CN112958096B - Preparation method and application of flower-ball-shaped nickel-aluminum hydrotalcite/titanium dioxide in-situ growth in sheet-shaped tri-titanium carbide composite photocatalyst - Google Patents
Preparation method and application of flower-ball-shaped nickel-aluminum hydrotalcite/titanium dioxide in-situ growth in sheet-shaped tri-titanium carbide composite photocatalyst Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 42
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 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 title claims abstract description 40
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 40
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 40
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 30
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 230000001699 photocatalysis Effects 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 19
- -1 tri-titanium dicarbonate Chemical compound 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000002135 nanosheet Substances 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 5
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- VSANUNLQSRKIQA-UHFFFAOYSA-K trichlororuthenium hexahydrate Chemical compound O.O.O.O.O.O.Cl[Ru](Cl)Cl VSANUNLQSRKIQA-UHFFFAOYSA-K 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 238000000527 sonication Methods 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 13
- 238000006722 reduction reaction Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000011160 research Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 238000012512 characterization method Methods 0.000 abstract 2
- 238000002474 experimental method Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 230000010757 Reduction Activity Effects 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005070 sampling Methods 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
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Classifications
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- B01J35/50—
-
- 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B01J35/39—
-
- B01J35/51—
-
- 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
Abstract
The invention relates to a preparation method and application of a flower-ball-shaped nickel-aluminum hydrotalcite/titanium dioxide in-situ growth sheet-shaped tri-titanium carbide composite photocatalyst, comprising the following steps: the flower-ball-shaped nickel-aluminum hydrotalcite/titanium dioxide prepared by the invention grows in situ on flaky tri-titanium carbide (NiAl-LDH/TiO) 2 TNS) composite photocatalyst, the preparation process of the composite photocatalyst is simple and convenient, and the preparation conditions are easy to control. According to the structure characterization and performance characterization experiments, the prepared flower-sphere-shaped nickel-aluminum hydrotalcite/titanium dioxide can be found to grow in situ on flaky tri-titanium carbide (NiAl-LDH/TiO) 2 TNS) composite photocatalyst has stable chemical property and uniform morphology and is used for photocatalysis of CO 2 In the reduction reaction, the catalyst has the advantages of high catalytic efficiency, high selectivity and the like, and has certain research and application values because the catalyst has the advantages of no secondary pollution, low preparation cost and the like.
Description
Technical Field
The invention relates to a preparation method and application of a flower-ball-shaped nickel-aluminum hydrotalcite/titanium dioxide in-situ growth sheet-shaped tri-titanium carbide composite photocatalyst, belonging to photocatalysis of CO 2 The field of reduction.
Background
With the increasing severity of ecological and energy problems, sustainable development has become the route of choice for modern society, with the two challenges facing energy and environmental problems. Solar energy is used as renewable energy source with the most application prospect, has the advantages of rich total resources, cleanness, safety, on-site development and utilization, small regional limitation and the like, and is a basis for realizing sustainable development of human society. The photocatalysis technology mainly surrounds the photocatalytic water splitting hydrogen production and the photocatalytic CO in the application of energy catalysis 2 The development of reduction direction, and the development and utilization of novel effective photocatalysts are more important subjects for the scientific research in the 21 st century. Aiming at the defect of high photo-generated electron-hole recombination rate of a single photocatalyst, the charge separation can be effectively enhanced by adopting a composite modification method, thereby improving the photo-catalytic activitySex. Due to good metal conductivity and a large number of exposed metal sites, ti 3 C 2 T x MXene as a cocatalyst has great potential in the field of photocatalysis. Accordion-like multilayer Ti 3 C 2 T x In contrast, flake-shaped Ti 3 C 2 T x Not only has larger specific surface area and more active site exposure, but also can shorten the migration distance of photo-generated charges. Thus, the sheet-like Ti 3 C 2 T x The separation of the photo-generated electrons and the holes can be effectively promoted. It was found that Ti was produced by a high-temperature hydrothermal method 3 C 2 T x Partial oxidation to form Ti 3 C 2 T x Growing TiO in situ 2 By using Ti 3 C 2 (OH) x Acting as a reservoir of holes, facilitating TiO 2 Carrier transport through the interfacial schottky junction, thereby enhancing photocatalytic activity. In recent years, layered Double Hydroxides (LDHs) have attracted considerable attention in many fields due to their inherent properties, i.e. adjustable composition and exchangeable interlayer anions. In the field of photocatalysis, the unique layered structure of LDH allows metal cations to be uniformly distributed between layers, thereby flexibly adjusting cations and anions to exhibit excellent chemical stability and high adsorption capacity.
