CN113649056A - Photocatalytic carbon dioxide reduction catalyst and preparation method and application thereof - Google Patents
Photocatalytic carbon dioxide reduction catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN113649056A CN113649056A CN202111048167.1A CN202111048167A CN113649056A CN 113649056 A CN113649056 A CN 113649056A CN 202111048167 A CN202111048167 A CN 202111048167A CN 113649056 A CN113649056 A CN 113649056A
- Authority
- CN
- China
- Prior art keywords
- carbon dioxide
- reduction catalyst
- reactor
- porous carbon
- photocatalytic
- 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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 40
- 230000009467 reduction Effects 0.000 title claims abstract description 31
- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 29
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000006260 foam Substances 0.000 claims abstract description 46
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006722 reduction reaction Methods 0.000 claims abstract description 32
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 27
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 27
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 16
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 15
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000007146 photocatalysis Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 8
- 229910052724 xenon Inorganic materials 0.000 claims description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000004817 gas chromatography Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 238000005273 aeration Methods 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000010335 hydrothermal treatment Methods 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 101100459440 Caenorhabditis elegans nac-3 gene Proteins 0.000 description 4
- 206010021033 Hypomenorrhoea Diseases 0.000 description 4
- 102100038141 Nucleus accumbens-associated protein 1 Human genes 0.000 description 4
- 101710108740 Nucleus accumbens-associated protein 1 Proteins 0.000 description 4
- 102100038140 Nucleus accumbens-associated protein 2 Human genes 0.000 description 4
- 101710108739 Nucleus accumbens-associated protein 2 Proteins 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- -1 Transition metal nitrides Chemical class 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- QANIADJLTJYOFI-UHFFFAOYSA-K aluminum;magnesium;carbonate;hydroxide;hydrate Chemical compound O.[OH-].[Mg+2].[Al+3].[O-]C([O-])=O QANIADJLTJYOFI-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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
- 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
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a photocatalytic carbon dioxide reduction catalyst, and a preparation method and application thereof, and belongs to the technical field of carbon dioxide reduction. The preparation method comprises the steps of preparing a three-dimensional network structure of the melamine porous carbon nitride foam, preparing a hydrotalcite precursor aqueous solution, and putting the three-dimensional network structure of the porous carbon nitride foam into the hydrotalcite precursor aqueous solution for reaction to prepare the porous carbon nitride foam/hydrotalcite three-dimensional heterojunction material. The photocatalysis performance of the composite material can be effectively improved by utilizing the photocatalysis synergistic effect of the heterojunction, the CO yield can reach 159.62 mu mol/g which is about 4.2 times of that of a pure LDHs powder material, and the photocatalysis CO is greatly improved2Yield of the reduction reaction.
Description
Technical Field
The invention relates to the technical field of carbon dioxide reduction, in particular to a photocatalytic carbon dioxide reduction catalyst and a preparation method and application thereof.
Background
Photocatalytic CO2The reduction means that the semiconductor catalyst with photocatalytic activity is driven by light energy to generate photo-generated electrons and holes, and water molecules are oxidized by oxygenConversion to provide hydrogen protons to CO2Reducing the carbon-based compound into a carbon-based compound, and simultaneously realizing environmental protection and resource reutilization. Noble metals such as Pt and Pd are difficult to oxidize, have low overpotential, stable performance and the like, and are considered to be ideal catalytic materials. However, the storage of precious metals is limited, the cost is too high, and the industrial use of the precious metals in large quantities is not easy to realize, so the research on photochemical catalysts with low cost and excellent catalytic performance is urgent.
Transition metal nitrides, transition metal carbides and transition metal chalcogenides have the characteristics of low cost, good catalytic stability and the like, and have been applied as electrocatalytic cathode materials. The band gap of the two-dimensional layered transition metal chalcogenide is mainly distributed in a range of 1-2eV, is located in a visible light region, has high-efficiency electron mobility and low overpotential, and has good application prospect.
Chinese patent ZL01127860.9 describes a method for photocatalytic reduction of carbon dioxide to formic acid and formaldehyde using tetravalent and trivalent titanium composite oxides as catalysts under ultraviolet irradiation. The catalyst material is easy to agglomerate, so that the number of effective active sites is reduced, and the catalytic efficiency is reduced. Therefore, it is necessary to develop a new catalyst and a method which have higher efficiency and are less likely to cause a decrease in catalytic activity.
