was 265.23. Mu. Mol g -1 h -1 。
Comparative example 1:
growing TiO on the surface of a piece in situ 2 Titanium sheet (denoted as TiO) 2 ) Directly used as catalyst (1X 1 cm) 2 ) Placing on a quartz tripod in a photocatalytic reactor (200 mL) with high purity CO 2 Mixed with water vapor by means of a bubbler and introduced into the reactor. The process was continued for 1h to ensure CO of the catalyst 2 And (4) carrying out adsorption-desorption balance. A300W xenon lamp is used as a light source for photocatalytic reaction to illuminate for 5h, and gas chromatography (Agilent 7890B) is used for carrying out quantitative analysis on reaction products in the whole reaction process. As shown in FIG. 6 (a), tiO 2 The CO production rate of the Ti foil material was 35.30. Mu. Mol g -1 h -1 。
Growing TiO on the surface in situ 2 Titanium sheet (denoted as TiO) 2 ) Directly used as a catalyst (1X 1 cm) 2 ) Placing on a quartz tripod in a photocatalytic reactor (200 mL) with high purity CO 2 Mixed with water vapor by a bubbler and introduced into the reactor. The process was continued for 1h to ensure CO of the catalyst 2 And (4) carrying out adsorption-desorption balance. A300W xenon lamp is used as a light source for photocatalytic reaction to illuminate for 5 hours, three groups of parallel tests are carried out by respectively keeping circulating water of a reaction system at 30 ℃, 50 ℃ and 70 ℃ in the whole reaction process, a gas chromatography (Agilent 7890B) is used for carrying out quantitative analysis on reaction products, and meanwhile, no additional light source is used as a comparative example. As shown in FIG. 6 (b), tiO 2 The CO production rate of the/Ti foil material was 213.31. Mu. Mol g, respectively -1 、285.86μmol g -1 、398.06μmol g -1 。
Comparative example 2:
weighing 20g of urea, placing the urea into a crucible, placing the crucible into a muffle furnace, heating the urea to 500 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 4 hours to obtain g-C 3 N 4 And (3) powder.
Mixing 10mgg-C 3 N 4 The powder sample was uniformly dispersed on a quartz tripod in a photocatalytic reactor (200 mL) with high purity CO 2 Mixed with water vapor by a bubbler and introduced into the reactor. The process was continued for 1h to ensure CO of the catalyst 2 And (4) carrying out adsorption-desorption balance. A300W xenon lamp is used as a light source for photocatalytic reaction to illuminate for 5h, and gas chromatography (Agilent 7890B) is used for carrying out quantitative analysis on reaction products in the whole reaction process. As shown in FIG. 6, g-C 3 N 4 The CO production rate of the material was 29.66. Mu. Mol g -1 h -1 。
And (3) experimental verification:
experiment 1: SEM and TEM images
Inventive example BCT-500 and comparative example TiO 2 The SEM image shown in FIG. 1 was obtained by scanning electron microscopy. As can be seen from FIGS. 1 and 7, tiO grown in situ on a titanium sheet 2 Is in a nanometer flower structure, and is subjected to thermal reduction treatment to obtain TiO 2 g-C with ultrathin nanosheet structure deposited on surface 3 N 4 And TiO 2 2 The structure of (2) is almost unchanged, and the elements are uniformly distributed. The nanosheet base structure is beneficial to improving the utilization rate of light and the adsorption of reactants, exposing more active sites and shortening the migration distance of photon-generated carriers.