For photocatalytic reduction of CO 2 The photocatalyst of (2) and the photocatalytic reduction of carbon dioxide can obtain C 1 Or the above carbon-based molecules such as CO, methane, methanol, ethanol, formaldehyde, formic acid, or other molecules. Wherein carbon monoxide CO can also be used in energy terms as a mixture with hydrogen for the formation of fuel by fischer-tropsch synthesis, which is extremely beneficial from an industrial point of view. Therefore, how to prepare the catalyst with high catalytic efficiency and high selectivity for photocatalysis of CO 2 Photocatalysts are the focus of research in the present invention in the reduction reaction.
The invention is based on synthesizing nickel-aluminum hydrotalcite and flaky tri-titanium dicarbonate, and the nickel-aluminum hydrotalcite and the flaky tri-titanium dicarbonate are compounded by a high-temperature hydrothermal method to construct a novel composite photocatalyst. In which due to TiO 2 Nanoparticle and sheetTi in the shape of 3 C 2 T x And a Schottky junction is formed between the two layers, and a heterojunction is formed between the two layers and NiAl-LDH, so that the life of the photo-generated electrons is greatly prolonged. The composite photocatalyst is based on Ti 3 C 2 T x The MXene nano structure design aims at improving the light capturing capability, obtaining higher quantum efficiency and enhancing the separation of photon-generated carriers, and widens the application of the novel composite material in the field of photocatalysis.
Disclosure of Invention
The invention aims to prepare Ti 3 C 2 T x The MXene-based high-efficiency photocatalyst provides a preparation method of a flower-ball-shaped nickel-aluminum hydrotalcite/titanium dioxide in-situ growth sheet-shaped tri-titanium carbide composite photocatalyst, and the prepared composite catalyst has higher catalytic activity and simple whole preparation process.
The invention adopts the following specific scheme:
the flower-ball-shaped nickel aluminum hydrotalcite/titanium dioxide in-situ grown on the flaky tri-titanium carbide composite photocatalyst is prepared by a high-temperature hydrothermal method, and comprises the following steps of:
(1) Preparation of flaky tri-titanium carbide (TNS): lithium fluoride (LiF) was weighed and stirred at room temperature in HCl solution, followed by aluminum titanium carbide (Ti) 3 AlC 2 ) Slowly adding the powder into the solution, and stirring in an oil bath at 75-85 ℃ for 20-28h. After stirring was completed and cooled to room temperature, centrifugation was performed and the upper layer solution was washed with deionized water to a pH > 6, and the black precipitate was collected and dried overnight at 60 ℃. Dispersing the dried black powder in deionized water, and performing ultrasonic treatment to separate the lamellar sheets to form lamellar Ti 3 C 2 T x Centrifuging at 3000-4000 rpm for 25-35 min, and drying the upper layer liquid to obtain TNS (Ti) 3 C 2 T x Nanosheets)。
Further, as preferable: wherein the mass ratio of lithium fluoride to carbon-titanium aluminum in the step (1) is 1:1, and the molar concentration of the HCl solution is 9mol/L.
(2) Flower-ball-shaped nickel-aluminum hydrotalcite/titanium dioxide in-situ grown on sheet-shaped tri-titanium carbide (NiAl-LDH/TiO) 2 TNS) composite photocatalystPreparation: dispersing the sheet-shaped tri-titanium carbide (TNS) with a certain mass after drying in the step (1) in deionized water, and fully dissolving the titanium carbide by ultrasonic treatment. Weighing nickel nitrate hexahydrate [ Ni (NO) 3 ) 2 ·6H 2 O]And aluminum nitrate nonahydrate [ Al (NO) 3 ) 3 ·9H 2 O]Dispersed in the above solution and stirred to form a homogeneous solution. Thereafter, ammonium fluoride (NH) 4 F) And urea (CH) 4 N 2 O), stirring to mix thoroughly. Then, the mixed solution is transferred into a high-pressure reaction kettle to be subjected to hydrothermal reaction for 20-28h at the temperature of 110-130 ℃. After the reaction, cooling to room temperature, centrifuging, washing with deionized water to pH about 7, collecting precipitate, and drying at 60deg.C overnight.