Disclosure of Invention
The invention aims to provide a photocatalytic carbon dioxide reduction catalyst, a preparation method and application thereof, and solves the technical problem that a carbon dioxide reduction material is easy to agglomerate.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a photocatalytic carbon dioxide reduction catalyst is a NiAl-LDH/porous carbon nitride foam three-dimensional heterojunction composite material.
A preparation method of a photocatalytic carbon dioxide reduction catalyst comprises the following steps:
step 1: preparing a three-dimensional network structure of the melamine porous carbon nitride foam;
step 2: preparing a hydrotalcite precursor aqueous solution;
and step 3: and putting the porous carbon nitride foam three-dimensional network structure into a hydrotalcite precursor aqueous solution for reaction to prepare the porous carbon nitride foam/hydrotalcite three-dimensional heterojunction material.
Further, the specific process of step 1 is,
heating melamine sponge to 600 ℃ at a heating rate of 10 ℃/min in nitrogen atmosphere, roasting for 100min, naturally cooling to room temperature, alternately washing with deionized water and ethanol, and drying to obtain the product rich in g-C3N4The melamine porous carbon nitride foam has a smooth three-dimensional network structure.
Further, the specific process of step 2 is,
0.872-3.488g of Ni (NO) are weighed3)2·9H2O, 0.375-1.5g Al (NO)3)3·6H2O, 2.402g of CO (NH)2)2And 0.593g of NH4F was dissolved in 70mL of deionized water and stirred to form a homogeneous hydrotalcite precursor aqueous solution.
Further, the specific process of step 3 is,
immersing the three-dimensional network structure of the melamine porous carbon nitride foam into the reaction liquid of a high-pressure reaction kettle, carrying out ultrasonic treatment for 30min, sealing, placing in a 120 ℃ oven for hydrothermal treatment for 8h, naturally cooling to room temperature after the reaction is finished, taking out, respectively cleaning for 3 times by using deionized water and absolute ethyl alcohol to remove impurities adsorbed on the surface of the composite material, and drying in the oven at 60 ℃ to obtain the porous carbon nitride foam/hydrotalcite three-dimensional heterojunction material.
The application of a photocatalytic carbon dioxide reduction catalyst is used for reducing carbon dioxide into carbon monoxide under the photocatalysis.
Further, the specific process of the reduction is,
placing the reduction catalyst in a reactor, heating in a water bath to generate water vapor, and passing CO2Introducing steam and CO into the reactor2The mixed gas is carried into the reactor, purged for a certain time, and then light is applied to the outside of the reactor from the reaction chamber every hour1 ml of gaseous product was sampled and then analyzed using gas chromatography equipped with FID and TCD detectors.
Further, before introducing the mixed gas, introducing CO2And (3) purging with gas for 1.5h to remove air in the reactor, wherein the aeration speed is 10mL/min, the reactor is a transparent quartz reactor, a 300W xenon lamp is used for simulating sunlight, the distance between the xenon lamp and the catalytic reduction material is 8cm, the volume of the reactor is 200mL, and the mixed gas is subjected to atmosphere equilibrium for 30min to ensure that gas molecules are completely adsorbed.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
the invention takes simple and easily obtained substances as raw materials and has simple synthesis steps. Photocatalytic CO of porous carbon nitride foam on composite material compared to traditional hydrotalcite powder photocatalyst2The improvement of the reducing performance has good promoting effect. The catalyst not only can be used as a carrier, improves the dispersibility of LDH, enables the NiAl-LDH catalyst to be uniformly distributed in a composite material, solves the problem that hydrotalcite is easy to agglomerate, but also has good air permeability and light transmittance, enables the catalyst to expose more active sites, most importantly, the catalyst is rich in g-C3N4 semiconductor material, can construct a heterojunction material with the hydrotalcite, can effectively improve the photocatalytic performance of the composite material by utilizing the photocatalytic synergistic effect of the heterojunction, can achieve a CO yield of 159.62 mu mol/g which is about 4.2 times of that of a pure LDHs powder material, and greatly improves the photocatalytic CO2Yield of the reduction reaction.
