CN112517082A - Organic metal compound modified inorganic semiconductor composite photocatalyst and preparation method and application thereof - Google Patents
Organic metal compound modified inorganic semiconductor composite photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 239000004065 semiconductor Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 150000002736 metal compounds Chemical class 0.000 title abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 98
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 98
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 60
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 34
- 230000001699 photocatalysis Effects 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000001311 chemical methods and process Methods 0.000 claims abstract description 4
- 238000013329 compounding Methods 0.000 claims abstract description 3
- 239000011521 glass Substances 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 21
- MUNARLQNCCGPQU-UHFFFAOYSA-L dichloropalladium;2-pyridin-2-ylpyridine Chemical compound Cl[Pd]Cl.N1=CC=CC=C1C1=CC=CC=N1 MUNARLQNCCGPQU-UHFFFAOYSA-L 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 238000010168 coupling process Methods 0.000 claims description 13
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- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 238000005859 coupling reaction Methods 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 9
- 238000009489 vacuum treatment Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 230000008878 coupling Effects 0.000 claims description 6
- 125000002524 organometallic group Chemical group 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
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- 238000011161 development Methods 0.000 abstract description 6
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- 230000001737 promoting effect Effects 0.000 abstract 1
- 230000001131 transforming effect Effects 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 42
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 229910052697 platinum Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
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- -1 octahedron Substances 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910016553 CuOx Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- B01J35/39—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
- C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
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- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/76—Dehydrogenation
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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention belongs to the field of catalytic chemistry, and particularly relates to Pd (bpy)/TiO2A preparation method of an organic metal compound modified inorganic semiconductor composite photocatalyst. The Pd (bpy)/TiO2The organic metal inorganic semiconductor composite photocatalyst is a material obtained by compounding (2,2' -bipyridyl) dichloropalladium (II) and titanium dioxide, wherein the mass fraction of palladium is 0.2-5.0%. The invention adopts a surface metal organic chemistry method, which comprises the following steps: grafting (2,2' -bipyridine) palladium (II) dichloride onto the surface of titanium dioxide by a surface grafting method to obtain the composite material. Pd (bpy)/TiO prepared by the invention2Not only has higher methane conversion photocatalytic efficiency, but also overcomes the defect of inactivation when the titanium dioxide based photocatalyst is converted into methane, and the preparation method is simpleHas important significance for promoting the green development of social industry by transforming energy structures.
Description
Technical Field
The invention belongs to the field of catalytic chemistry, and particularly relates to Pd (bpy)/TiO2The preparation of the organic metal compound modified inorganic semiconductor composite photocatalyst and the application thereof in the anaerobic coupling of the photocatalytic methane.
Background
Since the industrial revolution, society has entered the modernization development stage thanks to the power provided by traditional fossil energy sources (petroleum, coal). Nowadays, in the face of the decreasing of petrochemical energy reserves and the increasing pollution caused by the large consumption of the petrochemical energy reserves, the seeking of energy structure transformation and the relief of environmental pressure potential become more important.
Methane is widely present in natural gas, shale gas, combustible ice, etc., is abundant in reserves, and can be converted into hydrocarbons having high added values, and thus is considered as an ideal choice for replacing fossil energy. Among the many efficient pathways for methane conversion, anaerobic coupling of methane has attracted the attention of many researchers as one of them. The activation of methane is very difficult due to the high degree of symmetry of the methane molecule and the extreme stability of the C-H bond. Anaerobic coupling reaction of methane 2CH4 →C2H6 +H2 ,ΔG298 K = 69 kJ/mol, the Gibbs free energy is far more than 0, the energy consumption of the high temperature (600-2+Product selectivity is not ideal and catalytic materials are prone to deactivation. The consumption of heat energy in the thermal catalysis process often produces indirect pollution, the catalytic reaction is driven by a photocatalysis mode to break through thermodynamic limitation, and the renewable solar energy is utilized to realize the development concept of green chemistry while the reaction temperature is reduced.