Further preferably, the hydrothermal temperature in the step (2) is 120 ℃ and the reaction time is 24 hours, so that TiO grows in situ on TNS 2 And (3) particles. The reaction is carried out for 24 hours at 120 ℃ which is the optimal condition after the optimization of the invention, and the temperature is higher or lower than 120 ℃, and the longer or shorter reaction time can destroy the structural morphology of the product or can not generate the complete flower sphere assembled by the thin-layer nano-sheets.
Further, wherein Ni (NO) 3 ) 2 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 The molar ratio of O, ammonium fluoride and urea is 3:1:8:20, and the TNS is added in an amount of 20-100mg, wherein the TNS is added according to a certain amount of NiAl-LDH (300 mg). TNS (Ti) 3 C 2 T x ) The addition amount of the catalyst is 6 to 25 percent of the total mass of NiAl-LDH and TNS.
In step (2) Ti 3 C 2 T x Not only is TiO 2 Providing a titanium source, and generating TiO in situ under high-temperature hydrothermal condition 2 In the form of flake, ti with different mass is added under a certain amount of NiAl-LDH by controlling the proportion of NiAl-LDH precursor and reaction condition 3 C 2 T x Thus preparing complexes in different proportions. And Ti is 3 C 2 T x The addition amount plays an important role in the catalytic activity of the catalyst.
According to the method, respectively synthesizing NiAl-LDH/TTNS-20 (6%), niAl-LDH/TTNS-50 (14%), niAl-LDH/TTNS-75 (20%), and NiAl-LDH/TTNS-100 (25%).
Application of flower-ball-shaped nickel-aluminum hydrotalcite/titanium dioxide in-situ growth in sheet-shaped tri-titanium carbide composite photocatalyst for photocatalytic CO 2 Reduction Activity test, catalyst for photocatalytic reduction of CO 2 CO and H production 2 。
The method comprises the following steps of:
7.5mg of the catalyst and 7.5mg of terpyridyl ruthenium chloride hexahydrate ([ Ru (bpy)) were weighed out 3 ]Cl 2 ·6H 2 O) dissolved in 6mL acetonitrile (MeCN) to 4mL H by sonication 2 O/2mL of Triethanolamine (TEOA). Then, the solution was poured into a 200mL glass reactor and stirring was continued. Before illumination, CO is required to be introduced 2 (99.95%) the reactor was evacuated of gases for about 30 minutes. In the test, a 300W xenon lamp (lambda is more than or equal to 420 nm) is used as a light source, 500 mu L of gas is taken by a gas phase sampling needle every 30min, and H is detected by a gas chromatography TCD signal 2 FID signal detection of CO and CO 2 。
The invention adopts a high-temperature hydrothermal method to prepare the flower-ball-shaped nickel aluminum hydrotalcite/titanium dioxide in-situ grown sheet-shaped tri-titanium carbide composite material, and prepares the composite catalysts with different proportions by changing the addition amount of TNS, thereby obtaining the composite with different catalytic activities.
The invention has the advantages that: the NiAl-LDH/TTNS composite photocatalyst prepared by the method has better stability, no secondary pollution and photocatalysis of CO 2 The reduction activity is good, and the CO yield and selectivity can reach 2128.46 mu mol h under the visible light range -1 g -1 And 90.2%. In addition, the preparation method of the composite photocatalyst is simple, the preparation conditions are easy to control, the preparation cost is low, and the like, so that the composite photocatalyst has certain research and application values.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is an X-ray diffraction diagram of a pure flaky tri-titanium dicarbonate, pure nickel aluminum hydrotalcite and flower-shaped spherical nickel aluminum hydrotalcite/titanium dioxide in-situ grown on a flaky tri-titanium dicarbonate composite photocatalyst with different TNS contents, which are prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope and a transmission electron microscope of the pure flower spherical nickel-aluminum hydrotalcite and NiAl-LDH/TTNS-75 composite photocatalyst prepared in the embodiment 1 of the invention;
FIG. 3 shows the in situ growth of flower-shaped spherical nickel aluminum hydrotalcite/titanium dioxide on sheet-shaped tri-titanium carbide composite photocatalyst and pure sheet-shaped tri-titanium carbide and pure nickel aluminum hydrotalcite under different TNS contents in the method of example 1 of the present invention for catalytic reduction of CO under visible light 2 Obtaining CO and H 2 Yield histogram of (2);
FIG. 4 is a graph showing the CO and H of the NiAl-LDH/TTNS-75 composite photocatalyst prepared in example 1 of the present invention 2 Stability test patterns of yields of (2).