Drawings
FIG. 1 is a comparison Raman spectrum and an X-ray photoelectron spectrum of the present invention;
FIG. 2 is an XRD spectrum of NCA-3 obtained in example 3;
FIG. 3 shows the photocatalytic reduction of CO for the materials obtained in comparative examples 1 to 2 and examples 1 to 42And (6) performance graphs.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings by way of examples of preferred embodiments. It should be noted, however, that the numerous details set forth in the description are merely for the purpose of providing the reader with a thorough understanding of one or more aspects of the present invention, which may be practiced without these specific details.
Example 1: preparation of NiAl-LDH/CF (NAC-1)
1) Heating melamine sponge to 600 ℃ at a heating rate of 10 ℃/min in nitrogen atmosphere, roasting for 100min, naturally cooling to room temperature, alternately washing with deionized water and ethanol, and drying to obtain the product rich in g-C3N4CF for short.
The following table shows the elemental analysis data of the melamine foam before carbonization and after carbonization.
Table 1 elemental analysis data sheet
To maximize the degree of graphitization, the melamine foam (abbreviated as MF) was annealed at 400, 500, 600, 700 and 800 ℃ for 100 minutes in a nitrogen atmosphere. Raman spectra of the CF foam at different temperatures were collected as shown in fig. 1 a. Typical peaks for graphite appear at 1360(D band) and 1592cm-1(G band), which are respectively attributed to A of the disordered graphite structure1gBreathing pattern and E of graphite2gA stretch mode. I of CF foams carbonized at 400, 500, 600, 700 and 800 deg.CD/IGThe ratios were 0.96, 1.01, 1.07, 1.03, and 1.00, respectively. In particular, CF foams show the highest I when carbonized at 600 ℃D/IGThe ratio indicates the highest concentration of defect sites in all CF foams. The elemental analysis data (Table 1) show that the melamine foam has a relatively high nitrogen content of 43.37 wt.%. The nitrogen content gradually decreases with increasing carbonization temperature. After charring at 600 ℃ for 100min, the nitrogen content was 25.86 wt%, indicating that half of the nitrogen element was retained. The surface composition and chemical state of the CF foam were further investigated by XPS analysis. As shown in fig. 1b, XPS full spectrum of CF foam confirmed the presence of C, N, O element. The high resolution C1s spectrum in FIG. 1C can be fittedThree main peaks centered at 284.7eV, 286.2eV and 288.4eV, belonging to sp of CF foams carbonized at 400, 500, 600, 700 and 800 ℃ respectively2Hybrid carbon (C-C), sp2Carbon hybridizes with nitrogen (C-N) and some oxygen-containing groups (C ═ O). The N1s spectrum of the CF foam had three peaks, with the 398.1eV peak due to pyridine-N, the 400.5eV peak due to pyrrole-N, and the 401eV peak due to graphite-N (FIG. 1 d). The XPS results above show that g-C rich foams were successfully synthesized by annealing MF foams in an inert atmosphere3N4The foam of (1).
2) 0.872g (3mmol) of Ni (NO) were weighed3)2·9H2O, 0.375g (1mmol) of Al (NO)3)3·6H2O, 2.402g (40mmol) of CO (NH)2)2And 0.593g (16mmol) of NH4F was dissolved in 70mL of deionized water and stirred to form a homogeneous hydrotalcite precursor aqueous solution. It was transferred to a 100mL teflon lined autoclave. Subjecting the porous carbon nitride foam (3X 2 cm) treated in step 1) to3) Immersing the porous carbon nitride foam/hydrotalcite three-dimensional heterojunction composite material into the reaction solution, carrying out ultrasonic treatment for 30 minutes, sealing, placing in a 120 ℃ oven for hydrothermal reaction for 8 hours, naturally cooling to room temperature after reaction, taking out, washing for 3 times by deionized water and absolute ethyl alcohol to remove impurities adsorbed on the surface of the composite material, and drying in the 60 ℃ oven to obtain the porous carbon nitride foam/hydrotalcite three-dimensional heterojunction composite material. Denoted as NAC-1.