Experiment 2: XRD pattern
Inventive examples BCT-400, BCT-500 and BCT-600 and comparative example TiO 2 The XRD pattern shown in figure 2 is obtained by X-ray powder diffraction detection. As can be seen from FIG. 2, all samples were TiO 2 Anatase type (JCPDS card number 83-2243) and metal Ti phase (JCPDS card number 11-1294). Diffraction peaks appeared at 25.2 °,37.9 °,47.9 °,53.8 °,54.9 °, corresponding to TiO 2 (101) The (004), (200), (105), (211) planes of anatase. The weak diffraction peak at 27.4 ℃ is g-C 3 N 4 Is characterized in thatSign peak, which shows that CN is successfully loaded on TiO 2 The above. The diffraction peak does not change significantly with increasing reduction temperature, indicating g-C 3 N 4 Introduction of (2) into TiO 2 Has no significant effect.
Experiment 3: ultraviolet-visible diffuse reflectance spectroscopy
Inventive examples BCT-400, BCT-500 and BCT-600 and comparative example TiO 2 The catalysts were respectively examined to obtain the uv-visible diffuse reflectance spectra shown in fig. 5. FIG. 5 shows TiO 2 The powder has strong absorption in the ultraviolet region, and the absorption edge of the BCT composite material gradually red shifts along with the increase of the annealing temperature.
Experiment 4: photothermal catalytic activity and temperature rise measurement
Inventive examples BCT-400, BCT-500 and BCT-600 and comparative example TiO 2 The catalysts were tested separately to obtain different results as shown in fig. 7. Comparative example pure TiO 2 And the BCT-500 catalyst in the embodiment has no obvious reduction product detected in a pure thermal reaction experiment, and CO is greatly increased after light is introduced in a pure light and photo-thermal synergistic control experiment, and the generation of CO is gradually increased along with the increase of temperature, so that the photo-thermal synergistic effect is proved to be beneficial to further improving the photocatalytic reduction performance. FIG. 7 additionally records examples BCT-400, BCT-500, BCT-600 and comparative TiO in the light 2 Real-time photothermal imaging of the catalyst. As can be seen from fig. 7, the temperature of the catalyst rapidly increased after the light irradiation, and reached the maximum temperature within 8 minutes. In particular, the introduction of OV and B dopants imparts a more effective thermal effect to the BCT-500 catalyst, which rapidly increases in temperature from room temperature to 140.5 ℃. But once g-C 3 N 4 In an amount exceeding a certain amount, tiO 2 The surface will be g-C 3 N 4 Over-coverage, the catalyst color changed from matte gray to yellow (fig. 7 a). However, although g-C 3 N 4 The increase in the content favors the absorption of light, but the surface g-C is excessively covered 3 N 4 The layer will block photogenerated holes to TiO 2 The transfer of the catalyst is detrimental to the photothermal effect, thereby reducing the photothermal activity.
Experiment 5: electron paramagnetic resonance bopp diagram
Inventive example BCT-500 and comparative example TiO 2 The EPR chart shown in FIG. 3 was obtained by electron paramagnetic resonance (ESR) wavefront detection. From FIG. 3, it can be seen that TiO 2 No signal peak was detected, while the BCT-500 composite detected a single Lorentz force signal, indicating that BCT-500 has unpaired electrons, i.e., the formation of oxygen vacancies, thereby enhancing CO 2 The conversion efficiency.
Claims (10)
1. A preparation method of a defect modified graphite phase carbon nitride titanium dioxide heterojunction composite material is characterized by comprising the following steps: in-situ growth of TiO on the surface of a metal titanium sheet by adopting a hydrothermal method 2 Then with urea and NaBH 4 And carrying out thermal reduction reaction to obtain the defect modified graphite phase carbon nitride titanium dioxide heterojunction composite material.
2. The preparation method according to claim 1, wherein the hydrothermal method is used for growing TiO on the surface of the metallic titanium sheet in situ 2 The specific operation of the method is as follows: cleaning a metal titanium sheet, putting the cleaned metal titanium sheet into an alkaline solution, carrying out a hydrothermal reaction for 12-24h at 160-200 ℃ in a polytetrafluoroethylene reaction kettle, cooling the reaction kettle to room temperature, taking out the titanium sheet, rinsing the titanium sheet with deionized water, soaking the titanium sheet in an acidic solution for 5-24h, taking out the titanium sheet, washing the titanium sheet to be neutral, and finally calcining the titanium sheet at 300-700 ℃ for 2-4h to obtain TiO 2 Growing on the surface of the metallic titanium sheet in situ.