Detailed Description
The present invention will now be further described with reference to specific examples for the purpose of more clearly explaining the present invention, but the content of the present invention is not limited to the following examples.
Example 1
(1) Preparation of flaky tri-titanium carbide (TNS): 1.0g of lithium fluoride (LiF) was weighed out and stirred at room temperature for 10min in 20mL of 9mol/L HCl solution, after which 1.0g of aluminum titanium carbide (Ti 3 AlC 2 ) The powder was slowly added to the solution and stirred in an oil bath at 80 ℃ for 24h. After stirring was completed and cooled to room temperature, centrifugation was performed and the upper layer solution was washed with deionized water to a pH > 6, and the black precipitate was collected and dried overnight at 60 ℃. Dispersing dried black powder 0.5g in 50mL deionized water, and ultrasonic treating for 1 hr to separate the lamellar sheet to form lamellar Ti 3 C 2 T x Centrifuging at 3500rpm for 30min, and drying the upper liquid to obtain TNS.
(2) Flower-ball-shaped nickel-aluminum hydrotalcite/titanium dioxide in-situ grown on sheet-shaped tri-titanium carbide (NiAl-LDH/TiO) 2 TNS) preparation of the composite photocatalyst: dispersing 75mg of flaky tri-titanium carbide (TNS) dried in the step (1) in 60mL of deionized water, and carrying out ultrasonic treatment for 30min to fully dissolve the titanium carbide. 0.42g of nickel nitrate hexahydrate [ Ni (NO) 3 ) 2 ·6H 2 O]And 0.18g of aluminum nitrate nonahydrate [ Al (NO) 3 ) 3 ·9H 2 O]Dispersed in the above solution and stirred for 10min to form a homogeneous solution. Thereafter, 0.1422g of ammonium fluoride (NH) 4 F) And 0.5766g urea (CH) 4 N 2 O), stirring for 30min to allow thorough mixing. Then, the mixed solution was transferred to a 100mL autoclave and reacted hydrothermally at 120℃for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, centrifuged and washed with deionized water to a pH of about 7, and the light gray precipitate was collected and dried overnight at 60℃to give NiAl-LDH/TTNS-75.
Example 2
According to the method of example 1, the above 75mg of flaky tri-titanium dicarbonate was replaced with 20mg, 50mg and 100mg, respectively, and the other operations were the same as in example 1, to obtain NiAl-LDH/TTNS-20, niAl-LDH/TTNS-50 and NiAl-LDH/TTNS-100 composite catalysts, respectively.
Comparative example 1
Only synthesizing NiAl-LDH single catalyst, the synthesis method is as follows:
0.42g of nickel nitrate hexahydrate [ Ni (NO) 3 ) 2 ·6H 2 O]And 0.18g of aluminum nitrate nonahydrate [ Al (NO) 3 ) 3 ·9H 2 O]Dispersed in the aqueous solution and stirred for 10min to form a homogeneous solution. Thereafter, 0.1422g of ammonium fluoride (NH) 4 F) And 0.5766g urea (CH) 4 N 2 O), stirring for 30min to allow thorough mixing. Then, the mixed solution was transferred to a 100mL autoclave and reacted at 120℃for 24 hours. After the reaction is finished, cooling to room temperature, centrifuging, washing with deionized water to pH about 7, collecting light gray precipitate, and drying at 60 ℃ overnight to obtain NiAl-LDH.