CO simulating sunlight under a 300W xenon lamp at a distance of about 8cm from the sample2The reduction experiment was carried out in the bottom of a quartz reactor having a volume of about 200 ml. Before illumination, NAC-1 was placed in the bottom of the photoreactor and high purity CO was used2The photoreactor was purged with gas for 1.5 hours to remove air from the reactor. High purity CO2Gas passing through water bath to produce CO2And water vapor. In CO2/H2And (4) balancing in an O atmosphere for 30min to ensure that gas molecules are completely adsorbed. During the light period, 1 ml of the gaseous product was sampled from the reaction chamber every hour, and the performance was characterized by gas chromatography (using Ar as a carrier gas). As shown in FIG. 3, the CO yield of NAC-1 was 76.75. mu. mol g-1。
Example 2: preparation of NiAl-LDH/CF (NAC-2)
1) Heating melamine sponge to 600 ℃ at a heating rate of 10 ℃/min in nitrogen atmosphere, roasting for 100min, naturally cooling to room temperature, alternately washing with deionized water and ethanol, and drying to obtain the product rich in g-C3N4CF for short.
2) 1.744g (6mmol) of Ni (NO) were weighed out3)2·9H2O, 0.75g (2mmol) of Al (NO)3)3·6H2O, 2.402g (40mmol) of CO (NH)2)2And 0.593g (16mmol) of NH4F was dissolved in 70mL of deionized water and stirred to form a homogeneous hydrotalcite precursor aqueous solution. It was transferred to a 100mL teflon lined autoclave. Subjecting the porous carbon nitride foam (3X 2 cm) treated in step 1) to3) Immersing the porous carbon nitride foam/hydrotalcite three-dimensional heterojunction composite material into the reaction solution, carrying out ultrasonic treatment for 30 minutes, sealing, placing in a 120 ℃ oven for hydrothermal reaction for 8 hours, naturally cooling to room temperature after reaction, taking out, washing for 3 times by deionized water and absolute ethyl alcohol to remove impurities adsorbed on the surface of the composite material, and drying in the 60 ℃ oven to obtain the porous carbon nitride foam/hydrotalcite three-dimensional heterojunction composite material. Denoted as NAC-2.
CO simulating sunlight under a 300W xenon lamp at a distance of about 8cm from the sample2The reduction experiment was carried out in the bottom of a quartz reactor having a volume of about 200 ml. Before illumination, NAC-2 was placed in the bottom of the photoreactor and high purity CO was used2The photoreactor was purged with gas for 1.5 hours to remove air from the reactor. High purity CO2Gas passing through water bath to produce CO2And water vapor. In CO2/H2And (4) balancing in an O atmosphere for 30min to ensure that gas molecules are completely adsorbed. During the light period, 1 ml of the gaseous product was sampled from the reaction chamber every hour, and the performance was characterized by gas chromatography (using Ar as a carrier gas). As shown in FIG. 3, the CO yield of NAC-2 was 106.44. mu. mol g-1。
Example 3: preparation of NiAl-LDH/CF (NAC-3)
1) Mixing melamineHeating sponge to 600 deg.C at a heating rate of 10 deg.C/min in nitrogen atmosphere, calcining for 100min, naturally cooling to room temperature, alternately washing with deionized water and ethanol, and drying to obtain the product rich in g-C3N4CF for short.
2) 2.616g (9mmol) of Ni (NO) were weighed out3)2·9H2O, 1.125g (3mmol) of Al (NO)3)3·6H2O, 2.402g (40mmol) of CO (NH)2)2And 0.593g (16mmol) of NH4F was dissolved in 70mL of deionized water and stirred to form a homogeneous hydrotalcite precursor aqueous solution. It was transferred to a 100mL teflon lined autoclave. Subjecting the porous carbon nitride foam (3X 2 cm) treated in step 1) to3) Immersing the porous carbon nitride foam/hydrotalcite three-dimensional heterojunction composite material into the reaction solution, carrying out ultrasonic treatment for 30 minutes, sealing, placing in a 120 ℃ oven for hydrothermal reaction for 8 hours, naturally cooling to room temperature after reaction, taking out, washing for 3 times by deionized water and absolute ethyl alcohol to remove impurities adsorbed on the surface of the composite material, and drying in the 60 ℃ oven to obtain the porous carbon nitride foam/hydrotalcite three-dimensional heterojunction composite material. Denoted as NAC-3.