Among numerous methane conversion technologies, photocatalytic methane conversion is unique due to low energy consumption, greenness and no pollution. Methane is converted into organic compounds with high added value through a photocatalysis technology, so that the storage of solar energy with reduced density is realized, and micromolecular methane is converted into organic compounds such as methanol, ethylene and the like which can be directly utilized. The anaerobic coupling of the photocatalytic methane can realize the production of high value-added chemicals such as ethane and ethylene, and the hydrogen is also used as a green energy product as a product. The significance of methane photocatalytic conversion is more prominent.
Titanium dioxide as a star material in the field of photocatalysis has the advantages of strong stability, fast migration of photon-generated carriers, rich surface structure and the like. In the development of photocatalysis in recent years, titanium dioxide has not only made a breakthrough in structure, but also made a significant progress in heterostructures. Meanwhile, the shape regulation of titanium dioxide is involved, such as nano-sheet, octahedron, quantum dot and the like. However, titanium dioxide as a photocatalyst still has some disadvantages. The first is the low utilization of sunlight. The ultraviolet part of sunlight only accounts for 5%, and most of the sunlight exists in visible light and infrared light. However, titanium dioxide has a forbidden band width of about 3.1eV and is therefore only responsive to ultraviolet light. Second, photogenerated carriers recombine severely. Severe coincidence efficiency directly leads to low photocatalytic activity. Therefore, in view of the above two problems, the photoresponse range is widened by regulating the energy band structure of the titanium dioxide. The surface of the material is modified with metal and metal organic compound to promote the separation of carriers.
The metal organic compound is a compound with excellent photoelectric property. The metal moiety acts as a catalytically active site to activate methane between carbon-hydrogen bonds. The organic ligand is used as an excellent light absorption group, and can effectively promote the absorption of light. Meanwhile, the organic ligand can also be used as a bridge for electron transfer to realize the rapid transfer of photo-generated electrons. The metal bipyridine compound is representative thereof. The bipyridine can play a role of a photosensitizer to widen the light absorption range, and meanwhile, the bipyridine group can also realize the transfer of photo-generated electrons from an inorganic semiconductor to prevent the reduction of the photocatalytic performance due to the recombination of carriers.
Jinlong Zhang et al reportedThe Ga-doped titanium dioxide can realize the photocatalytic conversion of methane to ethane after loading noble metal platinum. Among them, the doping of Ga causes anatase titania to generate a large amount of oxygen defect structures. Meanwhile, platinum exists in two valence states on titanium dioxide. The double catalytic promoter composed of high-valence and low-valence platinum realizes the high-efficiency catalytic conversion of methane. In addition, professor Tang dynasty developed Pt and CuOxCo-modified TiO2The photocatalytic methane oxidative coupling in the mobile phase is realized. By photo-deposition on TiO2Depositing Pt nanoparticles on the surface. The introduction of Pt nanoparticles greatly promotes TiO2Separation of photo-generated charges. Simultaneously, the equal-volume impregnation method introduces copper clusters which can not only accept TiO2And the oxidation potential of the holes can also be reduced, thereby reducing further oxidation of high value-added products to carbon dioxide.
The above documents respectively use metal oxide and noble metal modified titanium dioxide as photocatalysts to realize the photocatalytic conversion of methane. There are several problems that remain.
Firstly, the method comprises the following steps: the catalytic activity is low. Although the current system has achieved certain conversion efficiency for the conversion of methane, the problems of low catalytic activity, poor selectivity and the like still exist.
Secondly, the method comprises the following steps: the stability of the catalyst is poor. The current photocatalyst can realize the photocatalytic conversion of methane. However, it was found that the catalytic activity did not increase further as the reaction proceeded. This may be due to the presence of excessive oxidation. Therefore, it is very meaningful to design and develop a high-efficiency photocatalyst to realize the high-efficiency catalytic conversion of methane.