1. Components and morphology measurement of flower-ball-shaped nickel-aluminum hydrotalcite/titanium dioxide in-situ growth on flaky tri-titanium dicarbonate composite photocatalyst
The crystalline phase structures of the pure flaky tri-titanium dicarbonate, the pure nickel aluminum hydrotalcite and the flower-spherical nickel aluminum hydrotalcite/titanium dioxide in-situ grown on the flaky tri-titanium dicarbonate composite photocatalyst with different TNS contents prepared in example 1 are analyzed by an X-ray diffractometer. The X-ray diffraction pattern is shown in figure 1, from which it can be seen that the preparationIn-situ growth of flower-shaped nickel-aluminum hydrotalcite/titanium dioxide in a platy tri-titanium dicarbonate composite photocatalyst XRD diffraction pattern can see that characteristic diffraction peaks of nickel-aluminum hydrotalcite appear at 11.54 degrees, 23.16 degrees, 34.94 degrees, 39.32 degrees, 46.82 degrees, 60.90 degrees and 62.28 degrees respectively correspond to (003) (006) (012) (015) (018) (110) and (113) crystal faces of nickel-aluminum hydrotalcite, and anatase type TiO appears at 25.06 degrees and 37.80 degrees with gradual increase of TNS content 2 The intensity of the characteristic diffraction peak of (C) is gradually increased and respectively corresponds to anatase type TiO 2 When the TNS content is increased to 100mg, characteristic diffraction peaks of the tri-titanium dicarbonate appear at 35.94 DEG and 41.74 DEG. While the characteristic diffraction peaks at 6.56 °, 35.94 °, 41.74 ° and 60.70 ° are the (002) (008) (010) and (110) crystal planes of the plate-like tri-titanium di-carbide, respectively. Therefore, it can be demonstrated that the composite photocatalyst contains flaky tri-titanium dicarbonate, nickel aluminum hydrotalcite and anatase type titanium dioxide, and the chemical structure and crystal form are not changed in the composite process.
The morphology of the pure nickel-aluminum hydrotalcite prepared in comparative example 1 was observed by using a scanning electron microscope, and a scanning electron microscope image is shown in fig. 2, and it can be seen from the image that the pure nickel-aluminum hydrotalcite prepared in this embodiment is a spherical flower-like structure composed of a plurality of nano-sheets, and the average diameter of the flower-like sphere is about 4 μm; the morphology of the NiAl-LDH/TTNS-75 composite photocatalyst prepared in the embodiment 1 is that granular titanium dioxide nano particles grow on the surface of flaky titanium sesquicarbide, and meanwhile, flower-spherical nickel-aluminum hydrotalcite is also loaded on the surface.
2. Photocatalytic CO of flower-ball-shaped nickel-aluminum hydrotalcite/titanium dioxide in-situ growth on flaky tri-titanium carbide composite photocatalyst 2 Reduction Activity and stability test
The prepared pure flaky tri-titanium dicarbonate, pure flower-shaped spherical nickel-aluminum hydrotalcite, flower-shaped spherical nickel-aluminum hydrotalcite prepared in the embodiment/titanium dioxide in-situ grows on the flaky tri-titanium dicarbonate compound as a catalyst to carry out photocatalytic reduction of CO 2 。
7.5mg of the different catalysts and 7.5mg of terpyridyl ruthenium chloride hexahydrate ([ Ru (bpy)) were weighed separately 3 ]Cl 2 ·6H 2 O) is dissolved by ultrasoundSolution in 6mL acetonitrile (MeCN)/4 mL H 2 O/2mL of Triethanolamine (TEOA). Then, the solution was poured into a 200mL glass reactor and stirring was continued. Before illumination, CO is required to be introduced 2 (99.95%) the reactor was evacuated of gases for about 30 minutes. In the test, a 300W xenon lamp (lambda is more than or equal to 420 nm) is used as a light source, 500 mu L of gas is taken by a gas phase sampling needle every 30min, and H is detected by a gas chromatography TCD signal 2 FID signal detection of CO and CO 2 . Calculation of CO and H from fitting equations obtained by calibration curve and external standard method 2 Is contained in the composition.
In-situ growth of flower-spherical nickel-aluminum hydrotalcite/titanium dioxide under different TNS contents prepared in examples on CO and H of flaky tri-titanium carbide composite photocatalyst under visible light 2 Yield of (mu mol h) -1 g -1 ) The histogram is shown in fig. 3. As can be seen from FIG. 3, when the TNS content was 75mg, that is, niAl-LDH/TTNS-75, the CO yield was high (2128.46. Mu. Mol h -1 g -1 ) Highest, H 2 Yield of 230.68. Mu. Mol h -1 g -1 The selectivity of CO (90.2%) is best; when the TNS content was 20mg, namely NiAl-LDH/TTNS-20, the yield of CO after photocatalysis was 518.61. Mu. Mol h -1 g -1 The selectivity to CO was 85.7%; when the TNS content was 50mg, namely NiAl-LDH/TTNS-50, the yield of CO after photocatalysis was 1628.18. Mu. Mol h -1 g -1 The selectivity to CO was 89.7%; when the TNS content was 100mg, namely NiAl-LDH/TTNS-100, the yield of CO after photocatalysis was 1123.52. Mu. Mol h -1 g -1 The selectivity of CO was 89.5%;
the yield of CO after photocatalysis of the NiAl-LDH single catalyst is only 246.53 mu mol h -1 g -1 The selectivity to CO was 84.0%; pure TNS has poor photocatalytic activity, and CO is difficult to generate by selective reaction.