CO simulating sunlight under a 300W xenon lamp at a distance of about 8cm from the sample2The reduction experiment was carried out in the bottom of a quartz reactor having a volume of about 200 ml. Before illumination, NAC-3 was placed in the bottom of the photoreactor and high purity CO was used2The photoreactor was purged with gas for 1.5 hours to remove air from the reactor. High purity CO2Gas passing through water bath to produce CO2And water vapor. In CO2/H2And (4) balancing in an O atmosphere for 30min to ensure that gas molecules are completely adsorbed. During the light period, 1 ml of the gaseous product was sampled from the reaction chamber every hour, and the performance was characterized by gas chromatography (using Ar as a carrier gas). As shown in FIG. 3, the CO yield of NAC-3 was 159.62. mu. mol g-1. While the CO yield decreases as the concentration of the complex continues to increase (i.e., NAC-4). The possible reason is that when the amount of catalyst is too large, the supersaturated LDH forms an aggregate state in the CF itself, resulting in severe recombination of photo-generated electrons and holes, so that the CO yield decreases.
Example 4: preparation of NiAl-LDH/CF (NAC-4)
1) Heating melamine sponge to 600 ℃ at a heating rate of 10 ℃/min in nitrogen atmosphere, roasting for 100min, naturally cooling to room temperature, alternately washing with deionized water and ethanol, and drying to obtain the product rich in g-C3N4CF for short.
2) 3.488g (12mmol) of Ni (NO) were weighed out3)2·9H2O, 1.5g (4mmol) of Al (NO)3)3·6H2O, 2.402g (40mmol) of CO (NH)2)2And 0.593g (16mmol) of NH4F was dissolved in 70mL of deionized water and stirred to form a homogeneous hydrotalcite precursor aqueous solution. It was transferred to a 100mL teflon lined autoclave. Subjecting the porous carbon nitride foam (3X 2 cm) treated in step 1) to3) Immersing the porous carbon nitride foam/hydrotalcite three-dimensional heterojunction composite material into the reaction solution, carrying out ultrasonic treatment for 30 minutes, sealing, placing in a 120 ℃ oven for hydrothermal reaction for 8 hours, naturally cooling to room temperature after reaction, taking out, washing for 3 times by deionized water and absolute ethyl alcohol to remove impurities adsorbed on the surface of the composite material, and drying in the 60 ℃ oven to obtain the porous carbon nitride foam/hydrotalcite three-dimensional heterojunction composite material. Denoted as NAC-4.
CO simulating sunlight under a 300W xenon lamp at a distance of about 8cm from the sample2The reduction experiment was carried out in the bottom of a quartz reactor having a volume of about 200 ml. Before illumination, NAC-4 was placed in the bottom of the photoreactor and high purity CO was used2The photoreactor was purged with gas for 1.5 hours to remove air from the reactor. High purity CO2Gas passing through water bath to produce CO2And water vapor. In CO2/H2And (4) balancing in an O atmosphere for 30min to ensure that gas molecules are completely adsorbed. During the light period, 1 ml of the gaseous product was sampled from the reaction chamber every hour, and the performance was characterized by gas chromatography (using Ar as a carrier gas). As shown in FIG. 3, the CO yield of NAC-4 was 125.5. mu. mol g-1。
Comparative example 1: NiAl-LDH.
As shown in FIG. 3, the CO yield of NiAl-LDH was 38.02. mu. mol g-1。
Comparative example 2: porous carbon nitride foam (CF for short).
As shown in FIG. 3, the CO yield of CF was 45.33. mu. mol g-1。
FIG. 2 is the XRD spectrum of NCA-3 obtained in example 3, and it can be seen that the NiAl-LDH/porous carbon nitride foam three-dimensional heterojunction material is successfully synthesized.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (8)
1. A photocatalytic carbon dioxide reduction catalyst characterized by: the reduction catalyst is a NiAl-LDH/porous carbon nitride foam three-dimensional heterojunction composite material.
2. The method for preparing a photocatalytic carbon dioxide reduction catalyst according to claim 1, characterized in that: the preparation method comprises the following steps:
step 1: preparing a three-dimensional network structure of the melamine porous carbon nitride foam;
step 2: preparing a hydrotalcite precursor aqueous solution;
and step 3: and putting the porous carbon nitride foam three-dimensional network structure into a hydrotalcite precursor aqueous solution for reaction to prepare the porous carbon nitride foam/hydrotalcite three-dimensional heterojunction material.
3. The method for preparing a photocatalytic carbon dioxide reduction catalyst according to claim 2, characterized in that: the specific process of the step 1 is that,
heating melamine sponge to 600 ℃ at a heating rate of 10 ℃/min in nitrogen atmosphere, roasting for 100min, naturally cooling to room temperature, alternately washing with deionized water and ethanol, and drying to obtain the product rich in g-C3N4The melamine porous carbon nitride foam has a smooth three-dimensional network structure.