3. The preparation method according to claim 1, characterized in that the thermal reduction reaction is specifically operated as follows: growing TiO on the surface in situ 2 Titanium sheet of (2) insert into urea and NaBH 4 Then placing the titanium substrate in a tube furnace, calcining for 2-4h at 400-600 ℃ in nitrogen or inert atmosphere to obtain the defect modified graphite phase carbon nitride titanium dioxide heterojunction composite material loaded on the titanium sheet.
4. The method according to claim 2, wherein the alkaline solution is one or more of NaOH, KOH and LiOH solution.
5. The method according to claim 2, wherein the concentration of the alkaline solution is 1 to 7mol/L.
6. The preparation method according to claim 2, wherein the acidic solution is one or more of nitric acid, hydrochloric acid and sulfuric acid.
7. The method according to claim 2, wherein the concentration of the acidic solution is 0.1 to 0.5mol/L.
8. The process of claim 3, wherein the urea is reacted with NaBH 4 The mass ratio of (A) to (B) is 6-14.
9. The use of the defect-modified graphite-phase titanium carbonitride heterojunction composite material prepared by the method according to any one of claims 1 to 8 in a photo-thermal catalytic reduction carbon dioxide reaction.
10. The use according to claim 9, characterized in that the photothermal catalytic reduction of carbon dioxide is carried out in particular by: placing the defect modified graphite phase carbon nitride titanium dioxide heterojunction composite material into a reactor, introducing carbon dioxide mixed steam into the reactor, removing air, and performing illumination reaction at room temperature to 70 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211400247.3A CN115814832A (en) | 2022-11-09 | 2022-11-09 | Defect-modified graphite-phase carbon nitride titanium dioxide heterojunction composite material and application thereof in photo-thermal catalytic reduction of carbon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211400247.3A CN115814832A (en) | 2022-11-09 | 2022-11-09 | Defect-modified graphite-phase carbon nitride titanium dioxide heterojunction composite material and application thereof in photo-thermal catalytic reduction of carbon dioxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115814832A true CN115814832A (en) | 2023-03-21 |
Family
ID=85527428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211400247.3A Pending CN115814832A (en) | 2022-11-09 | 2022-11-09 | Defect-modified graphite-phase carbon nitride titanium dioxide heterojunction composite material and application thereof in photo-thermal catalytic reduction of carbon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115814832A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899709A (en) * | 2010-08-13 | 2010-12-01 | 浙江大学 | Method for preparing titanium dioxide nano rod array with adjustable size and density on titanium surface |
| CN109876843A (en) * | 2019-03-08 | 2019-06-14 | 北京化工大学 | Copper alloy modified titanic oxide/carbonitride heterojunction photocatalyst and preparation method |
| CN111111634A (en) * | 2019-12-04 | 2020-05-08 | 华南师范大学 | Titanium dioxide macroporous microsphere/metallic titanium composite material and preparation method and application thereof |
| CN114177928A (en) * | 2021-12-27 | 2022-03-15 | 吉林大学 | Composite photocatalyst Bi @ H-TiO with visible light response2/B-C3N4Preparation method and application thereof |
-
2022
- 2022-11-09 CN CN202211400247.3A patent/CN115814832A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899709A (en) * | 2010-08-13 | 2010-12-01 | 浙江大学 | Method for preparing titanium dioxide nano rod array with adjustable size and density on titanium surface |
| CN109876843A (en) * | 2019-03-08 | 2019-06-14 | 北京化工大学 | Copper alloy modified titanic oxide/carbonitride heterojunction photocatalyst and preparation method |