From the above, the prepared flower ball type nickel aluminum hydrotalcite/titanium dioxide in-situ growth on the flaky tri-titanium dicarbonate composite photocatalyst has certain photocatalysis CO 2 Reduction activity.
The NiAl-LDH/TTNS-75 composite photocatalyst prepared in example 1CO and H 2 A stability test chart of the yield of (C) is shown in FIG. 4. After four cycle tests, the NiAl-LDH/TTNS-75 composite photocatalyst was tested for CO and H 2 The yield of (C) is still kept above 90% of the initial value, which shows that the NiAl-LDH/TTNS-75 composite photocatalyst has good stability.
Claims (3)
1. The application of flower-ball-shaped nickel-aluminum hydrotalcite/titanium dioxide in-situ growth in a flaky tri-titanium carbide composite photocatalyst is characterized in that: the catalyst is used for photocatalytic reduction of CO 2 CO and H production 2 The method comprises the steps of carrying out a first treatment on the surface of the The specific application method is as follows: 7.5mg of catalyst and 7.5mg of terpyridyl ruthenium chloride hexahydrate were weighed and dissolved in 6mL of acetonitrile/4 mL of H by sonication 2 O/2mL of the triethanolamine, then the solution was poured into a 200mL glass reactor and stirred continuously, and 99.95% CO was introduced before illumination 2 Evacuating the gas in the reactor, exhausting for 30min, and illuminating with a 300W xenon lamp as a light source;
the flower ball-shaped nickel aluminum hydrotalcite/titanium dioxide in-situ growth is carried out on the flaky tri-titanium carbide composite photocatalyst according to the following steps:
(1) Preparing flaky titanium sesquicarbide: weighing lithium fluoride, stirring at room temperature, dissolving in HCl solution, then weighing titanium carbide aluminum powder, slowly adding the titanium carbide aluminum powder into the solution, stirring in an oil bath at 75-85 ℃ for 20-28h, centrifuging after stirring is finished and cooling to room temperature, washing with deionized water until the pH value of the upper solution is more than 6, collecting black precipitate, and drying; dispersing the dried black powder in deionized water, and ultrasonically separating the lamellar sheets to form lamellar Ti 3 C 2 T x Centrifuging at high speed, and drying the upper layer liquid to obtain Ti 3 C 2 T x A nanosheet;
(2) Flower-ball-shaped nickel-aluminum hydrotalcite/titanium dioxide in-situ grown on sheet-shaped tri-titanium dicarbonate NiAl-LDH/TiO 2 Preparing a TNS composite photocatalyst;
taking Ti of step (1) 3 C 2 T x The nano-sheets are dispersed in deionized water, and the nano-sheets are fully dissolved by ultrasonic waves; weighing nickel nitrate hexahydrateDispersing aluminum nitrate nonahydrate in the solution, stirring to form a uniform solution, adding ammonium fluoride and urea, stirring to fully mix the solution to obtain a mixed solution, transferring the mixed solution into a high-pressure reaction kettle, carrying out a hydrothermal reaction at 120 ℃ for 24h, and growing TiO on TNS in situ after the reaction 2 And (3) granulating, cooling to room temperature after the reaction is finished, centrifuging, washing with deionized water, collecting precipitate, and drying to obtain flower-spherical nickel-aluminum hydrotalcite/titanium dioxide in-situ grown on sheet-shaped titanium carbide NiAl-LDH/TiO 2 TNS composite photocatalyst; the addition amount of TNS is 20% of the total mass of NiAl-LDH and TNS.
2. The application of the flower-shaped nickel aluminum hydrotalcite/titanium dioxide in-situ growth in a flaky tri-titanium carbide composite photocatalyst according to claim 1, which is characterized in that: the mass ratio of the lithium fluoride to the carbon titanium aluminum is 1:1, and the molar concentration of the HCl solution is 9mol/L.
3. The application of the flower-shaped nickel aluminum hydrotalcite/titanium dioxide in-situ growth in a flaky tri-titanium carbide composite photocatalyst according to claim 1, which is characterized in that: ni (NO) in the step (2) 3 ) 2 •6H 2 O、Al(NO 3 ) 3 •9H 2 The molar ratio of O, ammonium fluoride and urea is 3:1:8:20.
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