4. The method for preparing a photocatalytic carbon dioxide reduction catalyst according to claim 3, characterized in that: the specific process of the step 2 is that,
0.872-3.488g of Ni (NO) are weighed3)2·9H2O, 0.375-1.5g Al (NO)3)3·6H2O, 2.402g of CO (NH)2)2And 0.593g of NH4F was dissolved in 70mL of deionized water and stirred to form a homogeneous hydrotalcite precursor aqueous solution.
5. The method for preparing a photocatalytic carbon dioxide reduction catalyst according to claim 4, characterized in that: the specific process of the step 3 is that,
immersing the three-dimensional network structure of the melamine porous carbon nitride foam into the reaction liquid of a high-pressure reaction kettle, carrying out ultrasonic treatment for 30min, sealing, placing in a 120 ℃ oven for hydrothermal treatment for 8h, naturally cooling to room temperature after the reaction is finished, taking out, respectively cleaning for 3 times by using deionized water and absolute ethyl alcohol to remove impurities adsorbed on the surface of the composite material, and drying in the oven at 60 ℃ to obtain the porous carbon nitride foam/hydrotalcite three-dimensional heterojunction material.
6. The use of a photocatalytic carbon dioxide reduction catalyst according to claim 1, wherein: used for reducing carbon dioxide into carbon monoxide under the photocatalysis.
7. The use of a photocatalytic carbon dioxide reduction catalyst according to claim 6, wherein: the specific process of the reduction is that,
placing the reduction catalyst in a reactor, heating in a water bath to generate water vapor, and passing CO2Introducing steam and CO into the reactor2The mixed gas was introduced into the reactor, purged for a certain period of time, then light was applied to the outside of the reactor, 1 ml of the gas product was sampled from the reaction chamber per hour, and then gas chromatography using FID and TCD detectors was performedAnd (6) analyzing.
8. Use of a photocatalytic carbon dioxide reduction catalyst according to claim 7, characterized in that: introducing CO before introducing the mixed gas2And (3) purging with gas for 1.5h to remove air in the reactor, wherein the aeration speed is 10mL/min, the reactor is a transparent quartz reactor, a 300W xenon lamp is used for simulating sunlight, the distance between the xenon lamp and the catalytic reduction material is 8cm, the volume of the reactor is 200mL, and the mixed gas is subjected to atmosphere equilibrium for 30min to ensure that gas molecules are completely adsorbed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111048167.1A CN113649056A (en) | 2021-09-08 | 2021-09-08 | Photocatalytic carbon dioxide reduction catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111048167.1A CN113649056A (en) | 2021-09-08 | 2021-09-08 | Photocatalytic carbon dioxide reduction catalyst and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113649056A true CN113649056A (en) | 2021-11-16 |
Family
ID=78493669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111048167.1A Pending CN113649056A (en) | 2021-09-08 | 2021-09-08 | Photocatalytic carbon dioxide reduction catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113649056A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108554439A (en) * | 2018-05-11 | 2018-09-21 | 北京化工大学 | A kind of photo-reduction CO2 ultra-thin Ti bases LDHs composite photo-catalysts and preparation method thereof |
| CN109012731A (en) * | 2018-08-17 | 2018-12-18 | 南京理工大学 | Sea urchin shape CoZnAl-LDH/RGO/g-C3N4Z-type hetero-junctions and its preparation method and application |
| CN110743596A (en) * | 2019-10-31 | 2020-02-04 | 江苏大学 | Ruthenium nanoparticle/three-dimensional porous carbon nitride composite material, and preparation method and application thereof |
| CN111167499A (en) * | 2020-01-21 | 2020-05-19 | 佛山科学技术学院 | NiM-LDH/g-C3N4Composite photocatalytic material and preparation method thereof |
| CN111545235A (en) * | 2020-04-23 | 2020-08-18 | 宁德师范学院 | 2D/2Dg-C3N4CoAl-LDH hydrogen-production heterojunction material and preparation method and application thereof |
-
2021
- 2021-09-08 CN CN202111048167.1A patent/CN113649056A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108554439A (en) * | 2018-05-11 | 2018-09-21 | 北京化工大学 | A kind of photo-reduction CO2 ultra-thin Ti bases LDHs composite photo-catalysts and preparation method thereof |
