CN114318388B - Photoelectrocatalysis olefin hydrogenation device and application thereof - Google Patents
Photoelectrocatalysis olefin hydrogenation device and application thereof Download PDFInfo
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- CN114318388B CN114318388B CN202210089342.XA CN202210089342A CN114318388B CN 114318388 B CN114318388 B CN 114318388B CN 202210089342 A CN202210089342 A CN 202210089342A CN 114318388 B CN114318388 B CN 114318388B
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 48
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 36
- 239000012528 membrane Substances 0.000 claims abstract description 90
- 239000000243 solution Substances 0.000 claims abstract description 37
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000002209 hydrophobic effect Effects 0.000 claims description 30
- 238000005341 cation exchange Methods 0.000 claims description 27
- 239000003011 anion exchange membrane Substances 0.000 claims description 23
- 238000005266 casting Methods 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920002492 poly(sulfone) Polymers 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical group CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- JRTYPQGPARWINR-UHFFFAOYSA-N palladium platinum Chemical compound [Pd].[Pt] JRTYPQGPARWINR-UHFFFAOYSA-N 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 2
- 229940073608 benzyl chloride Drugs 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- 125000001302 tertiary amino group Chemical group 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 28
- 239000001257 hydrogen Substances 0.000 abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 15
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000005286 illumination Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000011941 photocatalyst Substances 0.000 description 12
- 150000003254 radicals Chemical class 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 230000005684 electric field Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- -1 hydrogen ions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000852 hydrogen donor Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- YSRQRFIVCMIJJE-UHFFFAOYSA-M 2,3-dihydroxypropyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC(O)CO YSRQRFIVCMIJJE-UHFFFAOYSA-M 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007646 directional migration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229940080469 phosphocellulose Drugs 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000009901 transfer hydrogenation reaction Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Catalysts (AREA)
Abstract
The invention belongs to the field of olefin hydrogenation, and particularly relates to a photoelectrocatalysis olefin hydrogenation device and application thereof. In order to solve the problem that olefin molecules are difficult to effectively contact with H free radicals and the generation rate of the H free radicals is difficult to effectively regulate and control, the invention relates to a device containing a photoelectrocatalysis composite membrane, which can take water as a hydrogen source to realize the continuous reaction device of photoelectrocatalysis hydrogen production and in-situ olefin hydrogenation reaction. The photoelectrocatalysis composite membrane is used as a diaphragm of an anode chamber and a cathode chamber, an electrolyte aqueous solution is added into the anode chamber, an organic solution containing olefin is added into the cathode chamber, and photoelectrocatalysis olefin hydrogenation reaction is carried out under the illumination of a xenon lamp and the external voltage.
Description
Technical Field
The invention belongs to the field of olefin hydrogenation, and particularly relates to a photoelectrocatalysis olefin hydrogenation device and application thereof.
Background
The hydrogenation reaction of olefin is a very important tool for basic conversion in organic chemistry, and is widely applied to the pharmaceutical and fine chemical industries. However, the current hydrogenation process usually uses hydrogen as a hydrogen source, and needs to be performed under high temperature and high pressure conditions, which brings about considerable potential safety hazards. In recent years, hydrogen transfer reactions have received increasing attention, such as alcohols, alkanes, and hydrazines, and the like, as hydrogen donors for the hydrogenation of various unsaturated olefins. Water has overwhelming advantages as the most widely used solvent and hydrogen source on earth, such as non-toxicity and low cost, and thus may be a desirable choice for organic hydrogen donors. However, since water molecules are stable, difficult to activate and dehydrogenate, rarely used for transfer hydrogenation reactions, how to activate water to generate hydrogen is a great challenge.
Semiconductor photocatalysis has become one of the most promising hydrogen production technologies, and under irradiation of light, photoexcited electrons can migrate and transfer to protons or water to form H free radicals, which are then combined to generate H 2 And (3) gas. In recent years, some researchers have tried to use water as a hydrogen source to carry out in-situ hydrogenation reaction of H radicals generated by photocatalysis and olefins by designing a highly efficient bifunctional catalyst. However, in the conventionally used oil-water mixed system, the surface of the hydrophilic catalyst is usually surrounded by water molecules, so that the olefin molecules are difficult to contact with H free radicals, and the hydrogenation efficiency of the olefin is greatly reduced. In addition, the traditional method directly adds the photocatalyst powder into an oil-water mixed system, the speed of H free radical generated by photocatalysis is difficult to regulate and control, and H is separated out due to too high speed 2 The reaction is aggravated and the rate is too slow resulting in an insufficient hydrogen source for the olefin hydrogenation reaction. Thus, how to effectively contact an olefin molecule with H radicals and to be able to effectively regulate the rate of H radical production is currently the most challenging obstacle.