Disclosure of Invention
Aiming at the defects existing in the process of converting methane by using the titanium dioxide-based photocatalyst, the invention provides the organometallic inorganic semiconductor composite photocatalyst Pd (bpy)/TiO with higher photocatalytic efficiency2And preparation and application thereof. Prepared Pd (bpy)/TiO2Not only has higher methane conversion photocatalytic efficiency, but also overcomes the defect of inactivation when the titanium dioxide-based photocatalyst is converted into methane. Preparation ofPd(bpy)/TiO2The organic-metal inorganic semiconductor composite photocatalyst adopts a surface metal organic chemical grafting method, has simple and clear operation steps, and has important significance for energy structure transformation and promotion of green development of social industry.
In order to achieve the purpose, the invention adopts the following technical scheme:
the Pd (bpy)/TiO2The organic metal inorganic semiconductor composite photocatalyst is a material obtained by compounding (2,2' -bipyridyl) dichloropalladium (II) and titanium dioxide, wherein the mass fraction of palladium is 0.2-5.0%.
The Surface organometallics chemistry method is adopted, and the following steps are carried out: the composite material obtained by grafting (2,2' -bipyridyl) dichloropalladium (II) to the surface of titanium dioxide by a surface grafting method specifically comprises the following steps:
(1) placing 0.01-20 g of commercial titanium dioxide in a glass reactor, and calcining for 0.5-20 hours at 200-500 ℃ under the oxygen atmosphere to obtain a white sample A;
(2) treating the white sample A obtained in the step (1) at the temperature of 200 ℃ and 500 ℃ for 0.5-5 hours under high vacuum to obtain a dark gray sample B;
(3) introducing 0.1-50 mg of (2,2' -bipyridyl) dichloropalladium (II) into the sample B obtained in the step (2) under the condition of strictly removing water and oxygen, and reacting for 6-40 hours at the temperature of 100-2An organometallic inorganic semiconductor composite photocatalyst.
The Pd (bpy)/TiO2The application of the organic metal inorganic semiconductor composite photocatalyst in the photocatalysis of anaerobic coupling of methane, wherein the photocatalysis of anaerobic coupling reaction of methane comprises the following specific steps:
(1) weighing 2-50 mg Pd (bpy)/TiO2Placing the organic-metal inorganic semiconductor composite photocatalyst in a glass reactor;
(2) carrying out vacuum treatment on the reactor added with the catalyst by using a mechanical pump;
(3) filling 10-60 ml of methane into the glass reactor by using a methane gas bag, and sealing;
(4) the sealed glass reactor was placed under a xenon lamp for 1-6 hours.
The wavelength range of the xenon lamp light source is 200-800 nanometers.
The invention has the following remarkable advantages:
the invention takes (2,2' -bipyridyl) dichloropalladium (II) and titanium dioxide as precursors, adopts a surface metal organic chemistry method, successfully anchors the (2,2' -bipyridyl) dichloropalladium (II) on the surface of the titanium dioxide in a covalent bond mode through the reaction between organic metal (2,2' -bipyridyl) dichloropalladium (II) and hydroxyl on the surface of the titanium dioxide, and obtains Pd (bpy)/TiO2An organometallic inorganic semiconductor composite photocatalytic material. In addition, research results show that the composite photocatalyst shows excellent catalytic capability in the anaerobic coupling reaction of photocatalytic methane. This is because (2,2' -bipyridine) dichloropalladium (II) acts as a photosensitizer to enhance light absorption, while the bipyridine ring accelerates the transport of photo-generated electrons and holes. Pd (bpy)/TiO prepared by the invention2The organic-metal inorganic semiconductor composite photocatalytic material is expected to have a more considerable development prospect in the field of photocatalytic methane conversion.