| CN109012731A (en) * | 2018-08-17 | 2018-12-18 | 南京理工大学 | Sea urchin shape CoZnAl-LDH/RGO/g-C3N4Z-type hetero-junctions and its preparation method and application |
| CN110743596A (en) * | 2019-10-31 | 2020-02-04 | 江苏大学 | Ruthenium nanoparticle/three-dimensional porous carbon nitride composite material, and preparation method and application thereof |
| CN111167499A (en) * | 2020-01-21 | 2020-05-19 | 佛山科学技术学院 | NiM-LDH/g-C3N4Composite photocatalytic material and preparation method thereof |
| CN111545235A (en) * | 2020-04-23 | 2020-08-18 | 宁德师范学院 | 2D/2Dg-C3N4CoAl-LDH hydrogen-production heterojunction material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| SURENDAR TONDA: "g‑C3N4/NiAl-LDH 2D/2D Hybrid Heterojunction for High-Performance Photocatalytic Reduction of CO2 into Renewable Fuels", ACS APPL. MATER. INTERFACES * |
| 许艳旗;谭玲;王泽林;郝晓杰;王纪康;赵宇飞;宋宇飞;: "水滑石多尺度结构精准调控及其光驱动催化应用研究", 科学通报 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107824210B (en) | Titanium dioxide composite photocatalyst coated by nitrogen-doped mesoporous carbon and preparation method and application thereof | |
| CN112169819A (en) | g-C3N4 (101)-(001)-TiO2Preparation method and application of composite material | |
| CN110433844B (en) | Be used for high-efficient processing to contain Cr6+(B, O) Co-doping of waste Water with g-C3N4Method for preparing photocatalyst | |
| CN113457711B (en) | Graphite-phase carbon nitride-loaded magnesium monoatomic composite material, preparation method thereof and method for preparing hydrogen peroxide through photocatalysis | |
| CN110605137B (en) | Preparation method of CdS-based composite photocatalyst and application of CdS-based composite photocatalyst in aspect of hydrogen production through water splitting | |
| CN112517043B (en) | Nitrogen vacancy and hydroxyl synergistically modified graphite-phase carbon nitride photocatalyst, preparation method thereof and application thereof in photocatalytic hydrogen production | |
| CN112473717B (en) | Nickel monoatomic/functionalized graphite-phase carbon nitride composite catalyst | |
| CN110038605B (en) | AgInS applied to photocatalytic nitrogen reduction synthesis of ammonia2/Ti3C2Application method of nano catalyst | |
| CN112473712A (en) | CeO treated with different atmospheres2/g-C3N4Heterojunction material, preparation method and application thereof | |
| CN115999614A (en) | Ultraviolet-visible-near infrared light responsive carbon dioxide reduction photocatalyst | |
| CN114985004B (en) | Sulfur-indium-cadmium/PDDA/NiFe-LDH photocatalytic composite material and preparation method and application thereof | |
| CN113578358B (en) | Pt/NVC-g-C 3 N 4 Photocatalytic material and preparation method and application thereof | |
| CN113649039B (en) | Red phosphorus/bismuth oxide carbonate S-type heterojunction photocatalyst and preparation method thereof | |
| CN113975946A (en) | Method for converting carbon dioxide by synergy of plasma and photocatalyst | |
| CN114425392A (en) | Carbon-nitrogen-based composite material, preparation method and application thereof | |
| CN114054036A (en) | Preparation method and application of catalyst | |
| CN113649056A (en) | Photocatalytic carbon dioxide reduction catalyst and preparation method and application thereof | |
| CN113398968B (en) | MOF-derived TiO 2 Porous g-C 3 N 4 Composite photocatalyst, preparation method and application thereof | |
| CN113600225B (en) | Heterojunction composite material and application thereof | |
| CN115532298A (en) | Preparation method of diatom cluster photocatalyst | |
| CN114849761B (en) | Photocatalytic material and preparation method and application thereof | |
| CN113926454A (en) | Preparation method and application of CoAl-LDH/porous carbon nitride foam three-dimensional heterojunction composite material | |
| CN107159197B (en) | Solid solution photocatalyst with dodecahedron morphology and preparation method thereof | |
| CN113060771B (en) | Preparation method and application of amorphous small-size cobalt oxide loaded tantalum oxynitride | |
| CN113908873B (en) | Method for selectively oxidizing glucose by photocatalysis of carbon nitride-based photocatalyst |
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 |