| CN111111634A (en) * | 2019-12-04 | 2020-05-08 | 华南师范大学 | Titanium dioxide macroporous microsphere/metallic titanium composite material and preparation method and application thereof |
| CN114177928A (en) * | 2021-12-27 | 2022-03-15 | 吉林大学 | Composite photocatalyst Bi @ H-TiO with visible light response2/B-C3N4Preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 沈立言: "黑色TiO2/g-C3N4光催化剂的制备及其应用研究", 《中国优秀硕士学位论文全文数据库：工程科技Ⅰ辑》, no. 7, 15 July 2018 (2018-07-15), pages 014 - 482 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109174145B (en) | Dimolybdenum carbide/titanium dioxide composite photocatalyst and preparation method and application thereof | |
| CN110624550B (en) | In-situ carbon-coated copper-nickel alloy nanoparticle photocatalyst and preparation method and application thereof | |
| CN107649168B (en) | Method for degrading bisphenol A in water through photocatalysis and catalyst used by method | |
| CN110465286A (en) | A kind of bismuth tungstate photocatalyst and its preparation method and application of Surface Oxygen vacancy defect modification | |
| CN112076777B (en) | For CO2Reduced photocatalyst and preparation method thereof | |
| CN110743601A (en) | Nitrogen-doped two-dimensional disulfide compound/sulfur-doped graphite-phase carbon nitride composite material and preparation method and application thereof | |
| CN115069262B (en) | Oxygen vacancy modified MoO 3-x /Fe-W 18 O 49 Photocatalyst, preparation thereof and application thereof in nitrogen fixation | |
| CN108325555A (en) | Nitrogen auto-dope is graphitized azotized carbon nano piece photochemical catalyst and its preparation method and application | |
| CN112604690A (en) | Method for preparing rare earth perovskite/biochar composite material by using agricultural and forestry wastes and application thereof | |
| CN107349951A (en) | A kind of CuO/g C3N4The preparation method of blood capillary tubulose nano-complex | |
| CN114054036A (en) | Preparation method and application of catalyst | |
| CN113813983A (en) | Erbium-modified carbon nitride-based catalyst and preparation method and application thereof | |
| CN117160509A (en) | Ruthenium-loaded crystalline carbon nitride/doped nano diamond composite material and preparation method and application thereof | |
| CN111644185A (en) | Bi stripping by cell crusher3O4Method for Cl and in photocatalytic reduction of CO2Application of aspects | |
| CN114558601B (en) | Porous ultrathin g-C modified by donor-acceptor unit 3 N 4 Tube photocatalyst, preparation method and application thereof | |
| CN116903021A (en) | Porous cerium oxide nano-sheet catalyst, preparation thereof and application thereof in photo-thermal synergistic carbon dioxide decomposition reaction | |
| CN107662906B (en) | A kind of preparation method of two selenizings W film and the application of photocatalytic reduction of carbon oxide | |
| CN115814832A (en) | Defect-modified graphite-phase carbon nitride titanium dioxide heterojunction composite material and application thereof in photo-thermal catalytic reduction of carbon dioxide | |
| CN110404572A (en) | A kind of preparation method of titanium dioxide and the compound heterojunction photocatalyst of carbonitride | |
| CN113877556B (en) | Indium oxyhydroxide/modified attapulgite photocatalytic composite material and preparation method and application thereof | |
| CN113697783B (en) | Porous g-C 3 N 4 Preparation method and application of nano-sheet | |
| CN115090318A (en) | Preparation method and application of intermolecular heterojunction carbon nitride photocatalyst with high specific surface area | |
| CN113797940A (en) | Cobalt selenide graphite carbon nitride composite material and preparation method and application thereof | |
| CN112871165A (en) | Two-dimensional WO modified by noble metal loading3Preparation method of nanosheet photocatalyst | |
| CN116351437B (en) | Bismuth sulfide nanorod photocatalyst and 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 |