Drawings
FIG. 1(2,2' -bipyridine) Palladium (II) dichloride grafting of TiO2A process in situ ir spectrum;
FIG. 2(2,2' -bipyridine) Palladium (II) dichloride grafting of TiO2Sample (I)13C-NMR spectrum.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
Comparative example 1
Weighing 2 mg of commercial titanium dioxide in a glass reactor, vacuumizing by using a mechanical pump to ensure that the interior of the reactor is in a vacuum state, filling 25 ml of high-purity methane gas into the reactor by using an air bag, and repeating the steps for more than three times to ensure that the air in the reactor is completely removed. Then the glass is placed under 200-800 nm simulated sunlight for 4 hours.
Comparative example 2
Weighing 20 mg of commercial titanium dioxide in a glass reactor, treating for 8 hours at 400 ℃ in an oxygen atmosphere, connecting the glass reactor with a high vacuum device, and performing high vacuum treatment at 400 ℃ (10℃)-2Pa) for 2 hours and then cooled to room temperature. An amount of (2,2 '-bipyridine) dichloropalladium (II) was weighed out in a glove box after strict removal of water and oxygen and dissolved in ultra-dry acetonitrile to give a 0.5 mg per ml acetonitrile solution of (2,2' -bipyridine) dichloropalladium (II). Subsequently, 0.5 ml of (2,2' -bipyridine) dichloropalladium (II) solution in acetonitrile was measured by syringe and injected into a glass reactor, and the whole process was carried out in a glove box without water and oxygen. Then, the glass reactor was placed in a tube furnace and heat-treated at 360 ℃ for 6 hours. Cooling to room temperature after heat treatment, high vacuum (10)-1Pa) for 0.5 hour to obtain a (2,2' -bipyridyl) dichloropalladium (II) grafted titanium dioxide catalyst Pd (bpy)/TiO with the mass fraction of palladium of 0.4 percent2. Weighing 0.4 percent (2,2' -bipyridyl) dichloropalladium (II) grafted titanium dioxide catalyst Pd (bpy)/TiO 2 mg of palladium by mass fraction2In the glass reactor, a mechanical pump is used for vacuumizing to ensure that the inside of the reactor is in a vacuum state, and then 25 ml of high-purity argon gas is filled into the reactor by an air bag, and the steps are repeated for more than three times to ensure that the air in the reactor is completely removed. Then the glass is placed under 200-800 nm simulated sunlight for 4 hours.
Example 1
Weighing 20 mg of commercial titanium dioxide in a glass reactor, treating for 8 hours at 400 ℃ in an oxygen atmosphere, connecting the glass reactor with a high vacuum device, and performing high vacuum treatment at 400 ℃ (10℃)-2Pa) for 2 hours and then cooled to room temperature. A certain amount of (2,2 '-bipyridine) dichloropalladium (II) is weighed in a glove box after strictly removing water and oxygen and dissolved in ultra-dry acetonitrile to obtain an acetonitrile solution of 0.5 mg per ml of (2,2' -bipyridine) dichloropalladium (II). Subsequently, 0.25 ml of (2,2' -bipyridine) dichloropalladium (II) solution in acetonitrile was measured by syringe and injected into a glass reactor, and the whole process was carried out in a glove box without water and oxygen. The glass reactor was then placed in a tube furnace and heated at 360 degrees CelsiusThe treatment was carried out for 6 hours. Cooling to room temperature after heat treatment, high vacuum (10)-1Pa) for 0.5 hour to obtain a (2,2' -bipyridyl) dichloropalladium (II) grafted titanium dioxide catalyst Pd (bpy)/TiO with the mass fraction of palladium of 0.2 percent2. Weighing 2 mg Pd (bpy)/TiO2The catalyst is put in a glass reactor, the glass reactor is vacuumized by a mechanical pump, then 25 ml of high-purity methane gas is filled into the glass reactor by an air bag, and the reaction is repeated for more than three times until the air in the reactor is completely exhausted. Then, the reactor is sealed and then placed under 200-800 nm quasi-sunlight for 6 hours.