Disclosure of Invention
The invention aims to solve the specific technical problems that in an oil-water mixed system for olefin catalytic hydrogenation reaction in the prior art, olefin molecules are difficult to contact with H free radicals and the speed of the H free radicals generated by photocatalysis is difficult to regulate and control, and provides a device containing a photoelectrocatalysis composite membrane, which can realize continuous reaction device and application of photoelectrocatalysis hydrogen production and in-situ olefin hydrogenation reaction by taking water as a hydrogen source.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a photoelectrocatalysis olefin hydrogenation device comprises a reactor, a photoelectrocatalysis composite membrane, a cathode, an anode, a light source and a direct current power supply; the photoelectric catalytic composite membrane is arranged in the reactor, the reactor is divided into an anode chamber and a cathode chamber, the cathode and the anode are respectively arranged in the cathode chamber and the anode chamber, the anode and the cathode of the direct current power supply are respectively connected with the anode and the cathode, and the light source is arranged above the cathode chamber;
the photoelectrocatalysis composite membrane consists of a bipolar membrane and a hydrophobic membrane with a surface loaded with a photoelectrocatalyst, the bipolar membrane is formed by compositing an anion exchange membrane and a cation exchange membrane, the anode chamber is an electrolyte aqueous solution, the cathode chamber is an olefin organic solution, and the light source is a xenon lamp.
Further, the preparation method of the photoelectric composite film comprises the following steps:
(1) One or a mixture of several of polyvinyl alcohol, polyvinylpyrrolidone, polysulfone, polyphenyl ether and polyvinyl benzyl chloride in any proportion is used as the support of the anion exchange membrane, one or a plurality of compounds containing primary amino, secondary amino, tertiary amino or quaternary amino which are mixed according to any proportion are used as the fixed groups of the anion exchange membrane, glutaraldehyde solution is added as a cross-linking agent to prepare anion exchange membrane solution, and the anion exchange membrane is prepared by a tape casting method;
(2) The method comprises the steps of taking one or a mixture of more than one of polyvinyl alcohol, polyvinylpyrrolidone, polyphenyl ether, polysulfone and styrene in any proportion as a support of a cation exchange membrane, taking one or a mixture of more than one of a compound containing sulfonic acid groups, carboxylic acid groups or phosphoric acid groups in any proportion as a fixed group of the cation exchange membrane, and adding FeCl 3 Or CaCl 2 Preparing a cation exchange membrane solution by taking the solution as a cross-linking agent, and casting the solution on the surface of the anion exchange membrane prepared in the step (1) to obtain the cation exchange membrane;
(3) And loading the photoelectrocatalyst on the surface of a hydrophobic material, then dispersing the photoelectrocatalyst in aqueous solution or absolute ethyl alcohol by ultrasonic, and casting the solution on the surface of a cation exchange membrane to obtain the hydrophobic membrane loaded with the photoelectrocatalyst.
Further, the photoelectric catalyst is Pt/C 3 N 4 、Pt/TiO 2 、Pt/MoS 2 、Pd/C 3 N 4 、Pd/TiO 2 、Pd/MoS 2 、Pd-Pt/TiO 2 、Pd-Pt/C 3 N 4 、Pd-Pt/MoS 2 One of them.
Further, the hydrophobic material is carbon fiber, carbon nanotube, hydrophobic mesoporous SiO 2 Hydrophobic molecular sieve, hydrophobic metallo-organicOne of the frame materials.
Further, the voltage of the direct current power supply is 0.8-2.5V; the electrolyte aqueous solution is Na 2 SO 4 One of the solution, naOH solution or KOH solution, the concentration is 0.01-3.0 mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the The olefin organic solution is one of styrene, decene, octene, diphenylethylene and cinnamyl alcohol solution, and the solvent is octane, heptane or hexane.