Example 2
Weighing 20 mg of commercial titanium dioxide in a glass reactor, treating for 8 hours at 400 ℃ in an oxygen atmosphere, connecting the glass reactor with a high vacuum device, and performing high vacuum treatment at 400 ℃ (10℃)-2Pa) for 2 hours and then cooled to room temperature. A certain amount of (2,2 '-bipyridine) dichloropalladium (II) is weighed in a glove box after strictly removing water and oxygen and dissolved in ultra-dry acetonitrile to obtain an acetonitrile solution of 0.5 mg per ml of (2,2' -bipyridine) dichloropalladium (II). Subsequently, 0.5 ml of (2,2' -bipyridine) dichloropalladium (II) solution in acetonitrile was measured by syringe and injected into a glass reactor, and the whole process was carried out in a glove box without water and oxygen. Then, the glass reactor was placed in a tube furnace and heat-treated at 360 ℃ for 6 hours. Cooling to room temperature after heat treatment, high vacuum (10)-1Pa) for 0.5 hour to obtain a (2,2' -bipyridyl) dichloropalladium (II) grafted titanium dioxide catalyst Pd (bpy)/TiO with the mass fraction of palladium of 0.4 percent2. Weighing 2 mg Pd (bpy)/TiO2The catalyst is put in a glass reactor, the glass reactor is vacuumized by a mechanical pump, then 25 ml of high-purity methane gas is filled into the glass reactor by an air bag, and the reaction is repeated for more than three times until the air in the reactor is completely removed. Then, the reactor is sealed and then placed under 200-800 nm quasi-sunlight for 6 hours.
Example 3
The preparation of the catalyst and the photocatalytic anaerobic coupling process of methane were the same as in example 1 of this section, except that (2,2' -bipyridine) bisThe addition amount of the acetonitrile solution of the palladium (II) chloride is 0.75 ml, and the (2,2' -bipyridyl) dichloropalladium (II) grafted titanium dioxide catalyst Pd (bpy)/TiO with the mass fraction of palladium of 0.6 percent is finally obtained2。
Example 4
The preparation of the catalyst and the photocatalytic anaerobic coupling process of methane are the same as those in the example 1, except that the acetonitrile solution of (2,2 '-bipyridyl) dichloropalladium (II) is added in an amount of 1.0 ml, and the (2,2' -bipyridyl) dichloropalladium (II) grafted titanium dioxide catalyst Pd (bpy)/TiO (TiO) with the mass fraction of palladium of 0.8 percent is finally obtained2。
Example 5
The preparation of the catalyst and the photocatalytic anaerobic coupling process of methane were the same as in example 1, except that the amount of acetonitrile solution of (2,2 '-bipyridine) dichloropalladium (II) was 1.25 ml, and the final (2,2' -bipyridine) dichloropalladium (II) grafted titania catalyst Pd (bpy)/TiO 2 with 1.0% palladium mass fraction was obtained2。
Example 6
The preparation of the catalyst and the photocatalytic anaerobic coupling process of methane were the same as in example 1, except that 3.75 ml of acetonitrile solution of (2,2 '-bipyridine) dichloropalladium (II) was added to obtain a 3.0% palladium (2,2' -bipyridine) dichloropalladium (II) grafted titania catalyst Pd (bpy)/TiO (TiO) with a Pd content of 3.0%2。
Example 7
The preparation of the catalyst and the photocatalytic anaerobic coupling process of methane were the same as in example 1, except that the amount of acetonitrile solution of (2,2 '-bipyridine) dichloropalladium (II) was 6.25 ml, and the final (2,2' -bipyridine) dichloropalladium (II) grafted titania catalyst Pd (bpy)/TiO 2 with 5.0% palladium mass fraction was obtained2。
Example 8
The preparation of the catalyst and the photocatalytic anaerobic coupling process of methane were the same as in example 2 of this section, except that the light irradiation time was 1 hour.
Example 9
The preparation of the catalyst and the photocatalytic anaerobic coupling process of methane were the same as in example 2 of this section, except that the light irradiation time was 35 hours.
The palladium contents, the light irradiation times and the corresponding ethane yields in the examples and comparative examples are shown in the following table:
through in-situ infrared technology and solid nuclear magnetic resonance carbon spectrum characterization, through the graphs in fig. 1-2, the (2,2' -bipyridyl) dichloropalladium (II) can be successfully anchored on the surface of the titanium dioxide through covalent bonding.
The above data show that Pd (bpy)/TiO is present in this example compared to commercial titanium dioxide without treatment2The organic metal inorganic semiconductor composite photocatalyst shows the capability of activating methane, and the performance of catalyzing methane coupling is greatly improved.
The above description is only a few embodiments of the present invention, and all changes and modifications that can be made according to the claimed invention are within the scope of the present invention.
Claims (10)
1. Pd (bpy)/TiO2An organometallic compound-modified inorganic semiconductor composite photocatalyst, characterized in that: the Pd (bpy)/TiO2The organic metal inorganic semiconductor composite photocatalyst is a material obtained by compounding metal organic complex (2,2' -bipyridyl) palladium dichloride (II) and titanium dioxide, wherein the mass fraction of palladium is 0.2-5.0%.
2. The Pd (bpy)/TiO compound of claim 12The preparation method of the organic metal inorganic semiconductor composite photocatalyst is characterized by comprising the following steps: grafting (2,2' -bipyridyl) dichloropalladium (II) onto the surface of titanium dioxide by a surface grafting method by adopting a surface metal organic chemistry method to obtain the composite material.
3. Pd (bpy)/TiO according to claim 22The preparation method of the organic metal inorganic semiconductor composite photocatalyst is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) placing 0.01-20 g of commercial titanium dioxide in a glass reactor for calcining to obtain a white sample A;
(2) treating the white sample A obtained in the step (1) in high vacuum to obtain a dark gray sample B;
(3) 0.1 to 50 mg of (2,2' -bipyridine) dichloropalladium (II) was introduced into the sample B obtained in the step (2) under anhydrous and oxygen-free conditions, and reacted to obtain a brown sample C.
4. Pd (bpy)/TiO according to claim 32The preparation method of the organic metal inorganic semiconductor composite photocatalyst is characterized by comprising the following steps: the calcination condition in the step (1) is calcination at 200-500 ℃ for 0.5-20 hours in an oxygen atmosphere.
5. Pd (bpy)/TiO according to claim 32The preparation method of the organic metal inorganic semiconductor composite photocatalyst is characterized by comprising the following steps: the high vacuum treatment in the step (2) is specifically 200-500 ℃ high-temperature vacuum treatment for 0.5-5 hours.
6. Pd (bpy)/TiO according to claim 32The preparation method of the organic metal inorganic semiconductor composite photocatalyst is characterized by comprising the following steps: the high vacuum pressure in the step (2) is in the range of: 10-1 – 10-4And (6) handkerchief.
7. Pd (bpy)/TiO according to claim 32The preparation method of the organic metal inorganic semiconductor composite photocatalyst is characterized by comprising the following steps: the reaction in the step (3) is specifically carried out at the temperature of 100 ℃ and 400 ℃ for 6-40 hours.
8. The Pd (bpy)/TiO compound of claim 12The application of the organic metal inorganic semiconductor composite photocatalyst in the photocatalytic anaerobic coupling of methane is characterized in that: the photocatalytic anaerobic methane coupling reaction comprises the following specific steps:
(1) weighing 2-50 mg Pd (bpy)/TiO2Placing the organic-metal inorganic semiconductor composite photocatalyst in a glass reactor;
(2) carrying out vacuum treatment on the reactor added with the catalyst by using a mechanical pump;
(3) filling 10-60 ml of methane into the glass reactor by using a methane gas bag, and sealing;
(4) the sealed glass reactor was placed under a xenon lamp for 1-6 hours.
9. Use according to claim 8, characterized in that: the vacuum treatment in the step (2) is specifically 10-1-10-4And (6) handkerchief.
10. Use according to claim 8, characterized in that: the wavelength range of the xenon lamp is 200-800 nanometers.
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