The application of a photoelectric catalytic olefin hydrogenation device is applied to olefin hydrogenation.
Compared with the prior art, the invention has the following advantages:
(1) The invention provides hydrogen ions for photocatalysis by utilizing a bipolar membrane water dissociation technology, the hydrogen ions migrate to the surface of a hydrophobic membrane through a cation exchange membrane under the action of an electric field driving force, contact with a photoelectric catalyst and are reduced into zero-valent hydrogen by photo-generated electrons, and then the zero-valent hydrogen and olefin undergo in-situ hydrogenation reaction under the action of a metal catalyst; therefore, the rate of H free radical generation by photocatalysis is controlled by regulating and controlling the water dissociation rate of the bipolar membrane, so that H precipitation caused by too high rate is avoided 2 The reaction is aggravated and the rate is too slow resulting in an insufficient hydrogen source for the olefin hydrogenation reaction.
(2) The surface of the hydrophobic membrane is a fibrous, tubular and porous hydrophobic material, which is favorable for hydrophobic olefin molecules to enter the surface of the catalyst to react, and solves the problem that the olefin molecules are difficult to reach the surface of the catalyst to contact with H free radicals in the traditional oil-water two-phase mixed system.
(3) According to the invention, the electric field is formed at two sides of the photoelectrocatalysis composite membrane by applying voltage, so that on one hand, the effective separation of photo-generated electrons and holes is facilitated, the photoelectrocatalysis efficiency is improved, and on the other hand, the effect of the electric field has a promoting effect on the directional migration of hydrogen ions and H free radicals, and the hydrogenation reaction of olefin is facilitated.
(4) The hydrophobic membrane can effectively prevent the water solution in the anode chamber from entering the cathode chamber, thereby effectively preventing water molecules from entering the cathode chamber to generate hydrogen evolution reaction.
(5) According to the invention, the characteristic that the membrane liquid has viscosity is utilized, and the hydrophobic membrane material loaded with the photocatalyst is cast on the surface of the cation exchange membrane, so that the agglomeration phenomenon caused by directly adding the catalyst powder into an oil-water two-phase system in the traditional method is effectively avoided, and the catalyst powder is convenient for recycling.
(6) The water consumed by the water dissociation of the interface layer in the middle of the bipolar membrane is supplemented by the water in the electrolyte aqueous solution of the anode chamber through the anion exchange membrane.
Drawings
FIG. 1 is a schematic diagram of a photoelectrocatalytic olefin hydrogenation unit of the present invention;
FIG. 2 is a cross-sectional SEM image of a bipolar membrane after brittle fracture in liquid nitrogen;
FIG. 3 is a schematic illustration of the preparation of a cation exchange membrane according to example 1 of the present invention using FeCl 3 Schematic solution cross-linking;
FIG. 4 is a MoS prepared in example 1 of the present invention 2 A topography of the photocatalyst;
FIG. 5 is a MoS prepared in example 1 of the present invention 2 XRD pattern of the photocatalyst;
FIG. 6 is a MoS prepared in example 1 of the present invention 2 Ultraviolet-visible absorption spectrum of photocatalyst.
Detailed Description
Example 1
As shown in FIG. 1, the photoelectrocatalysis olefin hydrogenation device comprises a reactor, a photoelectrocatalysis composite membrane, a cathode, an anode, a light source and a direct current power supply; the photoelectric catalytic composite membrane is arranged in the reactor, the reactor is divided into an anode chamber and a cathode chamber, the cathode and the anode are respectively arranged in the cathode chamber and the anode chamber, the anode and the cathode of the direct current power supply are respectively connected with the anode and the cathode, and the light source is arranged above the cathode chamber;
the photoelectrocatalysis composite membrane consists of a bipolar membrane and a hydrophobic membrane with a surface loaded with a photoelectrocatalyst, the bipolar membrane is formed by compositing an anion exchange membrane and a cation exchange membrane, the anode chamber is an electrolyte aqueous solution, the cathode chamber is an olefin organic solution, and the light source is a xenon lamp.
The preparation method of the photoelectrocatalysis composite membrane comprises the following steps:
(1) Mixing polyvinyl alcohol and chitosan with equal mass, pouring into a beaker, adding acetic acid aqueous solution with mass fraction of 0.01%, continuously stirring in a constant-temperature water bath at 60 ℃, adding glutaraldehyde after complete dissolution, continuously stirring for 1h, standing for deaeration, casting on a flat and dry glass plate with a frame, and drying in a blast drying box to obtain an anion exchange membrane;
(2) Mixing polyvinyl alcohol and sodium carboxymethylcellulose with equal mass, pouring into beaker, stirring, adding deionized water, heating to 60deg.C for dissolving, and adding FeCl after complete dissolving 3 And continuously stirring the solution for 1h, standing for deaeration, and casting on the surface of the prepared anion exchange membrane to obtain the cation exchange membrane.
(3) Photoelectrocatalyst Pt/MoS 2 The hydrophobic membrane is loaded on the surface of hydrophobic carbon fiber, then dispersed in aqueous solution or absolute ethyl alcohol by ultrasonic, and cast on the surface of a cation exchange membrane to obtain the hydrophobic membrane loaded with the photoelectric catalyst.
The photoelectrocatalysis composite membrane is used as a diaphragm of an anode chamber and a cathode chamber, na with the concentration of 0.01mol L-1 is added into the anode chamber 2 SO 4 And (3) adding an octane solution containing 0.30mmol of styrene into the cathode chamber of the electrolyte aqueous solution, and carrying out the photoelectrocatalytic olefin hydrogenation reaction under the irradiation of a xenon lamp light source and the direct current power supply voltage of 1.0V. After 6 hours of reaction, a sample was taken from the cathode chamber, and the conversion of styrene was 98% as measured by gas chromatography.
Fig. 2 is a cross-sectional SEM image of a bipolar membrane after breaking down in liquid nitrogen, from which the anion-exchange membrane and the cation-exchange membrane constituting the bipolar membrane, as well as the intermediate interface layer between the two membrane layers, can be clearly seen. The thickness of the middle interface layer of the bipolar membrane is usually only nano-scale, so that even if a small voltage is applied to two sides of the bipolar membrane, a strong electric field can be formed by the middle interface layer of the bipolar membrane, and water molecules of the middle interface layer of the bipolar membrane can be dissociated under the action of the strong electric field.
FIG. 3 is a schematic diagram of FeCl 3 Schematic representation of solution-crosslinked cation exchange membranes, as can be seen from the figure, by FeCl 3 After the solution is crosslinked, the cation exchange membrane forms a net structure, which is beneficial to improving the mechanical property of the membraneAnd the service life of the membrane can be improved.
FIG. 4 is a MoS produced 2 Morphology of photocatalyst, from which it can be seen that MoS 2 The photocatalyst has a single-layer or less-layer lamellar structure, which is beneficial to improving the separation efficiency of photo-generated carriers, thereby improving the photo-catalytic efficiency.
FIG. 5 is a MoS produced 2 The XRD pattern of the photocatalyst is consistent with diffraction peaks reported in the literature, which shows that MoS is successfully prepared 2 A photocatalyst.
FIG. 6 illustrates MoS 2 Ultraviolet-visible absorption spectrum of photocatalyst, from which can be seen MoS 2 The photocatalyst not only can absorb ultraviolet light, but also has stronger visible light absorption capacity, and is beneficial to the photoelectrocatalysis reaction.
Example 2
The photoelectrocatalysis olefin hydrogenation device is different from the photoelectrocatalysis composite membrane in preparation in example 1, and the specific preparation method is as follows:
(1) Mixing polyvinylpyrrolidone and quaternary ammonium polysulfone in a mass ratio of 2:1, pouring into a beaker, adding acetic acid aqueous solution with a mass fraction of 0.02%, continuously stirring in a constant-temperature water bath kettle at 50 ℃, adding glutaraldehyde after complete dissolution, continuously stirring for 1h, standing for deaeration, casting on a flat and dry glass plate with a frame, and drying in a blast drying box to obtain an anion exchange membrane;
(2) Mixing polyvinylpyrrolidone and phosphocellulose with equal mass, pouring into beaker, stirring, adding deionized water, heating to 60deg.C for dissolving, and adding CaCl after complete dissolving 2 And continuously stirring the solution for 1h, standing for deaeration, and casting on the surface of the prepared anion exchange membrane to obtain the cation exchange membrane.
(3) Photo-catalyst Pd/TiO 2 Loading the membrane on the surface of a hydrophobic carbon nano tube, then dispersing the membrane in aqueous solution or absolute ethyl alcohol by ultrasonic, and casting the membrane on the surface of a cation exchange membrane to obtain the hydrophobic membrane loaded with the photoelectric catalyst.
The photoelectrocatalysis composite membrane is used as a diaphragm of an anode chamber and a cathode chamber, and the concentration of the added anode chamber is 0.03mol L -1 K of (2) 2 SO 4 In the aqueous electrolyte solution, a heptane solution containing 0.25mmol decene is added into a cathode chamber, and under the irradiation of a xenon lamp light source, the photoelectric catalytic olefin hydrogenation reaction is carried out under the condition that the direct current power supply voltage is 1.2V. After 10 hours of reaction, a sample was taken from the cathode chamber and the decene conversion was 87.4% as measured by gas chromatography.
Example 3
The photoelectrocatalysis olefin hydrogenation device is different from the photoelectrocatalysis composite membrane in preparation in example 1, and the specific preparation method is as follows:
(1) Mixing polyphenyl ether and polyimide in a mass ratio of 3:1, pouring into a beaker, adding an acetic acid aqueous solution with a mass fraction of 0.03%, continuously stirring in a constant-temperature water bath at 60 ℃, adding glutaraldehyde after complete dissolution, continuously stirring for 1.5h, standing for defoaming, casting on a flat and dry glass plate with a frame, and putting into a blast drying box for drying to obtain an anion exchange membrane;
(2) Mixing polyvinylpyrrolidone and sulfocellulose with equal mass, pouring into beaker, stirring, adding deionized water, heating to 70deg.C for dissolving, and adding CaCl after complete dissolution 2 And continuously stirring the solution for 1h, standing for deaeration, and casting on the surface of the prepared anion exchange membrane to obtain the cation exchange membrane.
(3) Photoelectrocatalyst Pt/C 3 N 4 Loading the membrane on the surface of a hydrophobic molecular sieve, then dispersing the membrane in aqueous solution or absolute ethyl alcohol by ultrasonic, and casting the membrane on the surface of a cation exchange membrane to obtain the hydrophobic membrane loaded with the photoelectric catalyst.
The photoelectrocatalysis composite membrane is used as a diaphragm of an anode chamber and a cathode chamber, and the concentration of the added anode chamber is 0.01mol L -1 Adding a hexane solution containing 0.50mmol of diphenylethylene into a cathode chamber, and carrying out photoelectric catalytic olefin hydrogenation reaction under the irradiation of a xenon lamp light source and the direct current power supply voltage of 2.5V. After 12 hours of reaction, a sample was taken from the cathode chamber, and the conversion of diphenylethylene was 95.4% as measured by gas chromatography.
Example 4
The photoelectrocatalysis olefin hydrogenation device is different from the photoelectrocatalysis composite membrane in preparation in example 1, and the specific preparation method is as follows:
(1) Mixing polysulfone and glyceryl trimethyl ammonium chloride with the mass ratio of 0.5:1, pouring into a beaker, adding acetic acid aqueous solution with the mass fraction of 0.005%, continuously stirring in a constant-temperature water bath kettle at 70 ℃, adding glutaraldehyde after complete dissolution, continuously stirring for 2.5h, standing for deaeration, casting on a flat and dry glass plate with a frame, and drying in a blast drying box to obtain an anion exchange membrane;
(2) Mixing polyvinylpyrrolidone and cellulose acetate with equal mass, pouring into beaker, adding phosphoric acid aqueous solution with mass fraction of 0.05% under stirring, heating to 70deg.C for dissolving, and adding FeCl after complete dissolution 3 Continuously stirring the solution for 1h, standing for deaeration, and casting on the surface of the prepared anion exchange membrane to obtain a cation exchange membrane;
(3) Photoelectrocatalyst Pd-Pt/C 3 N 4 Loaded on hydrophobic mesoporous SiO 2 And then dispersing the surface of the porous membrane in aqueous solution or absolute ethyl alcohol by ultrasonic, and casting the surface of the porous membrane on the surface of a cation exchange membrane to obtain the hydrophobic membrane loaded with the photoelectrocatalyst.
The photoelectrocatalysis composite membrane is used as a diaphragm of an anode chamber and a cathode chamber, and the concentration of the anode chamber is 3.0mol L -1 Adding octane solution containing 0.6mmol of cinnamyl alcohol into a cathode chamber, and carrying out photoelectric catalytic olefin hydrogenation reaction under the irradiation of a xenon lamp light source and the direct current power supply voltage of 0.8V. After 8 hours of reaction, the reaction chamber was sampled and the conversion of cinnamyl alcohol was 96.2% by gas chromatography.
Claims (5)
1. The photoelectrocatalysis olefin hydrogenation device is characterized by comprising a reactor, a photoelectrocatalysis composite membrane, a cathode, an anode, a light source and a direct current power supply; the photoelectric catalytic composite membrane is arranged in the reactor, the reactor is divided into an anode chamber and a cathode chamber, the cathode and the anode are respectively arranged in the cathode chamber and the anode chamber, the anode and the cathode of the direct current power supply are respectively connected with the anode and the cathode, and the light source is arranged above the cathode chamber;
the photoelectrocatalysis composite membrane consists of a bipolar membrane and a hydrophobic membrane with a surface loaded with a photoelectrocatalyst, the bipolar membrane is formed by compositing an anion exchange membrane and a cation exchange membrane, the anode chamber is an electrolyte aqueous solution, the cathode chamber is an olefin organic solution, and the light source is a xenon lamp; the photoelectric catalyst is Pt/C 3 N 4 、Pt/TiO 2 、Pt/MoS 2 、Pd/C 3 N 4 、Pd/TiO 2 、Pd/MoS 2 、Pd-Pt/TiO 2 、Pd-Pt/C 3 N 4 、Pd-Pt/ MoS 2 One of the following; the electrolyte aqueous solution is Na 2 SO 4 One of the solution, naOH solution or KOH solution, the concentration is 0.01-3.0 mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the The olefin organic solution is one of styrene, decene, octene, diphenylethylene and cinnamyl alcohol solution, and the solvent is octane, heptane or hexane.
2. The photoelectrocatalytic olefin hydrogenation device according to claim 1, wherein the photoelectrocatalytic composite membrane is prepared by the following method:
(1) One or a mixture of several of polyvinyl alcohol, polyvinylpyrrolidone, polysulfone, polyphenyl ether and polyvinyl benzyl chloride in any proportion is used as the support of the anion exchange membrane, one or a plurality of compounds containing primary amino, secondary amino, tertiary amino or quaternary amino which are mixed according to any proportion are used as the fixed groups of the anion exchange membrane, glutaraldehyde solution is added as a cross-linking agent to prepare anion exchange membrane solution, and the anion exchange membrane is prepared by a tape casting method;
(2) The method comprises the steps of taking one or a mixture of more than one of polyvinyl alcohol, polyvinylpyrrolidone, polyphenyl ether, polysulfone and styrene in any proportion as a support of a cation exchange membrane, taking one or a mixture of more than one of a compound containing sulfonic acid groups, carboxylic acid groups or phosphoric acid groups in any proportion as a fixed group of the cation exchange membrane, and adding FeCl 3 Or CaCl 2 Preparing a cation exchange membrane solution by taking the solution as a cross-linking agent, and casting the solution on the surface of the anion exchange membrane prepared in the step (1) to obtain the cation exchange membrane;
(3) And loading the photoelectrocatalyst on the surface of a hydrophobic material, then dispersing the photoelectrocatalyst in aqueous solution or absolute ethyl alcohol by ultrasonic, and casting the solution on the surface of a cation exchange membrane to obtain the hydrophobic membrane loaded with the photoelectrocatalyst.
3. The photoelectrocatalytic olefin hydrogenation device according to claim 2, wherein the hydrophobic material is carbon fiber, carbon nanotube, hydrophobic mesoporous SiO 2 One of hydrophobic molecular sieve and hydrophobic metal organic frame material.
4. The photoelectrocatalytic olefin hydrogenation device according to claim 1, wherein the voltage of the direct current power supply is 0.8-2.5 v.
5. Use of the photoelectrocatalytic olefin hydrogenation unit of claim 1 for the hydrogenation of olefins.
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